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

Abstract

SOLUTION: There is provided a cyclic diene-containing composition having a cyclic diene content of 99.5 GC area% or less and a cyclic monoene content of 3.0 GC area% or less. There is also provided a method for producing a corresponding aldehyde by subjecting a cyclic diene in a cyclic diene-containing composition to a hydroformylation reaction, the method including controlling the cyclic monoene content included in the cyclic diene-containing composition to be a predetermined threshold value (1) or less. There is further provided a method for producing a cyclic diene-containing composition containing a cyclic diene by performing purifying by distillation of a hydrocarbon decomposition product obtained via pyrolysis of a hydrocarbon-containing composition, the method including controlling the cyclic monoene content included in the cyclic diene-containing composition to be a predetermined threshold value (1) or less.SELECTED DRAWING: Figure 1

Description

[Technical Field]

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

[0002] Aldehydes such as alicyclic aldehydes are useful as raw materials for plasticizer additives, adhesives, disinfectants, etc. Furthermore, alcohols such as alicyclic alcohols obtained by hydrogenating 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 monocyclic dienes such as cyclopentadiene in the C5 hydrocarbon fraction to form the corresponding polycyclic dienes such as dicyclopentadiene, and then purifying the C5 hydrocarbon fraction after the dimerization reaction to obtain a cyclic diene-containing composition containing polycyclic dienes such as dicyclopentadiene at a high concentration, and then subjecting the obtained cyclic diene-containing composition to a hydroformylation reaction to convert the cyclic diene into an alicyclic aldehyde corresponding to the cyclic diene.

[0004] As a method for obtaining an alicyclic aldehyde by subjecting the above-mentioned cyclic diene-containing composition to a hydroformylation reaction, for example, Patent Document 1 discloses in its Examples a technology for producing bisformyltricyclodecane by hydroformylating highly purified dicyclopentadiene. Patent Document 2 focuses on conjugated dienes contained in dicyclopentadiene as impurities that inhibit the hydroformylation reaction, and discloses a technique for reducing the amount of these conjugated dienes. Patent Document 3 describes that when producing tricyclodecane dicarbaldehyde or pentacyclopentadecanedicarbaldehyde, the starting materials dicyclopentadiene and tricyclopentadiene are preferably of high purity, and discloses a technique for removing impurities such as butadiene, isoprene, cyclopentadiene, and 1,3-pentadiene.

[0005] However, the techniques disclosed in Patent Documents 1 to 3 involve removing as many impurities as possible from a composition (hereinafter referred to as a "cyclic diene-containing composition") containing a polycyclic diene such as dicyclopentadiene (also referred to as a "cyclic diene" or "cyclic diene" in the present invention) and separating and recovering a high-purity cyclic diene, which results in problems such as complicated production processes and increased capital investment, production costs, and utility costs. Furthermore, even if the impurities contained in the cyclic diene-containing composition are reduced while taking economic efficiency into consideration, the impurities that affect the hydroformylation reaction have not been fully elucidated.

[0006] Furthermore, highly purified cyclic dienes have the problem that they are solid at room temperature and are difficult to handle industrially. For example, high-purity dicyclopentadiene has a melting point of 32.5°C and is a white crystalline solid at room temperature, but for industrial use as a starting material for the synthesis of various compounds, it is preferable that it is liquid in terms of ease of handling. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-139181 [Patent Document 2] Japanese Patent Application Publication No. 11-80067 [Patent Document 3] Japanese Patent Application Laid-Open No. 2001-11008 Summary of the Invention [Problem to be solved by the invention]

[0008] The present invention aims to solve these problems. That is, an object of the present invention is to provide a cyclic diene-containing composition that can be used as a starting material for an alicyclic aldehyde, and that can produce the alicyclic aldehyde in a short reaction time and in a high yield.

[0009] Another object of the present invention is to provide a cyclic diene-containing composition that is liquid at room temperature and has excellent industrial handleability.

[0010] Another object of the present invention is to provide a method for producing a cyclic diene-containing composition containing a cyclic diene such as dicyclopentadiene, which is used as a starting material for an alicyclic aldehyde such as tricyclodecane dicarbaldehyde, and which is capable of producing an alicyclic aldehyde corresponding to the cyclic diene in a short reaction time and in a high yield.

[0011] Another object of the present invention is to provide a method for producing an aldehyde, which comprises using the cyclic diene-containing composition to produce an aldehyde corresponding to the cyclic diene.

[0012] Alternatively, an object of the present invention is to provide a method for producing an aldehyde, which is capable of producing an alicyclic aldehyde such as tricyclodecane dicarbaldehyde corresponding to a cyclic diene, such as dicyclopentadiene, in a short reaction time and in a high yield, using a cyclic diene-containing composition containing the cyclic diene as a starting material. Alternatively, an object of the present invention is to provide a method for producing an aldehyde, which comprises producing a cyclic diene-containing composition by the method for producing a cyclic diene-containing composition of the present invention, and producing a corresponding aldehyde from the cyclic diene contained in the cyclic diene-containing composition.

[0013] A further 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 a corresponding alcohol from the aldehyde. [Means for solving the problem]

[0014] 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 controlling the content of cyclic monoenes, and further the contents of high-boiling by-products and cyclic dienes, contained in the cyclic diene-containing composition. That is, the present invention provides the following.

[0015] [1] A cyclic diene-containing composition having a cyclic diene content of 99.5 GC area % or less and a cyclic monoene content of 14.0 GC area % or less.

[0016] [2] The cyclic diene-containing composition according to [1], wherein the content of high-boiling by-products having a boiling point higher than that of the cyclic diene is 0.3 GC area % or more.

[0017] [3] The cyclic diene-containing composition according to [1] or [2], wherein the cyclic monoene has a vinyl group.

[0018] [4] The cyclic diene-containing composition according to [3], wherein the cyclic monoene comprises a cyclic monoene having 9 carbon atoms and a vinyl group.

[0019] [5] The cyclic diene-containing composition according to [4], wherein the content of the cyclic monoene having a vinyl group and 9 carbon atoms is 3.0 GC area % or less.

[0020] [6] The cyclic diene-containing composition according to any one of [1] to [5], wherein the cyclic diene content is 60 GC area % or more.

[0021] [7] The cyclic diene-containing composition according to any one of [1] to [6], wherein the content of the cyclic monoene is 0.001 GC area % or more.

[0022] [8] The cyclic diene-containing composition according to any one of [1] to [7], wherein the content of high-boiling by-products having boiling points higher than that of the cyclic diene is 25 GC area % or less.

[0023] [9] The cyclic diene-containing composition according to any one of [2] to [8], wherein the content of the high-boiling by-products is measured by the following measurement method 1. <Measurement method 1> Analyze under the following GC measurement conditions and measure the total content ratio of peaks with retention times between 15.0 and 30.0 minutes. (GC measurement conditions) GC device: Gas chromatogram measuring device Detector: Hydrogen flame ionization detector Carrier gas: Helium (column flow rate 1.65 mL / min) Column: Capillary column (size: length 30 m x inner diameter 0.25 mm, film thickness 1.00 μm) Column temperature: 50°C (hold time 5 minutes) → Heat at 10°C / minute → 300°C (hold time: none) Inlet temperature: 200℃ Detector temperature: 300℃

[0024]

[10] The cyclic diene-containing composition according to any one of [1] to [9], which has fluidity at 25°C.

[0025]

[11] The cyclic diene-containing composition according to any one of [1] to

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

[0026]

[12] The cyclic diene-containing composition according to

[11] , wherein the polycyclic diene is dicyclopentadiene.

[0027]

[13] The cyclic diene-containing composition according to any one of [1] to

[12] , wherein the cyclic monoene is a polycyclic monoene.

[0028]

[14] The cyclic diene-containing composition according to

[13] , wherein the polycyclic monoene comprises 5-vinyl-2-norbornene.

[0029]

[15] The cyclic diene-containing composition according to any one of [1] to

[14] , wherein the cyclic diene-containing composition is a composition obtained by purifying and separating hydrocarbon decomposition products obtained by thermally decomposing a hydrocarbon-containing composition.

[0030]

[16] The cyclic diene-containing composition according to

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

[0031]

[17] A method for producing an aldehyde, comprising subjecting the cyclic diene-containing composition according to any one of [1] to

[16] to a hydroformylation reaction to produce an aldehyde corresponding to the cyclic diene.

[0032]

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

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

[0033]

[19] A method for producing a corresponding aldehyde by hydroformylating a cyclic diene in a cyclic diene-containing composition, comprising: A method for producing an aldehyde, comprising controlling the content of a cyclic monoene contained in the cyclic diene-containing composition to a predetermined threshold value (1) or less.

[0034]

[20] The method for producing an aldehyde according to

[19] , wherein the predetermined threshold (1) is 14.0 GC area %.

[0035]

[21] The method for producing an aldehyde according to

[19] or

[20] , comprising controlling the content of high-boiling by-products having boiling points higher than those of the cyclic diene contained in the cyclic diene-containing composition to a predetermined threshold value (2) or higher.

[0036]

[22] The method for producing an aldehyde according to

[21] , wherein the predetermined threshold value (2) is 0.3 GC area %.

[0037]

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

[19] to

[22] , wherein the content of the cyclic diene in the cyclic diene-containing composition is 99.5 GC area % or less.

[0038]

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

[19] to

[23] , wherein the cyclic monoene has a vinyl group.

[0039]

[25] The method for producing an aldehyde according to

[24] , wherein the cyclic monoene includes a cyclic monoene having 9 carbon atoms and a vinyl group.

[0040]

[26] The method for producing an aldehyde according to

[25] , wherein the content of the cyclic monoene having a vinyl group and 9 carbon atoms in the cyclic diene-containing composition is 3.0 GC area % or less.

[0041]

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

[19] to

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

[0042]

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

[19] to

[27] , wherein the cyclic diene-containing composition contains the cyclic monoene in an amount of 0.001 GC area % or more.

[0043]

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

[19] to

[28] , wherein the cyclic diene-containing composition contains high-boiling by-products having boiling points higher than those of the cyclic diene in an amount of 25 GC area % or less.

[0044]

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

[21] to

[29] , wherein the content of the high-boiling by-products is measured by the following measurement method 1. <Measurement method 1> Analyze under the following GC measurement conditions and measure the total content ratio of peaks with retention times between 15.0 and 30.0 minutes. (GC measurement conditions) GC device: Gas chromatogram measuring device Detector: Hydrogen flame ionization detector Carrier gas: Helium (column flow rate 1.65 mL / min) Column: Capillary column (size: length 30 m x inner diameter 0.25 mm, film thickness 1.00 μm) Column temperature: 50°C (hold time 5 minutes) → Heat at 10°C / minute → 300°C (hold time: none) Inlet temperature: 200℃ Detector temperature: 300℃

[0045]

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

[19] to

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

[0046]

[32] The method for producing an aldehyde according to

[31] , wherein the polycyclic diene is dicyclopentadiene.

[0047]

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

[19] to

[32] , wherein the cyclic monoene is a polycyclic monoene.

[0048]

[34] The method for producing an aldehyde according to

[32] , wherein the polycyclic monoene comprises 5-vinyl-2-norbornene.

[0049]

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

[19] to

[34] , 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.

[0050]

[36] The method for producing an aldehyde according to

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

[0051]

[37] The method for producing an aldehyde according to

[35] or

[36] , comprising controlling the conditions of the distillation purification so that the content of the cyclic monoene contained in the cyclic diene-containing composition is equal to or less than a predetermined threshold value (1).

[0052]

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

[35] to

[37] , comprising controlling the conditions of the distillation purification so that the content of the high-boiling by-products contained in the cyclic diene-containing composition is equal to or greater than a predetermined threshold value (2).

[0053]

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

[35] to

[38] , wherein the distillation purification comprises a first distillation column and a second distillation column, the first distillation column having a number of theoretical plates of 10 or more and 20 or less, and the second distillation column having a number of theoretical plates of 10 or more and 20 or less.

[0054]

[40] The method for producing an aldehyde according to

[39] , wherein the reflux ratio of the first distillation column is 20 or more and 30 or less, and the reflux ratio of the second distillation column is 1.0 or more and 1.5 or less.

[0055]

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

[19] to

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

[0056]

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

[39] or

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

[0057]

[43] 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, comprising: A method for producing a cyclic diene-containing composition, comprising controlling the content of cyclic monoene contained in the cyclic diene-containing composition to a predetermined threshold value (1) or less.

