JPH0665125A - Production of alcohol - Google Patents

Abstract

PURPOSE:To produce a alcohol by reducing a carboxylic acid or a carboxylic acid ester. CONSTITUTION:A carboxylic acid or a carboxylic acid ester is reduced into the corresponding alcohol with an alcohol as a hydrogen source in the presence of the composite oxide of zirconium and bismuth as a catalyst. The carboxylic acid or the carboxylic acid ester can be reduced into the corresponding alcohol in the presence of the alcohol in high yield. Particularly, a carboxylic acid having many carbon atoms or its ester having given the corresponding alcohol in a low yield by the single use of the zirconium can more effectively be reduced into the alcohol.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for reducing carboxylic acids or carboxylic acid esters to their corresponding alcohols.

[0002]

2. Description of the Related Art Conventionally, as a method for producing a corresponding alcohol from a carboxylic acid, for example, a method by hydrogen reduction using a rhenium catalyst (JP-A-57-32237).
However, a high pressure condition of 50 to 500 atm is required, and a method by electrolytic reduction (Japanese Patent Laid-Open No. 58-117887).
No.) is limited to the production of para-substituted benzyl alcohol. On the other hand, as a method for producing an alcohol from a carboxylic acid ester, a copper-based oxide catalyst such as a copper-chromium-based, copper-zinc-based, copper-molybdenum-based, copper-iron-based, copper-zirconium-based catalyst (see, for example, Japanese Patent Application Laid-Open No. Sho 63-141937, JP-A-2-36135, JP-A-3-220143, JP-A-54-32191, and JP-A-52-156192.
No. 3-128334).
Other than copper-based catalysts, nickel catalysts modified with tin, germanium or lead (EP-A-017209)
No.), a rhodium catalyst (EP-A-95408 or JP-A-58-216131), a catalyst composed of rhenium and a noble metal element of Group 8 (DE-A-317429).
No.) etc. have been proposed. In addition, a catalyst in which a mixed metal oxide containing palladium or rhenium and zinc oxide is supported on a carrier (Japanese Patent Laid-Open No. 36136/1990) has been proposed.

On the other hand, as a method for producing a corresponding alcohol by reducing alcohol with a hydrogen source, a method using zirconium oxide hydroxide as a catalyst from carboxylic acid and its ester (Japanese Patent Laid-Open No. 64-15136) or aldehyde or ketone is used. There is a method for producing alcohol using a heterogeneous catalyst (JP-A-61-204143, JP-A-62-252737, JP-A-2-718).

[0004]

However, the reduction method using hydrogen gas requires relatively high temperature and high pressure conditions, and there is a problem in that hydrogen gas is often accompanied by danger such as ignition. is there. On the other hand, the reduction method using alcohol as a hydrogen source has improved the above-mentioned problems, but has a limit to applicable carboxylic acids. For example, there is a problem that it is difficult to obtain a desired alcohol in a sufficient yield with a long-chain carboxylic acid or the like.

Therefore, an object of the present invention is to provide a method for producing an alcohol from a carboxylic acid or a carboxylic acid ester having a large molecular weight which can be safely carried out in a high yield.

[0006]

The present invention relates to a method of reducing a carboxylic acid or a carboxylic acid ester with an alcohol in the presence of a catalyst to an alcohol corresponding to the carboxylic acid or the carboxylic acid ester, wherein the atomic molar ratio is zirconium. : Bismuth = 1: 0.05 to 1: 0.1 is used as a catalyst in the production method of alcohol.

The complex oxide used as a catalyst in this reduction reaction is a white solid, is insoluble in water, alcohol and other organic solvents, and is a stable substance which acts as a heterogeneous catalyst. Further, it exhibits high activity as a reducing catalyst that can use alcohol as a reducing agent, and is stable to heat. This composite oxide can be easily and inexpensively prepared by drying and firing a zirconium salt and a bismuth compound through a hydroxide. The hydroxide of zirconium and bismuth can be obtained by making a mixed solution of a zirconium salt and a bismuth compound alkaline.

The zirconium salt is preferably a zirconium salt which is soluble in an aqueous solution such as zirconium oxychloride, zirconium oxynitrate, zirconium chloride, zirconium nitrate. As the bismuth compound, for example, a compound soluble in an aqueous solution such as bismuth nitrate or bismuth oxide is preferable. The ratio of the zirconium salt and the bismuth compound may be appropriately selected in the atomic molar ratio of 1: 0.05 to 1: 0.1. In the range other than this, the activity is lowered and the degree thereof is lower than that of hydrous zirconium oxide.

A method for producing a hydroxide from a mixed solution of a zirconium salt and a bismuth compound and depositing a precipitate may be carried out with an alkali. For example, the precipitate may be precipitated with sodium hydroxide or aqueous ammonia.
The pH adjustment with alkali is 6.5 to 9.2, preferably 7.0 to 9.0.

The obtained precipitate is treated at 100 ° C to 500 ° C.
A composite oxide of zirconium and bismuth can be obtained by calcining at 200 ° C. to 400 ° C. for 1 to 8 hours, preferably 3 to 6 hours.

