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

Abstract

To provide a cyclic diene-containing composition capable of efficiently producing aldehyde such as alicyclic aldehyde while preventing an activity deterioration of a hydroformylation reaction catalyst to be recovered and reused from a hydroformylation reaction liquid, and also to provide a production method of aldehyde using the cyclic diene-containing composition, and a production method of the cyclic diene-containing composition.SOLUTION: A cyclic diene-containing composition has a peroxide concentration of 2.8 m mol / L or less. A production method of aldehyde produces aldehyde through a hydroformylation reaction from the cyclic diene-containing composition, and includes setting the peroxide concentration to be equal to or lower than a prescribed threshold value. A production method of the cyclic diene-containing composition distills and refines a thermal decomposition product of a hydrocarbon-containing composition to produce the cyclic diene-containing composition, and includes setting the peroxide concentration in the cyclic diene-containing composition to be equal to or lower than a prescribed threshold value.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 aldehydes such as alicyclic aldehydes are useful as raw material monomers for improving the heat resistance, flex resistance, or low retardation of polyurethane resins, polyester resins, and polycarbonate resins. Specifically, alicyclic aldehydes such as tricyclodecane dicarbaldehyde and alicyclic alcohols such as tricyclodecane dimethanol and pentacyclopentadecanedimethanol have attracted attention from the viewpoints of high functionality in various applications and excellent industrial productivity.

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

[0004] The catalyst used in the hydroformylation reaction of the cyclic diene-containing composition described above contains an expensive Group 8 to 10 metal such as rhodium, and therefore, ideally, it should be used semi-permanently by repeatedly recovering and reusing it from the reaction solution after the hydroformylation reaction.

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

[0006] However, the techniques disclosed in Patent Documents 1 and 2 have the problem that the production process becomes complicated and the capital investment, production costs, and utility costs increase in order to remove as many impurities as possible from the cyclic diene-containing composition and separate and recover a high-purity cyclic diene. Moreover, even if the impurities contained in the cyclic diene-containing composition are reduced while taking economic efficiency into consideration, it has not been fully elucidated what impurities affect the activity of a hydroformylation catalyst, particularly a catalyst that has been repeatedly recovered and reused from a process liquid after the hydroformylation reaction. [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 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 containing a cyclic diene such as dicyclopentadiene, which is used as a starting material for an aldehyde such as tricyclodecane dicarbaldehyde, and which is capable of efficiently producing an aldehyde corresponding to the cyclic diene by hydroformylating the cyclic diene-containing composition while suppressing a decrease in the catalytic activity of a hydroformylation reaction catalyst, even when the cyclic diene-containing composition is repeatedly recovered and reused from a reaction liquid after a hydroformylation reaction, and a method for producing the same.

[0009] Another object of the present invention is to provide a method for producing an aldehyde, which uses the cyclic diene-containing composition to produce an aldehyde corresponding to the cyclic diene.

[0010] Another object of the present invention is to provide a method for producing an alcohol, which comprises producing an aldehyde by the above-mentioned production method and then producing a corresponding alcohol from the aldehyde. [Means for solving the problem]

[0011] As a result of extensive research into solving the above problems, the present inventors discovered that the above problems can be solved by setting the concentration of peroxide contained in a cyclic diene-containing composition to a predetermined value or less, and thus completed the present invention. That is, the present invention provides the following.

[0012] [1] A cyclic diene-containing composition containing a cyclic diene, wherein the concentration of peroxide in the cyclic diene composition is 2.8 mmol / L or less.

[0013] [2] The cyclic diene-containing composition according to [1], wherein the concentration of the cyclic diene is 60 GC area % or more.

[0014] [3] The cyclic diene-containing composition according to [1] or [2], wherein the concentration of the peroxide is 2.0 mmol / L or less, preferably 1.0 mmol / L or less, more preferably 0.6 mmol / L or less, and particularly preferably 0.3 mmol / L or less.

[0015] [4] The cyclic diene-containing composition according to any one of [1] to [3], wherein the peroxide comprises a peroxide of an alkene compound.

[0016] [5] The cyclic diene-containing composition according to any one of [1] to [4], wherein the concentration of the peroxide is measured by the following measurement method 1. <Measurement method 1> Under a nitrogen atmosphere, a mixture of chloroform and acetic acid is added to the cyclic diene-containing composition, followed by the addition of a saturated aqueous potassium iodide solution, followed by stirring, and then dilution with distilled water to prepare a measurement sample. The obtained measurement sample is subjected to iodine reduction titration using a 0.01 mol / L aqueous sodium thiosulfate solution as a standard solution, and the concentration of peroxide (mmol / L) in the cyclic diene-containing composition is determined based on the amount of the standard solution consumed.

[0017] [6] The cyclic diene-containing composition according to any one of [1] to [5], wherein the cyclic diene is a polycyclic diene.

[0018] [7] The cyclic diene-containing composition according to [6], wherein the polycyclic diene is dicyclopentadiene.

[0019] [8] A method for producing an aldehyde, comprising subjecting the cyclic diene-containing composition according to any one of [1] to [7] to a hydroformylation reaction to produce an aldehyde corresponding to the cyclic diene.

[0020] [9] A method for producing an alcohol, comprising producing an aldehyde by the production method according to [8] and producing a corresponding alcohol from the aldehyde.

[0021]

[10] A method for producing a corresponding aldehyde by hydroformylating a cyclic diene in a cyclic diene-containing composition, the method comprising reducing the concentration of peroxides contained in the cyclic diene-containing composition to a predetermined threshold value or less.

[0022]

[11] The method for producing an aldehyde according to

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

[0023]

[12] The method for producing an aldehyde according to

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

[0024]

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

[10] to

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

[0025]

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

[10] to

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

[0026]

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

[10] to

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

[0027]

[16] The method for producing an aldehyde according to

[15] , wherein the polycyclic diene is dicyclopentadiene.

[0028]

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

[10] to

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

[0029]

[18] The method for producing an aldehyde according to

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

[0030]

[19] The method for producing an aldehyde according to

[17] or

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

[0031]

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

[17] to

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

[0032]

[21] The method for producing an aldehyde according to

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

[0033]

[22] The method for producing an aldehyde according to

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

[0034]

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

[10] to

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

[0035]

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

[10] to

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

[0036]

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

[24] , wherein the alcohol is decanedimethanol.

[0037]

[26] 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 reducing the concentration of peroxide contained in the cyclic diene-containing composition to a predetermined threshold value or less.

[0038]

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

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

[0039]

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

[26] or

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

[0040]

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

[26] to

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

[0041]

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

[26] to

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

[0042]

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

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

[0043]

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

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

[0044]

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

[26] to

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

[0045]

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

[26] to

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

[0046]

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

[33] or

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

[0047]

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

[26] to

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

[0048]

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

[26] to

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

[0049]

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

[37] , wherein the polycyclic diene is dicyclopentadiene.

[0050]

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

[26] to

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

[0051] According to the present invention, it is possible to provide a cyclic diene-containing composition that is used as a starting material for aldehydes such as alicyclic aldehydes, and that is capable of efficiently producing aldehydes corresponding to the cyclic dienes while suppressing a decrease in the catalytic activity of a hydroformylation reaction catalyst even when the cyclic diene-containing composition is repeatedly recovered and reused from a reaction liquid after a hydroformylation reaction. Furthermore, according to the present invention, the cyclic diene-containing composition can be used to efficiently produce an aldehyde and further an alcohol corresponding to the cyclic diene. [Brief explanation of the drawings]

[0052] [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. DETAILED DESCRIPTION OF THE INVENTION

[0053] The present invention will be described in detail below, but the present invention is not limited to the following description and can be practiced with any modifications within the scope of the gist of the present invention.

[0054] 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, "% by mass" refers to the content ratio of a specified component contained in a total amount of 100% by mass, and "% by mass" refers to the content ratio of a specified component contained in a total amount of 100% by mass. "% by mass" and "% by mass" have the same meaning. "Optional" or "optionally" means that the subsequently described circumstance may or may not occur, and thus the description includes both the occurrence and non-occurrence of the circumstance. As used herein, the term "about" can mean above and below 20% of the stated value. For example, about 75°C encompasses the range of 60°C to 90°C. All steps described herein can be performed in any suitable order unless otherwise stated herein or clearly contradicted by context.

[0055] 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.

[0056] The cyclic diene-containing composition according to the first embodiment of the present invention, the method for producing an aldehyde according to the second embodiment of the present invention, the method for producing an alcohol according to the third embodiment of the present invention, and the method for producing a cyclic diene-containing composition according to the fourth embodiment of the present invention (hereinafter, the inventions of the first to fourth embodiments may be collectively referred to as "the present invention") will be described below.

