JPS61249940A - Production of 3-methylpentane-1,5-diol - Google Patents

Abstract

PURPOSE:To obtain the titled substance in high selectivity and rate of reaction, by reacting 3-methyl-3-buten-1-ol with CO and H2 in the presence of a Rh compound which is not modified with a ligand containing group V element of periodic table, and hydrogenating the product. CONSTITUTION:The titled substance can be produced by reacting 3-methyl-3- buten-1-ol with CO and H2 in the presence of a Rh compound (preferably Rh carbonyl, etc.) which is not modified with a ligand (e.g. triphenylphosphine) containing group V element of periodic table at 90-120 deg.C under 80-300 atm, recovering the Rh compound, and hydrogenating the resultant hydroformylation reaction product (e.g. 2-hydroxy-4-methyltetrahydropyran) in the presence of water, a hydrogenation catalyst (e.g. Raney nickel) and a solid acid (e.g. silica- alumina). EFFECT:Expensive Rh compound can be recovered easily. USE:Raw material for the production of polyurethane and polymeric plasticizer.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a method for producing 3-methylpentane-1,5-diol, and more specifically, 3-methyl-3-buten-1-ol is treated with carbon monoxide and Reacting hydrogen with a ligand having an element of group V of the periodic table in the presence of an unmodified rhodium compound and hydrogenating the resulting product in the presence of water, a hydrogenation catalyst and a solid acid. The present invention relates to a method for producing 3-methylpentane-1,5-diol, characterized by:

3-Methylpentane-1 produced by the uninvented method
, 5-diol is a compound useful as a raw material for producing polyurethanes and polymeric plasticizers.

[Conventional technology]

Conventionally, as an industrial method for producing 3-methylpentane-1,5-diol, 3-methyl-3-buten-1-ol is hydroformylated in the presence of a rhodium carbonyl complex compound modified with an organic tertiary phosphine. , a method of hydrogenating the obtained 2-hydroyac-4-methyltetrahydropin has been proposed (% Kosho 58-4053).
(See Publication No. 3) 0 [Problems to be Solved by the Invention] Organic tertiary phosphine, such as the one used as a catalyst for the hydroformylation reaction in the above-mentioned method for producing 3-methylpentane-1,5-diol, The highly modified nine-rhodium carbonyl complex compound is widely known as a catalyst in the hydroformylation reaction of olefinic compounds, and is generally modified with a ligand containing an element of group Ⅰ of the periodic table, such as an organic tertiary phosphine. It has the characteristic of providing hydroformylation reaction products with high selectivity compared to rhodium carbonyl complex compounds that are not used. However, the hydroformylation reaction of 3-methyl-3-buten-1-ol in the presence of a large rhodium carbonyl complex compound modified with an organo-tertiary phosphine was The reaction rate is extremely slow compared to the hydroformylation reaction of α-olefins such as prohylene and 1-octene in the presence of this compound. If the reaction rate is slow, a large amount of an expensive rhodium compound is required to compensate for the slow reaction rate, and the reactor needs to be large, so the above method is inappropriate as an industrial production method. Second, in the above conventional method, the reaction mixture is added before hydrogenating the hydroformylation product 2-hydroxy-4-methyltetrahydrobilane in order to facilitate the purification of 3-methylpentane-1,5-diol. Distillation separation from the liquid is recommended, and the residue containing the catalyst rhodium carbonyl complex compound can be reused for hydroformylation. However, rhodium carbonyl complex compounds are relatively thermally unstable even in the coexistence of organic tertiary phosphine that stabilizes them, and 2-hydroxy-4-methyltetrahydrobilane, which has a high boiling point, is mixed in a hydroformylation reaction. When separating the rhodium carbonyl complex from the liquid by distillation, a part of the rhodium carbonyl complex in the reaction mixture is thermally altered (see JP-A-54-160312), and by-products with a high boiling point are Accumulation in the distillation residue reduces the catalytic activity of the rhodium carbonyl complex. Therefore, when actually carrying out this method, the rhodium carbonyl complex compound used must be stably circulated as a catalyst for a long period of time.
It is extremely difficult to reuse. used as a catalyst,
Substantial recovery of expensive rhodium carbonyl complex compounds.

The above method is also industrially disadvantageous because it cannot be reused.

