Production method of aldehyde and production method of alcohol, and polycyclic diene-containing composition

Abstract

To provide a production method of an aldehyde with which a high-purity alicyclic monocarbaldehyde such as tricyclodecene monocarbaldehyde corresponding to a polycyclic diene can be produced from a polycyclic diene-containing composition such as dicyclopentadiene as a starting raw material.SOLUTION: Provided is a production method of an aldehyde which is a method of making a polycyclic diene in a polycyclic diene-containing composition conduct a hydroformylation reaction so as to produce the corresponding aldehyde, and includes controlling a content ratio of a monocyclic diene contained in the polycyclic diene-containing composition to a predetermined threshold value or more.SELECTED DRAWING: Figure 1

Description

[Technical Field]

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

[0002] Aldehydes such as alicyclic monocarbaldehydes are useful as raw materials for plasticizer additives, adhesives, disinfectants, etc. Furthermore, alcohols such as alicyclic monoalcohols obtained by hydrogenating alicyclic monocarbaldehydes are useful as raw material monomers for improving the heat resistance, flexibility, or retardation of acrylate resins and methacrylate resins. Specifically, alicyclic monocarbaldehydes such as tricyclodecene monocarbaldehyde and alicyclic monoalcohols such as tricyclodecane monomethanol and pentacyclopentadecane monomethanol have attracted attention from the viewpoint of high functionality and excellent industrial productivity in the above-mentioned applications.

[0003] A known method for producing an alicyclic monocarbaldehyde such as tricyclodecene monocarbaldehyde is to heat a C5 hydrocarbon fraction obtained by thermal cracking a hydrocarbon-containing composition such as naphtha, coal, or natural gas, thereby dimerizing monocyclic dienes such as cyclopentadiene in the C5 hydrocarbon fraction to form the corresponding polycyclic dienes such as dicyclopentadiene, and then purifying the C5 hydrocarbon fraction after the dimerization reaction to obtain a polycyclic diene-containing composition containing polycyclic dienes such as dicyclopentadiene at a high concentration, and then subjecting the obtained polycyclic diene-containing composition to a hydroformylation reaction to convert the polycyclic diene into an alicyclic monocarbaldehyde corresponding to the polycyclic diene.

[0004] For example, Patent Document 1 discloses a technique in which highly purified dicyclopentadiene is hydroformylated in the presence of a transition metal (e.g., rhodium)-water-soluble organophosphorus compound complex catalyst of Group VIII of the periodic table to obtain tricyclodecene monocarbaldehyde, and then the resulting product is hydroformylated in the presence of a transition metal (e.g., rhodium) of Group VIII of the periodic table to produce tricyclodecane dicarbaldehyde. Patent Documents 2 and 3 focus on conjugated dienes (e.g., cyclopentadiene) contained in dicyclopentadiene as impurities that inhibit the hydroformylation reaction, and disclose a method for reducing the amount of this conjugated diene to obtain a mixture of tricyclodecene monocarbaldehyde and tricyclodecane dicarbaldehyde. Patent Document 4 discloses a method for obtaining tricyclodecene monocarbaldehyde by hydroformylating dicyclopentadiene in the presence of an aqueous solution of a complex formed by complex bonding a transition metal of Group VIII of the periodic table (e.g., rhodium) with a water-soluble organic phosphorus compound, particularly alkali metal and alkaline earth metal salts of sulfonated arylphosphines and aryldiphosphines. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-139181 [Patent Document 2] Japanese Patent Application Publication No. 11-80067 [Patent Document 3] Japanese Patent Application Publication No. 11-80068 [Patent Document 4] Japanese Patent Application Laid-Open No. 2005-139179 Summary of the Invention [Problem to be solved by the invention]

[0006] However, the present inventors have found that even when an attempt is made to obtain a polycyclic monocarbaldehyde such as tricyclodecene monocarbaldehyde according to the techniques disclosed in Patent Documents 1 to 4, the purity of the obtained polycyclic monocarbaldehyde is insufficient. That is, even when an attempt is made to obtain a polycyclic monocarbaldehyde such as tricyclodecene monocarbaldehyde by simply hydroformylating a polycyclic diene such as dicyclopentadiene, a portion of the obtained polycyclic monocarbaldehyde is further hydroformylated, and a considerable amount of polycyclic dicarbaldehyde is by-produced, making it difficult to obtain a highly pure polycyclic monocarbaldehyde.

[0007] The present invention aims to solve these problems. That is, an object of the present invention is to provide a method for producing an aldehyde, which is capable of producing a high-purity alicyclic monocarbaldehyde, such as tricyclodecene monocarbaldehyde, corresponding to a polycyclic diene, using a composition containing a polycyclic diene such as dicyclopentadiene as a starting material. Another object of the present invention is to provide a polycyclic diene-containing composition that enables the production of a highly pure alicyclic monocarbaldehyde such as tricyclodecene monocarbaldehyde.

[0008] Another object of the present invention is to provide a method for producing an alcohol, which comprises producing an aldehyde such as an alicyclic monocarbaldehyde by the above-mentioned production method and then producing a corresponding alcohol from the aldehyde. [Means for solving the problem]

[0009] As a result of extensive investigations into solving the above problems, the present inventors discovered that the above problems can be solved by controlling the content of monocyclic dienes contained in a polycyclic diene-containing composition, and thus completed the present invention. That is, the present invention provides the following.

[0010] [1] A method for producing a corresponding aldehyde by hydroformylating a polycyclic diene in a polycyclic diene-containing composition, comprising: A method for producing an aldehyde, comprising controlling the content of monocyclic dienes in the polycyclic diene-containing composition to a predetermined threshold value or higher.

[0011] [2] The method for producing an aldehyde according to [1], wherein the content of the monocyclic diene in the polycyclic diene-containing composition is 1500 ppm by mass or more.

