Method for producing alcohol

Abstract

Provided is a method that is for producing an alcohol from an olefin compound with an improved selectivity and that enables a catalyst to be easily reused. This method for producing an alcohol comprises: reacting an olefin compound, carbon monoxide, and hydrogen molecules, using a group-9 transition metal complex as a catalyst, in an organic solvent containing at least 30 mol% of an amine compound having at least two nitrogen atoms that form a tertiary amine.

Description

Technical Field

[0001] The present invention relates to a method for producing an alcohol from an olefin compound in one step.

Background Art

[0002] The hydroformylation reaction of reacting an olefin compound with carbon monoxide and hydrogen molecules to produce an aldehyde has high industrial utility value. In particular, propionaldehyde and butyraldehyde obtained from ethylene and propylene, respectively, are further derived into alcohols such as 1-propanol and butanol, and are widely used as raw materials for industrial solvents and various products such as medical and agricultural chemicals.

[0003] In the hydroformylation reaction, generally, cobalt carbonyl complex catalysts, cobalt phosphine complex catalysts, rhodium carbonyl complex catalysts, rhodium phosphine complex catalysts, etc. are used, and the reaction is carried out in a state where these complex catalysts are uniformly dissolved in a solvent. Both cobalt and rhodium are metals with low production amounts and high prices, and from the perspective of manufacturing costs, it is required to recover and reuse them.

[0004] The main product in the hydroformylation reaction of an olefin compound is an aldehyde with one more carbon than the olefin compound. In order to produce a useful alcohol, it is necessary to reduce the aldehyde. Usually, this reduction is carried out by installing a reactor different from hydroformylation and using different types of catalysts. Therefore, two catalysts and two reaction steps are required to produce an alcohol from an olefin compound. Furthermore, after the hydroformylation step, complicated steps such as recovery of the hydroformylation catalyst and removal of carbon monoxide to prevent deactivation of the catalyst used in the reduction step are required. Therefore, a technique for producing an alcohol from an olefin compound in one step using one catalyst has been demanded.

[0005] On the other hand, it is known that by adding a trialkylphosphine to a cobalt complex catalyst, alcohol can be produced in one step from an olefin compound (Patent Document 1; U.S. Patent No. 3,420,898). However, in this method, there are concerns about toxicity due to the large amount of phosphine compound used, and a high temperature exceeding 180 °C is required to increase the alcohol selectivity. Therefore, when using olefin compounds with a small number of carbon atoms such as ethylene and propylene as raw materials, the pressure becomes extremely high under high temperature conditions, and there is a problem that production becomes difficult.

[0006] As a catalyst that can react under milder conditions, a rhodium complex catalyst is known. For example, a gas-phase reaction for producing 1-propanol by contacting ethylene, carbon monoxide, and hydrogen with a catalyst in which a cobalt compound and a rhodium compound are supported on alumina is known (Patent Document 2; Japanese Patent Publication No. 8-790), but there is a problem that the selectivity of 1-propanol is low because ethane formation by hydrogenation of ethylene proceeds simultaneously. As a reaction in the liquid phase, a reaction for obtaining 1-propanol using a rhodium triethylphosphine complex catalyst is also known (Non-Patent Document 1; J. Chem. Soc., Dalton Trans. 1996, 1161), but there are concerns about toxicity because a phosphine ligand is used.

[0007] As a rhodium complex catalyst that does not use a phosphine ligand, a system in which hexene or octene is reacted with Rh2O3 as a catalyst in a mixed solvent of water and an amine is known (Non-Patent Document 2; Chem. Ing. Tech. 1972, 44(11), 708). However, there is a problem that the purity of the obtained alcohol cannot be increased due to the water used as a solvent.

[0008] As a reaction in an organic solvent, a reaction of octene in a system in which a tertiary amine is added to Rh(acac)(CO)2 is known (Non-Patent Document 3; J. Catal. 2021, 400, 234). However, the turnover frequency (TOF) of the Rh catalyst per unit time for alcohol production is 93 h -1is low, and a large amount of expensive Rh catalyst is required for industrial alcohol production. Although systems adding N,N,N’,N’-tetramethylethylenediamine or N,N,N’,N’-tetramethylbutanediamine having two nitrogen atoms constituting a tertiary amine in the molecule have been studied, the alcohol yield is less than 10%. In Non-Patent Document 3, a reaction system using triethylamine as the amount of solvent has also been studied, but it has been reported that the alcohol yield remains at 23%, and the development of a catalyst system having high activity under mild conditions has been demanded.