[0058]

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

[43] , comprising controlling the content of high-boiling by-products having boiling points higher than those of the cyclic diene contained in the cyclic diene-containing composition to a predetermined threshold value (2) or more.

[0059]

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

[43] or

[44] , wherein the predetermined threshold (1) is 14.0 GC area %.

[0060]

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

[44] or

[45] , wherein the predetermined threshold (2) is 0.3 GC area %.

[0061]

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

[43] to

[46] , comprising controlling the conditions of the distillation purification so that the content of cyclic monoene contained in the cyclic diene-containing composition is equal to or less than a predetermined threshold value (1).

[0062]

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

[44] to

[47] , comprising controlling the conditions of the distillation purification so that the content of the high-boiling by-products contained in the cyclic diene-containing composition is equal to or greater than a predetermined threshold value (2).

[0063]

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

[43] to

[48] , wherein the distillation purification comprises a first distillation column and a second distillation column, the first distillation column having a number of theoretical plates of 10 or more and 20 or less, and the second distillation column having a number of theoretical plates of 10 or more and 20 or less.

[0064]

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

[49] , wherein the reflux ratio of the first distillation column is 20 or more and 30 or less, and the reflux ratio of the second distillation column is 1.0 or more and 1.5 or less.

[0065]

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

[43] to

[50] , wherein the content of the cyclic diene contained in the cyclic diene-containing composition is 99.5 GC area % or less.

[0066]

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

[43] to

[51] , wherein the cyclic monoene has a vinyl group.

[0067]

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

[52] , wherein the cyclic monoene includes a cyclic monoene having 9 carbon atoms and a vinyl group.

[0068]

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

[53] , wherein the content of the cyclic monoene having a vinyl group and 9 carbon atoms in the cyclic diene-containing composition is 3.0 GC area % or less.

[0069]

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

[43] to

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

[0070]

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

[43] to

[55] , wherein the content of the cyclic monoene contained in the cyclic diene-containing composition is 0.001 GC area % or more.

[0071]

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

[43] to

[56] , wherein the content of high-boiling by-products having a boiling point higher than that of the cyclic diene contained in the cyclic diene-containing composition is 25 GC area % or less.

[0072]

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

[44] to

[57] , wherein the content of the high-boiling by-products is measured by the following measurement method 1. <Measurement method 1> Analyze under the following GC measurement conditions and measure the total content ratio of peaks with retention times between 15.0 and 30.0 minutes. (GC measurement conditions) GC device: Gas chromatogram measuring device Detector: Hydrogen flame ionization detector Carrier gas: Helium (column flow rate 1.65 mL / min) Column: Capillary column (size: length 30 m x inner diameter 0.25 mm, film thickness 1.00 μm) Column temperature: 50°C (hold time 5 minutes) → Heat at 10°C / minute → 300°C (hold time: none) Inlet temperature: 200℃ Detector temperature: 300℃

[0073]

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

[43] to

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

[0074]

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

[59] , wherein the polycyclic diene is dicyclopentadiene.

[0075]

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

[43] to

[60] , wherein the cyclic monoene is a polycyclic monoene.

[0076]

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

[61] , wherein the polycyclic monoene comprises 5-vinyl-2-norbornene.

[0077]

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

[43] to

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

[0078]

[64] A method for producing an aldehyde, comprising producing a cyclic diene-containing composition by the production method according to any one of

[43] to

[48] and

[51] to

[63] , and producing a corresponding aldehyde from the cyclic diene contained in the cyclic diene-containing composition.

[0079]

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

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

[0080]

[66] A method for producing an aldehyde, comprising producing a cyclic diene-containing composition by the production method according to

[49] or

[50] , and producing a corresponding aldehyde from the cyclic diene contained in the cyclic diene-containing composition.

[0081]

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

[66] , and producing a corresponding alcohol from the aldehyde. [Effects of the Invention]

[0082] According to the present invention, there is provided a cyclic diene-containing composition that can be used as a starting material for an alicyclic aldehyde to efficiently produce the alicyclic aldehyde. The cyclic diene-containing composition can be used to efficiently produce the corresponding aldehyde and further alcohol. Furthermore, the cyclic diene-containing composition of the present invention can be liquid at room temperature, and therefore a cyclic diene-containing composition with excellent industrial handleability can be provided.

[0083] Furthermore, according to the present invention, it is possible to provide a method for producing an aldehyde, which is capable of producing an alicyclic aldehyde, such as tricyclodecane dicarbaldehyde, corresponding to a cyclic diene, in a short reaction time and in a high yield, using a cyclic diene-containing composition containing a cyclic diene such as dicyclopentadiene as a starting material, and further to provide a method for producing a corresponding alcohol from the aldehyde. Furthermore, according to the method for producing an aldehyde of the present invention, the cyclic diene-containing composition used as a starting material can be made liquid at room temperature, so that a method for producing an aldehyde with excellent operability can be provided.

[0084] Furthermore, according to the present invention, there can be provided a method for producing a cyclic diene-containing composition that contains a cyclic diene such as dicyclopentadiene and is used as a starting material for an alicyclic aldehyde such as tricyclodecane dicarbaldehyde, the cyclic diene-containing composition being capable of producing an alicyclic aldehyde corresponding to the cyclic diene in a short reaction time and in a high yield; a method for producing an aldehyde from the cyclic diene contained in the cyclic diene-containing composition; and a method for producing an alcohol from the aldehyde. Furthermore, according to the method for producing a cyclic diene-containing composition of the present invention, the obtained cyclic diene-containing composition can be made liquid at room temperature, thereby providing a cyclic diene-containing composition that is easy to handle industrially. [Brief explanation of the drawings]

[0085] [Figure 1] FIG. 1 is a schematic system diagram illustrating one embodiment of a production process for separating and recovering the cyclic diene-containing composition of the present invention from a C5 hydrocarbon fraction according to the present invention. [Figure 2A] FIG. 2A is a graph showing the relationship between the content (GC area %) of cyclic monoenes (total of vinylnorbornene and isopropenylnorbornene) contained in cyclic diene-containing compositions (fractions 1 to 7) and the reaction completion time of the hydroformylation reaction when fractions 1 to 7 used in Experimental Examples 1 to 7 were subjected to a hydroformylation reaction. [Figure 2B] FIG. 2B is a graph showing the relationship between the content (GC area %) of vinylnorbornene in the cyclic diene-containing composition (fractions 1 to 7) and the reaction completion time of the hydroformylation reaction when the hydroformylation reaction was carried out using fractions 1 to 7 used in Experimental Examples 1 to 7. [Figure 3A] FIG. 3A is a graph showing the relationship between the content (GC area %) of cyclic monoenes (total of vinylnorbornene and isopropenylnorbornene) contained in cyclic diene-containing compositions (fractions 1 to 7) and the TCDDD yield of the hydroformylation reaction when fractions 1 to 7 used in Experimental Examples 1 to 7 were subjected to a hydroformylation reaction. [Figure 3B] FIG. 3B is a graph showing the relationship between the content (GC area %) of vinylnorbornene in the cyclic diene-containing composition (fractions 1 to 7) and the TDD yield of the hydroformylation reaction when the hydroformylation reaction was carried out using fractions 1 to 7 used in Experimental Examples 1 to 7. [Figure 4]FIG. 4 is a graph showing the relationship between the content (GC area %) of high-boiling by-products contained in cyclic diene-containing compositions (fractions 7 to 14, commercially available DCPD) and the completion time of the hydroformylation reaction when fractions 7 to 14 used in Experimental Examples 7 to 14 and commercially available DCPD used in Experimental Example 15 were subjected to a hydroformylation reaction. [Figure 5] FIG. 5 is a graph showing the relationship between the content (GC area %) of high-boiling by-products contained in the cyclic diene-containing composition (fractions 7 to 14, commercially available DCPD) and the TCDDD yield when a hydroformylation reaction was carried out using fractions 7 to 14 used in Experimental Examples 7 to 14 and commercially available DCPD used in Experimental Example 15. [Figure 6] FIG. 6 is a gas chromatogram of the heavy C5 fraction composition obtained in Reference Experimental Example 1. [Figure 7] FIG. 7 is a gas chromatogram of fraction 2 obtained in Reference Experimental Example 2. DETAILED DESCRIPTION OF THE INVENTION

[0086] The present invention will be described in detail below. 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.

[0087] Unless otherwise specified, in this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​written before and after "to" as the lower and upper limits, and "A to B" means A or more and B or less. In this specification, unless otherwise specified, "including A or B" means "including A," "including B," or "including A and B." In this specification, "GC area %" refers to the composition ratio of each component measured using a gas chromatograph (GC) measuring device and a gas chromatography total area method, and is calculated as the area content ratio (unit: GC area %) of each peak component when the total area of ​​the GC peaks of all products on the gas chromatogram is taken as 100%. Details of the GC measurement conditions will be explained in the experimental examples below. In this specification, "mass %" indicates the content ratio of a specified component contained in a total amount of 100% by mass. "Wt %" indicates the content ratio of a specified component contained in a total amount of 100% by weight. "Wt %" and "wt %" have the same meaning. "Optional" or "optionally" means that the subsequently described circumstance may or may not occur, and thus the description includes both the occurrence and non-occurrence of the circumstance. As used herein, "room temperature" refers to a temperature of 25°C. As used herein, the term "about" can mean above and below 20% of the stated value. For example, about 75°C encompasses the range of 60°C to 90°C. All steps described herein can be performed in any suitable order unless otherwise stated herein or clearly contradicted by context.

[0088] As used herein, "hydrocarbon" refers to naphtha, coal, and natural gas. More specifically, it refers to hydrocarbons such as fossil fuels and refined petroleum products, including naphtha, heavy aromatic naphtha, crude oil, gasoline, kerosene, diesel oil, light oil, heavy oil, extra heavy oil, heavy oil A, heavy oil B, heavy oil C, jet fuel, tar, gas to liquids (GTL), coal to liquids (CTL), coal, coke, natural gas, liquefied natural gas (LNG), liquefied petroleum gas (LPG), sour gas, oil field gas, and oil field concentrate.

[0089] 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, and a method for producing a cyclic diene-containing composition according to a third embodiment of the present invention (hereinafter, the inventions of the first to third embodiments may be collectively referred to as "the present invention"). ) will be explained below.

[0090] <Cyclic Diene-Containing Composition> The cyclic diene-containing composition according to the first embodiment of the present invention will be described below.

[0091] (Embodiment 1-1) A 1-1 embodiment of the cyclic diene-containing composition of the present invention is a composition containing a cyclic diene described below, in which the content of the cyclic diene is 99.5 GC area % or less and the content of a cyclic monoene described below is 14.0 GC area % or less, relative to 100% of the total GC area of ​​the cyclic diene-containing composition. Details of the content of the cyclic monoene in the cyclic diene-containing composition will be described later.

[0092] Furthermore, the cyclic diene-containing composition of the present invention can contain high-boiling by-products, which will be described later. The content of the high-boiling by-products in the cyclic diene-containing composition is preferably 0.3 GC area% or more relative to 100% of the total GC area of ​​the cyclic diene-containing composition. Details of the content of the high-boiling by-products in the cyclic diene-containing composition will be described later.

[0093] (First and second embodiments) The first-second embodiment of the cyclic diene-containing composition of the present invention is a cyclic diene-containing composition produced by the method for producing a cyclic diene-containing composition according to the third embodiment of the present invention, which will be described later.

[0094] The cyclic diene-containing compositions according to the embodiments 1-1 and 1-2 of the present invention will hereinafter be collectively referred to simply as "the cyclic diene-containing composition of the present invention."

[0095] In this specification, the cyclic diene-containing composition of the present invention, the cyclic diene-containing composition related to the aldehyde production method of the second embodiment of the present invention, and the cyclic diene-containing composition related to the cyclic diene-containing composition production method of the third embodiment of the present invention are collectively referred to as the "cyclic diene-containing composition of the present invention." In other words, the "cyclic diene-containing composition" in the first to third embodiments of the present invention can be treated as synonymous.

[0096] (cyclic diene) The cyclic diene (also referred to as "cyclic diene") in the present invention is one component that constitutes the cyclic diene-containing composition of the present invention.

