JP2006232749A - Method for producing tertiary pentanol - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing tertiary pentanol remarkably improving yield in a short time, imparting a high yield and high productivity by using a solid acid catalyst in hydration of chain olefin with five carbon atoms. <P>SOLUTION: The invention relates to the method for producing tertiary pentanol by using the solid acid catalyst in hydration of the chain olefin with five carbon atoms, wherein the hydration is carried out in the presence of 0.01-10 mol times of phenols to the 5C chain olefin at 20-100°C. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing alcohol, and more particularly to a method for producing tertiary pentanol with high yield and high productivity by hydrating a chain olefin having 5 carbon atoms using a strongly acidic ion exchange resin. The obtained tertiary pentanol is useful as an intermediate material for fragrances, agricultural chemicals and the like.

  The so-called indirect method for obtaining an alcohol by hydrolyzing an intermediate ester using a mineral acid such as sulfuric acid as a catalyst is widely known as an olefin hydration method. It requires a step of neutralizing and purifying the product and a concentration step for reusing the diluted sulfuric acid. Therefore, this method has a problem that the process is complicated and there are many by-products, and the energy cost is high because a large amount of steam is used in the hydrolysis process and the sulfuric acid concentration process. In addition, since sulfuric acid is highly corrosive, the apparatus also has a drawback of requiring expensive materials such as Hastelloy.

On the other hand, a direct method for obtaining an alcohol without using an intermediate ester by using a solid acid such as a strongly acidic ion exchange resin or a heteropolyacid used as an aqueous solution as a catalyst is also conventionally known.
There is a method of using a strongly acidic ion exchange resin as a catalyst (see, for example, Patent Document 1).
In Patent Document 1, a first-stage hydration reaction is performed on a homogeneous mixture containing acetone, water, amylene, and a small amount of t-amyl alcohol in the presence of a strongly acidic ion exchange resin, and the reaction mixture and amylene are added. In this method, the second stage hydration reaction and the third stage hydration reaction are disclosed. However, in this method, a long reaction time and a large amount Since acetone is used, there is a problem that energy and cost required for separation / purification and recycling become enormous.

In addition, since the ion exchange resin is an insoluble resin and cannot be mixed with the reactant olefin and water at the molecular level, it is mixed with water and olefin in order to compensate for the shortage of contact and low activity. There is a method for increasing the hydration reaction rate by adding a large amount of an organic acid such as acetic acid to form a homogeneous phase (see, for example, Patent Document 2).
However, in this method, since the produced tertiary alcohol and organic acid easily form an ester in the presence of a strongly acidic ion exchange resin, the yield of the alcohol is low.
U.S. Pat. No. 4,182,920 Japanese Examined Patent Publication No. 56-22855

  The method for producing alcohol by hydration of olefins using a strongly acidic ion exchange resin catalyst has industrially excellent aspects such as easy separation of the catalyst, but has a low yield and a slow reaction rate. It has become a problem.

  The present inventors have been made in view of such problems of the prior art, and hydrate a chain olefin having 5 carbon atoms using a solid acid catalyst as a catalyst to produce tertiary pentanol. As a result of extensive research on the method, it was found that the yield of the alcohol was remarkably improved in a short reaction by conducting a hydration reaction in the presence of phenols. As a result, high yield and high production were achieved. The present inventors have found a method for producing a tertiary pentanol having properties.

  That is, in the present invention, when a tertiary pentanol is produced by hydrating a chain olefin having 5 carbon atoms using a solid acid catalyst, 0.01 to 10 mol with respect to the chain olefin having 5 carbon atoms. The present invention relates to a method for producing tertiary pentanol, characterized in that a hydration reaction is carried out at a temperature of 20 ° C. to 100 ° C. in the presence of double phenols.

  According to the present invention, in a reaction of hydrating a chain olefin having 5 carbon atoms using a solid acid catalyst to produce a tertiary pentanol, a phenol can be added to the reaction system for a short time. The reaction can significantly improve the yield of tertiary pentanol. Therefore, since this production method can be produced with high yield and high productivity, it is an industrially excellent production method.

  Hereinafter, the present invention will be described in detail. The solid acid catalyst used in the present invention is an acidic solid substance, such as an acidic ion exchange resin, an inorganic oxide such as zeolite, titanium dioxide, aluminum oxide, and silicon dioxide, or a composite oxide thereof, and further, such as scumite and kaolitite. Illustrative examples include ion-exchanged layered compounds obtained by treating a layered compound with one or more metal oxides selected from aluminum, silicon, titanium, and zirconium. As the solid acid catalyst in the present invention, an acidic ion-exchange resin is used. preferable. Examples of acidic ion exchange resins include a polymer substrate obtained by polycondensation of phenol and formaldehyde as a polymer substrate, and a styrene or halogenated styrene and divinylbenzene. And those having a copolymer as a polymer substrate. Among these, a strongly acidic ion exchange resin having a sulfone group is particularly preferable in terms of availability, handleability, and the like.