Prior Art Documents

Patent Documents

[0009]

Patent Document 1

Patent Document 2

Non-Patent Documents

[0010]

Non-Patent Document 1

Non-Patent Document 2

Non-Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0011] An object of the present invention is to provide a method for producing alcohol with improved selectivity from an olefin compound and enabling easy reuse of the catalyst.

Means for Solving the Problems

[0012] As a result of intensive studies to solve the above problems, the present inventors have found that by reacting an olefin compound, carbon monoxide, and hydrogen molecules in an organic solvent containing a Group 9 transition metal complex catalyst and a specific amine compound having a concentration of 30 mol% or more of an amine compound having two or more nitrogen atoms constituting a tertiary amine, alcohol can be produced with improved selectivity and the catalyst can be easily reused, and thus the present invention has been completed.

[0013] That is, the present invention relates to the following [1] to

[13] . [1] A method for producing alcohol, comprising reacting an olefin compound, carbon monoxide, and hydrogen molecules in an organic solvent containing a Group 9 transition metal complex as a catalyst and containing 30 mol% or more of an amine compound having two or more nitrogen atoms constituting a tertiary amine. [2] The amine compound having two or more nitrogen atoms constituting the tertiary amine is represented by the general formula (1) [Chemical formula] or the general formula (2) [Chemical formula] (In the formula, R 1 ~R 5 each independently represents an alkyl group having 1 to 10 carbon atoms, and x, y, and z each independently represent an integer of 2 to 10.) The method for producing alcohol according to [1] represented by the formula. [3] In the general formula (1) or (2), R 1 ~R 5 are all methyl groups or all ethyl groups, and x, y, and z are each independently an integer of 2 to 6. The method for producing alcohol according to [2]. [4] The method for producing an alcohol according to [1], wherein the amine compound having two or more nitrogen atoms constituting the tertiary amine is at least one selected from the group consisting of N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethyl-1,3-propanediamine, N,N,N',N'-tetramethyl-1,4-butanediamine, N,N,N',N'-tetramethyl-1,6-hexanediamine, and N,N,N',N",N"-pentamethyldiethylenetriamine. [5] The method for producing an alcohol according to [1], wherein the amine compound having two or more nitrogen atoms constituting the tertiary amine is N,N,N',N'-tetramethyl-1,3-propanediamine. [6] The method for producing an alcohol according to any one of [1] to [5], wherein the Group 9 transition metal complex is a metal complex composed of acetylacetonato dicarbonyl and a Group 9 transition metal. [7] The method for producing an alcohol according to any one of [1] to [6], wherein the Group 9 transition metal is rhodium. [8] The method for producing an alcohol according to any one of [1] to [7], wherein the organic solvent containing 30 mol% or more of the amine compound having two or more nitrogen atoms constituting the tertiary amine is an organic solvent composed of the amine compound having two or more nitrogen atoms constituting the tertiary amine and at least one selected from the group consisting of toluene, xylene, and n-butanol. [9] The method for producing an alcohol according to any one of [1] to [8], wherein the molar ratio of the amine compound having two or more nitrogen atoms constituting the tertiary amine to the Group 9 transition metal is 500 to 10,000.

[10] The method for producing an alcohol according to any one of [1] to [9], wherein the olefin compound is a monoolefin having 2 to 4 carbon atoms.

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

[10] , wherein the olefin compound is ethylene and the product is 1-propanol.

[12] A method for producing an alcohol according to any one of [1] to

[11] , comprising separating the alcohol of the product after the reaction and recovering an organic solvent containing a Group 9 transition metal complex, and adding an olefin compound, carbon monoxide, and hydrogen molecules to the recovered organic solvent and reacting them.

[13] A method for producing an alcohol according to

[12] , comprising distilling off the alcohol of the product at a temperature of less than 200 °C and recovering an organic solvent containing a Group 9 transition metal complex.

Advantages of the Invention

[0014] According to the present invention, it is possible to provide a method for producing an alcohol with an improved selectivity from an olefin compound and easily reuse the catalyst used.

Embodiments for Carrying Out the Invention

[0015] In this specification, when "~" is used for a numerical range, the numerical values at both ends are the upper limit value and the lower limit value, respectively, and are included in the numerical range.

[0016] A method for producing an alcohol according to one embodiment is a production method in which an olefin compound, carbon monoxide, and hydrogen molecules are reacted in an organic solvent containing 30 mol% or more of an amine compound having two or more nitrogen atoms constituting a tertiary amine in the presence of a Group 9 transition metal complex, thereby producing an alcohol with high selectivity and easily reusing the catalyst.