[0012] [3] The method for producing an aldehyde according to [1] or [2], wherein the content of the monocyclic diene in the polycyclic diene-containing composition is 100,000 ppm by mass or less.

[0013] [4] The method for producing an aldehyde according to any one of [1] to [3], wherein the content of the polycyclic diene in the polycyclic diene-containing composition is 60.0 mass% or more.

[0014] [5] The method for producing an aldehyde according to any one of [1] to [4], wherein the content of the polycyclic diene in the polycyclic diene-containing composition is 99.5 mass% or less.

[0015] [6] The method for producing an aldehyde according to any one of [1] to [5], wherein the aldehyde is a polycyclic monocarbaldehyde corresponding to the polycyclic diene.

[0016] [7] The method for producing an aldehyde according to any one of [1] to [6], wherein the polycyclic diene is dicyclopentadiene.

[0017] [8] The method for producing an aldehyde according to [7], wherein the monocyclic diene is cyclopentadiene.

[0018] [9] The method for producing an aldehyde according to [8], wherein the aldehyde is tricyclodecene monocarbaldehyde.

[0019]

[10] The method for producing an aldehyde according to any one of [1] to [9], wherein the hydroformylation reaction is carried out in the presence of a rhodium-organophosphorus compound complex catalyst.

[0020]

[11] The method for producing an aldehyde according to any one of [1] to

[10] , comprising controlling the content of the polycyclic diene contained in the polycyclic diene-containing composition to a predetermined threshold value or more using information on the concentration of monocarbaldehyde in the obtained aldehyde.

[0021]

[12] The method for producing an aldehyde according to any one of [1] to

[11] , wherein the polycyclic diene-containing composition is a composition obtained by distilling and purifying a hydrocarbon decomposition product obtained by thermally decomposing a hydrocarbon-containing composition.

[0022]

[13] The method for producing an aldehyde according to

[12] , comprising controlling the conditions of the distillation purification so that the content of monocyclic dienes in the polycyclic diene-containing composition is equal to or greater than a predetermined threshold value.

[0023]

[14] The method for producing an aldehyde according to

[12] or

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

[0024]

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

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

[0025]

[16] The method for producing an alcohol according to

[15] , wherein the polycyclic diene is dicyclopentadiene, the aldehyde is tricyclodecene monocarbaldehyde, and the alcohol is tricyclodecane monomethanol.

[0026]

[17] A polycyclic diene-containing composition containing a polycyclic diene, the polycyclic diene-containing composition having a monocyclic diene content of 1,500 ppm by mass or more, for producing a corresponding aldehyde from the polycyclic diene.

[0027]

[18] The polycyclic diene-containing composition according to

[17] , wherein the content of the monocyclic diene contained in the polycyclic diene-containing composition is 100,000 ppm by mass or less.

[0028]

[19] The polycyclic diene-containing composition according to

[17] or

[18] , wherein the content of the polycyclic diene contained in the polycyclic diene-containing composition is 60.0 mass% or more.

[0029]

[20] The polycyclic diene-containing composition according to any one of

[17] to

[19] , wherein the content of the polycyclic diene in the polycyclic diene-containing composition is 99.5 mass% or less.

[0030]

[21] The polycyclic diene-containing composition according to any one of

[17] to

[20] , wherein the aldehyde is a polycyclic monocarbaldehyde corresponding to the polycyclic diene. [Effects of the Invention]

[0031] According to the method for producing an aldehyde of the present invention, a high-purity alicyclic monocarbaldehyde, such as tricyclodecene monocarbaldehyde, corresponding to a polycyclic diene such as dicyclopentadiene can be produced from a composition containing the polycyclic diene as a starting material.Furthermore, a method for producing a corresponding alcohol from the aldehyde can be provided. Furthermore, according to the polycyclic diene-containing composition of the present invention, an alicyclic monocarbaldehyde, such as tricyclodecene monocarbaldehyde, corresponding to the polycyclic diene can be produced with high purity using the polycyclic diene-containing composition as a starting material. [Brief explanation of the drawings]

[0032] [Figure 1] FIG. 1 is a schematic system diagram illustrating one embodiment of a production process for separating and recovering the polycyclic diene-containing composition of the present invention from a C5 hydrocarbon fraction according to the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0033] The present invention will be described in detail below, but the present invention is not limited to the following description and can be practiced in any modified form without departing from the gist of the present invention.

[0034] 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.

[0035] In this specification, unless otherwise specified, "including A or B" means "including A," "including B," or "including A and B."

[0036] In this specification, "% by mass" indicates the content of a given component in a total amount of 100% by mass. In this specification, "mass %" and "wt %", "mass ppm" and "wt ppm", and "parts by mass" and "parts by weight" have the same meaning. In this specification, when simply written as "ppm", it means "ppm by mass".

[0037] "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.

[0038] 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.

[0039] All steps described herein can be performed in any suitable order unless otherwise stated herein or clearly contradicted by context.

[0040] 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.

[0041] [Method for producing aldehydes] The method for producing an aldehyde of the present invention is a method for producing a corresponding aldehyde by subjecting a polycyclic diene in a polycyclic diene-containing composition described below to a hydroformylation reaction, and includes controlling the content of monocyclic dienes in the polycyclic diene-containing composition to a predetermined threshold value or higher. By controlling the content of the monocyclic diene contained in the polycyclic diene-containing composition to a predetermined threshold value or more, it becomes possible to produce a highly pure alicyclic monocarbaldehyde corresponding to the polycyclic diene. The method for controlling the content ratio of monocyclic dienes contained in the polycyclic diene-containing composition to a predetermined threshold value or more is not particularly limited, and an example thereof includes a method of controlling the conditions for distillation purification when a hydrocarbon decomposition product obtained by thermally decomposing a hydrocarbon-containing composition such as naphtha is distilled to obtain the polycyclic diene-containing composition, as will be described later.