[0057] <Cyclic Diene-Containing Composition> The cyclic diene-containing composition of the present invention is a composition containing a cyclic diene described below, in which the concentration of peroxide in the cyclic diene composition is 2.8 mmol / L or less.

[0058] (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. The cyclic diene in the present invention is not particularly limited as long as it is a compound having a ring structure in the molecule and having two non-conjugated carbon-carbon double bonds in the ring structure, but is preferably a compound that can be used as a starting material when producing an alicyclic alcohol. One embodiment of the cyclic diene includes a polycyclic diene having two or more ring structures in the molecule, each of the two ring structures having a non-conjugated carbon-carbon double bond. Alternatively, another embodiment of the cyclic diene includes a compound in which a cyclic diene having one ring structure is dimerized.

[0059] 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.

[0060] The lower limit of the cyclic diene content (unit: GC area%) of the present invention is not particularly limited, but from the viewpoint of producing an aldehyde such as an alicyclic aldehyde in a short reaction time and in a high yield using a cyclic diene-containing composition as a starting material, it can be 60.0 GC area% or more, preferably 63.0 GC area% or more, more preferably 66.0 GC area% or more, even more preferably 70.0 GC area% or more, particularly preferably 75.0 GC area% or more, and most preferably 80.0 GC area% or more, relative to 100% of the total GC area of the cyclic diene-containing composition. On the other hand, the upper limit of the cyclic diene content (unit: GC area%) in the cyclic diene-containing composition of the present invention is not particularly limited, but from the viewpoint of economic efficiency such as the production costs required for purifying and separating the cyclic diene-containing composition, and from the viewpoint of fluidity at room temperature and excellent handleability, it can be 99.95 GC area% or less, with 99.9 GC area% or less being preferred, more preferably 97.5 GC area% or less, even more preferably 95.0 GC area% or less, particularly preferably 90.0 GC area% or less, and most preferably 85.0 GC area% or less, relative to 100% of the total GC area of the cyclic diene-containing composition.

[0061] The upper and lower limits can be arbitrarily combined. For example, the content of the cyclic diene in the cyclic diene-containing composition (unit: GC area%) is not particularly limited, and can be 60.0 GC area% or more and 99.95 GC area% or less, preferably 63.0 GC area% or more and 99.9 GC area% or less, more preferably 66.0 GC area% or more and 97.5 GC area% or less, even more preferably 70.0 GC area% or more and 95.0 GC area% or less, particularly preferably 75.0 GC area% or more and 90.0 GC area% or less, and most preferably 80.0 GC area% or more and 85.0 GC area% or less.

[0062] The method for measuring the content of the cyclic diene in the cyclic diene-containing composition will be described in detail below. Methods for controlling the content of the cyclic diene in the cyclic diene-containing composition include, for example, extraction methods, methods for controlling the amount by adjusting purification conditions or distillation conditions, and combinations of these methods.

[0063] (peroxide) In the cyclic diene-containing composition and production method thereof of the present invention, and the aldehyde production method of the present invention, by controlling the concentration of peroxide contained in the cyclic diene-containing composition to a predetermined value or less, when the cyclic diene-containing composition is used as a starting material for an aldehyde such as an alicyclic aldehyde, even if the cyclic diene-containing composition is repeatedly recovered and reused from the reaction liquid after the hydroformylation reaction, the cyclic diene-containing composition can be hydroformylated to efficiently produce an aldehyde corresponding to the cyclic diene while suppressing a decrease in the catalytic activity of the hydroformylation reaction catalyst.

[0064] The peroxide in the present invention is not particularly limited, and examples thereof include peroxides of alkene compounds. Examples of the alkene compound include the cyclic diene of the present invention, isopropylnorbornene, and methyltetrahydroindene. Specific examples of the peroxide of the alkene compound include a compound having a four-membered ring structure composed of two carbon molecules and two oxygen molecules, and a compound having a hydroperoxy group at the vinyl position. More specific examples of the peroxide of an alkene compound include compounds represented by the following formula when the alkene compound is dicyclopentadiene, which is a cyclic diene.

[0065] [ka]

[0066] The peroxide concentration in the present invention can be measured by the following measurement method 1. A more specific measurement method is as described in the Examples section below. <Measurement method 1> Under a nitrogen atmosphere, a mixture of chloroform and acetic acid is added to the cyclic diene-containing composition, followed by the addition of a saturated aqueous potassium iodide solution, followed by stirring, and then dilution with distilled water to prepare a measurement sample. The obtained measurement sample is subjected to iodine reduction titration using a 0.1 N aqueous sodium thiosulfate solution as a standard solution, and the concentration of peroxide (mmol / L) in the cyclic diene-containing composition is determined based on the amount of the standard solution consumed.

[0067] When an aldehyde is produced by a hydroformylation reaction using the cyclic diene-containing composition as a starting material, the upper limit of the peroxide concentration in the cyclic diene-containing composition of the present invention is typically 2.8 mmol / L or less, preferably 2.0 mmol / L or less, more preferably 1.0 mmol / L or less, even more preferably 0.6 mmol / L or less, and particularly preferably 0.3 mmol / L or less, from the viewpoint of efficiently producing an aldehyde corresponding to the cyclic diene while suppressing a decrease in the catalytic activity of a hydroformylation catalyst that is repeatedly recovered and reused from the reaction liquid after the hydroformylation reaction. On the other hand, the lower limit of the concentration of the peroxide is not particularly limited, and it is acceptable for the peroxide to be substantially absent (0.0 mmol / L). However, from the viewpoint of economic efficiency, such as the production costs required for purifying and separating the cyclic diene-containing composition, the concentration can be 0.001 mmol / L or more relative to the cyclic diene-containing composition, preferably 0.005 mmol / L or more, more preferably 0.01 mmol / L or more, even more preferably 0.02 mmol / L or more, and particularly preferably 0.03 mmol / L or more.

[0068] The upper and lower limits can be combined arbitrarily. For example, the concentration of peroxide in the cyclic diene-containing composition is not particularly limited, and may be substantially free (0.0 mmol / L), or may be 0.001 mmol / L or more and 2.8 mmol / L or less, preferably 0.005 mmol / L or more and 2.0 mmol / L or less, more preferably 0.01 mmol / L or more and 1.0 mmol / L or less, even more preferably 0.02 mmol / L or more and 0.6 mmol / L or less, and particularly preferably 0.03 mmol / L or more and 0.3 mmol / L or less.

[0069] Methods for controlling the concentration of peroxide in the cyclic diene-containing composition include, for example, an extraction method, a method for controlling the amount by adjusting purification conditions or distillation conditions, a method for adding an antioxidant as described below, and a combination of these methods.

[0070] <Method of producing cyclic diene-containing composition> The method for producing the cyclic diene-containing composition of the present invention is not particularly limited, and examples thereof include the method for producing the cyclic diene-containing composition of the present invention.

[0071] The method for producing a cyclic diene-containing composition of the present invention is a method for producing a cyclic diene-containing composition containing a cyclic diene by distilling and purifying a hydrocarbon decomposition product obtained by thermal decomposition of a hydrocarbon-containing composition, and is characterized in that it includes reducing the concentration of peroxides contained in the cyclic diene-containing composition to a predetermined threshold value or less.

[0072] As a method for controlling the concentration of peroxides contained in the cyclic diene-containing composition to a predetermined threshold or less, a method for producing a cyclic diene-containing composition by thermal decomposition of a hydrocarbon-containing composition to obtain a hydrocarbon decomposition product, which is then purified by distillation, as described below, can be mentioned. In this distillation purification, it is preferable to control the distillation purification conditions. In this case, the peroxides in the present invention are usually high-boiling components having a boiling point higher than that of the cyclic diene in the cyclic diene-containing composition of the present invention. Therefore, these peroxides can be removed together with other high-boiling components, for example, in the distillation purification step in the production method for the cyclic diene-containing composition of the present invention described below, and their concentrations can be appropriately controlled.

[0073] Furthermore, as a method for controlling the concentration of peroxides contained in the cyclic diene-containing composition to be equal to or lower than a predetermined threshold, there can be mentioned a method of adding an antioxidant to the hydrocarbon decomposition products obtained by thermal decomposition of the hydrocarbon-containing composition so that the concentration of peroxides contained in the cyclic diene-containing composition is equal to or lower than a predetermined threshold. That is, the hydrocarbon decomposition products obtained by thermal decomposition of the hydrocarbon-containing composition may contain an antioxidant. In the method for producing a cyclic diene-containing composition of the present invention, the hydrocarbon decomposition product contains an antioxidant, which can prevent the cyclic diene, such as dicyclopentadiene, from being oxidized to produce peroxides derived from the cyclic diene. The type and suitable amount of antioxidant to be added here will be described in detail in the section explaining the method for producing an aldehyde of the present invention.