On the other hand, when an olefinic compound is hydroformylated using as a catalyst a rhodium compound that is not modified with a ligand containing an element of V11JC of the periodic table such as an organic tertiary phosphine, the reaction mixture after the reaction is completed. It is known that rhodium compounds can be easily separated and recovered from liquids (for example, Japanese Patent Publication No. 40-22735
(see publication). However, there is no detailed report on the hydroformylation reaction of 3-methyl-3-buten-1-ol in the presence of a rhodium compound that has not been modified with a ligand containing an element of group V of the periodic table. According to the studies of the present inventors, when 3-methyl-3-buten-1-ol is hydroformylated in the presence of a rhodium compound unmodified by a ligand containing an element of group V of the periodic table, 1 Although the reaction rate improves dramatically, 2-
It has been found that the selectivity to hydroxy-4-methyltetrahydrobilane is extremely low and that many types of acetalization products, which are difficult to separate, are produced as by-products.

The object of the present invention is to produce 3-methylpentane-1-ol from 3-methyl-3-buten-1-ol with a fast reaction rate and high selectivity.
Not only can 1,5-diol be produced, but expensive rhodium compounds can be easily recovered from the hydroformylation reaction system.
An object of the present invention is to provide an industrially advantageous method for producing reusable 3-methylpentane-1,5-diol.

[Means for solving problems]

According to the invention, the above object is achieved by combining 3-methyl-3-buten-1-ol with carbon monoxide and hydrogen
3-, characterized in that the reaction is carried out in the presence of a rhodium compound unmodified with a ligand having an element of group 3-, and the resulting product is hydrogenated in the presence of water, a hydrogenation catalyst and a solid acid This is accomplished by providing a method for producing methylpentane-1,5-diol.

The rhodium compound used in the present invention is a compound that has a hydroformylation catalytic ability and is a compound that changes to have a catalytic ability in a hydroformylation reaction system, and is a compound that changes to have a catalytic ability in a hydroformylation reaction system, and is a compound that changes to have a catalytic ability in a hydroformylation reaction system, and is Any unmodified rhodium compound can be used. Elements in Group III of the periodic table include nitrogen, phosphorus, arsenic, antimony, etc.; ligands containing such elements include organic tertiary phosphines such as triphenylphosphine and tributylphosphine; triphenylphosphite and tributylphosphine; Organic tertiary phosphites such as phyto; organic tertiary arsines such as triphenylarsine and trioctylarsine; and organic tertiary stibines such as triphenylstibine. Representative examples of rhodium compounds used in the present invention include rhodium chloride; rhodium organic carboxylates such as rhodium acetate and rhodium propionate; Rh4(Go)tz, Rh5(Co)t
rhodium carbonyl compounds such as s, [Rh(Co)2α]2; and dimerized cyclopentadienyl rhodium chloride, dimerized cyclooctagenyl rhodium chloride, etc. Among these, especially rhodium carbonyl compounds, dimerized cyclopentadienyl di,
Cod b Um chloride, trimerized cyclooctagenyl chloride, etc. are preferably used. It is known that metal rhodium supported on a carrier such as activated carbon coordinates with carbon monoxide in a hydroformylation reaction system to form a compound having catalytic ability (for example.

(See Japanese Patent Publication No. 46-11805) 1 Such metal rhodium can also be used in the present invention. The concentration of the rhodium compound in the reaction mixture is preferably about 0.01 to 5 milligram atoms/l, more preferably about 0.0.2 to 0.5 milligram atoms/l in terms of rhodium atoms.