[0017] [Alcohol Formation Reaction] By the reaction of an olefin compound, carbon monoxide, and hydrogen molecules, an alcohol having one more carbon atom than the starting olefin compound is produced. As the catalyst, a Group 9 transition metal complex is used. As the solvent, an organic solvent containing 30 mol% or more of an amine compound having two or more nitrogen atoms constituting a tertiary amine is used.

[0018] When the olefin compound is ethylene and the alcohol produced is 1-propanol, the reaction formula is shown below. CH2=CH2 + CO + 2H2 → CH3-CH2-CH2OH This reaction proceeds in two steps as follows. (First step) CH2=CH2 + CO + H2 → CH3-CH2-CHO (Second step) CH3-CH2-CHO + H2 → CH3-CH2-CH2OH

[0019] Generally, group 9 transition metal complexes act as catalysts for the first-step reaction but not for the second-step reaction. However, although not bound by theory, in the method of the present invention, when an amine compound having two or more nitrogen atoms constituting a tertiary amine is present at a certain concentration or higher, the group 9 transition metal complex is activated through an unknown mechanism of action, and the group 9 transition metal complex acts as a catalyst for both the first and second steps. Therefore, it is possible to produce alcohol highly selectively from an olefin compound in one step using a single catalyst. When the number of carbon atoms of the olefin compound is 3 or more, isomers may be formed for the resulting alcohol depending on the position where carbon monoxide is added.

[0020] [Olefin compound] The olefin compound of one embodiment is a monoolefin having one carbon-carbon double bond. As the olefin compound, a monoolefin having 2 to 20 carbon atoms is preferable, and a monoolefin having 2 to 4 carbon atoms is more preferable. Specifically, acyclic aliphatic olefin compounds such as ethylene, propylene, butene, pentene, and hexene, alicyclic olefin compounds such as cyclobutene, cyclopentene, and cyclohexene, aromatic olefin compounds such as styrene and indene, and the like can be mentioned. The olefin compound of one embodiment is preferably an α-olefin from the viewpoint of increasing the yield. From the viewpoint of producing industrially useful alcohols, ethylene, propylene, and butene are preferable. When the olefin compound has 3 or more carbon atoms, isomers exist in the produced alcohol. Ethylene is particularly preferable from the viewpoint that no isomeric alcohol is produced.

[0021] [Group 9 transition metal complex] In the Group 9 transition metal complex of one embodiment, the Group 9 transition metal is cobalt (Co), rhodium (Rh), iridium (Ir), or meitnerium (Mt), and it is preferably cobalt (Co), rhodium (Rh), or iridium (Ir). Rhodium (Rh) is particularly preferable from the viewpoint of improving alcohol selectivity.

[0022] Examples of the ligand constituting the Group 9 transition metal complex include acetylacetonato, halogen, carbonyl, cyclooctadienyl, triphenylphosphine, and hydride. Acetylacetonato, halogen, carbonyl, and cyclooctadienyl are preferable, and acetylacetonato and carbonyl are more preferable from the viewpoint of improving the stability of the complex. From the viewpoint of suppressing toxicity, it is preferable not to use phosphine.

[0023] Specific examples of the Group 9 transition metal complex include acetylacetonatodicarbonylrhodium (Rh(acac)(CO)2), hexadecarbonylhexarhodium (Rh6(CO) 16) Cyclooctadiene rhodium chloride dimer ([RhCl(cod)]2), acetylacetonato carbonyl triphenylphosphine rhodium (Rh(acac)(CO)(PPh3)), hydrido carbonyl tris(triphenylphosphine) rhodium (RhH(CO)(PPh3)3), acetylacetonato dicarbonyl iridium (Ir(acac)(CO)2), hydrido carbonyl tris(triphenylphosphine) iridium (IrH(CO)(PPh3)3), and the like can be mentioned. From the viewpoint of improving alcohol selectivity and suppressing toxicity, as the Group 9 transition metal complex, a metal complex composed of acetylacetonato dicarbonyl and a Group 9 transition metal is preferable, and acetylacetonato dicarbonyl rhodium is more preferable. The Group 9 transition metal complex may be used alone or in combination of two or more kinds.