[0074] In addition, in the cyclic diene-containing composition of the present invention, the storage conditions may be controlled so that the concentration of peroxide contained in the starting cyclic diene-containing composition is equal to or lower than the threshold value. In this case, examples of a method for controlling the storage conditions of the cyclic diene-containing composition include adding an antioxidant to the cyclic diene-containing composition to be stored, or controlling the dissolved oxygen concentration of the cyclic diene-containing composition to be stored. As with the addition of an antioxidant, controlling the dissolved oxygen concentration can also prevent cyclic dienes such as dicyclopentadiene from being oxidized to produce peroxides derived from the cyclic diene.

[0075] When an antioxidant is added to the cyclic diene-containing composition, the type of antioxidant and the lower or upper limit of the content or amount of antioxidant added are synonymous with the type of antioxidant and the lower or upper limit of the content or amount of antioxidant added for controlling storage conditions so that the concentration of peroxide contained in the starting cyclic diene-containing composition is equal to or lower than a predetermined threshold, as described in the aldehyde production method of the present invention described below.

[0076] When the control of the storage conditions includes controlling the dissolved oxygen concentration of the cyclic diene-containing composition being stored, the control method and control concentration of the dissolved oxygen concentration are synonymous with the control method and control concentration of the dissolved oxygen concentration for controlling the dissolved oxygen concentration under storage conditions so that the concentration of peroxides contained in the raw material cyclic diene-containing composition is below a predetermined threshold, as described in the aldehyde production method of the present invention described below.

[0077] The threshold value of the peroxide concentration in the method for producing a cyclic diene-containing composition of the present invention is preferably 2.8 mmol / L or less, more preferably 2.0 mmol / L or less, even more preferably 1.0 mmol / L or less, particularly preferably 0.6 mmol / L or less, and most preferably 0.3 mmol / L or less, as the peroxide concentration of the cyclic diene-containing composition produced. The same applies to the threshold value in the aldehyde production method of the present invention described below.

[0078] In the method for producing the cyclic diene-containing composition of the present invention, the production conditions and the like are controlled so as to obtain a cyclic diene-containing composition having the above-mentioned preferred peroxide concentration and preferred cyclic diene concentration of the cyclic diene-containing composition of the present invention.

[0079] (Method of producing a cyclic diene-containing composition) The method for producing the cyclic diene-containing composition of the present invention is not particularly limited, and examples include a method in which a hydrocarbon-containing composition is thermally decomposed in a hydrocarbon decomposition product treatment facility such as an ethylene production facility described below, and the resulting hydrocarbon decomposition product is purified by distillation to obtain the cyclic diene-containing composition; or a method in which the hydrocarbon decomposition product is separated and purified to obtain a C5 hydrocarbon fraction described below, and the resulting C5 hydrocarbon fraction is purified by distillation to obtain the cyclic diene-containing composition.

[0080] When producing the cyclic diene-containing composition, the distillation purification is carried out so that the concentration of the peroxide contained in the cyclic diene-containing composition is equal to or lower than a predetermined threshold value. By doing so, when an aldehyde is produced by a hydroformylation reaction using the cyclic diene-containing composition as a starting material, it becomes possible to efficiently produce an aldehyde corresponding to the cyclic diene, i.e., in a short reaction time and in a high yield, while suppressing a decrease in the catalytic activity of a hydroformylation catalyst that has been repeatedly recovered and reused from the reaction liquid after the hydroformylation reaction.

[0081] 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.

[0082] (Ethylene production facility) The ethylene production facility in the present invention refers to a production facility for obtaining a C5 hydrocarbon fraction, which will be described later, as one of the fractions separated and purified from naphtha cracking products, and refers to a facility that thermally cracks naphtha at high temperatures to produce hydrogen, hydrocarbons having a carbon number of 4 such as methane, ethane, ethylene, propane, propylene, butane, or butadiene, hydrocarbons having a carbon number of 5, aromatic hydrocarbons such as benzene, and other heavy oils, and then separates and refines these.

[0083] 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): Pyrolysis step in which raw materials such as naphtha, coal, and natural gas are thermally decomposed 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.

[0084] (C5 hydrocarbon fraction) The C5 hydrocarbon fraction in the present invention is a fraction containing hydrocarbons with a carbon number of 5 as a main component, which is obtained by separating heavy oil from a hydrocarbon cracking product obtained by thermally cracking a hydrocarbon-containing composition such as naphtha, and then separating and removing hydrogen and hydrocarbons with a carbon number of 1 to 4. Specific examples of the C5 hydrocarbon fraction include a mixture containing C5 hydrocarbons such as isoprene, isopentane, normal pentane, and cyclopentadiene as main components. Here, the C5 hydrocarbon fraction contains a small amount of a C4 hydrocarbon fraction and a small amount of a C6 hydrocarbon fraction for separation performance reasons. Furthermore, since the C5 hydrocarbon fraction contains cyclopentadiene, the cyclopentadiene polymerizes over time to form dicyclopentadiene, resulting in the presence of dicyclopentadiene in the C5 hydrocarbon fraction.

[0085] An example of the composition of the C5 hydrocarbon fraction is shown in Table 1. Although it varies depending on the type of hydrocarbon-containing composition such as naphtha subjected to thermal cracking, the C5 hydrocarbon fraction generally contains cyclopentadiene and dicyclopentadiene in a total amount in the range of 10 to 35 mass%.

[0086] [Table 1]

[0087] (Distillation and refining of hydrocarbon cracking products or C5 hydrocarbon fractions) In the present invention, the distillation purification of the hydrocarbon cracking product or the C5 hydrocarbon fraction may be carried out in a single distillation operation or in a combination of multiple distillation operations. When multiple distillation operations are carried out in combination, a method of carrying out multiple distillation operations under the same conditions or a method of carrying out two or more distillation operations under different conditions may be employed.

[0088] In particular, from the viewpoint of keeping the concentration of peroxide contained in the cyclic diene-containing composition of the present invention below a predetermined threshold, specifically, keeping the peroxide concentration below 2.8 mmol / L, a method in which distillation operations under the same or different conditions are combined and carried out two or more times is preferred. When the distillation operation is carried out multiple times, two or more distillation columns are used and the number of theoretical plates or reflux ratio of each distillation column is controlled within the ranges described below, thereby reliably achieving separation and removal of peroxides that would not be possible with a single distillation column.

[0089] For example, when two distillation columns are used in the distillation purification, i.e., when a first distillation column and a second distillation column are included, it is preferable to set the reflux ratio of the first distillation column to 20 or more and 30 or less, preferably 23 or more and 27 or less, and the reflux ratio of the second distillation column to 1.8 or more and 4.5 or less, preferably 2.0 or more and 2.8 or less. By doing so, peroxides can be efficiently separated and removed, and the peroxide concentration can be efficiently controlled to be equal to or less than the predetermined threshold value.

[0090] Furthermore, when the distillation purification includes a first distillation column and a second distillation column, it is preferable to set the number of theoretical plates of the first distillation column to 22 or more and 28 or less, preferably 23 or more and 27 or less, and to set the number of theoretical plates of the second distillation column to 10 or more and 20 or less, preferably 13 or more and 17 or less. By setting the numbers in this manner, peroxides can be efficiently separated and removed, and the peroxide concentration can be efficiently controlled to be equal to or less than the predetermined threshold value.

[0091] (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.

[0092] 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.

[0093] 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.

[0094] 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.

[0095] Step (IV): A step of removing high boiling components in which the fraction rich in cyclic dienes such as dicyclopentadiene from the bottom of the column in step (III) is introduced into a high boiling component removal column for distillation, and the peroxides of the present invention, which have boiling points higher than those of cyclic dienes such as dicyclopentadiene, and high boiling co-dimers by-produced during the dimerization reaction in 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.

[0096] The steps (I) to (IV) will be described in more detail below.

[0097] [Process (I)] The C5 hydrocarbon fraction is first supplied to the dimerization step (I), where cyclic diene precursors such as cyclopentadiene contained in the C5 hydrocarbon fraction are dimerized to produce cyclic dienes such as dicyclopentadiene corresponding to the cyclic diene precursors. The conditions for the dimerization are not particularly limited and are appropriately selected depending on the content of cyclic diene precursors such as cyclopentadiene in the C5 hydrocarbon fraction, and other factors. Typically, the dimerization temperature is set within a range of 50 to 110°C, and the reaction time is set within a range of 1 to 6 hours, and 30 to 99 mass% of the cyclic diene precursors such as cyclopentadiene contained in the C5 hydrocarbon fraction is dimerized.

[0098] [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.