The reaction temperature of hydroformylation in the present invention is 60 to 1
Suitable temperature is within the range of 50℃, preferably 90~120℃
within the range of ℃. If the reaction temperature is less than 60°C, the reaction rate will be slow, and if the reaction temperature exceeds 150°C, it will be difficult to maintain the stability of the rhodium compound present as a catalyst. The reaction pressure is usually in the range of about 80 to 300 atmospheres, although it depends on the reaction temperature used. The ratio of hydrogen gas and carbon monoxide gas, which are raw material gases, is desirably within the range of about 3/1 to 1/3 in terms of hydrogen/carbon monoxide molar ratio of the gas entering one reactor. Note that in one reaction system, a gas inert to the hydroformylation reaction, such as methane, ethane, propane,
There is no problem even if nitrogen, helium, argon, carbon dioxide gas, etc. coexist in the reaction system. The hydroformylation reaction can be carried out in the absence of a solvent, but it can also be carried out in the presence of an inert solvent in one reaction system. Such solvents include alcohols such as ethanol, butanol, 3-methylbutanol, and 3-methylpentane-1,5-diol; saturated aliphatic hydrocarbons such as pentane, hex, sane, heptane, octane, nonane, and decane; Examples include aromatic hydrocarbons such as benzene, toluene, and xylene; and ethers such as tetrahydrofuran. The reaction time varies depending on the type of rhodium catalyst used and its concentration, but if the reaction is to be carried out so that the conversion rate of 3-methyl-3-buten-1-ol is close to 100%, it is usually about 1 to 10 hours. If the conversion rate is lower than 100%, unreacted 3-methyl-3-buten-1-ol can be separated from the resulting reaction mixture and used again as a raw material for the hydroformylation reaction. .

Recovery of the rhodium compound from the reaction mixture obtained by the hydroformylation reaction can be easily carried out by one of various methods. For example, if water is added or not added to the reaction mixture after the hydroformylation reaction and the pressure in the system is lowered while maintaining the temperature of the reaction mixture at 40°C or the reaction temperature of hydroformylation, the rhodium compound is Or it precipitates as its compound. The precipitated metal rhodium and its compounds were collected from the combined solution in one reactor.

In addition to being able to be separated and recovered by methods such as centrifugation, it is also possible to easily separate and recover by adsorbing it on an adsorbent such as activated carbon or diatomaceous earth.

In addition, if metals such as aluminum, zinc, chromium, iron, copper, nickel, etc. are present in the reaction mixture and the pressure in the system is lowered in the same manner as above, rhodium compounds can be formed by metal rhodium or the above-mentioned metals as rhodium and its compounds. Since the rhodium compound precipitates on the surface, the rhodium compound can be efficiently separated and recovered from the reaction mixture by this method. The precipitated metal rhodium or its compound can also be separated and recovered from a distillation residue obtained by subjecting the hydroformylation reaction mixture to a distillation operation such as thin-layer distillation. The metal rhodium or its compound thus recovered is subjected to treatments such as purification or conversion into the above-mentioned rhodium compound by a known method, if necessary.

It can be reused as a catalyst for hydroformylation reactions. On the other hand, when the hydroformylation reaction is carried out in the presence of a rhodium compound modified with a ligand containing an element of Group V of the periodic table, the system is Even if the pressure is reduced, the rhodium compound does not substantially precipitate in the reaction mixture or its distillation residue, so the above separation and recovery method cannot be applied. accompanied by difficulties. Furthermore, when metal rhodium or its compounds are separated and recovered, expensive ligands such as triphenylphosphine are often damaged.

The hydroformylation reaction mixture, which has been subjected to separation operations such as removing the rhodium compound or, if necessary, further removing the starting material 3-methyl-3-buten-1-ol, is then treated with 2-hydroxy-4- In addition to methyltetrahydropyran, 2-hydroxy-4-methyltetrahydropyran and 3-methyl-3-buten-1-ol 1:& is 3-
Acetals with methyl-2-buten-1-ol and 2-hydroxy-4-methyltetrahydropyran 2f
These hydroformylation products, which contain many types of acetalization products such as dimers whose + molecules are acetalized, are hydrogenated in the presence of water, a hydrogenation catalyst, and a solid acid according to the method of the present invention. By doing so, it can be easily converted to 3-methylpentane-1,5-diol with high selectivity and high yield. When this hydrogenation reaction is carried out in the absence of water or in the absence of a solid acid even in the presence of water, the yield of the desired 3-methylpentane-1,5-diol is extremely low; In addition to the target product, many types of compounds are produced as by-products.

As the hydrogenation catalyst, known catalysts used for hydrogenation of aldehydes can be used, and specific examples include nickel, Raney nickel, Raney cobalt, haladium, copper chromium oxide, and the like. These catalysts may be supported on a carrier such as activated carbon, diatomaceous earth, or alumina, or may be partially modified with chromium, molybdenum, manganese, tungsten, or the like.