The carboxylic acids and carboxylic acid esters which are reduced to the corresponding alcohols by the method of the present invention are straight chain or branched saturated or unsaturated carboxylic acids having 1 to 18 carbon atoms and their esters. For example, n-
Carboxylic acids such as valeric acid, n-hexanoic acid, n-decanoic acid, n-pentadecanoic acid, isovaleric acid, isodecanic acid, isostearic acid, pivalic acid, 5-hexenoic acid, 10-undecenoic acid, oleic acid and the like. It is an ester. The above compounds may be substituted with other substituents such as halogen.

The alcohol used as the reducing agent (hydrogen source) in the present invention is preferably a primary or secondary lower alcohol, but 2-propanol is most preferred in terms of cost and efficiency.

To reduce a carboxylic acid or its ester to an alcohol using the composite oxide of the present invention, for example, the reaction tube is filled with the composite oxide, and the reaction temperature is set at the reduction temperature.
For example, the mixture is heated to 200 ° C. to 450 ° C., preferably 230 ° C. to 350 ° C., and the mixture of the starting carboxylic acid or carboxylic acid ester and the reducing agent alcohol is treated with an inert carrier gas such as N ₂ , Ar, He or the like is used to continuously feed the catalyst layer. During the reaction, a solvent inert to the mixed solution for the purpose of dissolving the raw materials, such as 1,
An appropriate amount of 4-dioxane or the like may be added. The outlet of the reaction tube is cooled with, for example, water, ice, or another appropriate refrigerant to condense effluents such as products and unreacted materials. Product isolation is accomplished by fractional distillation of the effluent as is,
It can be done easily. The mixing molar ratio of the carboxylic acid or carboxylic acid ester as the starting material and the alcohol as the reducing agent may be appropriately selected within the range of 5 to 500 with respect to the starting material 1.

Further, this reaction may be carried out in a liquid phase, for example, using an autoclave, a mixed liquid of a complex oxide, a carboxylic acid or carboxylic acid ester as a starting material and an alcohol as a reducing agent. Is charged in a reaction vessel to carry out the reaction, and the complex oxide, the carboxylic acid or carboxylic acid ester as a starting material and the alcohol as a reducing agent are mixed in an inert solvent such as a hydrocarbon having a boiling point higher than the reduction temperature. A method of filling the reaction mixture with the mixed solution and carrying out the reaction may be used.

However, the implementation method is not limited to this example.

[0016]

EXAMPLES The present invention will be described in more detail below with reference to production examples and examples of catalysts used in the present invention, but the present invention is not limited thereto.

<Preparation of Catalyst> [Preparation Example 1-Catalyst A] Zirconium: bismuth (atomic ratio) = 1: 0.05 50 g (0.155) of zirconium oxychloride (octahydrate)
2 mol) aqueous solution and bismuth nitrate pentahydrate 3.764
An aqueous solution of g (0.00776 mol) was mixed, and concentrated nitric acid was added and dissolved. While stirring, an aqueous sodium hydroxide solution was gradually added to adjust the pH to 8.5. The resulting hydrated gel was filtered to separate excess saline solution, and the gel was washed with fresh deionized water. The gel was spread on a glass plate and dried at room temperature. The composite hydrous oxide thus obtained is classified, and those having a particle size range of 24-60 mesh are collected and heat-treated in an electric furnace at 300 ° C. for 5 hours to prepare a catalyst A. .

[Preparation Example 2-Catalyst B] Zirconium: bismuth (atomic ratio) = 1: 0.05 Prepared in the same manner as in Preparation Example 1 except that the aqueous sodium hydroxide solution in Preparation Example 1 was replaced with an aqueous ammonia solution. ,
This is designated as catalyst B.

[Preparation Example 3-Catalyst C] Zirconium: bismuth (atomic ratio) = 1: 0.1 7.53 g (0.01552 mo) of bismuth nitrate pentahydrate
l) is mixed with water and concentrated nitric acid is added to dissolve it, and 50 g (0.1552 mo) of zirconium oxychloride (octahydrate) is dissolved therein.
The aqueous solution of 1) is added and mixed, and concentrated nitric acid is added to this and dissolved. While stirring, an aqueous ammonia solution was gradually added to adjust the pH to 8.2. The hydrated gel thus produced was filtered in the same manner as in Preparation Example 1 to separate excess saline solution, and then the gel was washed with fresh deionized water. The gel was spread on a glass plate and dried at room temperature. The composite hydrous oxide thus obtained is classified, and those having a particle size range of 24-60 mesh are collected and heat-treated in an electric furnace at 300 ° C. for 5 hours to prepare a catalyst C. .

[Preparation Example 4-Catalyst D] Zirconium: bismuth (atomic ratio) = 1: 0.05 Zirconium oxychloride (octahydrate) 5 in Preparation Example 3
0 g to 25.0 g (0.0776 mol), bismuth nitrate pentahydrate 7.53 g to bismuth oxide 1.81 g
(0.00388 mol), a sodium hydroxide aqueous solution was used instead of the ammonia aqueous solution, and the same procedure as in Preparation Example 3 was carried out except that pH 8.2 was changed to 8.5, and this was designated as catalyst D.