[0099] [Process (III)] The heavy C5 fraction composition withdrawn from the bottom of the distillation column in step (II) is liquefied in a condenser as necessary and then sent to a low-boiling component removal step (III) (light-boiling component removal column) for distillation. The heavy C5 fraction composition sent to step (III) is controlled so that the content of cyclic dienes such as dicyclopentadiene is usually within the range of 50 to 95 mass%. The low boiling components contained in the heavy C5 fraction composition are removed from the top of the low boiling component removal column, while a fraction rich in cyclic dienes such as dicyclopentadiene is taken out from the bottom of the column.

[0100] 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.

[0101] The low-boiling component removal column is preferably controlled so that the content of cyclic dienes such as cyclopentadiene in the bottom effluent obtained from the column bottom is 0.5 GC area % or less and the content of hydrocarbons having a carbon number of 5 is 2.0 GC area % or less. The distillation conditions in the light-removal column are controlled as follows: vacuum degree 5 to 200 torr, preferably 10 to 50 torr; column bottom temperature 50 to 120°C, preferably 80 to 110°C; theoretical plate number 22 to 28, preferably 23 to 27; and reflux ratio 20 to 30, preferably 23 to 27. Under these conditions, peroxides contained in the C5 heavy fraction obtained from the bottom of the light-removal column in step (II) can be efficiently removed from the bottom effluent obtained from the bottom of the light-removal column, and 90 mass% or more of cyclic monoenes such as vinylnorbornene and similar co-dimers can be removed. Specifically, the content of cyclic dienes such as cyclopentadiene can be reduced to 0.5 GC area% or less and the content of hydrocarbons having 5 carbon atoms can be reduced to 2.0 GC area% or less in the bottom distillate.

[0102] [Process (IV)] In the low-boiling component removal step (III), the fraction (tower bottom liquid) rich in cyclic dienes such as dicyclopentadiene taken out from the bottom of the low-boiling component removal column is sent to the high-boiling component removal step (IV) (heavy-boiling component removal column) and subjected to distillation. The high-boiling components removed in step (IV) are the peroxides of the present invention and high-boiling co-dimers such as methylbicyclononadiene, which are dimers of cyclopentadiene and isoprene, which have boiling points higher than those of the cyclic dienes such as dicyclopentadiene produced as by-products in the dimerization reaction of step (I). When low-boiling products such as cyclopentadiene trimers are present, these low-boiling products are also removed.

[0103] The distillation conditions in the high-boiling component removal column in step (IV), particularly the distillation temperature, affect the thermal decomposition of dicyclopentadiene and significantly affect the purity of the final product, so it is preferable to pay attention to them so as to obtain the desired cyclic diene-containing composition. The heavy-boiler removal column is preferably a packed column to minimize pressure loss within the column, and is operated under controlled conditions of a 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 1.8 to 4.5, preferably 2.0 to 2.8. Under these conditions, a cyclic diene-containing composition of the present invention containing a high content of cyclic dienes such as dicyclopentadiene and having an appropriately controlled concentration of the peroxide of the present invention can be obtained from the top of the heavy-boiler removal column.

[0104] In the present invention, the high-boiling component removal column is preferably controlled so that the peroxide concentration in the cyclic diene-containing composition obtained from the top of the column is 2.8 mmol / L or less, preferably so that the concentration of cyclopentadiene, etc. is 60 GC area % or more and the peroxide concentration is 2.0 mmol / L or less.

[0105] A method for controlling the composition of the cyclic diene-containing composition obtained from the top of the heavy-boiling component removal column to the above-mentioned composition can be exemplified by a method in which the bottom temperature of the heavy-boiling component removal column is controlled to a range of 50 to 120°C, the degree of vacuum is controlled to a range of 5 to 100 torr, the number of theoretical plates is controlled to a range of 10 to 20, and the reflux ratio is controlled to a range of 1.8 to 4.5, and the distillation column feed liquid has a residence time in the column of 15 minutes or less, preferably 10 to 15 minutes. If the bottom temperature of the heavy-boiling component removal column is less than 50°C, the content of C5 hydrocarbons such as cyclopentadiene in the bottom effluent will be high, and if it exceeds 120°C, the content of heavy fractions such as tricyclopentadiene in the bottom effluent will be high. In either case, the content of cyclic dienes such as dicyclopentadiene in the bottom effluent will be low. By controlling the number of theoretical plates of the heavy-boiling component removal column within the range of 10 to 20 and the reflux ratio within the range of 1.8 to 4.5, peroxides can be efficiently separated and removed from the cyclic diene-containing composition of the present invention obtained from the top of the heavy-boiling component removal column, and the peroxide concentration can be controlled to be equal to or lower than the predetermined threshold value. Furthermore, if the residence time of the feed liquid in the distillation column exceeds 15 minutes, peroxides may be generated in the column, and the bottom effluent may contain a large amount of heavy fractions such as tricyclopentadiene. Furthermore, if the residence time in the column is less than 10 minutes, the bottom portion of the distillation column becomes small, making it difficult to install a meter for measuring the liquid level. Furthermore, the amount of liquid held at the bottom of the column becomes small, and the liquid in the bottom may become empty during normal distillation column operation, which may hinder stable operation.

[0106] A specific method for realizing the above residence time is to design the inner diameter of the bottom of the distillation column to a size that corresponds to the amount of the components effluent from the bottom of the column.

[0107] 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.

[0108] In the method for producing a cyclic diene-containing composition of the present invention, when the peroxide concentration of the resulting cyclic diene-containing composition is controlled by adding an antioxidant to the hydrocarbon decomposition product obtained by thermal decomposition of the aforementioned hydrocarbon-containing composition, the antioxidant may be added in a required amount, for example, before carrying out step (II). In the method for producing a cyclic diene-containing composition of the present invention, an antioxidant may be added to the produced cyclic diene-containing composition.

[0109] [One embodiment of a production facility for a cyclic diene-containing composition] Next, one embodiment of the production equipment for the cyclic diene-containing composition of the present invention will be described with reference to the accompanying drawing. In Fig. 1, a C5 hydrocarbon fraction obtained by thermal cracking of a hydrocarbon-containing composition such as naphtha is first supplied to dimerization vessel 1 via line 10, where dimerization of cyclic diene precursors such as cyclopentadiene is carried out to produce cyclic dienes such as dicyclopentadiene corresponding to the cyclic diene precursors [dimerization step (I)]. After the dimerization reaction, the content of dimerization vessel 1 is sent via line 11 to distillation column 2 [unreacted component recovery step (II)] and subjected to distillation. In distillation column 2, the unreacted C5 hydrocarbon fraction is removed from the top of distillation column 2 via pipe 13, and the bottom liquid (heavy C5 fraction composition) rich in cyclic dienes such as dicyclopentadiene is sent from the bottom of distillation column 2 via pipe 12 to light-boiling component removal column 3 [light-boiling component removal step (III)] for distillation. In the light-removal column 3, cyclic monoenes such as vinylnorbornene, which have lower boiling points than cyclic dienes such as cyclopentadiene, as well as C5 hydrocarbon fractions, C6 hydrocarbon fractions, and similar co-dimers, are removed from the top of the light-removal column 3 via pipe 15, and the fraction rich in cyclic dienes such as dicyclopentadiene is sent from the bottom of the light-removal column 3 via pipe 14 to the final heavy-removal column 4 [heavy-boiling component removal step (IV)] for distillation. In the heavy-boiling component removal column 4, the high-boiling peroxides of the present invention, which have boiling points higher than those of cyclic dienes such as dicyclopentadiene, similar co-dimers, and remaining oligomers are removed from the bottom of the heavy-boiling component removal column 4 via pipe 16, and a cyclic-diene-containing composition containing a high content of cyclic dienes such as dicyclopentadiene is obtained from the top of the heavy-boiling component removal column 4 via pipe 17.

[0110] 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.

[0111] <Method for producing aldehyde> The method for producing an aldehyde of the present invention comprises subjecting the cyclic diene-containing composition of the present invention to a hydroformylation reaction to produce an aldehyde corresponding to the cyclic diene. The method for producing an aldehyde of the present invention is a production method that includes reducing the concentration of peroxide contained in the cyclic diene-containing composition to a predetermined threshold value or less.

[0112] The cyclic diene in the aldehyde production method of the present invention can be treated as having the same meaning as the cyclic diene in the cyclic diene-containing composition of the present invention described above. In the method for producing an aldehyde of the present invention, the cyclic diene-containing composition of the present invention can be used as the cyclic diene-containing composition.

[0113] The method for reducing the concentration of peroxides contained in the cyclic diene-containing composition to a predetermined threshold or less is not particularly limited, and examples thereof include a method for reducing the concentration of peroxides to a predetermined threshold or less, as described above, by distilling and purifying hydrocarbon decomposition products obtained by thermally decomposing a hydrocarbon-containing composition such as naphtha. In this distillation purification, it is preferable to control the conditions for distillation purification.