[0042] Furthermore, in the aldehyde production method of the present invention, the content ratio of the polycyclic diene contained in the polycyclic diene-containing composition can be controlled to a predetermined threshold value or higher by using information on the concentration of monocarbaldehyde compounds in the produced aldehyde. In other words, if the content of the monocarbaldehyde in the produced aldehyde is lower than the required value, it means that the content of the polycyclic diene contained in the polycyclic diene-containing composition used as a raw material for producing the aldehyde is low. Therefore, the content of the monocarbaldehyde in the produced aldehyde may be measured, and if this value is low, feedback control may be performed to adjust the content of the polycyclic diene contained in the polycyclic diene-containing composition to be equal to or higher than a predetermined threshold value. In this case, the method for controlling the content ratio of polycyclic dienes in the polycyclic diene-containing composition to a predetermined threshold value or more is not particularly limited, and an example thereof includes a method, as will be described later, in which a hydrocarbon decomposition product obtained by thermally decomposing a hydrocarbon-containing composition such as naphtha is distilled and purified to obtain the polycyclic diene-containing composition, and the conditions for the distillation and purification are controlled. The monocyclic dienes and polycyclic dienes used in the present invention will be described in detail later.

[0043] <Polycyclic Diene-Containing Composition> The polycyclic diene-containing composition in the aldehyde production method of the present invention is a composition containing a polycyclic diene described below. In the method for producing an aldehyde of the present invention, by controlling the content of a monocyclic diene, which will be described later, contained in the polycyclic diene-containing composition to a predetermined threshold value or higher, it is possible to produce an alicyclic monocarbaldehyde corresponding to the polycyclic diene with high purity.

[0044] (polycyclic dienes) The polycyclic diene in the present invention is one component constituting the polycyclic diene-containing composition in the present invention. The polycyclic diene in the present invention is not particularly limited as long as it is a compound having two or more ring structures in the molecule and having two non-conjugated carbon-carbon double bonds in the same or different ring structures, but is preferably a compound that can be used as a starting material for producing an alicyclic alcohol. One embodiment of the polycyclic diene includes a polycyclic diene having two or more ring structures fused together in the molecule, and each of the two ring structures having a non-conjugated carbon-carbon double bond. Alternatively, another embodiment of the polycyclic diene is a compound obtained by dimerization of a monocyclic diene having one ring structure.

[0045] Specific examples of the polycyclic dienes include dicyclopentadiene, methyldicyclopentadiene, and methyltetrahydroindene. Among these polycyclic 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 polycyclic dienes can be used singly or in combination of two or more.

[0046] The upper limit of the polycyclic diene content (unit: mass%) in the polycyclic diene-containing composition of the present invention is preferably 99.5 mass% or less, more preferably 97.5 mass% or less, even more preferably 95.0 mass% or less, particularly preferably 90.0 mass% or less, and most preferably 85.0 mass% or less, relative to 100% total mass of the polycyclic diene-containing composition, from the viewpoint of having fluidity at room temperature, i.e., being liquid at room temperature, and providing excellent operability when producing an aldehyde. On the other hand, the lower limit of the content ratio of the polycyclic diene (unit: mass %), i.e., the threshold value, is not particularly limited, but from the viewpoint of producing a highly pure alicyclic monocarbaldehyde, it is preferably 60.0 mass % or more, more preferably 63.0 mass % or more, even more preferably 66.0 mass % or more, particularly preferably 70.0 mass % or more, and most preferably 75.0 mass % or more, relative to 100% of the total mass of the polycyclic diene-containing composition. The upper and lower limits can be combined arbitrarily. For example, the content (unit: mass%) of the polycyclic diene in the polycyclic diene-containing composition is preferably 60.0 mass% or more and 99.5 mass% or less, more preferably 63.0 mass% or more and 97.5 mass% or less, even more preferably 66.0 mass% or more and 95.0 mass% or less, particularly preferably 70.0 mass% or more and 90.0 mass% or less, and most preferably 75.0 mass% or more and 85.0 mass% or less, relative to 100% of the total mass of the polycyclic diene-containing composition.

[0047] The content of the polycyclic diene in the polycyclic diene-containing composition can be measured by GC in the same manner as the content of dicyclopentadiene in the hydroformylation reaction product liquid shown in the Examples section below. In addition, examples of methods for controlling the content ratio of polycyclic diene in the polycyclic diene-containing composition include extraction methods, crystallization methods, methods for adding appropriate chemical species from the outside, methods for controlling the amount by distillation conditions, and methods combining these.

[0048] (monocyclic diene) In the method for producing an aldehyde of the present invention, by adjusting the content of the monocyclic diene in the polycyclic diene-containing composition to a predetermined threshold value or more, when the polycyclic diene-containing composition is used as a starting material for an alicyclic monocarbaldehyde, the alicyclic monocarbaldehyde can be produced with high purity.

[0049] One embodiment of the monocyclic diene of the present invention is a compound having one ring structure in the molecule and two carbon-carbon double bonds contained in the ring structure, and more specifically, a compound having one ring structure in the molecule and two carbon-carbon double bonds contained in the ring structure.

[0050] Specific examples of the monocyclic dienes include cyclopentadiene, 1,4-cyclohexadiene, and methylcyclopentadiene.

[0051] When the monocyclic diene has optical activity, the monocyclic diene in the present invention may be a single enantiomer or a racemic mixture of enantiomers.