[0097] The cyclic diene in the present invention is not particularly limited as long as it has a ring structure in the molecule and has two non-conjugated carbon-carbon double bonds in the ring structure. The cyclic diene is preferably a compound that can be used as a starting material when producing an alicyclic alcohol. One embodiment of the cyclic diene includes a polycyclic diene having two or more ring structures in the molecule, each of which has a non-conjugated carbon-carbon double bond. Alternatively, another embodiment of the cyclic diene includes a compound obtained by dimerization of a monocyclic diene having one ring structure.

[0098] Specific examples of the cyclic dienes include dicyclopentadiene, 1,4-cyclohexadiene, methylcyclopentadiene, methyldicyclopentadiene, and methyltetrahydroindene. Among these cyclic dienes, dicyclopentadiene is preferred because it is easily available industrially, has excellent hydroformylation reactivity, and is excellent in the production efficiency of alicyclic alcohols. These cyclic dienes can be used alone or in combination of two or more.

[0099] In this specification, the cyclic dienes related to the cyclic diene-containing composition of the present invention, the cyclic dienes related to the method for producing an aldehyde that is the second embodiment of the present invention, and the cyclic dienes related to the method for producing a cyclic diene-containing composition that is the third embodiment of the present invention are collectively referred to as "cyclic dienes in the present invention." That is, the "cyclic diene" in the first to third embodiments of the present invention can be treated as having the same meaning.

[0100] The upper limit of the cyclic diene content (unit: GC area %) in the cyclic diene-containing composition of the present invention is preferably 99.5% or less, more preferably 97.5% or less, even more preferably 95.0% or less, particularly preferably 90.0% or less, and most preferably 85.0% or less, relative to 100% of the total GC area of ​​the cyclic diene-containing composition, from the viewpoint of having fluidity at room temperature, i.e., being liquid at room temperature and having excellent industrial handleability. On the other hand, the lower limit of the cyclic diene content (unit: GC area %) is not particularly limited, but from the viewpoint of producing an alicyclic aldehyde in a short reaction time and at a high yield using the cyclic diene-containing composition as a starting material, the cyclic diene content is preferably 60.0% or more, more preferably 63.0% or more, even more preferably 66.0% or more, particularly preferably 70.0% or more, and most preferably 75.0% or more, relative to 100% of the total GC area of ​​the cyclic diene-containing composition. The upper and lower limits can be combined arbitrarily. For example, the content of the cyclic diene in the cyclic diene-containing composition (unit: GC area%) is preferably 60.0% or more and 99.5% or less, more preferably 63.0% or more and 97.5% or less, still more preferably 66.0% or more and 95.0% or less, particularly preferably 70.0% or more and 90.0% or less, and most preferably 75.0% or more and 85.0% or less, relative to 100% of the total GC area of ​​the cyclic diene-containing composition.

[0101] The method for measuring the content of the cyclic diene in the cyclic diene-containing composition will be described in detail below. Methods for controlling the content of the cyclic diene in the cyclic diene-containing composition include, for example, an extraction method, a method for controlling the amount by adjusting the purification conditions or distillation conditions, and a combination of these methods. Preferably, the method involves controlling the distillation purification conditions.

[0102] (cyclic monoene) The cyclic diene-containing composition of the present invention has a cyclic monoene (also referred to as "cyclic monoene") content that is equal to or less than a predetermined threshold value (1), so that when the cyclic diene-containing composition is used as a starting material for an alicyclic aldehyde, the alicyclic aldehyde can be produced in a short reaction time and in a high yield.

[0103] In this specification, the cyclic monoenes related to the cyclic diene-containing composition of the present invention, the cyclic monoenes related to the aldehyde production method of the second embodiment of the present invention, and the cyclic monoenes related to the cyclic diene-containing composition production method of the third embodiment of the present invention are collectively referred to as "cyclic monoenes in the present invention." That is, the "cyclic monoene" in the first to third embodiments of the present invention can be treated as having the same meaning.

[0104] The cyclic monoene in the present invention is a compound having one or more ring structures in the molecule and one carbon-carbon double bond contained in the ring structure, and more specifically, a compound having one or more ring structures in the molecule, one carbon-carbon double bond contained in the ring structure, and one or more vinyl groups not contained in the ring structure.

[0105] One embodiment of the cyclic monoene is a polycyclic monoene having two or more ring structures in the molecule, one carbon-carbon double bond contained in the ring structure, and one vinyl group not contained in the ring structure. Alternatively, another embodiment of the cyclic monoene is a chiral compound of alkenylnorbornene, one enantiomer of which is represented by the following general formula (1).

[0106] [ka]

[0107] (In the above formula (1), R 1 and R 1’ R each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, which may be branched and may have a substituent.2 represents a hydrogen atom or a methyl group.

[0108] The cyclic monoene in the present invention may be the above-mentioned cyclic monoene having a vinyl group and 9 carbon atoms.

[0109] Specific examples of the cyclic monoene include 5-vinyl-2-norbornene (referred to as "vinylnorbornene" in this specification), isopropenyl-2-norbornene (referred to as "isopropenylnorbornene" in this specification), 2-(1-propenyl)-5-norbornene, 5-(1-methylenepropyl)norbornene, 5-(2-methyl-1-methylenepropyl)norbornene, and 5-(1-phenylethenyl)norbornene. When the cyclic diene is dicyclopentadiene, examples of the cyclic monoene include 5-vinyl-2-norbornene and isopropenyl-2-norbornene.

[0110] When the cyclic monoene is optically active, the cyclic monoene of the present invention may be a single enantiomer or a racemic mixture of enantiomers.

[0111] The upper limit of the cyclic monoene content (unit: GC area %) in the cyclic diene-containing composition of the present invention is, from the viewpoint of producing an alicyclic aldehyde in a short reaction time and in a high yield using the cyclic diene-containing composition as a starting material, preferably 14.0% or less, more preferably 12.0% or less, even more preferably 10.0% or less, particularly preferably 8.0% or less, and most preferably 7.0% or less, relative to 100% of the total GC area of ​​the cyclic diene-containing composition.

[0112] Therefore, from the above-mentioned viewpoint, the predetermined threshold value (1) is preferably 14.0% or less, more preferably 12.0% or less, even more preferably 10.0% or less, particularly preferably 8.0% or less, and most preferably 7.0% or less, relative to 100% of the total GC area of ​​the cyclic diene-containing composition. Therefore, in the aldehyde production method according to the second embodiment of the present invention, it is preferable to set the threshold value (1) of the cyclic monoene content in the cyclic diene-containing composition to be equal to or less than the upper limit, and to control the cyclic monoene content in the cyclic diene-containing composition. In addition, in the method for producing a cyclic diene-containing composition according to the third embodiment of the present invention, it is preferable to set the threshold value (1) of the cyclic monoene content in the cyclic diene-containing composition to be equal to or less than the upper limit, thereby controlling the cyclic monoene content in the cyclic diene-containing composition. On the other hand, the lower limit of the content of the cyclic monoene (unit: GC area %) in the cyclic diene-containing composition is not particularly limited, and it is acceptable for the cyclic monoene to be substantially absent (0.0%). However, from the viewpoint of economic efficiency, such as the production costs required for purifying and separating the cyclic diene-containing composition, the content is preferably 0.001% or more, more preferably 0.003% or more, even more preferably 0.01% or more, particularly preferably 0.03% or more, and most preferably 0.1% or more, relative to 100% of the total GC area of ​​the cyclic diene-containing composition. The upper and lower limits can be combined arbitrarily. For example, the content of cyclic monoenes in the cyclic diene-containing composition (unit: GC area%) may be substantially zero (0.0%), or may be preferably 0.001% to 14.0% relative to the total GC area of ​​the cyclic diene-containing composition (100%), more preferably 0.003% to 12.0%, even more preferably 0.01% to 10.0%, particularly preferably 0.03% to 8.0%, and most preferably 0.1% to 7.0%.

[0113] Furthermore, the upper limit of the content (unit: GC area%) of the cyclic monoene having a vinyl group and having 9 carbon atoms, such as vinylnorbornene, in the cyclic diene-containing composition of the present invention is, from the viewpoint of producing an alicyclic aldehyde in a short reaction time and in a high yield using the cyclic diene-containing composition as a starting material, preferably 3.0% or less, more preferably 2.5% or less, even more preferably 2.0% or less, particularly preferably 1.5% or less, and most preferably 1.0% or less, relative to 100% of the total GC area of ​​the cyclic diene-containing composition. Therefore, in the case of a cyclic monoene having a vinyl group and a carbon number of 9, the predetermined threshold value (1) is, from the above-mentioned viewpoint, preferably 3.0%, more preferably 2.5%, even more preferably 2.0%, particularly preferably 1.5%, and most preferably 1.0%, relative to 100% of the total GC area of ​​the cyclic diene-containing composition. Therefore, in the method for producing an aldehyde according to the second embodiment of the present invention, it is preferable to set the threshold value (1) of the content ratio of the cyclic monoene having a vinyl group and having 9 carbon atoms, such as vinylnorbornene, to be equal to or less than the upper limit, and to control the content ratio of the cyclic monoene in the cyclic diene-containing composition. In addition, in the method for producing a cyclic diene-containing composition according to the third embodiment of the present invention, it is preferable to set the threshold value (1) of the content ratio of the cyclic monoene having a vinyl group and having 9 carbon atoms, such as vinylnorbornene, to be equal to or less than the above-mentioned upper limit, and to control the content ratio of the cyclic monoene in the cyclic diene-containing composition. On the other hand, the lower limit of the content (unit: GC area %) of cyclic monoenes having a vinyl group and having 9 carbon atoms, such as vinylnorbornene, in the cyclic diene-containing composition is not particularly limited, and the cyclic monoene may be substantially absent (0.0%). However, from the viewpoint of economic efficiency, such as the production costs required for purifying and separating the cyclic diene-containing composition, the content is preferably 0.001% or more, more preferably 0.003% or more, even more preferably 0.01% or more, particularly preferably 0.03% or more, and most preferably 0.1% or more, relative to 100% of the total GC area of ​​the cyclic diene-containing composition. The upper and lower limits can be arbitrarily combined. For example, the content (unit: GC area%) of a cyclic monoene having a vinyl group and having 9 carbon atoms, such as vinylnorbornene, may be substantially absent (0.0%), or may be preferably 0.001% to 3.0%, more preferably 0.003% to 2.5%, even more preferably 0.01% to 2.0%, particularly preferably 0.03% to 1.5%, and most preferably 0.1% to 1.0%, relative to 100% of the total GC area of ​​the cyclic diene-containing composition.

[0114] The method for measuring the content of cyclic monoene in the cyclic diene-containing composition will be described in detail below. Methods for controlling the content of cyclic monoene in the cyclic diene-containing composition include, for example, an extraction method, a method for controlling the amount by adjusting purification conditions or distillation conditions, and a combination of these methods. Preferably, the method involves controlling the conditions for distillation purification.

[0115] (high boiling point byproduct) The high-boiling by-products in the present invention refer to high-boiling by-products (hereinafter simply referred to as "high-boiling by-products") that are by-produced during the production of the cyclic diene-containing composition of the present invention and have a boiling point higher than that of the cyclic diene in the present invention. Examples of the high-boiling by-products include trimers of indane, indene, and cyclopentadiene, and oligomers of combinations of these components. These high-boiling by-products correspond to, for example, the high-boiling components removed in step (IV) described below as a specific embodiment of the method for producing a cyclic diene-containing composition of the present invention.

[0116] In this specification, the high-boiling by-products related to the cyclic diene-containing composition of the present invention, the high-boiling by-products related to the aldehyde production method of the second embodiment of the present invention, and the high-boiling by-products related to the cyclic diene-containing composition production method of the third embodiment of the present invention are collectively referred to as "high-boiling by-products in the present invention." That is, the "high-boiling by-products" in the first to third embodiments of the present invention can be treated as synonyms.

[0117] The cyclic diene-containing composition of the present invention can be obtained by controlling the content of the high-boiling by-products. The cycloaliphatic aldehyde produced when the cyclic diene-containing composition is used as a starting material for the cycloaliphatic aldehyde is The production efficiency of aldehyde, the handling property of the cyclic diene-containing composition, and the This can improve the operability of the plant.