[0114] In the method for producing an aldehyde of the present invention, the hydrocarbon decomposition product may contain an antioxidant, as described above in the method for producing a cyclic diene-containing composition of the present invention. When the hydrocarbon decomposition product contains an antioxidant, it is possible to suppress the oxidation of cyclic dienes such as dicyclopentadiene to produce peroxides derived from the cyclic dienes.

[0115] Furthermore, in the method for producing an aldehyde of the present invention, as described above in the method for producing a cyclic diene-containing composition of the present invention, an antioxidant can be added to the hydrocarbon decomposition product so that the concentration of peroxides contained in the cyclic diene-containing composition is equal to or lower than a predetermined threshold. By adding an antioxidant to the hydrocarbon decomposition product, it is possible to suppress the oxidation of cyclic dienes such as dicyclopentadiene to produce peroxides derived from the cyclic dienes.

[0116] In the aldehyde production method of the present invention, the storage conditions may be controlled so that the concentration of peroxide contained in the starting cyclic diene-containing composition is equal to or lower than the threshold value. In this case, examples of a method for controlling the storage conditions of the cyclic diene-containing composition include adding an antioxidant to the cyclic diene-containing composition to be stored, or controlling the dissolved oxygen concentration of the cyclic diene-containing composition to be stored. As with the addition of an antioxidant, controlling the dissolved oxygen concentration can also prevent cyclic dienes such as dicyclopentadiene from being oxidized to produce peroxides derived from the cyclic diene.

[0117] The type of antioxidant used in the present invention is not particularly limited as long as it has excellent dispersibility and solubility in the reaction system and can suppress the oxidation of the cyclic diene and the generation of peroxides derived from the cyclic diene, and for example, a person skilled in the art can appropriately select and use known phenolic compounds, known sulfur-based compounds, known phosphorus-based compounds, known amine-based compounds, etc., which are used as antioxidants. Among these, phenolic compounds, particularly hindered phenolic compounds, are preferred, and it is preferable to use at least one of these.

[0118] The phenolic compounds include t-butylcatechol, 2,6-di-tert-butyl-4-hydroxytoluene (BHT), N,N'-(1,6-hexanediyl)bis[3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanamide], pentaerythritol tetrakis[3-[3,5-di(t-butyl)-4-hydroxyphenyl]propionate], 2,2thio[diethylbis-3(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4-hydroxybenzoylpropanol ... ,4',4''-[(2,4,6-trimethylbenzene-1,3,5-triyl)tris(methylene)]tris(2,6-di-t-butylphenol), bis(3-t-butyl-4-hydroxy-5-methylbenzenepropanoic acid)ethylenebis(oxyethylene), 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanuric acid, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-S-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro(5,5)undecane, and the like.

[0119] These antioxidants may be used alone or in combination of two or more.

[0120] When the hydrocarbon decomposition product contains an antioxidant, or when an antioxidant is added to the hydrocarbon decomposition product, the lower limit of the content or amount of the antioxidant to be added is not particularly limited, as long as it is an amount that can reduce the peroxide content according to the present invention to the threshold value or less. As an example, the content of the antioxidant in the hydrocarbon decomposition product is preferably 30 ppm by mass or more, more preferably 50 ppm by mass or more, and even more preferably 100 ppm by mass or more. On the other hand, when an antioxidant is added to the hydrocarbon decomposition product, the content or upper limit of the amount of the antioxidant is not particularly limited as long as the quality of the cyclic diene-containing composition of the present invention can be maintained at a satisfactory level and the increase in production costs for purification, etc. can be kept within an acceptable range. For example, the content of the antioxidant in the hydrocarbon decomposition product is preferably 1,000 ppm by mass or less, more preferably 500 ppm by mass or less, and even more preferably 300 ppm by mass or less. The above upper and lower limits can be combined in any manner.

[0121] Furthermore, when the cyclic diene-containing composition according to the present invention contains an antioxidant, or when an antioxidant is added to the cyclic diene-containing composition, the lower limit of the content or amount of the antioxidant added is not particularly limited, as long as it is an amount that can make the peroxide content according to the present invention equal to or less than the threshold value. For example, the content of the antioxidant in the cyclic diene-containing composition is preferably 30 ppm by mass or more, more preferably 50 ppm by mass or more, and even more preferably 100 ppm by mass or more. On the other hand, when the cyclic diene-containing composition contains an antioxidant, the upper limit of the content or amount of the antioxidant is not particularly limited as long as the quality of the cyclic diene-containing composition of the present invention can be maintained at a good level and the increase in production costs for purification, etc. can be kept within an acceptable range. For example, the content of the antioxidant in the cyclic diene-containing composition is preferably 1000 ppm by mass or less, more preferably 500 ppm by mass or less, and even more preferably 300 ppm by mass or less. The above upper and lower limits can be combined in any manner.

[0122] When the content of the antioxidant in the hydrocarbon decomposition product or cyclic diene-containing composition is equal to or greater than the above lower limit, the generation of peroxides can be effectively suppressed by a sufficient amount of the antioxidant, making it easier to reduce the peroxide concentration to below the threshold value. On the other hand, when the content of the antioxidant is equal to or less than the above upper limit, the quality of the cyclic diene-containing composition of the present invention can be maintained at a good level, and an increase in production costs for purification, etc. can be kept within an acceptable range. Furthermore, the risk of the antioxidant precipitating at the bottom of the distillation column and clogging the piping can be reduced.

[0123] Furthermore, in the method for producing an aldehyde of the present invention, when the dissolved oxygen concentration of the cyclic diene-containing composition to be stored is controlled so that the concentration of peroxides contained in the cyclic diene-containing composition is not more than the threshold value, the control of the dissolved oxygen concentration can be carried out, for example, by circulating an inert gas such as nitrogen through the cyclic diene-containing composition or under the storage atmosphere of the cyclic diene-containing composition. In this case, there is no particular limitation on the control concentration of the dissolved oxygen, and it is sufficient if the concentration can reduce the peroxide concentration in the cyclic diene-containing composition to the threshold value or less, but it is preferable to set the dissolved oxygen concentration in the cyclic diene-containing composition to 100 volume ppm or less, particularly 50 volume ppm or less, from the viewpoint of the peroxide production suppression effect. On the other hand, from the viewpoint of economics such as the production cost required for reducing the dissolved oxygen concentration, an excessively low dissolved oxygen concentration does not allow the dissolved oxygen concentration to be excessively low, and therefore the dissolved oxygen concentration in the raw material cyclic diene-containing composition is usually 1 volume ppm or more.

[0124] In the method for producing an aldehyde of the present invention, the method for producing an aldehyde corresponding to the cyclic diene by the hydroformylation reaction is not particularly limited, and can be carried out according to a conventional method. For example, according to the method described in Japanese Patent Application Laid-Open No. 2001-10999, 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.

[0125] Specifically, when the cyclic diene in the cyclic diene-containing composition of the present invention is dicyclopentadiene, tricyclodecane dicarbaldehyde can be produced by hydroformylating the dicyclopentadiene contained in the cyclic diene-containing composition using hydrogen and carbon monoxide in a hydroformylation reaction solvent comprising a hydrocarbon compound in the presence of a catalyst comprising a rhodium compound and an organophosphorus compound, as shown in the following reaction formula (I), according to the method described in JP 2001-10999 A:

[0126] [ka]

[0127] The rhodium compound used in this hydroformylation step may take any form of precursor, so long as it forms a complex with an organophosphorus compound and exhibits hydroformylation activity in the presence of hydrogen and carbon monoxide. Rhodium compounds include Rh(acac)(CO)2, Rh2O3, and Rh4(CO) 12 , Rh6(CO) 16 Alternatively, a catalyst precursor such as Rh(NO3)3 may be introduced into the reaction mixture together with an organophosphorus compound to form a catalytically active rhodium metal hydride carbonyl phosphorus complex in the reaction vessel, or a rhodium metal hydride carbonyl phosphorus complex catalyst may be prepared in advance and then introduced into the reaction vessel.

[0128] 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.

[0129] The organophosphorus compounds which form catalysts for the hydroformylation reaction with the rhodium compounds include known phosphites and known phosphines. Among these, the phosphite is a compound represented by the general formula P(-OR 11 )(-OR 12 )(-OR 13)(wherein, R 11 , R 12 and R 13 R represents an optionally substituted aryl group or alkyl group. 11 , R 12 and R 13 Specific examples of the alkyl group include aryl groups such as phenyl and naphthyl groups which may be substituted with a methyl group, ethyl group, isopropyl group, n-butyl group, t-butyl group, methoxy group, etc.; aliphatic alkyl groups such as methyl group, ethyl group, isopropyl group, n-butyl group, t-butyl group, etc.; and alicyclic alkyl groups such as cyclopentyl and cyclohexyl groups which may be substituted with a lower alkyl group such as a methyl group, ethyl group, isopropyl group, n-butyl group, t-butyl group, etc.