[0052] The lower limit of the content (unit: ppm by mass) of the monocyclic diene in the polycyclic diene-containing composition in the present invention, i.e., the threshold value, is preferably 1500 ppm by mass or more, more preferably 3000 ppm by mass or more, even more preferably 5000 ppm by mass or more, particularly preferably 7000 ppm by mass or more, and most preferably 10000 ppm by mass or more, relative to the total mass of the polycyclic diene-containing composition, from the viewpoint of enabling highly selective production of monocarbaldehyde corresponding to the polycyclic diene. On the other hand, the upper limit of the content (unit: ppm by mass) of the monocyclic diene in the polycyclic diene-containing composition is not particularly limited, but from the viewpoint of producing a highly pure alicyclic aldehyde, it is preferably 100,000 ppm by mass or less, more preferably 80,000 ppm by mass or less, even more preferably 70,000 ppm by mass or less, particularly preferably 60,000 ppm by mass or less, and most preferably 50,000 ppm by mass or less, relative to the total mass of the polycyclic diene-containing composition. The upper and lower limits can be combined arbitrarily. For example, the content (unit: mass ppm) of the monocyclic diene in the polycyclic diene-containing composition is preferably 1500 mass ppm or more and 100000 mass ppm or less, more preferably 3000 mass ppm or more and 80000 mass ppm or less, still more preferably 5000 mass ppm or more and 70000 mass ppm or less, particularly preferably 7000 mass ppm or more and 60000 mass ppm or less, and most preferably 10000 mass ppm or more and 50000 mass ppm or less, relative to the total mass of the polycyclic diene-containing composition.

[0053] The content of monocyclic dienes in the polycyclic diene-containing composition can be measured by GC in the same manner as the content of dicyclopentadiene in the hydroformylation reaction product liquid shown in the Examples section below. Methods for controlling the content of monocyclic dienes in a polycyclic diene-containing composition include, for example, extraction and crystallization, a method of adding an appropriate chemical species from the outside, a method of controlling the amount by distillation conditions, and a combination of these methods.

[0054] <Method for producing aldehyde> The method for producing an aldehyde of the present invention is a method for producing an aldehyde by subjecting the above-mentioned polycyclic diene-containing composition to a hydroformylation reaction to produce an aldehyde corresponding to the polycyclic diene.

[0055] In the method for producing an aldehyde of the present invention, the method for producing an aldehyde corresponding to the polycyclic 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 JP 2001-10999 A, the polycyclic diene contained in the polycyclic 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 polycyclic diene.

[0056] Specifically, when the polycyclic diene in the polycyclic diene-containing composition of the present invention is dicyclopentadiene, tricyclodecene monocarbaldehyde can be produced by hydroformylating the dicyclopentadiene contained in the polycyclic 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:

[0057] [ka]

[0058] 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.

[0059] In a preferred embodiment of the present invention, Rh(acac)(CO)2 is used as a rhodium precursor material, which is 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 compound complex catalyst.

[0060] 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 13Specific examples of the alkyl group include aryl groups such as phenyl and naphthyl which may be substituted with a methyl group, ethyl group, isopropyl group, n-butyl group, t-butyl group, methoxy group, etc.; aliphatic alkyl groups such as methyl group, ethyl group, isopropyl group, n-butyl group, t-butyl group, etc.; and alicyclic alkyl groups such as cyclopentyl and cyclohexyl which may be substituted with a lower alkyl group such as a methyl group, ethyl group, isopropyl group, n-butyl group, t-butyl group, etc.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] 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.

[0068] The hydroformylation reaction is carried out by a continuous feed method in which the polycyclic diene-containing composition described above as a raw material is fed alone or as a mixed solution of the polycyclic diene-containing composition of the present invention and a solvent to a reactor containing a rhodium-organophosphorus compound complex catalyst, a solvent, and a mixed gas of hydrogen and carbon monoxide. This method suppresses the by-production of polycyclic dicarbaldehyde and enables the production of polycyclic monocarbaldehyde with higher selectivity. To maintain the fluidity of the polycyclic diene-containing composition of the present invention, it is preferable to dilute it with the solvent described above and feed it to the reactor.

[0069] (Extraction of tricyclodecene monocarbaldehyde) After completion of the hydroformylation reaction, the method for extracting and separating the product tricyclodecene monocarbaldehyde from the reaction mixture is not particularly limited, and can be appropriately determined by a person skilled in the art according to well-known techniques. For example, the extraction and separation method described in JP-A-2001-10999 can be used.

[0070] [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.

[0071] 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 to produce an alcohol.

[0072] Specifically, when the polycyclic diene in the polycyclic diene-containing composition of the present invention is dicyclopentadiene, the dicyclopentadiene contained in the polycyclic diene-containing composition is hydroformylated to obtain tricyclodecene monocarbaldehyde, and then the obtained tricyclodecene monocarbaldehyde is subjected to a hydrogenation reaction in the presence of a hydrogenation catalyst and hydrogen, thereby producing tricyclodecane monomethanol.

[0073] 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. Among these, Ru-based catalysts are preferred as the hydrogenation catalyst used in the hydrogenation reaction. 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.

[0074] [Polycyclic Diene-Containing Composition] The polycyclic diene-containing composition of the present invention is a polycyclic diene-containing composition containing a polycyclic diene, and is a composition for producing a corresponding aldehyde from the polycyclic diene, and for the same reasons as those described in the aldehyde production method of the present invention, the content of the monocyclic diene is 1500 ppm by mass or more.

[0075] The polycyclic diene-containing composition of the present invention has the same meaning as the polycyclic diene-containing composition in the above-mentioned method for producing an aldehyde of the present invention.

[0076] The polycyclic diene in the polycyclic diene-containing composition of the present invention has the same meaning as the polycyclic diene in the above-mentioned method for producing an aldehyde of the present invention.

[0077] The monocyclic diene in the polycyclic diene-containing composition of the present invention has the same meaning as the monocyclic diene in the above-mentioned method for producing an aldehyde of the present invention.

[0078] The content of the monocyclic diene contained in the polycyclic diene-containing composition of the present invention is not particularly limited, but can be 100,000 mass ppm or less for the same reasons as those described in the aldehyde production method of the present invention.

[0079] The content of the polycyclic diene in the polycyclic diene-containing composition of the present invention is not particularly limited, but can be 60.0 mass% or more for the same reasons as those described in the method for producing an aldehyde of the present invention.