Although only water may be used as a solvent for the hydrogenation reaction,
Any organic solvent that is at least partially soluble in water and does not adversely affect the hydrogenation reaction can also be used. As the organic solvent, alcohols such as methanol, ethanol, propatool, butanol, isoamyl alcohol, and 3-methylpentane-1,5-diol, and ethers such as tetrahydrofuran and dioxane can be used. Regardless of whether or not an organic solvent is used in combination, the amount of water present in the hydrogenation reaction mixture is preferably about 0.05 or more in weight ratio to the hydroformylation reaction product, more preferably about 0. It is within the range of .1 to 5.

The hydrogenation reaction in the present invention is carried out in the presence of a solid acid. The solid acid mentioned here is any solid acid that is substantially insoluble in the reaction mixture during the hydrogenation reaction.

Known solid acids used for hydrolysis of carboxylic acid esters, acetals, etc. can be used. Specifically, the solid acid is silica-alumina.

Examples include activated clay, silica, alumina, cinnabar earth, and acid type ion exchange resin. Such a solid acid can also serve as a carrier for the aforementioned hydrogenation catalyst. The concentration of the solid acid present in the hydrogenation reaction mixture varies depending on the acid strength of the solid acid used and the number of its acidic points, but it is usually in the range of 0.05 to 10% by weight relative to the water bulking reaction mixture. Ruru inside.

It is preferable that the solid acid be present in the hydrogenation reaction mixture from the beginning of the hydrogenation reaction, but it can also be made to be present in the hydrogenation reaction mixture from the middle of the hydrogenation reaction.

The hydrogenation reaction can be carried out in solid or suspended beds.

The temperature of the hydrogenation reaction is usually preferably in the range of about 50 to 200°C.
and more preferably in the range of about 70 to 150°C.

Further, the hydrogen pressure is usually in the range of about 2 to 150 atmospheres, preferably in the range of about 10 to 100 atmospheres.

The hydrogenation reaction product obtained by the method of the present invention has 3-methylpentane-1,5-diol as its main component and also contains a small amount of isoamyl alcohol. Therefore, for example, the reaction mixture obtained by the hydrogenation reaction is
After removing the hydrogenation catalyst and solid acid as necessary, 3-methylpentane-1,5
- Diols can be easily separated and purified.

〔Example〕

EXAMPLES The present invention will be specifically explained below using five examples, but the present invention is not limited to these examples.

Example 1 In a magnetically stirred autoclave with a content of 1/3, in an atmosphere of a mixed gas of -carbon oxide and hydrogen (molar ratio 1:1), 3
-Methyl-3-buten-1-ol 516F (6,00
mol) and Rh4(Co)12 as a rhodium compound
11.7 mm (0.0625 milligram atoms in terms of rhodium atoms) was charged, and the atmosphere in the system was sufficiently replaced with a mixed gas of carbon monoxide and hydrogen (molar ratio 1:l). Next, while maintaining the pressure in the autoclave at 200 atm with this mixed gas, the reaction mixture was heated with stirring to bring the internal temperature to 100 atm.
The hydroformylation reaction was carried out for 5 hours while maintaining the temperature at 0°C. During the reaction, a mixed gas of carbon monoxide and hydrogen (molar ratio 1:1) was continuously supplied to the autoclave through a pressure regulating valve so that the internal pressure was maintained at 200 atm, and the gas flow rate from the autoclave was Approximately 573/h
I adjusted it so that it was r. Next, the reaction mixture in the autoclave was fed under pressure to an autoclave of Content 21 whose system was previously replaced with nitrogen gas.

The mixture was stirred at 20 atm and 100° C. for 30 minutes under a nitrogen gas atmosphere. The metallic rhodium extracted from the obtained contents was separated by F, and 95% of the rhodium compound used was recovered as metallic rhodium. When the reaction mixture g673y from which the precipitated metal rhodium was removed was analyzed by gas chromatography, the remaining amount of unreacted 3-methyl-3-buten-1-ol was found to be 0.01 mol (3-methyl-3-buten-1-ol). −
The conversion rate of 1-ol was 99.8%) and the amount of 2-hydroxy-4-methyltetrahydropyran produced was 2.1%.
molar (selectivity 35%). Other products include 3
The presence of 0.04 mol of -methyl-2-buten-1-ol, 0.43 mol of isovaleraldehyde and various acetalization products were observed.