[0118] In the present invention, the upper limit of the content (unit: GC area %) of the high-boiling by-products in the cyclic diene-containing composition is preferably 25.0% or less, more preferably 20.0% or less, even more preferably 15.0% or less, particularly preferably 10.0% or less, and most preferably 8.0% or less, relative to 100% of the total GC area of ​​the cyclic diene-containing composition, from the viewpoint of producing an alicyclic aldehyde in a short reaction time and at a high yield using the cyclic diene-containing composition as a starting material. On the other hand, the lower limit of the content of the high-boiling by-products (unit: GC area %) is not particularly limited, and it is acceptable for the composition to contain substantially no high-boiling by-products (0.0%). However, from the viewpoint of the fact that the composition is liquid at room temperature and has better industrial handleability, and from the viewpoint of economics such as the production costs required for purifying and separating the cyclic diene-containing composition, the content of the high-boiling by-products is preferably 0.3% or more, more preferably 0.6% or more, even more preferably 1.0% or more, particularly preferably 3.0% or more, and most preferably 5.0% or more, relative to 100% of the total GC area of ​​the cyclic diene-containing composition. Therefore, in the aldehyde production method according to the second embodiment of the present invention described below, it is preferable to set the threshold value (2) of the content ratio of high-boiling by-products in the cyclic diene-containing composition to be equal to or higher than the above-mentioned lower limit, thereby controlling the content ratio of high-boiling by-products in the cyclic diene-containing composition. In addition, in the method for producing a cyclic diene-containing composition, which is a third embodiment of the present invention described below, it is preferable to set the threshold value (2) of the content ratio of high-boiling by-products in the cyclic diene-containing composition to be equal to or higher than the above-mentioned lower limit, and control the content ratio of high-boiling by-products in the cyclic diene-containing composition. The upper and lower limits can be combined arbitrarily. For example, the content of high-boiling by-products in the cyclic diene-containing composition (unit: GC area%) may be substantially zero (0.0%), or may be preferably 0.3% to 25.0% relative to the total GC area of ​​the cyclic diene-containing composition (100%), more preferably 0.6% to 20.0%, even more preferably 1.0% to 15.0%, particularly preferably 3.0% to 10.0%, and most preferably 5.0% to 8.0%.

[0119] The content of high-boiling by-products in the cyclic diene-containing composition of the present invention can be measured by the following measurement method 1. The measurement method will be described in detail later. <Measurement method 1> Analyze under the following GC measurement conditions and measure the total content ratio of peaks with retention times between 15.0 and 30.0 minutes. (GC measurement conditions) GC device: Gas chromatogram measuring device Detector: Hydrogen flame ionization detector Carrier gas: Helium (column flow rate 1.65 mL / min) Column: Capillary column (size: length 30 m x inner diameter 0.25 mm, film thickness 1.00 μm) Column temperature: 50°C (hold time 5 minutes) → Heat at 10°C / minute → 300°C (hold time: none) Inlet temperature: 200℃ Detector temperature: 300℃ Sample volume: 0.3 μL (split ratio: 1 / 30)

[0120] Methods for controlling the content of high-boiling by-products in the cyclic diene-containing composition include, for example, extraction methods, methods for controlling the amount by adjusting purification conditions or distillation conditions, and combinations of these methods. Preferred is a method for controlling the conditions for distillation purification.

[0121] (Liquidity) The cyclic diene-containing composition of the present invention preferably has fluidity at room temperature (25° C.). The term "having fluidity" means that when placed in a container, the substance flows and changes shape when the container is tilted, and preferably means that the substance is a "liquid." That is, the cyclic diene-containing composition of the present invention is preferably a liquid at room temperature. The cyclic diene-containing composition of the present invention can be made to have fluidity at room temperature by adjusting the content of the cyclic diene in the composition to the above upper limit or less.

[0122] <Method of producing cyclic diene-containing composition> The method for producing the cyclic diene-containing composition of the present invention is not particularly limited, and examples thereof include the method for producing a cyclic diene-containing composition according to the third embodiment of the present invention.

[0123] A method for producing a cyclic diene-containing composition according to a third embodiment of the present invention is a method for producing a cyclic diene-containing composition containing the cyclic diene of the first or second embodiment by distilling and purifying a hydrocarbon decomposition product, which is obtained by thermal decomposition of a hydrocarbon-containing composition, which is described later, and which includes controlling the content of cyclic monoenes contained in the cyclic diene-containing composition to a predetermined threshold value (1) or less.

[0124] In the method for producing a cyclic diene-containing composition of the present invention, the method for thermally decomposing the hydrocarbon-containing composition to obtain hydrocarbon decomposition products is not particularly limited. As a specific embodiment, for example, there is mentioned a method for thermally decomposing a hydrocarbon-containing composition such as naphtha in a hydrocarbon decomposition product treatment facility such as an ethylene production facility described later to obtain hydrocarbon decomposition products.

[0125] In the method for producing a cyclic diene-containing composition of the present invention, the method for distillatively purifying the hydrocarbon decomposition product to obtain the cyclic diene-containing composition containing the cyclic diene is not particularly limited. As a specific embodiment, for example, there is mentioned a method in which the hydrocarbon decomposition product is separated and purified to obtain a C5 hydrocarbon fraction described below, and the obtained C5 hydrocarbon fraction is distillatively purified to obtain the cyclic diene-containing composition.

[0126] By controlling the content of the cyclic monoene contained in the cyclic diene-containing composition to a predetermined threshold value (1) or less, an alicyclic aldehyde corresponding to the cyclic diene can be produced in a short reaction time and in a high yield.

[0127] From the above-mentioned viewpoint, the predetermined threshold value (1) is preferably 14.0% or less, more preferably 12.0% or less, even more preferably 10.0% or less, particularly preferably 8.0% or less, and most preferably 7.0% or less, relative to 100% of the total GC area of ​​the cyclic diene-containing composition. When the cyclic monoene is a cyclic monoene having 9 carbon atoms and a vinyl group, such as vinylnorbornene, the predetermined threshold value (1) is preferably 3.0 GC area%, more preferably 2.5 GC area%, even more preferably 2.0 GC area%, particularly preferably 1.5 GC area%, and most preferably 1.0 GC area%, from the above-mentioned viewpoints.

[0128] In the method for producing a cyclic diene-containing composition of the present invention, it is preferable to control the content of high-boiling by-products having boiling points higher than that of the cyclic diene contained in the cyclic diene-containing composition to a predetermined threshold value (2) or more. By controlling the content of the high-boiling by-products to a predetermined threshold value (2) or more, the cyclic diene-containing composition of the present invention becomes liquid at room temperature (25°C), thereby improving fluidity and making it easier to handle industrially. From the above viewpoint, the predetermined threshold value (2) is preferably 0.3 GC area %, more preferably 0.6 GC area %, further preferably 1.0 GC area %, particularly preferably 3.0 GC area %, and most preferably 5.0 GC area %.

[0129] Furthermore, in the cyclic diene-containing composition of the present invention and the method for producing the cyclic diene-containing composition of the present invention, it is preferable to control the content of high-boiling by-products having boiling points higher than those of the cyclic diene contained in the cyclic diene-containing composition to a predetermined threshold value (3) or less. By controlling the content of the high-boiling by-products to a predetermined threshold value (3) or less, when the cyclic diene-containing composition is used as a starting material for an alicyclic aldehyde, it becomes possible to produce the alicyclic aldehyde corresponding to the cyclic diene in a short reaction time and in a high yield. From the above viewpoint, the predetermined threshold (3) is preferably 25.0 GC area %, more preferably 20.0 GC area %, even more preferably 15.0 GC area %, particularly preferably 10.0 GC area %, and most preferably 8.0 GC area %.

[0130] The means for adjusting the content of cyclic monoenes in the cyclic diene-containing composition to a predetermined threshold value (1) or less is not particularly limited, and examples thereof include a method of controlling the conditions for distillation purification when distilling the hydrocarbon decomposition product to produce a cyclic diene-containing composition containing the cyclic diene. The details of the distillation purification conditions will be described later.

[0131] Similarly to the above, the means for adjusting the content of high-boiling by-products contained in the cyclic diene-containing composition to a predetermined threshold value (2) or more or a predetermined threshold value (3) or less is not particularly limited, and examples thereof include a method of controlling the conditions for distillation purification when distilling the hydrocarbon cracking product to produce a cyclic diene-containing composition containing the cyclic diene. The details of the distillation purification conditions will be described later.

[0132] (Hydrocarbon-containing composition) The hydrocarbon-containing composition may be naphtha, coal, or natural gas. Among these, naphtha is preferred from the viewpoint of excellent productivity and quality of the resulting cyclic diene-containing composition.

[0133] As the "naphtha" in the present invention, known naphthas can be used. One embodiment of known naphthas can be a hydrocarbon-containing composition derived from crude oil having a boiling point range of about 30 to 230°C. Alternatively, another embodiment of known naphthas can be a hydrocarbon-containing composition containing 90% by mass or more of hydrocarbons having 5 to 12 carbon atoms, relative to 100% by mass of the total mass of the naphtha. The above-mentioned "hydrocarbons having 5 to 12 carbon atoms" are mainly aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and styrene; aliphatic hydrocarbons such as normal pentane, 1-hexene, normal octane, 1-nonene, normal decane, and normal dodecane; and naphthenes such as methylcyclohexane and ethylcyclohexane.

[0134] (Ethylene production facility) The ethylene production facility in the present invention is a production facility for obtaining a C5 hydrocarbon fraction, which will be described later, as one of the fractions separated and purified from naphtha cracking products. Specifically, the ethylene production facility refers to a facility that thermally cracks naphtha at high temperatures to produce hydrogen, hydrocarbons with a carbon number of 4 such as methane, ethane, ethylene, propane, propylene, butane, or butadiene, hydrocarbons with a carbon number of 5 such as benzene, aromatic hydrocarbons, and other heavy oils, and then separates and refines these.

[0135] The embodiment of the ethylene production apparatus is not particularly limited, and may have any configuration as long as it includes a distillation facility for a C5 hydrocarbon fraction and separates and purifies naphtha cracking products. For example, the ethylene production apparatus may have a configuration including facilities for sequentially performing the following steps (1) to (4): Step (1): A thermal cracking step in which raw materials such as naphtha, coal, and natural gas are thermally cracked in a cracking furnace. Step (2): A quenching step in which the resulting cracked gas is quenched and separated. Step (3): Compression step of compressing the quenched and separated cracked gas Step (4): The compressed cracked gas is separated and purified into its various fractions to obtain the main products, ethylene and propylene.

[0136] (C5 hydrocarbon fraction) The C5 hydrocarbon fraction in the present invention is a fraction containing hydrocarbons with a carbon number of 5 as a main component, which is obtained by separating heavy oil from a hydrocarbon cracking product obtained by thermally cracking a hydrocarbon-containing composition such as naphtha, and then separating and removing hydrogen and hydrocarbons with a carbon number of 1 to 4. Specific examples of the C5 hydrocarbon fraction include mixtures containing monocyclic dienes such as isoprene, isopentane, normal pentane, and cyclopentadiene, and C5 hydrocarbons as the main components. Here, the C5 hydrocarbon fraction contains a small amount of a C4 hydrocarbon fraction and a small amount of a C6 hydrocarbon fraction for the sake of separation performance. 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.

[0137] 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% by weight.

[0138] [Table 1]

[0139] (Distillation and refining of C5 hydrocarbon fraction) A single-stage or multi-stage distillation column can be used to distill and refine the C5 hydrocarbon fraction. In particular, from the viewpoint of keeping the content of cyclic monoene contained in the cyclic diene-containing composition of the present invention at or below a predetermined threshold value (1), or keeping the content of high-boiling by-products at or above a predetermined threshold value (2), and further keeping the content of high-boiling by-products at or below a predetermined threshold value (3), it is preferable to use a two-stage distillation column and control the number of theoretical stages and reflux ratio of each distillation column within the following ranges. When a two-stage distillation column is used, specifically, by controlling the number of theoretical plates in the first stage distillation column to within the ranges of 10 to 20, preferably 13 to 17, and the reflux ratio to within the ranges of 20 to 30, preferably 23 to 27, cyclic monoenes can be efficiently separated and removed, and the predetermined threshold value (1) can be efficiently controlled. Furthermore, by controlling the number of theoretical plates in the second stage distillation column to within the ranges of 10 to 20, preferably 13 to 17, and the reflux ratio to within the ranges of 1.0 to 1.5, high-boiling by-products can be efficiently separated and removed to an extent that does not inhibit the hydroformylation reaction described below, and the predetermined threshold values ​​(2) and (3) can be efficiently controlled.