[0080] The content of the polycyclic diene contained in the polycyclic diene-containing composition of the present invention is not particularly limited, but can be 99.5 mass% or less for the same reasons as described in the method for producing an aldehyde of the present invention.

[0081] In addition, examples of methods for controlling the content ratio of monocyclic dienes in a polycyclic diene-containing composition include the method for producing a polycyclic diene-containing composition described below, known purification methods such as known liquid-liquid extraction methods, distillation methods, and crystallization methods, and methods combining these.

[0082] The method for producing the polycyclic diene-containing composition will be described below.

[0083] <Method of producing polycyclic diene-containing composition> The method for producing the polycyclic diene-containing composition in the present invention is not particularly limited, and examples thereof 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, to obtain the polycyclic diene-containing composition by distilling and purifying the resulting hydrocarbon decomposition product.

[0084] More specifically, a method can be mentioned in which a hydrocarbon-containing composition described below is thermally decomposed to obtain a hydrocarbon decomposition product, which is purified by distillation to obtain a C5 hydrocarbon fraction described below, and the obtained C5 hydrocarbon fraction is purified by distillation to obtain the polycyclic diene-containing composition.

[0085] That is, the C5 hydrocarbon fraction obtained by distillation purification of hydrocarbon cracking products obtained by thermal cracking of a hydrocarbon-containing composition contains monocyclic dienes such as cyclopentadiene as well as polycyclic dienes such as dicyclopentadiene, as shown in Table 1 described below. Even if such a C5 hydrocarbon fraction is introduced into a dimerization vessel in step (I) described below and dimerized, monocyclic dienes (polycyclic diene precursors) such as cyclopentadiene will remain. The remaining monocyclic dienes such as cyclopentadiene are separated by distillation through steps (II) to (IV) described below. In these distillation purification steps, polycyclic dienes such as dicyclopentadiene are decomposed under the heating conditions in each step, resulting in the production of new monocyclic dienes such as cyclopentadiene. Therefore, by controlling the conditions for these distillation purifications, it is possible to obtain a polycyclic diene-containing composition of the present invention in which the content of monocyclic dienes such as cyclopentadiene is equal to or greater than a predetermined threshold, particularly in the preferred range described above, and the content of polycyclic dienes such as dicyclopentadiene is in the preferred range described above.

[0086] For these reasons, when the polycyclic diene-containing composition is produced from a C5 hydrocarbon fraction obtained by distillation purification of hydrocarbon decomposition products obtained by thermal decomposition of a hydrocarbon-containing composition, the conditions for the distillation purification are controlled so that the content of the monocyclic diene contained in the polycyclic diene-containing composition is equal to or greater than a predetermined threshold, thereby making it possible to obtain the polycyclic diene-containing composition of the present invention, which can produce a highly pure alicyclic monocarbaldehyde corresponding to the polycyclic diene.

[0087] 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 polycyclic diene-containing composition.

[0088] (Ethylene production facility) The ethylene production facility in the present invention is a production facility for obtaining a C5 hydrocarbon fraction, which will be described later, as one of the fractions separated and purified from naphtha cracking products, and refers to a facility that thermally cracks naphtha at high temperatures to produce hydrogen, hydrocarbons having a carbon number of 4 such as methane, ethane, ethylene, propane, propylene, butane, or butadiene, hydrocarbons having a carbon number of 5, aromatic hydrocarbons such as benzene, and other heavy oils, and then separates and refines these.

[0089] The embodiment of the ethylene production apparatus is not particularly limited, and may have any configuration as long as it includes a distillation facility for a C5 hydrocarbon fraction and separates and purifies naphtha cracking products. For example, the ethylene production apparatus may have a configuration including facilities for sequentially performing the following steps (1) to (4): Step (1): A thermal cracking step in which raw materials such as naphtha, coal, and natural gas are thermally cracked in a cracking furnace. Step (2): A quenching step in which the resulting cracked gas is quenched and separated. Step (3): Compression step of compressing the quenched and separated cracked gas Step (4): The compressed cracked gas is separated and purified into its various fractions to obtain the main products, ethylene and propylene.

[0090] (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.

[0091] 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%.

[0092] [Table 1]

[0093] (Specific embodiment of the method for producing a polycyclic diene-containing composition) A specific embodiment of the method for producing the polycyclic diene-containing composition of the present invention includes a method in which the following steps (I) to (IV) are carried out in order.

[0094] 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 polycyclic diene precursors such as cyclopentadiene contained in the C5 hydrocarbon fraction are dimerized to form polycyclic dienes such as dicyclopentadiene corresponding to the polycyclic diene precursors.

[0095] 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 polycyclic dienes such as dicyclopentadiene is taken out from the bottom of the column.

[0096] Step (III): A step for removing low boiling components in which the C5 fraction heavy composition from the bottom of the column in step (II) is introduced into a low boiling component removal column for distillation, and chemical species such as low boiling vinylnorbornene, which has a boiling point lower than that of polycyclic dienes such as dicyclopentadiene and is a by-product of the dimerization reaction in step (I), are removed from the top of the column, while a fraction rich in polycyclic dienes such as dicyclopentadiene is taken from the bottom of the column.

[0097] Step (IV): A step of removing high boiling components in which the fraction rich in polycyclic dienes such as dicyclopentadiene from the bottom of the column in step (III) is introduced into a high boiling component removal column for distillation, and high boiling point similar co-dimers having boiling points higher than those of polycyclic dienes such as dicyclopentadiene, which are by-produced in the dimerization reaction of step (I), are removed from the bottom of the column, while the polycyclic diene-containing composition of the present invention, which contains a high content of polycyclic dienes such as dicyclopentadiene, is taken out from the top of the column.

[0098] The steps (I) to (IV) will be described in more detail below.