In the electromagnetic stirring autoclave of Contents 21, 30 tons of powdered nickel diatomaceous earth catalyst (Kickel content 50% by weight),
and 1100 rlLt of water were charged. After the atmosphere in the system was sufficiently replaced with hydrogen gas, the internal pressure of the autoclave was maintained at 50 atm with hydrogen gas, and the internal temperature was maintained at a constant temperature of 140° C. while stirring. 670 t of the above hydroformylation reaction mixture was continuously supplied into this system over 6 hours using a metering pump. During the reaction, hydrogen gas was continuously supplied through a regulating valve so that the internal pressure was maintained at 50 atm, and the gas flow rate from the autoclave was adjusted to 201/hr. After continuous feeding of reaction mixture.

The reaction was continued with stirring for an additional hour. After cooling and depressurization, remove the contents from the autoclave.

The catalyst was separated by passing. The results of gas chromatography analysis of the obtained mourning reaction mixture.

A large amount of isoamyl alcohol 61f and 3-methylpentane-1,5-diol 609f were produced.

What is the yield of 3-methylpencune-1,5-diol?

8 based on the charged 3-methyl-3-buten-1-ol
It is 6.0%.

Example 2 Nikeika rhodium cyclooctagenyl chloride 15.4 If as a 0-dium compound (0 in terms of rhodium atoms)
．． 3-Methyl-3-buten-1-ol 51
6F (6,00 mol) was hydroformylated. The metal rhodium precipitated from the obtained large content was separated by P, and 96% of the rhodium contained in the rhodium compound used was recovered. Gas chromatography analysis revealed that 669 tons of the reaction mixture after filtering contained 0.05 mol of unreacted 3-methyl-3-buten-1-ol (3-methyl-3-buten-1-ol). conversion rate, 99.1%)
, 2-hydroxy-4-methyltetrahydrobilane 1
．． It contained 78 mol (selectivity 29.6%) and also contained many types of acetalization products.

In an autoclave, add 40f of Raney nickel catalyst and activated clay 409 to 600d of ethanol and 500ml of water.
The above hydroformylation reaction mixture $6 was prepared in the same manner as in Example 1 except that the reaction temperature was 120°C.
609 was hydrogenated. When the reaction mixture was analyzed by gas chromatography after the completion of the reaction, 3-methyl-3-diol containing 3-methylpentane-1°5-diol was detected.
It was produced at a concentration of 84.5-based on buten-1-ol.

Example 3 [Rh(Co)2αh15Mg(
3-Methyl-3-buten-1-ol 5169 (6,00 mol) was hydroformylated in the same manner as in Example 1 except that 0.077 milligram atom (calculated as a rhodium atom) was used. The metal rhodium precipitated from the obtained contents was separated by P, and the reaction mixture 667f after filtration, in which 93% of the rhodium contained in the rhodium compound used was recovered, was analyzed by gas chromatography. 0.01 mol of 3-methyl-3-buten-1-ol (
Conversion rate of 3-methyl-3-buten-1-ol 99.8
%), 1.7 mol (selectivity 28%) of 2-hydroxy-4-methyltetrahydropyran remained. Additionally, 0.40 mol of isovaleraldehyde and 3
- Generation of 0.03 mole of methyl-2-buten-1-ol was observed. Raney cobalt catalyst 40f and silica-alumina 60
When 667f of the above reaction mixture was hydrogenated in the same manner as in Example 1 except that 9 was charged with 600 d of ethanol and 500 d of water and the reaction temperature was 120°C, 3-
602 tons of methylpentane-1°5-diol were obtained. The yield of 3-methylpentane-1,5-diol was 85% based on the charged 3-methyl-3-buten-1-ol.
%〇Examples 4 to 7 3-Methyl-3-buten-1-ol 516f (6.0 mol) was hydroformylated in the same manner as in Example 3, and rhodium metal was precipitated from the resulting content. By separating with F, 664 t of reaction mixture was obtained. Mix 50 f each of this reaction mixture with the hydrogenation catalyst and solid acid shown in Table 1, 50 m of ethanol, and 5 ornl of water,
A hydrogenation reaction was carried out for 6 hours at the hydrogen pressure and temperature shown in Table 1. 3 charged in the hydroformylation reaction
-Produced 3 based on methyl-3-buten-1-ol
-The yield of methylpentane-1,5-diol is the highest! !
Shown below.