[0024] [An amine compound having two or more nitrogen atoms constituting a tertiary amine] An amine compound having two or more nitrogen atoms constituting a tertiary amine (hereinafter sometimes referred to as "amine compound") is not particularly limited as long as it is a compound having two or more nitrogen atoms constituting a tertiary amine. The number of nitrogen atoms constituting the tertiary amine present in the compound is preferably 2 to 4, more preferably 2 or 3. The nitrogen atom constituting the tertiary amine is a nitrogen atom covalently bonded to three hydrocarbon groups. The hydrocarbon group may be a group composed of an aliphatic group, an aromatic group, or a combination thereof. The nitrogen atom constituting the tertiary amine may form a dialkylamino group (-NRR'; R and R' are alkyl groups) or an alkylimino group (-NR-; R" is an alkyl group). The two alkyl groups of the dialkylamino group may be the same or different, but are preferably the same from the viewpoint of easy availability. When two or more dialkylamino groups are present in the amine compound, the dialkylamino groups may be the same or different, but are preferably the same from the viewpoint of easy availability. The number of carbon atoms of the alkyl group of the dialkylamino group and the alkylimino group is preferably 1 to 10. Specifically, a methyl group and an ethyl group are preferable from the viewpoint of improving the alcohol yield. The amine compound having two or more nitrogen atoms constituting a tertiary amine may be used alone or in combination of two or more kinds.

[0025] The amine compound having two or more nitrogen atoms constituting a tertiary amine has the general formula (1)

Chemical formula

Chemical formula

[0026] R 1 ~R 5is preferably an alkyl group having 1 to 6 carbon atoms independently, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. R 1 ~R 5 is preferably all methyl groups or all ethyl groups. x is an integer of 2 to 10, preferably an integer of 2 to 6, and more preferably 3. y and z are each independently an integer of 2 to 10, preferably an integer of 2 to 6, and more preferably 2. A particularly preferred amine compound is one in which, in general formula (1) or (2), R 1 ~R 5 are all methyl groups or all ethyl groups, and x, y and z are each independently an integer of 2 to 6.

[0027] An amine compound having two or more nitrogen atoms constituting a tertiary amine is preferably liquid in the range of 20 to 150 °C and 1 to 200 atm from the viewpoint of ease of separation from the alcohol produced.

[0028] Specific examples of the amine compound having two or more nitrogen atoms constituting a tertiary amine include, as those having two nitrogen atoms, N,N,N’,N’-tetramethylethylenediamine, N,N,N’,N’-tetraethylethylenediamine, N,N,N’,N’-tetramethyl-1,3-propanediamine, N,N,N’,N’-tetramethyl-1,4-butanediamine, N,N’-diethyl-N,N’dimethyl-1,4-butanediamine, N,N,N’,N’-tetramethyl-1,6-hexanediamine, N,N,N’,N’-tetramethyl-1,2-propanediamine, N,N,N’,N’-tetramethyl-2-methyl-1,3-propanediamine, N,N,N’,N’-tetraethyl-2,2-dimethyl-1,3-propanediamine, N,N’-diethyl-N,N’dimethyl-3-methyl-2,4-butanediamine, and the like.

[0029] Examples of those having three nitrogen atoms include N,N,N’,N”,N”-pentamethyldiethylenetriamine, N,N”-diethyl-N,N’,N”-trimethyldiethylenetriamine, and the like.

[0030] Among these, from the viewpoint of availability, N,N,N’,N’-tetramethylethylenediamine, N,N,N’,N’-tetramethyl-1,3-propanediamine, N,N,N’,N’-tetramethyl-1,4-butanediamine, N,N,N’,N’-tetramethyl-1,6-hexanediamine, and N,N,N’,N”,N”-pentamethyldiethylenetriamine are preferable, N,N,N’,N’-tetramethyl-1,3-propanediamine, N,N,N’,N’-tetramethyl-1,4-butanediamine, N,N,N’,N’-tetramethyl-1,6-hexanediamine, and N,N,N’,N”,N”-pentamethyldiethylenetriamine are more preferable, and N,N,N’,N’-tetramethyl-1,3-propanediamine is particularly preferable.

[0031] [Process for producing alcohol] In the process for producing alcohol according to one embodiment, an organic solvent containing 30 to 100 mol% of an amine compound having two or more nitrogen atoms constituting a tertiary amine is used. The organic solvent preferably consists only of an amine compound having two or more nitrogen atoms constituting a tertiary amine. The organic solvent may be a mixed solvent of an amine compound and another organic solvent.