[0099] [Process (I)] The C5 hydrocarbon fraction is first supplied to the dimerization step (I), where polycyclic diene precursors such as cyclopentadiene contained in the C5 hydrocarbon fraction are dimerized to produce polycyclic dienes such as dicyclopentadiene corresponding to the polycyclic diene precursors. The conditions for the dimerization are not particularly limited and are appropriately selected depending on the content of polycyclic diene precursors such as cyclopentadiene in the C5 hydrocarbon fraction, but 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 polycyclic diene precursors such as cyclopentadiene contained in the C5 hydrocarbon fraction is dimerized.

[0100] [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 polycyclic 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 polycyclic 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.

[0101] [Process (III)] The C5 heavy 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 C5 heavy fraction composition sent to this step (III) is controlled so that the content of polycyclic 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 polycyclic dienes such as dicyclopentadiene is taken out from the bottom of the column.

[0102] 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 chemical species such as vinylnorbornene, which are by-produced in the dimerization reaction in step (I) and have boiling points lower than those of dicyclopentadiene, 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 the C5 hydrocarbon fraction and the C6 hydrocarbon fraction, 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. The distillation conditions in the light-boiling component removal column are generally a reduced pressure of 5 to 200 torr, preferably 10 to 50 torr, and a column bottom temperature of 50 to 120°C, preferably 80 to 110°C. This makes it possible to remove 90 mass% or more of chemical species such as vinylnorbornene and similar co-dimers contained in the C5 fraction heavy composition obtained from the column bottom of the light-boiling component removal column in step (II) from the column bottom distillate obtained from the column bottom of the light-boiling component removal column.

[0103] [Process (IV)] In the low-boiling component removal step (III), the fraction (tower bottom liquid) rich in polycyclic dienes such as dicyclopentadiene taken out from the bottom of the low-boiling component removal column is sent to the high-boiling component removal step (IV) (heavy-boiling component removal column) and subjected to distillation. The high-boiling components removed in this step (IV) are high-boiling co-dimers such as methylbicyclononadiene, which are dimers of cyclopentadiene and isoprene, and have boiling points higher than those of polycyclic dienes such as dicyclopentadiene, which are by-produced in the dimerization reaction of step (I). When low-boiling products such as cyclopentadiene trimers are present, these low-boiling products are also removed. 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 composition of the final product, so it is preferable to pay attention to them so that the desired polycyclic diene-containing composition can be obtained. The high-boiling component removal column is preferably a packed column in order to minimize pressure loss within the column, and the degree of vacuum is usually within the range of 5 to 100 torr, preferably 10 to 40 torr, and the column bottom temperature is within the range of 50 to 110°C, preferably 70 to 90°C. The polycyclic diene-containing composition of the present invention, which contains polycyclic dienes such as dicyclopentadiene, is obtained from the top of the high-boiling component removal column.

[0104] In the present invention, the high-boiling component removal column is preferably controlled so that the polycyclic diene content, such as cyclopentadiene, in the polycyclic diene-containing composition obtained from the top of the column is 99.5 mass% or less and the monocyclic diene content is 1500 mass ppm or more, more preferably 60 mass% or more.

[0105] The method for controlling the composition of the polycyclic diene-containing composition obtained from the top of the heavy-boiling component removal column to the above-mentioned composition is not particularly limited, and examples include a method in which the bottom temperature of the heavy-boiling component removal column is maintained constant within a range of 50 to 110°C, the degree of vacuum is maintained constant within a range of 5 to 100 torr, and an apparatus is designed and manufactured so that the residence time of the distillation column feed liquid in the column is 15 minutes or less, preferably 10 to 15 minutes. If the bottom temperature of the heavy-boiling component removal column is less than 50°C, the overhead distillate will contain a large amount of monocyclic dienes such as cyclopentadiene, whereas if it exceeds 110°C, the overhead distillate will contain a large amount of heavy fractions such as tricyclopentadiene and a small amount of monocyclic dienes such as cyclopentadiene. In either case, the overhead distillate will contain a small amount of dicyclopentadiene, and it will be difficult to maintain the content of monocyclic dienes such as cyclopentadiene within the preferred range described above. Furthermore, if the residence time of the feed liquid in the distillation column exceeds 15 minutes, the overhead distillate will contain a large amount of heavy fractions such as tricyclopentadiene, resulting in a low dicyclopentadiene content, and it will be difficult to maintain the content of monocyclic dienes such as cyclopentadiene within the aforementioned preferred range. If the residence time is less than 10 minutes, the bottom of the distillation column will be too 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 will be too small, and during normal distillation column operation, the liquid in the bottom of the column may become empty, potentially hindering 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 distilled at 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] [One embodiment of a production facility for a polycyclic diene-containing composition] Next, one embodiment of the production equipment for the polycyclic 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 polycyclic diene precursors such as cyclopentadiene is carried out to produce polycyclic dienes such as dicyclopentadiene corresponding to the polycyclic 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, an arbitrary proportion of 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 polycyclic 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)] and subjected to distillation. In the light-removal column 3, chemical species such as vinylnorbornene, which have lower boiling points than polycyclic 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 polycyclic dienes such as dicyclopentadiene is sent from the bottom of the light-removal column 3 via pipe 14 to the final heavy-removal column 4 [heavy-boiling component removal step (IV)] for distillation. In the heavy-boiling component removal column 4, high-boiling homodimers having boiling points higher than those of polycyclic dienes such as dicyclopentadiene, and remaining oligomers are removed from the bottom of the heavy-boiling component removal column 4 via pipe 16, and a polycyclic diene-containing composition containing a high content of polycyclic dienes such as dicyclopentadiene and a monocyclic diene such as cyclopentadiene in an amount equal to or greater than the threshold value is obtained from the top of the heavy-boiling component removal column 4 via pipe 17.

[0109] 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. [Example]

[0110] The present invention will be explained in more detail below with reference to examples, reference examples and comparative 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 illustrative only and are not intended to limit any of the embodiments described herein. The following examples do not limit the invention in any way. The values ​​of various production conditions and evaluation results in the following examples 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.