[0130] 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.

[0131] As the phosphine, sterically hindered alkylphosphines are particularly effective in the hydroformylation reaction of dicyclopentadiene, and specific examples include tricyclopropylphosphine, tricyclobutylphosphine, tricyclopentylphosphine, tricyclohexylphosphine, tricycloheptylphosphine, and tricyclooctylphosphine. The phosphines are not limited to these. These phosphines may be used alone or in combination of two or more.

[0132] 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.

[0133] 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.

[0134] 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.

[0135] 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.

[0136] 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.

[0137] 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.

[0138] <Extraction of tricyclodecane dicarbaldehyde> After completion of the hydroformylation reaction, the method for extracting and separating the product tricyclodecane dicarbaldehyde from the reaction mixture is not particularly limited, and can be appropriately determined by a person skilled in the art according to well-known techniques. For example, the reaction product liquid obtained after the hydroformylation reaction, or a diluted product liquid obtained by diluting the reaction product liquid with a hydrocarbon compound that can be used as a hydroformylation reaction solvent, is mixed with an extraction solvent, and then the mixture is separated, whereby tricyclodecane dicarbaldehyde, which is the product in the reaction product liquid, can be extracted into the extraction solvent layer.

[0139] The extraction solvent is not particularly limited, and examples thereof include alcohol.

[0140] The alcohol is not particularly limited, and examples thereof include primary alcohols having 1 to 3 carbon atoms and polyhydric alcohols having 2 to 6 carbon atoms. Examples of the primary alcohols include methanol, ethanol, and propanol. Examples of the polyhydric alcohols having 2 to 6 carbon atoms include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, isomers of pentanediol, neopentyl glycol, hexanediol, glycerin, pentaerythritol, and trimethylolpropane. Among these, methanol, ethylene glycol, propanediol, and butanediol are preferably used because they have a relatively low boiling point, are available at relatively low cost, and are liquids that are easy to handle. These alcohols may be used alone or in combination of two or more. Alternatively, extraction may be carried out in the presence of water in addition to the alcohol, as the addition of water facilitates the distribution of the aldehyde and catalyst components into each layer.

[0141] From the viewpoint of efficiently extracting the product tricyclodecane dicarbaldehyde from the hydroformylation reaction solvent, the hydroformylation reaction solvent and the extraction solvent preferably have excellent liquid-liquid separation properties, specifically, a significant difference in density between the two solvents. From this viewpoint, examples of combinations of the hydroformylation reaction solvent and the extraction solvent include methylcyclohexane and ethylene glycol, or methylcyclohexane and a mixed solution of water and methanol.

[0142] The volume ratio of the extraction solvent to the reaction product liquid is not particularly limited, and can be determined based on, for example, the solubility of tricyclodecane dicarbaldehyde in the extraction solvent and the content of tricyclodecane dicarbaldehyde in the reaction product liquid.

[0143] For example, if the tricyclodecanedicarbaldehyde to be separated has high solubility in the extraction solvent and is present at a low concentration in the reaction product solution, tricyclodecanedicarbaldehyde can be effectively extracted by using an extraction solvent with a low volume ratio (extraction solvent / reaction product solution).As the product concentration increases, the volume ratio (extraction solvent / reaction product solution) required to extract tricyclodecanedicarbaldehyde from the reaction product solution increases. On the other hand, when tricyclodecane dicarbaldehyde has a relatively low solubility in the extraction solution, the volume ratio can be appropriately selected from the range of 10:1 to 1:10. Furthermore, in order to increase the amount of tricyclodecane dicarbaldehyde extracted using a small amount of extraction solvent, it is effective to divide the extraction solvent and perform the extraction operation several times. In the final stage of the extraction operation, a hydroformylation reaction solvent such as methylcyclohexane may be added to the reaction product liquid in an amount of about 5 to 20 mass %, which can improve the catalyst removal rate by adding the hydroformylation reaction solvent.

[0144] The temperature for the extraction operation is not particularly limited, and can be set to the hydroformylation reaction temperature or lower. The extraction method is not particularly limited, and examples thereof include a method in which an extraction solvent is added to the hydroformylation reactor after the hydroformylation reaction to carry out extraction treatment, and a method in which the hydroformylation reaction product liquid withdrawn from the hydroformylation reactor is introduced into an extraction tank to carry out extraction treatment.

[0145] The layer containing the reaction product liquid recovered after the extraction operation contains the hydroformylation catalyst and the hydroformylation solvent. Therefore, this layer can be returned to the hydroformylation reactor and reused. In this case, the catalyst components rhodium, organophosphorus ligand, or solvent may be added to the layer to be reused. The extraction operation described above can be carried out as both a batch process and a continuous process.

[0146] The cyclic diene-containing composition of the present invention used as a raw material for producing the aldehyde of the present invention has a peroxide concentration equal to or lower than a predetermined threshold value. Therefore, even when the thus recovered reaction product liquid containing the hydroformylation catalyst is repeatedly recovered and reused, the decrease in catalytic activity of the hydroformylation catalyst can be effectively suppressed, and an efficient hydroformylation reaction can be repeatedly carried out.

[0147] <Alcohol production method> The alcohol production method of the present invention is a method for producing an alcohol, which comprises producing an aldehyde by the aldehyde production method of the present invention and producing a corresponding alcohol from the aldehyde.

[0148] 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.

[0149] Specifically, when the cyclic diene in the cyclic diene-containing composition of the present invention is dicyclopentadiene, the dicyclopentadiene contained in the cyclic diene-containing composition is hydroformylated to obtain tricyclodecane dicarbaldehyde, and then the obtained tricyclodecane dicarbaldehyde is subjected to a hydrogenation reaction in the presence of a hydrogenation catalyst and hydrogen to obtain tricyclo[5.2.1.0 2,6 ]Decanedimethanol can be produced.

[0150] The hydrogenation catalyst used in the hydrogenation reaction may be a known solid catalyst in which a metal such as Ru, Ni, Cr, or Cu is supported on a carrier. The conditions for the hydrogenation reaction are usually a temperature of 60 to 200° C. and a hydrogen pressure of about 0.1 to 20 MPaG. [Example]

[0151] The present invention will be explained in more detail below by way of examples, but the present invention is not limited to the following examples as long as it does not depart from the gist of the invention. The following examples are merely illustrative and are not intended to limit any of the embodiments described herein. The following examples do not limit the present invention in any way. The values of various manufacturing conditions and evaluation results in the following examples and the like are meant as preferred upper or lower limit values in the embodiments of the present invention, and a preferred range may be defined by a combination of the above-mentioned upper or lower limit value and the values of the following examples or values of the examples themselves.

[0152] The compounds used in the following examples are as follows. DCPD: Dicyclopentadiene (Mitsubishi Chemical Corporation) Acetylacetonatodicarbonylrhodium (trade name: Rh(acac)(CO)2 , manufactured by N.E. Chemcat Corporation) Nickel-supported diatomaceous earth catalyst (nickel-chromium-supported diatomaceous earth with a nickel loading of 12% by mass and a chromium loading of 2% by mass, produced in accordance with the description in Example 1 of JP 2005-279587 A) DBPO: (trade name: tris(2,4-di-tert-butylphenyl)phosphite, manufactured by Tokyo Chemical Industry Co., Ltd.) Methylcyclohexane (product name: Methylcyclohexane, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) Methanol (product name: Methanol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0153] [Reference Experimental Example 1] <Distillation purification of dicyclopentadiene (DCPD)> 1912 g of DCPD was charged into a glass simple distillation column and distilled under conditions of a pressure of 0.1 kPa, a column bottom temperature of 65°C, and a column top temperature of 60°C to obtain 1832 g of a distillate, which was used as a DCPD-containing composition. The content of DCPD in the DCPD-containing composition was 99.7 GC area %.

[0154] The peroxide concentration in the DCPD-containing composition was measured using an iodometric titration method according to the following procedure. Under a nitrogen atmosphere, 5 mL of DCPD was added to a 50 mL pear-shaped flask, followed by 7.5 mL of a mixture of chloroform and acetic acid (acetic acid:chloroform = 3:2, volume ratio), followed by 0.2 mL of saturated potassium iodide solution and stirring until the solution in the flask turned yellow or brown. Further dilution with 12.5 mL of distilled water was added, followed by stirring for 1 minute to prepare a measurement sample. While stirring the measurement sample, a standard solution of sodium thiosulfate (0.01 mol / L) was added dropwise until the measurement sample became colorless and transparent, and iodine reduction titration was performed. The peroxide concentration (unit: mmol / L) in the DCPD-containing composition was calculated based on the consumption of the added sodium thiosulfate solution, and the peroxide concentration was found to be 0.031 mmol / L.