  The chain olefin having 5 carbon atoms used in the present invention is preferably one that forms a tertiary alcohol by a hydration reaction. Examples thereof include 2-methyl-1-butene and 2-methyl-2-butene. These compounds can be used alone or in a mixture. These chain olefins may be a mixture with a compound having a plurality of double bonds such as a saturated hydrocarbon such as isopentane or isoprene.

The phenols used in the present invention are phenol and phenol derivatives, and refer to compounds having one or more hydroxyl groups directly substituted on the benzene ring. Specifically, xylenol such as phenol, cresol, ethylphenol, isopropylphenol, t-butylphenol, t-amylphenol, hexylphenol, octylphenol, nonylphenol, 2,4-xylenol, dibutylphenol, diamylphenol, dioctylphenol, Chlorophenols such as 4-chlorophenol, butylphenols such as bromophenol, iodophenol, catechol, t-butylcatechol, nitrophenols such as 4-nitrophenol, hydroquinone, butylhydroquinone, 1-naphthol, 2-naphthol, bisphenol A And bisphenol F.
Among these, phenols are preferably phenol, catechol, 4-chlorophenol, 2,4-xylenol, 2-naphthol, 4-nitrophenol or t-butylcatechol.
The phenols to be added may be one type or a mixture of two or more types.
The addition amount of phenols in the present invention is not particularly limited, but is preferably about 0.01 to 10 mol with respect to 1 mol of chain olefin in consideration of the effect and economy.

  The amount of water used in the present invention is preferably about 0.1 to 100 mol per mol of chain olefin.

  In the present invention, a solvent that dissolves in olefin and / or water may be added. Specifically, alcohols such as ethanol, propanol, butanol and octanol, ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone and cyclohexanone, organic acids such as acetic acid, propionic acid and benzoic acid, ethyl acetate, methyl acetate, γ- Examples thereof include esters such as butyrolactone, methyl butyrate and ethyl formate, ethers such as diethyl ether, tetrahydrofuran, dioxane and trioxane, sulfolane, DMF, DMAc and DMSO aprotic polar compounds.

  The reaction temperature in this invention is about 20-100 degreeC, and 40-100 degreeC is especially preferable. If the reaction temperature is less than 20 ° C., the reaction rate is slow and it is not industrially significant. In addition, when the reaction temperature exceeds 100 ° C., the equilibrium is biased toward the olefin side, which is disadvantageous for the production of alcohol, and by-products such as polymers increase, resulting in a decrease in selectivity. Problems such as decomposition occur, which is not preferable.

  The reaction pressure in the present invention is not particularly limited, but is preferably a pressure at which the chain olefin can be maintained in a liquid state under the reaction conditions.

  As the reaction mode in the present invention, any of a normal batch method, a semi-batch method for continuously supplying a part of raw materials or catalysts, or a continuous flow reaction method can be used. Moreover, there are no particular limitations on the order of addition and the manner of addition of each component such as the reaction raw material and catalyst. Further, various methods such as a fixed bed, a moving bed, and a simulated moving bed can be adopted as the catalyst filling method.

The reaction time (retention time in flow reaction) is not particularly limited, but is usually 0.5 second to 24 hours, preferably 1 second to 20 hours.
After the reaction, if necessary, the reaction product can be separated and recovered from the catalyst or the like by a conventional separation method such as filtration separation, extraction or distillation.

Tertiary pentanol, which is the target product, is usually generally known from the separated and recovered product, such as a sequential method such as solvent extraction, distillation, alkali treatment, acid treatment, or an appropriate combination of these. The target product can be obtained in a more pure form by separation / purification by the separation / purification method. In addition, unreacted raw materials can be recovered and recycled to the reaction system again.
In the case of a batch system, the catalyst recovered after the reaction product obtained after the reaction is separated by filtration or the like can be reused in the reaction as a catalyst repeatedly as it is or after regenerating part or all of it. .
When the reaction is carried out in a fixed bed or moving bed flow continuous reaction system, a catalyst that has been partially or wholly deactivated or reduced in activity by being subjected to the reaction can be regenerated and used for the reaction after interrupting the reaction. . Further, a part of the catalyst can be extracted continuously or intermittently, regenerated and recycled to the reaction system, and reused. Furthermore, new catalyst can be fed continuously or intermittently to the reactor.

Hereinafter, the present invention will be described in more detail with reference to examples. In addition, this invention is not limited to the Example shown below.
Incidentally, “isoamylene” used in the following description has the composition (% by weight) shown in Table 1 below.