Comparative Example 1 Hydroformylation of 3-methyl-3-buten-1-ol was carried out in the same manner as in Example 1 except that 0.47 f (1.8 mmol) of triphenylphosphine was added to the reaction system. . After the reaction was completed, the pressure in the first reaction system was returned to normal pressure, but the rhodium compound in the reaction mixture did not precipitate, making it impossible to separate rhodium by F, which was dangerous. Gas chromatography analysis of this reaction mixture revealed that the conversion rate of 3-methyl-3-buten-1-ol was only 21% and 2%.
The selectivity to -hydroxy-4-methyltetrahydrobyran was found to be 859G. This reaction mixture was subjected to simple distillation to remove unreacted 3-methyl-3-buten-1-ol, and distillation 1A residue 128F was obtained. Upon hydrogenation, 3-methylpentane-1,5-diol 1
28f was obtained ft.

The yield of 63-methylpentane-1,5-diol obtained was 86% based on the reacted 3-methyl-3-buten-91-ol, but Comparative Example 2 3-Methyl-3-buten-1-ol 516f was hydroformylated in the same manner as in Example 1.

The metal rhodium precipitated from the obtained contents was separated by F and 6
A reaction mixture of 70 f was obtained. Analysis of the reaction mixture by gas chromatography revealed that unreacted 3-methyl-
0.01 mol of 3-buten-1-ol (3-methyl-
3-buten-1-ol (conversion rate: 99.8%) remained, and 2.0 moles of 2-hydroxy-4-methyltetrahydropyran (selectivity: 33%) was produced.

40f of Raney nickel catalyst was placed in an autoclave along with 11 parts of ethanol, and the hydrogen pressure was set to 50 atm and the internal temperature was set to 1.
The hydroformylation reaction mixture 6 was maintained at 00°C and stirred.
After 70 tons were continuously fed over 6 hours and the reaction was continued with stirring for 1 hour, the contents were taken out and the catalyst was separated by one-pass filtration. As a result of analyzing the obtained large reaction mixture by gas chromatography, it was found that 3-methylpentane-
The amount of 1,5-diol produced was only 260t and f
c (Charge 7' (3-methyl-3-buten-1-ol group 11 yield 37%).

Comparative Example 3 516t of 3-methyl-3-buten-1-ol was hydroformylated in the same manner as in Example 1. The metal rhodium precipitated from the resulting content was separated by F to obtain a reaction mixture of 6709. . As a result of gas chromatography analysis of the reaction mixture, unreacted 3-methyl-3-butene-1
-ol is 0.01 mol (3-methyl-3-butene-1
2-hydroxy-4-methyltetrahydrobilane (conversion rate of 99.8%) remained, and 2.0 mol (2-hydroxy-4-methyltetrahydrobilane)
Selection rate: 33%) Just in case it's generated.

Raney nickel catalyst 409 in water 11 in autoclave
I prepared it with Next, the hydrogen pressure was 50 atm and the internal temperature was 100.
670 t of the above hydroformylation reaction mixture was continuously fed over 6 hours while stirring at .degree. Thereafter, the reaction was continued with stirring for 1 hour. After cooling and releasing the pressure, the contents were taken out and the catalyst was separated by filtration.The resulting reaction mixture was analyzed by gas chromatography, and the amount of 3-methylpentane-1,5-diol produced was %. The yield was only 2752 (yield 39% based on the charged 3-methyl-3-buten-1-ol).

〔Effect of the invention〕

According to the present invention, as is clear from the above embodiments, 9.3
-3-Methylpentane-1,5-diol can be produced from -methyl-3-buten-1-ol at a fast reaction rate and high selectivity. Further, according to the present invention, since the expensive rhodium compound can be easily recovered from the hydroformylation reaction system, it can be economically reused as a catalyst in the hydroformylation reaction to produce 3-methylpentane-1,5-diol. can be manufactured. Therefore, the present invention provides an industrially advantageous method for producing 3-methylpentane-1,5-diol.

Claims (1)

[Claims] 1,3-methyl-3-buten-1-ol in the presence of carbon monoxide and hydrogen and an unmodified rhodium compound with a ligand containing an element of group V of the periodic table. 3-methylpentane-, which is characterized by reacting and hydrogenating the obtained product in the presence of water, a hydrogenation catalyst and a solid acid.
Method for producing 1,5-diol. 2. The production method according to claim 1, wherein the solid acid also serves as a carrier for the hydrogenation catalyst.