[0155] [Reference Experimental Example 2] <Hydroformylation reaction (first time)> A 100 mL stainless steel autoclave reactor was charged with 112.9 g of the DCPD-containing composition obtained in Reference Experimental Example 1 as a raw material compound for the hydroformylation catalyst, 13.4 mg (0.0519 mmol) of Rh(acac)(CO) as a catalyst, 1052.8 mg (1.623 mmol) of DBPO, and 85.4 g of methylcyclohexane as an organic solvent under a nitrogen atmosphere. While stirring at 1500 rpm, the temperature of the reaction solution in the reactor was raised to 70° C. A mixed gas of hydrogen and carbon monoxide (hydrogen:carbon monoxide = 1:1 (molar ratio)) was then rapidly introduced through the gas inlet valve to a pressure of 3 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 reaction time of the hydroformylation reaction (also referred to simply as "reaction time" in this specification) was the time from when the mixed gas of hydrogen and carbon monoxide was introduced into the reactor until the hydrogen and carbon monoxide were no longer consumed by the reaction, and was used as an index of reaction efficiency. During the reaction, the mixed gas consumed in the reaction was automatically introduced into the autoclave via an automatic pressure regulating valve, and the reaction was carried out such that the pressure inside the reactor was always maintained at 3 MPaG. After the reaction was completed, the reaction solution in the reactor was cooled to room temperature, and the pressure of the remaining gas in the reactor was released to obtain 244.6 g of a hydroformylation reaction product liquid.

[0156] <Evaluation of the hydroformylation reaction (first run)> The DCPD content (99.7 GC area%) of the DCPD-containing composition obtained in Reference Experimental Example 1 and the hydroformylation reaction product liquid obtained in Reference Experimental Example 2 were measured using a gas chromatograph (GC) measurement device and a gas chromatography total area method under the following GC measurement conditions. The DCPD content (99.7 GC area%) of the DCPD-containing composition obtained in Reference Experimental Example 1 was used to determine the DCPD content and tricyclodecane dicarbaldehyde (TCDDD) content (unit: GC area%) in the hydroformylation reaction product liquid, and the DCPD conversion (unit: %) and TDD yield (unit: %) were calculated to be 99.4% and 96.5%, respectively. The reaction time for the hydroformylation reaction was 5.21 hours.

[0157] <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 (holding time none) → temperature increase at 10 °C / min → 300 °C (holding time 12 minutes) Inlet temperature: 200 °C Detector temperature: 300 °C Sample amount: 0.3 μL (split ratio: 1 / 30)

[0158] (Extraction operation) To 224.6 g of the hydroformylation reaction product solution obtained in Reference Experimental Example 2, 74.04 g of methanol and 47.7 g of water were added, and then stirred for 30 minutes under a nitrogen atmosphere. Thereafter, it was allowed to stand for 30 minutes to separate into two phases, and the lower layer (a1) and the upper layer (b1) were separated and recovered. To the obtained lower phase (a1), 9.6 g of methylcyclohexane was added and then stirred for 40 minutes. Thereafter, it was allowed to stand for 30 minutes to separate into two phases, and 287.4 g of the lower phase (a2) and 84.01 g of the mixed solution of the upper layer (b1) and the upper layer (b2) were separated and recovered. When the composition of the obtained lower phase (a2) was analyzed by gas chromatography, it was 47% by mass of tricyclodecane dicarbaldehyde, 27% by mass of methanol, 16% by mass of water, 7% by mass of methylcyclohexane, and 3% by mass of other components. Also, regarding the mixed solution of the obtained upper layer (b1) and the upper layer (b2), when the recovery rates of rhodium (Rh) metal and tris(2,4-di-tert-butylphenyl) phosphite were analyzed by fluorescent X-ray analysis and inductively coupled plasma optical emission spectrometry, they were 99.0% and 99.0% respectively.

[0159] [Example 1] <Hydroformylation reaction (2nd to 4th times)> In Reference Experimental Example 2, the hydroformylation reaction and extraction operation were carried out in the same manner as in Reference Experimental Example 2, except that a mixture of upper phases (b1) and (b2) obtained by the extraction operation in Reference Experimental Example 2 was used instead of the catalyst and solvent for the hydroformylation reaction, and further, rhodium (Rh) metal and DBPO were added to the mixture in the amounts lost in the extraction operation in Reference Experimental Example 2 so that the contents of Rh metal and DBPO were equivalent to those in the first hydroformylation reaction in Reference Experimental Example 2. This operation is referred to as the "second" hydroformylation reaction. The above procedure was repeated two more times to obtain reaction solutions from the second to fourth hydroformylation reactions. The reaction solutions from the second to fourth hydroformylation reactions were analyzed using the gas chromatograph (GC) measurement device and the gas chromatography total area method, and the difference in reaction time between the second and fourth hydroformylation reactions (hereinafter also referred to as the "reaction time difference") was 1 minute. Furthermore, the rate of decrease in the reaction rate constant per hydroformylation reaction in the second to fourth hydroformylation reactions, as measured by the following measurement method 2, was 0.5%.

[0160] <Measurement method 2> (Decrease in reaction rate constant per hydroformylation reaction) Step 1) Measurement of the reaction rate constant for the hydroformylation reaction: Assuming that the reaction rate of the hydroformylation reaction can be approximated by a linear function relative to the concentration of the substrate DCPD, a graph is drawn on an XY graph with the hydroformylation reaction time on the X axis and the natural logarithm of "1-conversion rate / 100" on the Y axis. The slope of the approximation equation of the linear function within the conversion rate range of 60% to 80% is calculated, and this is taken as the reaction rate constant of the hydroformylation reaction. The "conversion rate" is measured by the same method as described in the evaluation of the hydroformylation reaction (first run). Step 2) On an XY graph, the X axis represents the number of hydroformylation reactions, and the Y axis represents the reaction rate constant of the hydroformylation reaction calculated in Step 1. The reaction rate constants for the second to fourth hydroformylation reactions are plotted, and the resulting value is approximated by a linear function. The slope is calculated, divided by the reaction rate constant for the second reaction, and multiplied by 100 to obtain the "rate of decrease in the reaction rate constant per hydroformylation reaction for the second to fourth hydroformylation reactions."

[0161] [Example 2] The DCPD-containing composition obtained in Reference Experimental Example 1 was placed in a 1 L glass bottle, and then 2,6-di-tert-butyl-4-hydroxytoluene (BHT) was added to a concentration of 150 ppm by mass to prevent the dicyclopentadiene from being oxidized to form dicyclopentadiene-derived peroxides. The glass bottle was then capped and stored for one month. The peroxide concentration in the DCPD-containing composition after one month of storage was measured in the same manner as in Example 1 and was found to be 0.323 mmol / L. Furthermore, when the hydroformylation reaction and extraction procedure were repeated three times in the same manner as in Example 1, the reaction time difference between the second and fourth hydroformylation reactions was 3 minutes. In addition, the rate of decrease in the reaction rate constant per hydroformylation reaction in the second to fourth hydroformylation reactions was 1.2%.

[0162] [Comparative Example 1] The DCPD-containing composition obtained in Reference Experimental Example 1 was placed in a 1 L glass bottle, and the glass bottle was closed with a lid, and then stored at room temperature (25° C.) for one month. The peroxide concentration in the DCPD-containing composition after one month of storage was measured in the same manner as in Example 1 and was found to be 2.933 mmol / L. Furthermore, when the hydroformylation reaction and extraction procedure were repeated three times in the same manner as in Example 1, the reaction time difference between the second and fourth hydroformylation reactions was 23 minutes. In addition, the rate of decrease in the reaction rate constant per hydroformylation reaction in the second to fourth hydroformylation reactions was 7.4%.

[0163] The results of Examples 1 and 2 and Comparative Example 1 are summarized in Table 2 below.

[0164] [Table 2]

[0165] In Examples 1 and 2, the time difference between the second and fourth hydroformylation reactions was small. In addition, the rate of decrease in the reaction rate constant per hydroformylation reaction in the second to fourth hydroformylation reactions was also small. On the other hand, in Comparative Example 1, the peroxide concentration in the cyclic diene-containing composition was high compared to Examples 1 and 2, so the time difference between the second and fourth hydroformylation reactions was large, and the rate of decrease in the reaction rate constant per hydroformylation reaction in the second to fourth hydroformylation reactions was also large. This indicates that when the peroxide concentration in the cyclic diene-containing composition is high, repeated hydroformylation reactions cause the activity of the rhodium-organic ligand complex catalyst contained in the reaction product liquid after the hydroformylation reactions to be impaired by the peroxide.