[0032] Other organic solvents are preferably organic solvents that do not affect the reaction. Specifically, acyclic aliphatic hydrocarbons such as hexane, octane, decane, dodecane; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, cyclododecane; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene; halogenated hydrocarbons such as chloroform, 1,2-dichloroethane; esters such as ethyl acetate, n-propyl acetate; ethers such as diethyl ether, anisole; ketones such as methyl ethyl ketone, cyclohexanone; alcohols such as ethanol, n-propanol, n-butanol, isobutanol; aldehydes such as propionaldehyde, n-butyl aldehyde, isobutyl aldehyde, etc. can be mentioned. Among these, acyclic aliphatic hydrocarbons, aromatic hydrocarbons, and alcohols are preferred, decane, toluene, xylene, and n-butanol are more preferred, and toluene, xylene, and n-butanol are particularly preferred. An organic solvent composed of an amine compound having two or more nitrogen atoms constituting a tertiary amine and at least one selected from the group consisting of toluene, xylene, and n-butanol is also preferably used. It is also preferable to mix the alcohol and aldehyde obtained from the olefin compound, carbon monoxide, and hydrogen molecule used in the reaction. Other organic solvents may be used alone or in combination of two or more. In addition, from the viewpoint of increasing the purity of the obtained alcohol, the organic solvent used in the method for producing alcohol preferably does not contain an inorganic solvent such as water. The content of the inorganic solvent in the organic solvent can be 1 mol% or less, 0.5 mol% or less, or 0.1 mol% or less.

[0033] In the method for producing alcohol according to one embodiment, the content of the amine compound having two or more nitrogen atoms constituting the tertiary amine in the organic solvent (amine compound (mol) / organic solvent (mol)×100) is 30 to 100 mol%, preferably 60 to 100 mol%, more preferably 80 to 100 mol%. If it is less than 30 mol%, the selectivity of alcohol may decrease.

[0034] In the method for producing alcohol according to one embodiment, the molar ratio of the amine compound having two or more nitrogen atoms constituting the tertiary amine to the Group 9 transition metal (amine compound (mol) / Group 9 transition metal (mol)) is preferably from 500 to 10,000, more preferably from 500 to 5,000, and particularly preferably from 500 to 2,000. If it is from 500 to 10,000, the selectivity of alcohol will not decrease.

[0035] In the method for producing alcohol according to one embodiment, the molar ratio of carbon monoxide to the olefin compound (carbon monoxide (mol) / olefin compound (mol)) is, for example, from 1 to 5, preferably from 1.2 to 4, and more preferably from 1.5 to 3. When it is 1 or more, the total yield of aldehyde and alcohol increases, and when it is 5 or less, the selectivity of alcohol increases.

[0036] In the method for producing alcohol according to one embodiment, the molar ratio of hydrogen molecules to the olefin compound (hydrogen molecules (mol) / olefin compound (mol)) is, for example, from 2 to 10, preferably from 2 to 5, and more preferably from 2 to 3. When it is 2 or more, the total yield of aldehyde and alcohol increases, and when it is 10 or less, the selectivity of alcohol increases.

[0037] In the method for producing alcohol according to one embodiment, the molar ratio of the olefin compound to the Group 9 transition metal complex (olefin compound (mol) / Group 9 transition metal complex (mol)) is, for example, from 100 to 100,000, preferably from 200 to 20,000, and more preferably from 500 to 10,000. When it is 100 or more, the production cost of alcohol can be suppressed, and when it is 100,000 or less, the yield of alcohol can be increased.

[0038] In the method for producing alcohol according to one embodiment, the reaction temperature is, for example, from 20°C to 200°C, preferably from 50°C to 130°C, and more preferably from 70°C to 110°C. When the reaction temperature is 20°C or higher, the total yield of aldehyde and alcohol increases, and when it is 200°C or lower, the selectivity of alcohol increases.

[0039] In the production method of alcohol according to one embodiment, the reaction pressure is, for example, 20 to 200 atm, preferably 50 to 150 atm, more preferably 70 to 130 atm. When the reaction pressure is 20 atm or more, the yield of alcohol increases, and when the reaction pressure is 200 atm or less, the selectivity of alcohol increases. When carbon monoxide and hydrogen molecules are replenished during the reaction, the reaction can be carried out at a lower pressure. In this case, the reaction pressure is, for example, 10 to 150 atm, preferably 30 to 120 atm, more preferably 50 to 100 atm.

[0040] In the production method of alcohol according to one embodiment, the reaction time may be appropriately selected in consideration of the reaction temperature, reaction pressure, raw material conversion rate, etc. Specifically, it can be 0.1 to 10 hr.

[0041] The production of alcohol may be carried out by any of the batch method, semi-batch method, and continuous method.

[0042] In the production method of alcohol, by a simple operation of distilling the reaction solution after the reaction, distilling off and obtaining the target alcohol, the alcohol as the product can be easily separated, and the organic solvent containing the Group 9 transition metal complex can be recovered. The recovered organic solvent can be directly used as the solvent for the next reaction. That is, by adding an olefin compound, carbon monoxide, and hydrogen molecules to the reaction solution after alcohol distillation and reacting them, the second alcohol production reaction can be carried out. At this time, if necessary, an organic solvent containing a Group 9 transition metal complex may be newly added.