<Alcohol Production Test> [Example 1-2] Catalyst A2 produced in Preparation Example 1
g was filled and fixed in a reaction tube made of a glass tube having an inner diameter of 6.5 mm and a length of 50 cm so that the catalyst layer was uniform. This is installed in an electric furnace and the temperature in the furnace is raised to 280 ° C. A 2-propanol solution of 0.2 mol / l decanoic acid is prepared in advance as a starting material. Nitrogen gas as a carrier gas was allowed to flow at a rate of 1 ml / sec, and the above starting material solution was added and supplied thereto at a rate of 5 ml / hr by a micro feeder. The reaction product, which has passed through the catalyst layer of the reaction tube together with the carrier gas, was guided to the outside of the furnace, and was condensed and liquefied by water cooling or ice cooling to be collected. The analysis of the product was carried out by gas chromatography using comparison with a standard product, identification and quantification, and the conversion rate and the decanol yield were determined. The results are shown in Table 1. The catalyst B prepared in Preparation Example 2 was used in place of the catalyst A to carry out the reaction in the same manner. The results are shown in Table 1.

[Embodiment 3-4] In this embodiment, the first embodiment is described.
The catalyst C prepared in Preparation Example 3 was used instead of the catalyst A in Example 3, and the reaction temperature in Example 1 was 280 ° C.
The same procedure as in Example 1 was carried out except that, instead of 00 ° C,
The yield of decanol was determined. The results are shown in Table 1. Catalyst C
Instead of, the reaction was carried out in the same manner using the catalyst D prepared in Preparation Example 4 above. The results are shown in Table 1.

Example 5 In this example, 10 parts of a 2-propanol solution containing 0.2 mol / l of decanoic acid in Example 1 was used.
-Feeding rate 5 ml / instead of undecenoic acid 0.05 mol / l
Change the reaction temperature from 280 ° C to 300 ° C by changing the time to 10 ml / hour.
Instead of the above, the same reaction operation as in Example 1 was carried out, and the yield of 10-undecenol was determined. The results are shown in Table 1.
Shown in.

Example 6 In this example, 10-undecenoic acid in Example 5 was replaced with methyl 10-undecenoate, and the same reaction procedure as in Example 5 was performed except that 10-undecenoic acid was used. The yield was determined. The results are shown in Table 1.
Shown in.

[0025]

[Table 1] ──────────────────────────────────── Example catalyst raw material conversion rate% product yield Rate% (atomic ratio Zr: Bi) ──────────────────────────────────── 1 A (1: 0.05) Decanoic acid 100 Decanol 89 2 B (1: 0.05) Decanoic acid 100 Decanol 78 3 C (1: 0.1) Decanoic acid 100 Decanol 78 4 D (1: 0.05) Decanoic acid 100 Decanol 91 5 A (1: 0.05) 10-Undecenoic acid 100 10-Undecenol 75 6 A (1: 0.05) 10-Undecenoic acid methyl 100 10-Undecenol 65 ────────────────────────── ─────────────

Comparative Example 1 In this comparative example, the catalyst A in Example 1a was replaced with hydrous zirconium oxide, the reaction temperature was changed from 280 ° C. to 300 ° C., and otherwise, Example 1 was used.
The same reaction operation was carried out to determine the yield of decanol.
The results are shown in Table 2.

[Comparative Example 2] In this comparative example, the catalyst A in Example 5 was replaced with hydrous zirconium oxide hydroxide, and 10-undecenoic acid (0.05 mol / l) in 2-propanol solution was added.
-Instead of 0.1 mol / l undecenoic acid, the reaction solution supply rate was 10 ml / hr, 5 ml / hr, otherwise, Example 5
The same reaction operation as above was performed to determine the yield of 10-undecenol. The results are shown in Table 2.

[0028]

[Table 2] ──────────────────────────────────── Comparative example Catalyst Raw material conversion% Product yield Rate% (atomic ratio Zr: Bi) ──────────────────────────────────── 1 (1: 0 ) Decanoic acid 100 Decanol 34 2 (1: 0) 10-Undecenoic acid 95 10-Undecenol 10 ────────────────────────────── ───────

[0029]

INDUSTRIAL APPLICABILITY A carboxylic acid or a carboxylic acid ester can be reduced in high yield to a corresponding alcohol in the presence of alcohol. In particular, zirconium alone can more effectively reduce the reduction of a carboxylic acid having a large number of carbon atoms or an ester thereof having a low alcohol yield to an alcohol.

Claims (1)

[Claims] 1. A method of reducing a carboxylic acid or a carboxylic acid ester with an alcohol to an alcohol corresponding to the carboxylic acid or the carboxylic acid ester in the presence of a catalyst, wherein the atomic mole ratio is zirconium: bismuth =
A process for producing an alcohol, which comprises using a composite oxide of 1: 0.05 to 1: 0.1 as a catalyst.