[0140] (Specific embodiment of the method for producing a cyclic diene-containing composition) A specific embodiment of the method for producing a cyclic diene-containing composition of the present invention includes a method in which the following steps (I) to (IV) are carried out in order.

[0141] Step (I): A dimerization step in which a C5 hydrocarbon fraction (described below) obtained by thermal cracking of a hydrocarbon-containing composition such as naphtha is introduced into a dimerization tank and heated, and cyclic diene precursors such as cyclopentadiene contained in the C5 hydrocarbon fraction are dimerized to form cyclic dienes such as dicyclopentadiene corresponding to the cyclic diene precursors.

[0142] 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.

[0143] Step (III): A step for removing low boiling components in which the C5 fraction heavy composition from the column bottom in step (II) is introduced into a low boiling component removal column for distillation, and low boiling cyclic monoenes such as vinylnorbornene, which have a boiling point lower than that of cyclic dienes such as dicyclopentadiene and are by-produced during the dimerization reaction in step (I), are removed from the column top, while a fraction rich in cyclic dienes such as dicyclopentadiene is taken from the column bottom. As the distillation conditions in step (III), the distillation conditions for the first distillation column mentioned above in the description of the distillation purification of the C5 hydrocarbon fraction can be used.

[0144] Step (IV): A step of removing high boiling components in which the fraction rich in cyclic dienes such as dicyclopentadiene from the bottom of the column in step (III) is introduced into a high boiling component removal column for distillation, and high boiling by-products such as high boiling co-dimers, which have boiling points higher than those of cyclic dienes such as dicyclopentadiene produced as a by-product in the dimerization reaction of step (I), 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. As the distillation conditions in step (IV), the distillation conditions for the second distillation column mentioned above in the explanation of the distillation purification of the C5 hydrocarbon fraction can be used.

[0145] The steps (I) to (IV) will be described in more detail below.

[0146] [Process (I)] The C5 hydrocarbon fraction is first supplied to the dimerization step (I), where cyclic diene precursors such as cyclopentadiene contained in the C5 hydrocarbon fraction are dimerized to produce cyclic dienes such as dicyclopentadiene corresponding to the cyclic diene precursors. The conditions for the dimerization are not particularly limited and are appropriately selected depending on the content of cyclic diene precursors such as cyclopentadiene in the C5 hydrocarbon fraction, and other factors. Typically, the dimerization temperature is set within a range of 50 to 110°C, and the reaction time is set within a range of 1 to 6 hours, and 30 to 99% by weight of cyclic diene precursors such as cyclopentadiene contained in the C5 hydrocarbon fraction is dimerized.

[0147] [Process (II)] The product from the dimerization step (I) is then sent to the unreacted component recovery step (II) to separate and recover the unreacted C5 hydrocarbon fraction, which contains isoprene, piperylene (i.e., 1,3-pentadiene), etc., and is sent to a separate purification process as needed. For example, the boiling point of the cyclic diene dicyclopentadiene is 170°C, while the boiling points of the other unreacted components are about 30 to 50°C, so in this recovery step (II), the product from the dimerization step (I) is fed to a distillation column that takes advantage of this difference in boiling points. An unreacted C5 hydrocarbon fraction is recovered from the top of the distillation column, and a heavy C5 fraction composition rich in cyclic dienes such as dicyclopentadiene is taken out from the bottom. Distillation is usually carried out under normal pressure, but when it is desired to increase the recovery amount of the C5 hydrocarbon fraction and the C6 hydrocarbon fraction, reduced pressure distillation or steam distillation is carried out.

[0148] [Process (III)] The heavy C5 fraction composition withdrawn from the bottom of the distillation column in step (II) is liquefied in a condenser as necessary, and then sent to a low-boiling component removal step (III) (light-boiling component removal column) for distillation. The heavy C5 fraction composition sent to step (III) is controlled so that the content of cyclic dienes such as dicyclopentadiene is usually within the range of 50 to 95% by weight. The low boiling components contained in the heavy C5 fraction composition are removed from the top of the low boiling component removal column, while a fraction rich in cyclic dienes such as dicyclopentadiene is taken out from the bottom of the column.

[0149] Here, the low-boiling components include the C5 hydrocarbon fraction and C6 hydrocarbon fraction that could not be recovered in step (II), as well as low-boiling cyclic monoenes such as vinylnorbornene, which have a boiling point lower than that of dicyclopentadiene produced as a by-product in the dimerization reaction in step (I), and similar co-dimers such as propenylnorbornene, which is a co-dimer of cyclopentadiene and piperylene. Of these low boiling point components, it is easy to remove cyclic monoenes such as vinylnorbornene, and C5 hydrocarbon fractions and C6 hydrocarbon fractions, but it is difficult to remove similar co-dimer components such as propenylnorbornene. Therefore, conventionally, a distillation column with 50 to 100 plates is required as the low boiling point component removal column.

[0150] The low-boiling component removal column is preferably controlled so that the content of monocyclic dienes such as cyclopentadiene in the bottom distillate 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-removal column are typically controlled to a vacuum level of 5 to 200 torr, preferably 10 to 50 torr; a column bottom temperature of 50 to 120°C, preferably 80 to 110°C; the number of theoretical plates of 10 to 20, preferably 13 to 17; and a reflux ratio of 20 to 30, preferably 23 to 27. Under these conditions, the bottoms distillate obtained from the bottom of the light-removal column can efficiently separate and remove 90% by weight or more of cyclic monoenes such as vinylnorbornene and similar co-dimers contained in the C5 fraction heavy composition obtained from the bottom of the light-removal column in step (II). Specifically, the content of monocyclic dienes such as cyclopentadiene can be reduced to 0.5 GC area % or less and the content of hydrocarbons having 5 carbon atoms can be reduced to 2.0 GC area % or less in the bottoms distillate.

[0151] [Process (IV)] In the low-boiling component removal step (III), the fraction (tower bottom liquid) rich in cyclic dienes such as dicyclopentadiene taken out from the bottom of the low-boiling component removal column is sent to the high-boiling component removal step (IV) (heavy-boiling component removal column) and subjected to distillation. The high-boiling components removed in this step (IV) are high-boiling by-products such as high-boiling co-dimers, such as methylbicyclononadiene, which are dimers of cyclopentadiene and isoprene, and have boiling points higher than those of the cyclic dienes, such as dicyclopentadiene, produced as a by-product in the dimerization reaction of step (I). In cases where low-boiling products such as cyclopentadiene trimers are present, these low-boiling products are also removed.

[0152] The distillation conditions in the high-boiling component removal column in step (IV), particularly the distillation temperature, affect the thermal decomposition of dicyclopentadiene and significantly affect the purity of the final product, so it is preferable to pay attention to them so as to obtain the desired cyclic diene-containing composition. The heavy-boiler removal column is preferably a packed column to minimize pressure loss within the column, and is typically operated under controlled conditions of a vacuum degree of 5 to 100 torr, preferably 10 to 50 torr, a column bottom temperature of 50 to 120°C, preferably 70 to 110°C, a theoretical plate number of 10 to 20, preferably 13 to 17, and a reflux ratio of 1.0 to 1.5. Under these conditions, in the cyclic diene-containing composition of the present invention obtained from the top of the heavy-boiler removal column, high-boiling by-products contained in the column bottom distillate obtained from the bottom of the light-boiler removal column in step (III) can be efficiently separated and removed to an extent that does not inhibit the hydroformylation reaction described below.

[0153] Specifically, in the cyclic diene-containing composition obtained from the top of the high-boiling component removal column, the content of cyclic dienes such as dicyclopentadiene can be controlled to be preferably 99.5 GC area% or less, and the content of cyclic monoenes can be controlled to be the above-mentioned threshold value (1) or less, for example, 14.0 GC area% or less, preferably 3.0 GC area% or less of cyclic monoenes having a vinyl group and having 9 carbon atoms such as vinylnorbornene, more preferably 0.3 GC area% or more, and even more preferably 25 GC area% or less of the above-mentioned threshold value (3).

[0154] The method for controlling the composition of the cyclic diene-containing composition obtained from the top of the heavy-boiling component removal column to the above-mentioned composition is not particularly limited, and examples 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 1.0 to 1.5, and the apparatus is designed and manufactured so that the residence time of the liquid fed to the distillation column in the column is 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 bottom distillate will contain a large amount of C5 hydrocarbons, such as monocyclic dienes such as cyclopentadiene, and cyclic monoenes. If the bottom temperature exceeds 120°C, the bottom distillate will contain a large amount of high-boiling by-products, such as tricyclopentadiene. In either case, the dicyclopentadiene content in the bottom distillate will be low. By controlling the theoretical number of plates of the heavy-boiling component removal column within a range of 10 to 20 and the reflux ratio within a range of 1.0 to 1.5, high-boiling by-products can be separated and removed from the cyclic diene-containing composition of the present invention obtained from the top of the heavy-boiling component removal column to an extent that does not inhibit the hydroformylation reaction described below. If the residence time of the feed liquid in the distillation column exceeds 15 minutes, the amount of high-boiling by-products such as tricyclopentadiene in the bottom distillate will increase, while if it is less than 10 minutes, the bottom area of ​​the distillation column will be too small, making it difficult to install a meter for measuring the liquid level. In addition, the amount of liquid held at the bottom of the column will be too small, and during normal operation of the distillation column, the liquid in the bottom will become empty, which may hinder stable operation.

[0155] 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 distilled at the bottom of the column.

[0156] 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.

[0157] [One embodiment of a production facility for a cyclic diene-containing composition] Next, one embodiment of the production equipment for the cyclic diene-containing composition of the present invention will be described with reference to the accompanying drawing. In Fig. 1, a C5 hydrocarbon fraction obtained by thermal cracking of a hydrocarbon-containing composition such as naphtha is first supplied to dimerization vessel 1 via line 10, where dimerization of cyclic diene precursors such as cyclopentadiene is carried out to produce cyclic dienes such as dicyclopentadiene corresponding to the cyclic diene precursors [dimerization step (I)]. After the dimerization reaction, the content of dimerization vessel 1 is sent via line 11 to distillation column 2 [unreacted component recovery step (II)] and subjected to distillation. In distillation column 2, the unreacted C5 hydrocarbon fraction is removed from the top of distillation column 2 via pipe 13, and the bottom liquid (heavy C5 fraction composition) rich in cyclic dienes such as dicyclopentadiene is sent from the bottom of distillation column 2 via pipe 12 to light-boiling component removal column 3 [light-boiling component removal step (III)] for distillation. In the light-removal column 3, cyclic monoenes such as vinylnorbornene, which have lower boiling points than cyclic dienes such as dicyclopentadiene, as well as C5 hydrocarbon fractions, C6 hydrocarbon fractions, and similar co-dimers, are removed from the top of the light-removal column 3 via pipe 15, and the fraction rich in cyclic dienes such as dicyclopentadiene is sent from the bottom of the light-removal column 3 via pipe 14 to the final heavy-removal column 4 [heavy-boiling component removal step (IV)] for distillation. In the heavy-boiling component removal column 4, high-boiling co-dimers having boiling points higher than those of cyclic dienes such as dicyclopentadiene and remaining low polymers 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.

[0158] The order in which the above steps (I) to (IV), particularly steps (II) to (IV), are carried out is not particularly limited, and the order in which the steps are carried out can be changed as long as the effects of the present invention are not impaired.

[0159] <Method for producing aldehyde> The method for producing an aldehyde according to the second embodiment of the present invention will be described below.

[0160] (Embodiment 2-1) A 2-1 embodiment of the aldehyde production method of the present invention is a method for producing an aldehyde corresponding to the cyclic diene by hydroformylating a cyclic diene in a cyclic diene-containing composition described below, the method comprising controlling the content of cyclic monoenes contained in the cyclic diene-containing composition to be equal to or less than a predetermined threshold value (1). By controlling the content of the cyclic monoene contained in the cyclic diene-containing composition to a predetermined threshold value (1) or less, it becomes possible to produce an alicyclic aldehyde corresponding to the cyclic diene in a short reaction time and in a high yield. From the above-mentioned viewpoint, the predetermined threshold value (1) is preferably 14.0% or less, more preferably 12.0% or less, even more preferably 10.0% or less, particularly preferably 8.0% or less, and most preferably 7.0% or less, relative to 100% of the total GC area of ​​the cyclic diene-containing composition. When the cyclic monoene is a cyclic monoene having 9 carbon atoms and a vinyl group, such as vinylnorbornene, the predetermined threshold value (1) is preferably 3.0 GC area%, more preferably 2.5 GC area%, even more preferably 2.0 GC area%, particularly preferably 1.5 GC area%, and most preferably 1.0 GC area%, from the above-mentioned viewpoints. The details of the cyclic monoene are as described above.