[0043] The distillation method may be either batch or continuous as long as it can distill off the alcohol as the product and the by-produced aldehyde from the reaction solution. The distillation method may be any of simple distillation, flash distillation, and continuous distillation. The distillation may be carried out at normal pressure or under reduced pressure.

[0044] The distillation temperature can be appropriately selected according to the target alcohol and the organic solvent used. The distillation temperature is, for example, less than 200°C. The range of the distillation temperature is preferably 50°C or higher and less than 200°C, more preferably 70 - 180°C, and particularly preferably 80 - 150°C. At a temperature of 200°C or higher, the solvent may also distill out, which may reduce the purity of the alcohol. At a temperature lower than 50°C, the distillation of the resulting alcohol may be delayed.

[0045] When only an amine compound having two or more nitrogen atoms constituting a tertiary amine is used as the organic solvent in the reaction, since the catalyst solution is composed of only a Group 9 transition metal complex and the amine compound, the composition of the catalyst solution hardly changes before and after the distillation of the alcohol. In addition, due to the stabilization by the amine compound, the activity of the catalyst hardly decreases. Therefore, even when the catalyst solution is used multiple times, alcohol can be stably produced. From this perspective, the content of the amine compound having two or more nitrogen atoms constituting the tertiary amine in the organic solvent is preferably 100 mol%.

[0046] At normal pressure, ethylene, hydrogen molecules, and carbon monoxide are gases. The boiling point of 1-propanol is 97°C, the boiling point of propionaldehyde is 47°C, and the boiling point of N,N,N',N'-tetramethyl-1,3-propanediamine is about 145°C. Therefore, when the olefin compound is ethylene, the resulting alcohol is 1-propanol, and the amine compound having two or more nitrogen atoms constituting the tertiary amine is N,N,N',N'-tetramethyl-1,3-propanediamine, for example, by normal pressure distillation at about 120 - 130°C, only 1-propanol and propionaldehyde can be distilled off and obtained without distilling off the amine compound, and the catalyst solution composed of a Group 9 transition metal complex and the amine compound can be recovered. By adding ethylene, hydrogen molecules, and carbon monoxide to the recovered catalyst solution, 1-propanol can be produced again. 1-Propanol and propionaldehyde can be easily separated by a known method, and propionaldehyde can also be added to the catalyst solution to be converted into 1-propanol.

[0047] [Use] The alcohol obtained by the method for producing alcohol is useful as a solvent and an intermediate for medical and agricultural chemicals.

Examples

[0048] The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In the Examples, parts and % are based on mass unless otherwise specified.

[0049] The analysis, tests, and evaluations in the Examples and Comparative Examples were conducted by the following methods.

[0050] (1) Gas chromatography analysis of reaction solution The analysis of the reaction solution after the reaction was performed by gas chromatography. · Gas chromatography conditions Column oven: Held at 60 °C for 12 minutes, then heated to 80 °C at 10 °C / min and held for 12 minutes, then heated to 150 °C at 20 °C / min and held for 10 minutes, then heated to 230 °C at 30 °C / min and held for 5 minutes, then heated to 235 °C at 30 °C / min and held for 10 minutes Carrier gas: Helium Vaporization chamber temperature: 230 °C Detector temperature: 260 °C · Capillary column J&W Ultra 2 (manufactured by Agilent Technologies Co., Ltd., length 50 m, inner diameter 0.32 mm, film thickness 0.52 μm) · Detector FID

[0051] (Example 1): Synthesis of 1-propanol from ethylene 5 mg (0.019 mmol) of rhodium acetylacetonato dicarbonyl (Rh(acac)(CO)2, manufactured by Aldrich) and 3.9 g (30 mmol) of N,N,N’,N’-tetramethylpropane-1,3-diamine (TMPDA, manufactured by Aldrich), an amine compound having two or more nitrogen atoms constituting a tertiary amine, were placed in a 50-mL autoclave made of SUS, and the inside of the autoclave was purged with argon gas. Subsequently, after purging the inside with synthesis gas (CO:H2 = 1:1 molar ratio), 0.91 g (32 mmol) of ethylene (C2H4) and a mixed gas of CO and H2 were added at a total pressure of 90 atm such that C2H4:CO:H2 = 1 mol:2.5 mol:2.5 mol, and the mixture was heated at 110 °C for 3 hours with stirring. From the gas chromatography analysis results of the reaction solution after the reaction, it was confirmed that only 1-propanol and propionaldehyde were produced. The total yield of 1-propanol and propionaldehyde was 88%, the selectivity for 1-propanol was 97%, and the selectivity for propionaldehyde was 3%. After the reaction, the reaction solution was heated to 130 °C and distilled under normal pressure to distill off 1-propanol and propionaldehyde, and a catalyst solution (4.1 g) composed of Rh(acac)(CO)2 and TMPDA was recovered. The results are shown in Table 1.