[0111] The compounds used in the Examples, Reference Examples and Comparative Examples are as follows. Dicyclopentadiene (in-house production) Acetylacetonatodicarbonylrhodium (trade name: Rh(acac)(CO)2, manufactured by N.E. Chemcat Corporation) Tris(2,4-di-tert-butylphenyl)phosphite (trade name: DBPO, manufactured by Tokyo Chemical Industry Co., Ltd.) Methylcyclohexane (Fujifilm Wako Pure Chemical Industries, Ltd.) Methanol (Fujifilm Wako Pure Chemical Industries, Ltd.) Ruthenium-supported catalyst (dry basis Ru content 5%, water content 56%) (product name: Ru / C catalyst, manufactured by N.E. Chemcat Corporation)

[0112] [Hydroformylation Reaction] [Example 1] In a 500 mL autoclave reactor, 248.1 mg (0.186 mmol) of Rh(acac)(CO) and 3.64 g (5.63 mmol) of tris(2,4-di-t-butylphenyl)phosphite were weighed out as raw material compounds for a hydroformylation reaction catalyst under a nitrogen atmosphere, and 74.0 g of methylcyclohexane as an organic solvent, 95.3 g of dicyclopentadiene as a substrate, and cyclopentadiene in an amount equivalent to 1.20% by mass relative to the dicyclopentadiene were then charged, and the temperature of the reaction liquid in the reactor was then raised to 70°C. The cyclopentadiene used in this study was prepared by pyrolyzing dicyclopentadiene at 170°C, followed by separation and recovery by distillation. Here, the polycyclic diene-containing composition charged as a substrate for the hydroformylation reaction consisted of 95.3 g of dicyclopentadiene and 1.20 mass % of cyclopentadiene (1.14 g) relative to the dicyclopentadiene, with the dicyclopentadiene (DCPD) content being 98.8 mass % (= (95.3 / 96.44) × 100) and the cyclopentadiene (CPD) content being 1.19 mass % (= (1.14 / 96.44) × 100). Next, a mixed gas of hydrogen and carbon monoxide (hydrogen:carbon monoxide = 1:1 (molar ratio)) was quickly injected through the gas inlet valve so that the pressure inside the reactor was 3 MPaG, and the reaction was carried out for 0.4 hours. Thereafter, the temperature of the reaction liquid was raised to 100°C and heating was continued, and the reaction was carried out for a total of 1.9 hours. During the reaction, the amount of mixed gas consumed in the reaction was continuously introduced into the reactor while maintaining the pressure inside the reactor 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 192.55 g of a hydroformylation reaction product solution. When evaluating the conversion from dicyclopentadiene (DCPD) to tricyclodecenemonocarbaldehyde (TCDMD) at a reaction solution temperature of 70°C, approximating it as zero-order with respect to the raw material concentration, the rate constant (k1) was 12.63 mol / (L·h). When evaluating the conversion from tricyclodecenemonocarbaldehyde (TCDMD) to tricyclodecanedicarbaldehyde (TCDDD) at a reaction solution temperature of 100°C, approximating it as first-order with respect to the concentration of tricyclodecenemonocarbaldehyde (TCDMD), the rate constant (k2) was 0.12 / h. The amount of dicyclopentadiene (DCPD) in the reaction solution before the reaction, dicyclopentadiene (DCPD) in the reaction product solution after the reaction, and the production amounts of the hydroformylation products tricyclodecenemonocarbaldehyde (TCDMD), tricyclodecanedicarbaldehyde (TCDDD), and other components were analyzed under the following GC measurement conditions using a gas chromatograph (GC) measuring device and the gas chromatography total area method. Table 2 shows the conversion rate of DCPD and the content ratios of DCPD, TCDMD, TCDDD, and other components contained in the reaction product solution after the reaction (total mass 100%) calculated from the obtained analysis results.

[0113] <GC Measurement Conditions> GC device: GC-2025 (High-performance general-purpose gas chromatograph, manufactured by Shimadzu Corporation) Detector: Flame ionization detector (FID) Carrier gas: Helium (column flow rate 1.65 mL / min) Column: Capillary column DB-1 (manufactured by Agilent Technologies, size: length 30 m × inner diameter 0.25 mm, film thickness 1.00 μm) Column temperature: 50°C (holding time 5 minutes) → heating at 10°C / min → 300°C (holding time: none) Inlet temperature: 200°C Detector temperature: 300°C Sample volume: 0.3 μL (split ratio: 1 / 30)

[0114] [Reference Example 1] The hydroformylation reaction of dicyclopentadiene was carried out in the same manner as in Example 1, except that cyclopentadiene was charged in an amount equivalent to 0.13% by mass of dicyclopentadiene, to obtain 209.07 g of a hydroformylation reaction product liquid. The rate constant (k1) obtained using the same evaluation method as in Example 1 for the conversion of DCPD to tricyclodecene monocarbaldehyde at a reaction liquid temperature of 70°C was evaluated as a zero-order approximation relative to the raw material concentration, and the rate constant (k2) obtained using the same evaluation method as in Example 1 for the conversion of tricyclodecene monocarbaldehyde (TCDMD) to tricyclodecane dicarbaldehyde (TCDDD) at a reaction liquid temperature of 100°C was evaluated as a first-order approximation relative to the tricyclodecene monocarbaldehyde (TCDMD) concentration, as well as the analytical results of the reaction liquid before the reaction and the reaction product liquid after the reaction are shown in Table 2.

[0115] [Comparative Example 1] The hydroformylation reaction of dicyclopentadiene was carried out in the same manner as in Example 1, except that cyclopentadiene was not added. The rate constant (k1) obtained using the same evaluation method as in Example 1 for the conversion of DCPD to tricyclodecene monocarbaldehyde at a reaction liquid temperature of 70°C was evaluated as a zero-order approximation relative to the raw material concentration, and the rate constant (k2) obtained using the same evaluation method as in Example 1 for the conversion of tricyclodecene monocarbaldehyde (TCDMD) to tricyclodecane dicarbaldehyde (TCDDD) at a reaction liquid temperature of 100°C was evaluated as a first-order approximation relative to the tricyclodecene monocarbaldehyde (TCDMD) concentration, as well as the analytical results of the reaction liquid before the reaction and the reaction product liquid after the reaction are shown in Table 2.