[0161] Furthermore, in the method for producing an aldehyde of the present invention, it is preferable to control the content of high-boiling by-products having boiling points higher than those of the cyclic diene contained in the cyclic diene-containing composition to a predetermined threshold value (2) or more. By controlling the content of the high-boiling by-products to a predetermined threshold value (2) or more, the fluidity of the cyclic diene-containing composition of the present invention at room temperature (25° C.) can be made more excellent. From the above viewpoint, the predetermined threshold value (2) is preferably 0.3 GC area %, more preferably 0.6 GC area %, further preferably 1.0 GC area %, particularly preferably 3.0 GC area %, and most preferably 5.0 GC area %.

[0162] Furthermore, in the method for producing an aldehyde of the present invention, it is preferable to control the content of high-boiling by-products having boiling points higher than those of the cyclic diene contained in the cyclic diene-containing composition to a predetermined threshold value (3) or less. By controlling the content of the high-boiling by-products to a predetermined threshold value (3) or less, it becomes possible to produce an alicyclic aldehyde corresponding to the cyclic diene in a short reaction time and in a high yield. From the above viewpoint, the predetermined threshold (3) is preferably 25.0 GC area %, more preferably 20.0 GC area %, even more preferably 15.0 GC area %, particularly preferably 10.0 GC area %, and most preferably 8.0 GC area %. The details of the high-boiling by-products are as described above.

[0163] In embodiment 2-1 of the aldehyde production method of the present invention, the method for controlling the predetermined threshold value (1), the predetermined threshold value (2), and the predetermined threshold value (3) is not particularly limited, and an example thereof includes a method of controlling the conditions for distillation purification when 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, as described above.

[0164] (Embodiment 2-2) The 2-2 embodiment of the method for producing an aldehyde of the present invention is a method for producing an aldehyde, which comprises subjecting the cyclic diene-containing composition of the first embodiment of the present invention to a hydroformylation reaction to produce an aldehyde corresponding to the cyclic diene.

[0165] (Second-third embodiment) The second-third embodiment of the method for producing an aldehyde of the present invention is a method for producing an aldehyde, which comprises producing a cyclic diene-containing composition (hereinafter sometimes referred to as the "cyclic diene-containing composition of the present invention") by the method for producing a cyclic diene-containing composition of the third embodiment of the present invention, and producing a corresponding aldehyde from the cyclic diene contained in the cyclic diene-containing composition.

[0166] The aldehyde production methods according to the 2-1, 2-2 and 2-3 embodiments of the present invention are hereinafter collectively referred to simply as "the aldehyde production method of the present invention."

[0167] In the method for producing an aldehyde of the present invention, the method for producing an aldehyde corresponding to the cyclic diene from the cyclic diene contained in the cyclic diene-containing composition by the hydroformylation reaction is not particularly limited, and can be carried out according to a conventional method. For example, in accordance with the method described in JP 2001-10999 A, the cyclic diene contained in the cyclic diene-containing composition of the present invention can be hydroformylated 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, to produce an aldehyde corresponding to the cyclic diene.

[0168] 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 reaction formula (I) below, in accordance with the method described in JP 2001-10999 A.

[0169] [ka]

[0170] The rhodium compound used in this hydroformylation step may take any form of precursor, so long as it forms a complex with an organophosphorus compound and exhibits hydroformylation activity in the presence of hydrogen and carbon monoxide. Rhodium compounds include Rh(acac)(CO)2, Rh2O3, and Rh4(CO) 12 , Rh6(CO) 16Alternatively, a catalyst precursor such as Rh(NO3)3 may be introduced into the reaction mixture together with an organophosphorus compound to form a catalytically active rhodium metal hydride carbonyl phosphorus complex in the reaction vessel, or a rhodium metal hydride carbonyl phosphorus complex catalyst may be prepared in advance and then introduced into the reaction vessel.

[0171] In a preferred embodiment of the present invention, Rh(acac)(CO)2 is used as a rhodium precursor material and reacted with an organophosphorus compound in the presence of a solvent, and then introduced into a reactor together with an excess of free organophosphorus compound to form a catalytically active rhodium-organophosphorus complex catalyst.

[0172] The organophosphorus compounds which form catalysts for the hydroformylation reaction with the rhodium compounds include known phosphites and known phosphines. Among these, the phosphite is a compound represented by the general formula P(-OR 11 )(-OR 12 )(-OR 13 )(wherein, R 11 , R 12 and R 13 R represents an optionally substituted aryl group or alkyl group. 11 , R 12 and R 13 Specific examples of the alkyl group include aryl groups such as phenyl and naphthyl 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 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.

[0173] 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.

[0174] 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.

[0175] 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.

[0176] 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.

[0177] 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.

[0178] 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.

[0179] The molar ratio of hydrogen to carbon monoxide in the hydrogen / carbon monoxide mixed gas used in the reaction is not particularly limited and can be appropriately set by a person skilled in the art according to well-known techniques. Usually, the molar ratio of hydrogen to carbon monoxide (hydrogen / carbon monoxide) in the introduced gas composition can be set to be within the range of 0.2 to 5.0.

[0180] The hydroformylation reaction is carried out by a continuous feed method in which the cyclic diene-containing composition of the present invention as a raw material is fed alone or as a mixed solution of the cyclic diene-containing composition of the present invention and a solvent to a reactor containing a rhodium-organophosphorus complex catalyst, a solvent, and a mixed gas of hydrogen and carbon monoxide. This method reduces the production of cyclopentadiene, which inhibits the hydroformylation reaction due to thermal decomposition of dicyclopentadiene, the cyclic diene in the cyclic diene-containing composition of the present invention, in the reactor, thereby maintaining a good reaction rate and yield. In order to maintain the fluidity of the cyclic diene-containing composition of the present invention, it is preferable to dilute it with the aforementioned solvent and feed it to the reactor at a temperature at which it does not depolymerize and produce cyclopentadiene.

[0181] (Extraction of tricyclodecane dicarbaldehyde) After completion of the hydroformylation reaction, the method for extracting and separating the product tricyclodecane dicarbaldehyde from the reaction mixture is not particularly limited, and can be appropriately determined by a person skilled in the art according to well-known techniques. For example, the extraction and separation method described in JP-A-2001-10999 can be used.

[0182] <Alcohol production method> The alcohol production method of the present invention is a method for producing an alcohol, which comprises producing an aldehyde by the above-mentioned aldehyde production method of the present invention, and producing a corresponding alcohol from the aldehyde.

[0183] The method for producing an alcohol corresponding to the aldehyde is not particularly limited and can be carried out according to a conventional method. For example, according to the method described in JP-A-2001-10999, the aldehyde obtained by the method for producing an aldehyde of the present invention can be directly subjected to a known hydrogenation reaction, or the obtained aldehyde can be dimerized and then subjected to a known hydrogenation reaction to produce an alcohol.

[0184] 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, thereby producing tricyclo[5.2.1.0(2,6)]decanedimethanol.

[0185] 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, and a Ru-based catalyst is preferred. The conditions for the hydrogenation reaction are usually a temperature of 60 to 200° C. and a hydrogen pressure of about 0.1 to 20 MPaG. [Example]

[0186] The present invention will be explained in more detail below by giving reference examples and experimental examples (hereinafter simply referred to as "experimental examples") in place of examples and comparative examples. The present invention is not limited to the following experimental examples as long as they do not depart from the gist of the present invention. The following examples are merely illustrative and are not intended to limit any of the embodiments described herein. The following examples do not limit the present invention in any way. The values ​​of various manufacturing conditions and evaluation results in the following experimental examples are intended to represent preferred upper or lower limit values ​​in the embodiments of the present invention. A preferred range in the present invention may be a range defined by a combination of the above-mentioned upper or lower limit value and the values ​​of the following experimental examples or values ​​of the experimental examples.

[0187] The compounds used in the following experimental examples are as follows: Commercially available DCPD: (Product name: High-purity dicyclopentadiene, manufactured by Maruzen Petrochemical Co., Ltd.) Acetylacetonatodicarbonylrhodium (trade name: Rh(acac)(CO)2, manufactured by N.E. Chemcat Corporation) Ruthenium-supported catalyst (Ru-supported carbon, dry basis Ru content 5%, water content 56%) (product name: Ru / C, manufactured by N.E. Chemcat Corporation) Tris(2,4-di-tert-butylphenyl)phosphite (trade name: DBPO, manufactured by Tokyo Chemical Industry Co., Ltd.) Methylcyclohexane (product name: Methylcyclohexane, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) Methanol (product name: Methanol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0188] [Reference Experimental Example 1] <Production of heavy oil through thermal cracking of naphtha> Using commercially available naphtha as a hydrocarbon-containing composition and a naphtha cracking plant manufactured in-house, the naphtha was thermally cracked according to the following procedure, with reference to the naphtha thermal cracking method disclosed in Japanese Patent Publication No. 7-39354, to obtain a hydrocarbon cracking product. The resulting hydrocarbon cracking product was fed to a distillation column, and a C5 hydrocarbon fraction containing hydrocarbons with a carbon number of 5 as the main component was recovered. The resulting 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 heavy C5 fraction composition containing the cyclic diene dicyclopentadiene from the bottom of the distillation column.

[0189] The composition of the obtained C5 heavy fraction composition was analyzed using a gas chromatograph (GC) measuring device and a gas chromatography total area method under the following GC measurement conditions, and the results were as follows. The obtained gas chromatogram is shown in Figure 6. In the gas chromatography total area method, the composition ratio of each component was calculated as the area content ratio of each peak component (unit: GC area %) when the total area of the GC peaks of all product substances on the gas chromatogram was set to 100%.

[0190] <GC measurement conditions> GC apparatus: GC-2025 (high-performance general-purpose gas chromatograph, manufactured by Shimadzu Corporation) Detector: Flame ionization detector (FID) Carrier gas: Helium (column flow rate 1.65 ml / min) Column: Capillary column DB-1 (manufactured by Agilent Technologies, size: length 30 m × inner diameter 0.25 mm, film thickness 1.00 μm) Column temperature: 50°C (holding time 5 minutes) → temperature increase at 10°C / min → 300°C (holding time: none) Inlet temperature: 200°C Detector temperature: 300°C Sample volume: 0.3 μL (split ratio: 1 / 30)

[0191] (Composition of C5 fraction heavy composition) Component (1) 2.2 GC area % Vinyl norbornene 0.6 GC area % Component (2) 1.4 GC area % Isopropenyl norbornene 6.6 GC area % DCPD 75.9 GC area % High-boiling by-products 13.3 GC area %

[0192] "Component (1)" is the general term for a plurality of components observed as a plurality of GC peaks in the temperature condition region (holding time: 2.5 minutes or more and less than 11.2 minutes) with a lower boiling point than vinyl norbornene on the gas chromatogram. "Isopropenyl norbornene" is isopropenyl-2-norbornene (holding time: 14.0 minutes or more and less than 14.4 minutes). "Component (2)" is a collective term for multiple components observed as multiple GC peaks in a temperature condition region (retention time: 11.6 minutes or more and less than 14.0 minutes) on a gas chromatogram that has a boiling point higher than that of vinylnorbornene and lower than that of isopropenylnorbornene. "Vinyl norbornene" is 5-vinyl-2-norbornene (retention time: 11.2 minutes or more and less than 11.6 minutes). "DCPD" is dicyclopentadiene (retention time: 14.4 minutes or more and less than 15.0 minutes). "High-boiling by-products" are components for which a GC peak is observed in a temperature condition region (retention time: 15.0 minutes or more and 30.0 minutes or less) with a boiling point higher than that of dicyclopentadiene on a gas chromatogram.

[0193] The cyclic monoenes observed in the C5 heavy fraction composition were two types: vinylnorbornene and isopropenylnorbornene.