[0052] (Examples 2 to 4): Synthesis of 1-propanol from ethylene The reaction was carried out in the same manner as in Example 1 except that the reaction temperature and pressure were changed as shown in Table 1. The results are shown in Table 1.

[0053] (Example 5): Synthesis of 1-propanol from ethylene The reaction was carried out in the same manner as in Example 1 except that the solvent was changed to a mixed solvent of N,N,N’,N’-tetramethyl-1,3-propanediamine (30 mmol) and toluene (19 mmol) (61 mol% of amine compound). From the gas chromatography analysis results of the reaction solution after the reaction, the total yield of 1-propanol and propionaldehyde was 89%, the selectivity for 1-propanol was 96%, and the selectivity for propionaldehyde was 4%. The results are shown in Table 1.

[0054] (Examples 6 - 7): 1 - Propanol Synthesis from Ethylene The reaction was carried out in the same manner as in Example 5, except that n - decane (10 mmol) and n - butanol (22 mmol) were used instead of toluene, and the content of the amine compound was changed to 75 mol% and 58 mol% respectively. The results are shown in Table 1.

[0055] (Example 8): 1 - Propanol Synthesis from Ethylene The reaction was carried out in the same manner as in Example 5, except that the solvent was changed to a mixed solvent of N,N,N’,N’ - tetramethyl - 1,3 - propanediamine (12 mmol) and toluene (28 mmol) (amine compound 30 mol%). The results are shown in Table 1.

[0056] (Example 9): 1 - Propanol Synthesis from Ethylene The reaction was carried out in the same manner as in Example 8, except that the amine compound was changed to N,N,N’,N’ - tetramethyl - 1,4 - butanediamine (TMBDA) and the content of the amine compound was changed to 31 mol%. The results are shown in Table 1.

[0057] (Example 10): 1 - Propanol Synthesis from Ethylene The reaction was carried out in the same manner as in Example 8, except that the amine compound was changed to N,N,N’,N’ - tetramethyl - 1,6 - hexanediamine (TMHDA) and the content of the amine compound was changed to 34 mol%. The results are shown in Table 1.

[0058] (Example 11): 1 - Propanol Synthesis from Ethylene The reaction was carried out in the same manner as in Example 8, except that the amine compound was changed to N,N,N’,N”,N” - pentamethyldiethylenetriamine (PMDETA) and the content of the amine compound was changed to 34 mol%. The results are shown in Table 1.

[0059] (Example 12) Using the catalyst solution recovered in Example 1, the reaction was carried out in the same manner as in Example 1, except that TMPDA and Rh(acac)(CO)2 were not added. Almost the same reaction results as in Example 1 were obtained. The results are shown in Table 1.

[0060] (Example 13) Into a 50 mL SUS autoclave, 3 mL of a toluene solution of Rh(acac)(CO)2 (3.88 mmol / L) (0.012 mmol as Rh) and 2.3 g of TMPDA (18.0 mmol) were added, and the inside of the autoclave was purged with argon gas. Subsequently, after purging the inside with synthesis gas (CO:H2 = 1:1 molar ratio), 5 atm of ethylene (0.27 g, 9.6 mmol) and a mixed gas of CO and H2 were added at a total pressure of 30 atm such that C2H4:CO:H2 = 5 mol:12.5 mol:12.5 mol. Then, it was heated with stirring for 3 hours, during which a mixed gas of CO and H2 (CO:H2 = 1:1 molar ratio) was continuously supplied so that the total pressure was maintained at 30 atm. From the gas chromatography analysis results of the reaction solution after the reaction, it was confirmed that only 1-propanol and propionaldehyde were produced. The total yield of 1-propanol and propionaldehyde was 100%, the selectivity of 1-propanol was 96%, and the selectivity of propionaldehyde was 4%.

[0061] (Comparative Example 1): Synthesis of 1-propanol from ethylene The reaction was carried out in the same manner as in Example 8 except that the amine compound was changed to N,N,N’,N’-tetramethylethylenediamine (TMEDA) and the content of the amine compound was changed to 28 mol%. The results are shown in Table 1.