[0166] The above results demonstrate that by controlling the peroxide concentration in the cyclic diene-containing composition, even if the rhodium-organic ligand complex catalyst contained in the reaction product liquid after the hydroformylation reaction is repeatedly recovered and reused, the activity of the catalyst can be prevented from decreasing, and good hydroformylation reaction efficiency can be maintained.

[0167] [Example 3] <Alcohol production> A 0.2 L autoclave reactor was charged with 106.1 g of the lower phase (a2) obtained in Reference Experimental Example 1 and 2 g of nickel-chromium-supported diatomaceous earth catalyst. The mixture was stirred at 120 rpm while the temperature of the reaction mixture in the reactor was raised to 160°C. Hydrogen gas was then introduced into the reactor through the gas inlet valve until the pressure inside the reactor reached 3 MPaG. The reaction was allowed to proceed for 2.5 hours while maintaining this pressure and the temperature of the reaction mixture. During the reaction, hydrogen gas was continuously introduced into the reactor in the amount consumed during the reaction, while maintaining the pressure inside the reactor at 3 MPaG. After the reaction was completed, the reaction mixture in the reactor was cooled to room temperature, the remaining gas in the reactor was released, and the nickel-chromium supported diatomaceous earth catalyst was separated by filtration using a 5 μm filter, yielding 98.3 g of reaction product. The content of the raw material compound tricyclodecane dicarbaldehyde in the reaction mixture before the reaction and the product tricyclo[5.2.1.0] in the reaction mixture after the reaction were compared. 2,6 ] The content of decanedimethanol (hereinafter referred to as "TCDDM") was analyzed by gas chromatography, and the yield of TCDDM was found to be 98%. [Explanation of symbols]

[0168] 1 Dimerization tank 2. Distillation tower 3 Low boiling point component removal tower 4. High boiling point component removal tower

Claims

1. A cyclic diene-containing composition comprising a cyclic diene, A cyclic diene-containing composition, wherein the concentration of peroxide in the cyclic diene composition is 2.8 mmol / L or less.

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

3. The cyclic diene-containing composition according to claim 1, wherein the concentration of the peroxide is 2.0 mmol / L or less, preferably 1.0 mmol / L or less, more preferably 0.6 mmol / L or less, and particularly preferably 0.3 mmol / L or less.

4. 10. The cyclic diene-containing composition of claim 1, wherein the peroxide comprises a peroxide of an alkene compound.

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

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

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

8. A method for producing an aldehyde, comprising subjecting the cyclic diene-containing composition according to any one of claims 1 to 7 to a hydroformylation reaction to produce an aldehyde corresponding to the cyclic diene.

9. A method for producing an alcohol, comprising producing an aldehyde by the production method according to claim 8 and producing a corresponding alcohol from the aldehyde.

10. 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 reducing the concentration of peroxide contained in the cyclic diene-containing composition to a predetermined threshold value or less.

11. The method for producing an aldehyde according to claim 10, wherein the concentration of the peroxide contained in the cyclic diene-containing composition is 2.8 mmol / L or less.

12. The method for producing an aldehyde according to claim 11, wherein the concentration of the peroxide contained in the cyclic diene-containing composition is 2.0 mmol / L or less, preferably 1.0 mmol / L or less, more preferably 0.6 mmol / L or less, and particularly preferably 0.3 mmol / L or less.

13. The method for producing an aldehyde according to claim 10, wherein the peroxide comprises a peroxide of an alkene compound.

14. The method for producing an aldehyde according to claim 10, wherein the concentration of the peroxide is measured by the following measurement method 1. <Measurement method 1> Under a nitrogen atmosphere, a mixture of chloroform and acetic acid is added to the cyclic diene-containing composition, and then a saturated aqueous potassium iodide solution is added and stirred, followed by dilution with distilled water to prepare a measurement sample. The measurement sample thus obtained is subjected to iodine reduction titration using a 0.01 mol / L aqueous sodium thiosulfate solution as a standard solution, and the concentration of peroxide (mmol / L) in the cyclic diene-containing composition is determined based on the amount of the standard solution consumed.

15. The method for producing an aldehyde according to claim 10, wherein the cyclic diene is a polycyclic diene.

16. The method for producing an aldehyde according to claim 15, wherein the polycyclic diene is dicyclopentadiene.

17. the cyclic diene-containing composition is a composition obtained by distilling and purifying a hydrocarbon decomposition product obtained by thermally decomposing a hydrocarbon-containing composition, The method for producing an aldehyde according to claim 10, comprising carrying out the distillation purification so that the concentration of peroxides contained in the cyclic diene-containing composition is equal to or lower than a predetermined threshold value.

18. 18. The method for producing an aldehyde according to claim 17, wherein the hydrocarbon decomposition product contains an antioxidant.

19. 18. The method for producing an aldehyde according to claim 17, comprising adding an antioxidant to the hydrocarbon decomposition product so that the concentration of peroxides contained in the cyclic diene-containing composition is equal to or less than a predetermined threshold.

20. 18. The method for producing an aldehyde according to claim 17, comprising controlling storage conditions of the cyclic diene-containing composition so that the concentration of peroxide contained in the cyclic diene-containing composition is equal to or less than a predetermined threshold value.

21. The method for producing an aldehyde according to claim 20, wherein the control of the storage conditions comprises controlling the dissolved oxygen concentration in the cyclic diene-containing composition.

22. 21. The method for producing an aldehyde according to claim 20, wherein the controlling of the storage conditions comprises adding an antioxidant to the cyclic diene-containing composition.

23. 11. The method for producing an aldehyde according to claim 10, wherein the cyclic diene is dicyclopentadiene and the aldehyde is tricyclodecane dicarbaldehyde.

24. A method for producing an alcohol, comprising obtaining an aldehyde by the production method according to any one of claims 10 to 23, and producing a corresponding alcohol from the obtained aldehyde.

25. The cyclic diene is dicyclopentadiene, the aldehyde is tricyclodecane dicarbaldehyde, and the alcohol is tricyclo[5.2.1.0 ２，６ 25. The method for producing an alcohol according to claim 24, wherein the alcohol is decanedimethanol.

26. 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 reducing the concentration of peroxide contained in the cyclic diene-containing composition to a predetermined threshold value or less.

27. 27. The method for producing a cyclic diene-containing composition according to claim 26, comprising carrying out the distillation purification so that the concentration of peroxides contained in the cyclic diene-containing composition is equal to or less than a predetermined threshold value.

28. 27. The method for producing a cyclic diene-containing composition according to claim 26, wherein the hydrocarbon decomposition products contain an antioxidant.

29. 27. The method of claim 26, further comprising adding an antioxidant to the hydrocarbon decomposition product such that the concentration of peroxides in the cyclic diene-containing composition is below a predetermined threshold.

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

31. 31. The method for producing a cyclic diene-containing composition according to claim 30, wherein the control of the storage conditions comprises controlling the dissolved oxygen concentration in the cyclic diene-containing composition.

32. 31. The method for producing a cyclic diene-containing composition according to claim 30, wherein the controlling of storage conditions comprises adding an antioxidant to the cyclic diene-containing composition.

33. The method for producing a cyclic diene-containing composition according to claim 26, wherein the concentration of the peroxide contained in the cyclic diene-containing composition is 2.8 mmol / L or less.

34. The method for producing a cyclic diene-containing composition according to claim 26, wherein the concentration of the cyclic diene contained in the cyclic diene-containing composition is 60.0 GC area % or more.

35. The method for producing a cyclic diene-containing composition according to claim 33, wherein the concentration of the peroxide contained in the cyclic diene-containing composition is 2.0 mmol / L or less, preferably 1.0 mmol / L or less, more preferably 0.6 mmol / L or less, and particularly preferably 0.3 mmol / L or less.

36. The method for producing a cyclic diene-containing composition according to claim 26, wherein the concentration of the peroxide is measured by the following measurement method 1. <Measurement method 1> Under a nitrogen atmosphere, a mixture of chloroform and acetic acid is added to the cyclic diene-containing composition, and then a saturated aqueous potassium iodide solution is added and stirred, followed by dilution with distilled water to prepare a measurement sample. The measurement sample thus obtained is subjected to iodine reduction titration using a 0.01 mol / L aqueous sodium thiosulfate solution as a standard solution, and the concentration of peroxide (mmol / L) in the cyclic diene-containing composition is determined based on the amount of the standard solution consumed.

37. 27. The method for producing a cyclic diene-containing composition according to claim 26, wherein the cyclic diene is a polycyclic diene.

38. 38. The method for producing a cyclic diene-containing composition according to claim 37, wherein the polycyclic diene is dicyclopentadiene.

39. 27. The method for producing a cyclic diene-containing composition according to claim 26, wherein the hydrocarbon-containing composition is naphtha.

Images