[0194] [Reference Experimental Example 2] <Heavy oil distillation refining> 1,878 g of the C5 fraction heavy composition obtained in Reference Experimental Example 1 was charged into a simple glass distillation column and subjected to fractional distillation under the following fractional distillation conditions. The distillate from the top of the distillation column was collected in approximately 100 g portions and named fractions 1 to 14 in the order of distillation.

[0195] <Fractionation conditions> Bottom temperature: 40~113℃ Tower top temperature: 24~80℃ Pressure: 1 to 10 kPa (7.5 to 75 torr) Residence time of the liquid fed to the distillation column: Approximately 19 hours

[0196] The compositions of fractions 1 to 14 and commercially available DCPD were analyzed using a gas chromatograph (GC) measurement device and a gas chromatography total area method under the following GC measurement conditions. The results are shown in Table 2. In addition, the composition ratio of each component in the gas chromatography total area method was calculated as the area content ratio of each peak component (unit: GC area %) when the total area of the GC peaks of all product substances observed in the temperature condition region with a retention time of 2.5 to 30 minutes on the gas chromatogram was set to 100%. For fraction 2, the obtained gas chromatogram is shown in Fig. 7. The peak observed at a retention time of 2.2 minutes on the gas chromatogram is the peak of the solvent used in the GC measurement.

[0197] <GC measurement conditions> GC apparatus: GC-2025 (high-performance general-purpose gas chromatograph, manufactured by Shimadzu Corporation Detection detector: Flame ionization detector (FID) Carrier gas: Helium (column flow rate 1.65 ml / min) Column: Capillary column DB-1 (manufactured by Agilent Technologies, size: length 30 m × inner diameter 0.25 mm, film thickness 1.00 μm) Column temperature: 50 °C (holding time 5 minutes) → heating at 10 °C / min → 300 °C (holding time: none) Injection port temperature: 200 °C Detector temperature: 300 °C Sample volume: 0.3 μL (split ratio: 1 / 30)

[0198] In the obtained gas chromatogram, the retention times of each component were as follows. Also, "component (1)", "isopropenyl norbornene", "component (2)", "vinyl norbornene", and "high-boiling by-products" are synonymous with "component (1)", "isopropenyl norbornene", "component (2)", "vinyl norbornene", and "high-boiling by-products" in the gas chromatogram measurement of the C5 fraction heavy composition, respectively.

[0199] Component (1) 2.5 minutes or more and less than 11.2 minutes Vinyl norbornene 11.2 minutes or more and less than 11.6 minutes Component (2) 11.6 minutes or more and less than 14.0 minutes Isopropenyl norbornene 14.0 minutes or more and less than 14.4 minutes DCPD 14.4 minutes or more and less than 15.0 minutes High boiling point byproduct 15.0 minutes or more and 30.0 minutes or less

[0200] The cyclic monoenes observed in fractions 1 to 6 were vinylnorbornene and isopropenylnorbornene, while the cyclic monoene observed in fractions 7 to 14 and in the commercially available DCPD was isopropenylnorbornene.

[0201] In addition, the properties of fractions 1 to 14 and commercially available DCPD were visually observed at room temperature (25° C.).

[0202] [Table 2]

[0203] [Experimental Example 2] <Hydroformylation reaction> A 100 mL stainless steel autoclave reactor was charged with 14.0 g of fraction 2 as a raw material compound for the hydroformylation catalyst, 7.1 mg (0.0275 mmol) of Rh(acac)(CO) as a catalyst, 558.3 ​​mg (0.863 mmol) of tris(2,4-di-t-butylphenyl)phosphite, and 11.2 g of methylcyclohexane as an organic solvent under a nitrogen atmosphere. The mixture was stirred at 1500 rpm and the temperature of the reaction solution in the reactor was raised to 70 ° C. Next, a mixed gas of hydrogen and carbon monoxide (hydrogen:carbon monoxide = 1:1 (molar ratio)) was rapidly introduced through the gas inlet valve so that the pressure in the reactor became 5 MPaG. While maintaining this pressure, the temperature of the reaction solution was raised to 100 ° C., and the reaction was continued until hydrogen and carbon monoxide were no longer consumed by the reaction. The time when hydrogen and carbon monoxide were no longer consumed by the reaction was taken as the reaction completion time of the hydroformylation reaction and was used as an index of reaction efficiency. During the reaction, the mixed gas consumed in the reaction was automatically introduced into the autoclave via an automatic pressure regulating valve, and the reaction was carried out while constantly maintaining the pressure inside the reactor at 5 MPaG. After the reaction was completed, the reaction solution in the reactor was cooled to room temperature, the residual gas in the reactor was depressurized, and 31.3 g of the hydroformylation reaction product solution was obtained.

[0204] <Evaluation of Hydroformylation Reaction> Regarding the above hydroformylation reaction product solution, using a gas chromatograph (GC) measuring device and the gas chromatography total area method, under the following GC measurement conditions, the content ratio (unit: GC area%) of dicyclopentadiene contained in fraction 2, and the content ratios (unit: GC area%) of dicyclopentadiene (DCPD) and the product tricyclodecane dicarbaldehyde (TCDDD) contained in the hydroformylation reaction product were determined, and the DCPD conversion rate (%) and TCDDD yield (%) were calculated. As a result, they were 99.1% and 76.9% respectively. The evaluation results are shown in Table 3.

[0205] <GC Measurement Conditions> GC device: GC-2025 (High-performance general-purpose gas chromatograph, manufactured by Shimadzu Corporation) Detector: Flame ionization detector (FID) Carrier gas: Helium (column flow rate 1.23 ml / min) Column: Capillary column DB-1 (manufactured by Agilent Technologies, size: length 30 m × inner diameter 0.25 mm, film thickness 1.00 μm) Column temperature: 120 °C (no holding time) → heating at 10 °C / min → 300 °C (holding time 12 minutes) Inlet temperature: 200 °C Detector temperature: 300 °C Sample volume: <0.3 μL (split ratio: 1 / 30)

[0206] <Production of Alcohol> (Extraction operation) To 31.3 g of the obtained hydroformylation reaction product liquid, 5.0 g of methanol and 9.4 g of water were added and stirred for 10 minutes under a nitrogen atmosphere. After that, the mixture was left to stand for 10 minutes, separated into two phases, and then subjected to an extraction operation. 1.5 g of methylcyclohexane was added to the obtained lower phase (a1), and the mixture was stirred for 30 minutes. After that, the mixture was left to stand for 10 minutes, separated into two phases, and then subjected to an extraction operation, and 34.4 g of lower phase (a2) was obtained. The composition of the resulting lower phase (a2) was analyzed by gas chromatography, and was found to be 47% by mass of tricyclodecane dicarbaldehyde, 27% by mass of methanol, 14% by mass of water, 7% by mass of methylcyclohexane, and 5% by mass of other components.

[0207] (Hydrogenation reduction reaction) A 0.2 L autoclave reactor was charged with 34.4 g of the lower phase (a2) obtained by the above-mentioned extraction operation and 0.1 g of ruthenium-supported catalyst, 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 through the gas inlet valve so that the pressure in the reactor was 5 MPaG, and the reaction was carried out for 2.3 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 5 MPaG. After the reaction was completed, the reaction solution in the reactor was cooled to room temperature, the remaining gas in the reactor was released, and the ruthenium-supported catalyst was separated by filtration using a 5 μm filter, yielding 34.6 g of reaction product solution. The amount of the raw material compound tricyclodecane dicarbaldehyde contained in the reaction solution before the reaction and the amount of the product tricyclo[5.2.1.0(2,6)]decane dimethanol (hereinafter referred to as "TCDDM") produced in the reaction product solution after the reaction were analyzed by gas chromatography, and the yield of TCDDM was found to be 94%.

[0208] [Experimental Example 1 and Experimental Examples 3 to 15] The hydroformylation reaction of the raw material compounds was carried out under the same conditions as in Experimental Example 2, except that the fractions shown in Table 3 or commercially available DPCD were used as the raw material compounds in place of fraction 2. The evaluation results are shown in Table 3.

[0209] [Table 3]

[0210] As shown in Table 2, the total content (GC area %) of (a) vinylnorbornene and (b) isopropenylnorbornene ((a) + (b)) was defined as the cyclic monoene content (GC area %). For fractions 1 to 7 used in Experimental Examples 1 to 7, the relationship between the content of cyclic monoene (GC area %) and the reaction completion time of the hydroformylation reaction is shown in FIG. 2A. FIG. 2B shows the relationship between the content (GC area %) of vinylnorbornene, a cyclic monoene having a vinyl group and 9 carbon atoms, and the reaction completion time of the hydroformylation reaction.

[0211] The relationship between the content of cyclic monoene (GC area %) and the TCDDD yield in the hydroformylation reaction for the same fractions 1 to 7 is shown in FIG. 3A. For the same fractions 1 to 7, the relationship between the content (GC area %) of vinylnorbornene, a cyclic monoene having a vinyl group and 9 carbon atoms, and the TCDDD yield of the hydroformylation reaction is shown in FIG. 3B.

[0212] For fractions 7 to 14 used in Experimental Examples 7 to 14 and commercially available DCPD used in Experimental Example 15, in which vinylnorbornene was not detected, i.e., the GC area % was 0.0%, the relationship between the content of high-boiling by-products (GC area %) and the reaction completion time of the hydroformylation reaction is shown in Figure 4.

[0213] FIG. 5 shows the relationship between the content of high-boiling by-products (GC area %) and the TCDDD yield in the hydroformylation reaction for the same fractions 7 to 14 and commercially available DCPD.

[0214] The fractions 2 to 14 used in Experimental Examples 2 to 14 were liquid at room temperature (25° C.) and were easy to handle.

[0215] 2A and 2B show that when the content (GC area %) of cyclic monoenes in the raw material compound (fraction) is 14.0 GC area % or less, preferably 12.0 GC area % or less, and particularly when the content (GC area %) of vinylnorbornene, which is a cyclic monoene having a vinyl group and 9 carbon atoms, is 3.0 GC area % or less, the smaller the content of cyclic monoenes, particularly the content of vinylnorbornene, the shorter the reaction completion time in the hydroformylation reaction and the more excellent the reaction efficiency. 3A and 3B show that when the content (GC area %) of cyclic monoenes in the raw material compound (fraction) is 14.0 GC area % or less, preferably 12.0 GC area % or less, and particularly when the content (GC area %) of vinylnorbornene is 3.0 GC area % or less, preferably 1.5 GC area % or less, the TCDDD yield increases as the content of cyclic monoenes, particularly the content of vinylnorbornene, decreases. Therefore, it is understood that the content of cyclic monoenes, particularly cyclic monoenes having 9 carbon atoms and a vinyl group, is preferably equal to or less than the above-mentioned upper limit.

[0216] These results show that it is preferable to set a threshold value for the content of cyclic monoenes in the cyclic diene-containing composition, particularly cyclic monoenes having a vinyl group and a carbon number of 9, such as vinylnorbornene, and to control the content to be below this threshold value.

[0217] 4 and 5 show that even when the content (GC area %) of cyclic monoenes in the raw material compound (fraction) is 14.0 GC area % or less, preferably 12.0 GC area % or less, and particularly when the content (GC area %) of vinylnorbornene is 3.0 GC area % or less, the higher the content (GC area %) of high-boiling by-products, the longer the reaction completion time in the hydroformylation reaction and the lower the TCDDD yield. Therefore, it is clear that the content of high-boiling by-products is preferably below the upper limit mentioned above.

[0218] From these results, it is clear that it is preferable to set a threshold value for the content of high-boiling by-products in the cyclic diene-containing composition and to control the content to be equal to or lower than this threshold value.

[0219] Fraction 1 used in Experimental Example 1 and fraction 2 used in Experimental Example 2 had a higher content of cyclic monoenes (GC area %) than the other fractions 3 to 13. In particular, fraction 1 had a vinylnorbornene content of more than 3.0 GC area %, so the reaction completion time in the hydroformylation reaction was longer than that of the other fractions 2 to 13, and the reaction efficiency was insufficient.

[0220] Fraction 14 used in Experimental Example 14 had a content (GC area %) of high-boiling by-products exceeding 25.0 GC area %, and therefore the reaction completion time in the hydroformylation reaction was long and the TCDDD yield was low.