[0116] [Table 2]

[0117] A comparison between Example 1 and Comparative Example 1 in Table 2 reveals that in Example 1, in which cyclopentadiene was present at 12,000 ppm by mass relative to the raw material dicyclopentadiene so as to be equal to or greater than a predetermined threshold, a polycyclic monocarbaldehyde, tricyclodecene monocarbaldehyde (TCDMD), can be obtained with high purity. Moreover, the results of Reference Example 1 show that this threshold value is preferably 1500 mass ppm or more.

[0118] [Production of alcohol] [Example 2] (Hydrogenation reduction reaction) 91.37 g of tricyclodecene monocarbaldehyde (TCDMD) with a purity of 98.00% obtained by distillation purification from the reaction product liquid obtained in Example 1, 19.34 g of methanol, and 5.99 g of water were added to an autoclave reactor with a capacity of 0.2 L, and 18.10 mg of ruthenium-supported catalyst was added. The temperature of the reaction liquid in the reactor was then raised to 100 ° C. while stirring. Next, hydrogen gas was injected through the gas inlet valve so that the pressure in the reactor became 10 MPaG, and the reaction was carried out for 2.35 hours while maintaining this pressure and the temperature of the reaction liquid. During the reaction, the amount of hydrogen gas consumed in the reaction was continuously introduced into the reactor while maintaining the pressure in the reactor at 10 MPaG. After the reaction was completed, the reaction solution in the reactor was cooled to room temperature, the remaining gas in the reactor was released, and the ruthenium-supported catalyst was separated by filtration using a 5 μm filter to obtain a reaction product solution. The amount of tricyclodecane monomethanol (TCDMM), a product in the reaction product solution after the reaction, was analyzed by gas chromatography, and the yield of TCDMM was found to be 97.03%. [Explanation of symbols]

[0119] 1 Dimerization tank 2. Distillation tower 3 Low boiling point component removal column 4. High boiling point component removal tower

Claims

1. A method for producing a corresponding aldehyde by hydroformylating a polycyclic diene in a polycyclic diene-containing composition, comprising: A method for producing an aldehyde, comprising controlling the content of monocyclic dienes in the polycyclic diene-containing composition to a predetermined threshold value or higher.

2. The method for producing an aldehyde according to claim 1, wherein the content of the monocyclic diene in the polycyclic diene-containing composition is 1500 ppm by mass or more.

3. The method for producing an aldehyde according to claim 1, wherein the content of the monocyclic diene in the polycyclic diene-containing composition is 100,000 ppm by mass or less.

4. The method for producing an aldehyde according to claim 1, wherein the content of the polycyclic diene in the polycyclic diene-containing composition is 60.0 mass% or more.

5. The method for producing an aldehyde according to claim 1, wherein the content of the polycyclic diene in the polycyclic diene-containing composition is 99.5 mass% or less.

6. The method for producing an aldehyde according to claim 1, wherein the aldehyde is a polycyclic monocarbaldehyde corresponding to the polycyclic diene.

7. 2. The method for producing an aldehyde according to claim 1, wherein the polycyclic diene is dicyclopentadiene.

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

9. The method for producing an aldehyde according to claim 8, wherein the aldehyde is tricyclodecene monocarbaldehyde.

10. 2. The method for producing an aldehyde according to claim 1, wherein the hydroformylation reaction is carried out in the presence of a rhodium-organophosphorus compound complex catalyst.

11. 2. The method for producing an aldehyde according to claim 1, further comprising controlling the content of the polycyclic diene contained in the polycyclic diene-containing composition to a predetermined threshold value or higher using information on the concentration of monocarbaldehyde compounds in the obtained aldehyde.

12. 2. The method for producing an aldehyde according to claim 1, wherein the polycyclic diene-containing composition is a composition obtained by distilling and purifying a hydrocarbon decomposition product obtained by thermally decomposing a hydrocarbon-containing composition.

13. 13. The method for producing an aldehyde according to claim 12, comprising controlling the conditions of the distillation purification so that the content of monocyclic dienes in the polycyclic diene-containing composition is equal to or greater than a predetermined threshold value.

14. The method for producing an aldehyde according to claim 12, wherein the hydrocarbon-containing composition is naphtha.

15. A method for producing an alcohol, comprising producing an aldehyde by the production method according to any one of claims 1 to 14, and producing a corresponding alcohol from the aldehyde.

16. 16. The method for producing an alcohol according to claim 15, wherein the polycyclic diene is dicyclopentadiene, the aldehyde is tricyclodecene monocarbaldehyde, and the alcohol is tricyclodecane monomethanol.

17. A polycyclic diene-containing composition containing a polycyclic diene, The content of monocyclic dienes is 1500 ppm by mass or more. A polycyclic diene-containing composition for producing a corresponding aldehyde from the polycyclic diene.

18. The polycyclic diene-containing composition according to claim 17, wherein the content of the monocyclic diene in the polycyclic diene-containing composition is 100,000 ppm by mass or less.

19. The polycyclic diene-containing composition according to claim 17, wherein the content of the polycyclic diene contained in the polycyclic diene-containing composition is 60.0 mass% or more.

20. The polycyclic diene-containing composition according to claim 17, wherein the content of the polycyclic diene contained in the polycyclic diene-containing composition is 99.5 mass% or less.

21. 21. The polycyclic diene-containing composition according to any one of claims 17 to 20, wherein the aldehyde is a polycyclic monocarbaldehyde corresponding to the polycyclic diene.

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