[0062] (Comparative Example 2): Synthesis of 1-propanol from ethylene The reaction was carried out in the same manner as in Example 8 except that the content of the amine compound was changed to 7 mol%. The results are shown in Table 1.

[0063] (Comparative Example 3) A solution prepared by dissolving 607 mg (3.0 mmol) of tri-n-butylphosphine (P(nBu)3) in toluene to make 5 mL was used as the solvent, and the reaction was carried out in the same manner as in Example 1. The results are shown in Table 1. From the gas chromatography analysis results of the reaction solution after the reaction, it was confirmed that only propionaldehyde was produced, and the selectivity for 1-propanol was 0%.

[0064] (Comparative Example 4) The reaction was carried out in the same manner as in Example 1 except that 4.2 g (12 mmol) of triisooctylamine (TIOA) was used as the solvent. The results are shown in Table 1.

[0065]

Table 1

[0066] The TOF in the table represents the turnover number of the Group 9 transition metal complex catalyst ((Turnover Frequency), and is calculated by the following formula: TOF = number of moles of alcohol produced [mol] / number of moles of Group 9 transition metal [mol] / reaction time [h] The higher the TOF, the higher the catalytic activity per unit time. The TOF of the examples is 200 or more, and industrial alcohol production can be carried out with a relatively small amount of catalyst. In the reaction of the examples, propionaldehyde may be produced, but 1-propanol and propionaldehyde can be easily separated by distillation. The obtained propionaldehyde is also useful as a food additive and a pharmaceutical raw material, and can also be put into the catalyst solution to be used as a raw material for 1-propanol.

Claims

1. A method for producing an alcohol, comprising reacting an olefin compound, carbon monoxide, and hydrogen molecules in an organic solvent containing 30 mol% or more of an amine compound having two or more nitrogen atoms constituting a tertiary amine, using a Group 9 transition metal complex as a catalyst, wherein the amine compound having two or more nitrogen atoms constituting the tertiary amine is represented by the general formula (1) 【Chemical Formula 1】 or the general formula (2) 【Chemical Formula 2】 (wherein R １ ~R ５ each independently represents an alkyl group having 1 to 10 carbon atoms, and x, y, and z each independently represent an integer of 2 to 10). and the organic solvent containing 30 mol% or more of the amine compound having two or more nitrogen atoms constituting the tertiary amine is an organic solvent comprising the amine compound having two or more nitrogen atoms constituting the tertiary amine and at least one selected from the group consisting of toluene, xylene, and n-butanol, and the olefin compound is a monoolefin having 2 to 4 carbon atoms. A method for producing an alcohol.

2. In the general formula (1) or (2), R １ ~R ５ are all methyl groups or all ethyl groups, and x, y, and z are each independently an integer of 2 to 6. The method for producing an alcohol according to Claim 1.

3. The method for producing an alcohol according to Claim 1, wherein the amine compound having two or more nitrogen atoms constituting the tertiary amine is at least one selected from the group consisting of N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethyl-1,3-propanediamine, N,N,N',N'-tetramethyl-1,4-butanediamine, N,N,N',N'-tetramethyl-1,6-hexanediamine, and N,N,N',N",N"-pentamethyldiethylenetriamine.

4. The method for producing an alcohol according to claim 1, wherein the amine compound having two or more nitrogen atoms constituting the tertiary amine is N,N,N',N'-tetramethyl-1,3-propanediamine.

5. The method for producing an alcohol according to any one of claims 1 to 4, wherein the Group 9 transition metal complex is a metal complex composed of acetylacetonato dicarbonyl and a Group 9 transition metal.

6. The method for producing an alcohol according to claim 5, wherein the Group 9 transition metal is rhodium.

7. The method for producing an alcohol according to any one of claims 1 to 4, wherein the molar ratio of the amine compound having two or more nitrogen atoms constituting the tertiary amine to the Group 9 transition metal in the Group 9 transition metal complex is 500 to 10,000.

8. The method for producing an alcohol according to any one of claims 1 to 4, wherein the olefin compound is ethylene and the product is 1-propanol.

9. The method for producing an alcohol according to any one of claims 1 to 4, comprising separating the product alcohol after the reaction and recovering the organic solvent containing the Group 9 transition metal complex, and adding an olefin compound, carbon monoxide, and hydrogen molecules to the recovered organic solvent and reacting them.

10. The method for producing an alcohol according to claim 9, comprising distilling off the product alcohol by distillation at a temperature of less than 200 °C and recovering the organic solvent containing the Group 9 transition metal complex.

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