[0221] The commercially available DCPD used in Experimental Example 15 had a low content of high-boiling by-products (GC area %) and high DCPD purity, and therefore was solid at room temperature (25°C) and was difficult to handle.

[0222] Although the present invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various modifications can be made without departing from the spirit and scope of the invention. This application is based on Japanese Patent Application No. 2023-070230 filed on April 21, 2023, Japanese Patent Application No. 2023-077353 filed on May 9, 2023, and Japanese Patent Application No. 2023-173116 filed on October 4, 2023, and is incorporated by reference in its entirety. [Explanation of symbols]

[0223] 1 Dimerization tank 2. Distillation tower 3 Low boiling point component removal column 4. High boiling point component removal tower

Claims

1. A cyclic diene-containing composition having a cyclic diene content of 99.5 GC area % or less and a cyclic monoene content of 14.0 GC area % or less.

2. 2. The cyclic diene-containing composition according to claim 1, wherein the content of high-boiling by-products having boiling points higher than that of the cyclic diene is 0.3 GC area % or more.

3. The cyclic diene-containing composition of claim 1 , wherein the cyclic monoene has a vinyl group.

4. The cyclic diene-containing composition according to claim 3 , wherein the cyclic monoene comprises a cyclic monoene having 9 carbon atoms and a vinyl group.

5. 5. The cyclic diene-containing composition according to claim 4, wherein the content of the cyclic monoene having a vinyl group and 9 carbon atoms is 3.0 GC area % or less.

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

7. 2. The cyclic diene-containing composition according to claim 1, wherein the content of the cyclic monoene is 0.001 GC area % or more.

8. 2. The cyclic diene-containing composition according to claim 1, wherein the content of high-boiling by-products having boiling points higher than that of the cyclic diene is 25 GC area % or less.

9. 3. The cyclic diene-containing composition according to claim 2, wherein the content of the high-boiling by-products is measured by the following measurement method 1. <Measurement method 1> Analysis is carried out under the following GC measurement conditions, and the total content ratio of peaks with retention times of 15.0 minutes to 30.0 minutes is measured. (GC measurement conditions) GC device: gas chromatogram measuring device Detector: Hydrogen flame ionization detector Carrier gas: helium (column flow rate 1.65 mL / min) Column: Capillary column (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 / minute → 300°C (holding time: none) Inlet temperature: 200℃ Detector temperature: 300°C

10. The cyclic diene-containing composition according to claim 1, which is flowable at 25°C.

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

12. 12. The cyclic diene-containing composition of claim 11, wherein the polycyclic diene is dicyclopentadiene.

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

14. 14. The cyclic diene-containing composition of claim 13, wherein the polycyclic monoene comprises 5-vinyl-2-norbornene.

15. 2. The cyclic diene-containing composition according to claim 1, wherein the cyclic diene-containing composition is a composition obtained by purifying and separating hydrocarbon decomposition products obtained by thermally decomposing a hydrocarbon-containing composition.

16. 16. The cyclic diene-containing composition of claim 15, wherein the hydrocarbon-containing composition is naphtha.

17. A method for producing an aldehyde, comprising subjecting the cyclic diene-containing composition according to any one of claims 1 to 16 to a hydroformylation reaction to produce an aldehyde corresponding to the cyclic diene.

18. A method for producing an alcohol, comprising producing an aldehyde by the production method according to claim 17 and producing a corresponding alcohol from the aldehyde.

19. A method for producing a corresponding aldehyde by hydroformylating a cyclic diene in a cyclic diene-containing composition, comprising: A method for producing an aldehyde, comprising controlling the content of a cyclic monoene contained in the cyclic diene-containing composition to a predetermined threshold value (1) or less.

20. 20. The method for producing an aldehyde according to claim 19, wherein the predetermined threshold (1) is 14.0 GC area %.

21. 20. The method for producing an aldehyde according to claim 19, comprising controlling the content of high-boiling by-products having boiling points higher than those of the cyclic diene contained in the cyclic diene-containing composition to a predetermined threshold value (2) or higher.

22. 22. The method for producing aldehyde according to claim 21, wherein the predetermined threshold (2) is 0.3 GC area %.

23. The method for producing an aldehyde according to claim 19, wherein the content of the cyclic diene contained in the cyclic diene-containing composition is 99.5 GC area % or less.

24. The method for producing an aldehyde according to claim 19, wherein the cyclic monoene has a vinyl group.

25. The method for producing an aldehyde according to claim 24, wherein the cyclic monoene comprises a cyclic monoene having 9 carbon atoms and a vinyl group.

26. 26. The method for producing an aldehyde according to claim 25, wherein the content of the cyclic monoene having a vinyl group and 9 carbon atoms in the cyclic diene-containing composition is 3.0 GC area % or less.

27. The method for producing an aldehyde according to claim 19, wherein the content of the cyclic diene in the cyclic diene-containing composition is 60 GC area % or more.

28. The method for producing an aldehyde according to claim 19, wherein the cyclic diene-containing composition contains the cyclic monoene in an amount of 0.001 GC area % or more.

29. 20. The method for producing an aldehyde according to claim 19, wherein the cyclic diene-containing composition contains high-boiling by-products having boiling points higher than those of the cyclic diene in an amount of 25 GC area % or less.

30. The method for producing an aldehyde according to claim 21, wherein the content of the high-boiling by-products is measured by the following measurement method 1. <Measurement method 1> Analysis is carried out under the following GC measurement conditions, and the total content ratio of peaks with retention times of 15.0 minutes to 30.0 minutes is measured. (GC measurement conditions) GC device: gas chromatogram measuring device Detector: Hydrogen flame ionization detector Carrier gas: helium (column flow rate 1.65 mL / min) Column: Capillary column (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 / minute → 300°C (holding time: none) Inlet temperature: 200℃ Detector temperature: 300°C

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

32. 32. The method for producing an aldehyde according to claim 31, wherein the polycyclic diene is dicyclopentadiene.

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

34. The method for producing an aldehyde according to claim 33, wherein the polycyclic monoene comprises 5-vinyl-2-norbornene.

35. The method for producing an aldehyde according to claim 19, 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.

36. 36. The method for producing an aldehyde according to claim 35, wherein the hydrocarbon-containing composition is naphtha.

37. The method for producing an aldehyde according to claim 35, comprising controlling the conditions of the distillation purification so that the content of the cyclic monoene contained in the cyclic diene-containing composition is equal to or less than a predetermined threshold value (1).

38. The method for producing an aldehyde according to claim 35, comprising controlling the conditions of the distillation purification so that the content of the high-boiling by-products contained in the cyclic diene-containing composition is equal to or greater than a predetermined threshold value (2).

39. The method for producing an aldehyde according to claim 37 or 38, wherein the distillation purification comprises a first distillation column and a second distillation column, the first distillation column having a number of theoretical plates of 10 or more and 20 or less, and the second distillation column having a number of theoretical plates of 10 or more and 20 or less.

40. 40. The method for producing an aldehyde according to claim 39, wherein the reflux ratio of the first distillation column is 20 or more and 30 or less, and the reflux ratio of the second distillation column is 1.0 or more and 1.5 or less.

41. A method for producing an alcohol, comprising producing an aldehyde by the production method according to any one of claims 19 to 38, and producing a corresponding alcohol from the aldehyde.

42. A method for producing an alcohol, comprising producing an aldehyde by the production method according to claim 39 and producing a corresponding alcohol from the aldehyde.

43. A method for producing a cyclic diene-containing composition containing a cyclic diene, comprising distilling and purifying a hydrocarbon decomposition product obtained by thermal decomposition of a hydrocarbon-containing composition, the method comprising: A method for producing a cyclic diene-containing composition, comprising controlling the content of cyclic monoene contained in the cyclic diene-containing composition to a predetermined threshold value (1) or less.

44. The method for producing a cyclic diene-containing composition according to claim 43, comprising controlling the content of high-boiling by-products having boiling points higher than those of the cyclic diene contained in the cyclic diene-containing composition to a predetermined threshold value (2) or higher.

45. 44. The method for producing a cyclic diene-containing composition according to claim 43, wherein the predetermined threshold (1) is 14.0 GC area %.

46. 45. The method for producing a cyclic diene-containing composition according to claim 44, wherein the predetermined threshold (2) is 0.3 GC area %.

47. 44. The method for producing a cyclic diene-containing composition according to claim 43, comprising controlling the conditions of the distillation purification so that the content of cyclic monoene contained in the cyclic diene-containing composition is equal to or less than a predetermined threshold value (1).

48. 45. The method for producing a cyclic diene-containing composition according to claim 44, comprising controlling the conditions of the distillation purification so that the content of the high-boiling by-products contained in the cyclic diene-containing composition is equal to or greater than a predetermined threshold value (2).

49. The method for producing a cyclic diene-containing composition according to claim 47 or 48, wherein the distillation purification comprises a first distillation column and a second distillation column, the first distillation column having a theoretical plate number of 10 or more and 20 or less, and the second distillation column having a theoretical plate number of 10 or more and 20 or less.

50. 50. The method for producing a cyclic diene-containing composition according to claim 49, wherein the reflux ratio of the first distillation column is 20 or more and 30 or less, and the reflux ratio of the second distillation column is 1.0 or more and 1.5 or less.

51. The method for producing a cyclic diene-containing composition according to claim 43, wherein the content of the cyclic diene contained in the cyclic diene-containing composition is 99.5 GC area % or less.

52. 44. The method for producing a cyclic diene-containing composition according to claim 43, wherein the cyclic monoene has a vinyl group.

53. 53. The method for producing a cyclic diene-containing composition according to claim 52, wherein the cyclic monoene comprises a cyclic monoene having 9 carbon atoms and a vinyl group.

54. 54. The method for producing a cyclic diene-containing composition according to claim 53, wherein the content of the cyclic monoene having a vinyl group and 9 carbon atoms in the cyclic diene-containing composition is 3.0 GC area % or less.

55. The method for producing a cyclic diene-containing composition according to claim 43, wherein the content of the cyclic diene contained in the cyclic diene-containing composition is 60.0 GC area % or more.

56. The method for producing a cyclic diene-containing composition according to claim 43, wherein the content of the cyclic monoene contained in the cyclic diene-containing composition is 0.001 GC area % or more.

57. The method for producing a cyclic diene-containing composition according to claim 43, wherein the content of high-boiling by-products having boiling points higher than that of the cyclic diene contained in the cyclic diene-containing composition is 25 GC area % or less.

58. The method for producing a cyclic diene-containing composition according to claim 44, wherein the content of the high-boiling by-products is measured by the following measurement method 1. <Measurement method 1> Analysis is carried out under the following GC measurement conditions, and the total content ratio of peaks with retention times of 15.0 minutes to 30.0 minutes is measured. (GC measurement conditions) GC device: gas chromatogram measuring device Detector: Hydrogen flame ionization detector Carrier gas: helium (column flow rate 1.65 mL / min) Column: Capillary column (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 / minute → 300°C (holding time: none) Inlet temperature: 200℃ Detector temperature: 300°C

59. 44. The method for producing a cyclic diene-containing composition according to claim 43, wherein the cyclic diene is a polycyclic diene.

60. 60. The method for producing a cyclic diene-containing composition according to claim 59, wherein the polycyclic diene is dicyclopentadiene.

61. 44. The method for producing a cyclic diene-containing composition according to claim 43, wherein the cyclic monoene is a polycyclic monoene.

62. 62. The method for producing a cyclic diene-containing composition according to claim 61, wherein the polycyclic monoene comprises 5-vinyl-2-norbornene.

63. 44. The method for producing a cyclic diene-containing composition of claim 43, wherein the hydrocarbon-containing composition is naphtha.

64. A method for producing an aldehyde, comprising producing a cyclic diene-containing composition by the production method according to any one of claims 43 to 48 and claims 51 to 63, and producing a corresponding aldehyde from the cyclic diene contained in the cyclic diene-containing composition.

65. A method for producing an alcohol, comprising producing an aldehyde by the production method according to claim 64 and producing a corresponding alcohol from the aldehyde.

66. A method for producing an aldehyde, comprising producing a cyclic diene-containing composition by the production method according to claim 49, and producing a corresponding aldehyde from the cyclic diene contained in the cyclic diene-containing composition.

67. A method for producing an alcohol, comprising producing an aldehyde by the production method according to claim 66 and producing a corresponding alcohol from the aldehyde.

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