Moreover, the yield used in a present Example is defined by the following calculated values.
Yield = {(Mole number of tertiary pentanol produced) / (Mole number of chain olefin contained in raw material)} × 100 (%)

Example 1
9.6 g of strongly acidic ion exchange resin (sulfonated styrene-divinylbenzene copolymer Rohm and Haas Co., Ltd., trade name Amberlyst 15WET), 9.4 g of phenol and 7.6 g of isoamylene are added to a 30 ml stainless steel autoclave. The inner temperature was kept at 50 ° C., and the reaction was carried out with stirring for 7.5 hours. After completion of the reaction, the temperature was lowered to room temperature, the autoclave was opened, the reaction solution and the catalyst were separated, and then the reaction solution was subjected to gas chromatography analysis to determine the yield of tertiary pentanol. The results are shown in Table 2.

Example 2
The same procedure as in Example 1 was conducted except that 9.4 g of phenol in Example 1 was changed to 11.0 g of catechol. The results are shown in Table 2.

Example 3
The same procedure as in Example 1 was conducted except that 9.4 g of phenol in Example 1 was changed to 12.8 g of 4-chlorophenol. The results are shown in Table 2.

Example 4
The same procedure as in Example 1 was repeated except that 9.4 g of phenol in Example 1 was changed to 12.2 g of 2,4-xylenol. The results are shown in Table 2.

Example 5
The same procedure as in Example 1 was carried out except that 9.4 g of phenol in Example 1 was changed to 14.4 g of 2-naphthol. The results are shown in Table 2.

Example 6
The same procedure as in Example 1 was conducted except that 9.4 g of phenol in Example 1 was changed to 13.9 g of 4-nitrophenol. The results are shown in Table 2.

Example 7
The same procedure as in Example 1 was carried out except that 9.4 g of phenol in Example 1 was changed to 16.6 g of t-butylcatechol. The results are shown in Table 2.

Example 8
The same procedure as in Example 1 was performed except that 9.4 g of phenol in Example 1 was changed to 0.94 g. The results are shown in Table 2.

Example 9
The same procedure as in Example 1 was conducted except that 9.4 g of phenol in Example 1 was changed to 4.7 g. The results are shown in Table 2.

Example 10
The same operation as in Example 1 was performed except that the temperature in the container of Example 1 was changed to 70 ° C. and the reaction time was changed to 3 hours. The results are shown in Table 2.

Example 11
The same operation as in Example 10 was performed except that the amount of phenol added in Example 10 was changed from 9.4 g to 4.7 g. The results are shown in Table 2.

Comparative Example 1
The same procedure as in Example 1 was performed except that the phenol of Example 1 was not added. The results are shown in Table 2.

Comparative Example 2
The same procedure as in Example 1 was conducted except that 9.4 g of phenol in Example 1 was changed to 10.8 g of 4-methoxybenzene. The results are shown in Table 2.

Example 12
9.6 g of a strongly acidic ion exchange resin (sulfonated styrene-divinylbenzene copolymer Rohm and Haas Co., Ltd., trade name Amberlyst 15WET), 9.4 g of phenol and 2-methyl-2-butene (Tokyo) in a 50 ml stainless steel autoclave (Chemical conversion reagent purity 99%) 7.0 g was added to keep the temperature in the autoclave container at 50 ° C., and the reaction was carried out with stirring for 7.5 hours. After completion of the reaction, the temperature was lowered to room temperature, the autoclave was opened, the reaction solution and the catalyst were separated, and then the reaction solution was subjected to gas chromatography analysis to determine the yield of tertiary pentanol. The results are shown in Table 3.

Example 13
The same operation as in Example 12 was conducted except that the chain olefin was changed from 2-methyl-2-butene to 2-methyl-1-butene (purity 99%, manufactured by Tokyo Chemical Industry Co., Ltd.). The results are shown in Table 3.

Example 14
The same procedure as in Example 12 was conducted except that the chain olefin was changed to a mixture of 6.4 g of 2-methyl-2-butene and 0.6 g of 2-methyl-1-butene. The results are shown in Table 3.

Comparative Example 3
The same procedure as in Example 12 was carried out except that no phenol was added. The results are shown in Table 3.

Claims (4)

  When a tertiary pentanol is produced by hydrating a chain olefin having 5 carbon atoms using a solid acid catalyst, 0.01 to 10 mol times of phenols with respect to the chain olefin having 5 carbon atoms. A method for producing tertiary pentanol, which comprises performing a hydration reaction at a temperature of 20 ° C to 100 ° C in the presence.   The method for producing tertiary pentanol according to claim 1, wherein the solid acid catalyst is a strongly acidic ion exchange resin catalyst.   The method for producing tertiary pentanol according to claim 1 or 2, wherein the chain olefin having 5 carbon atoms is 2-methyl-1-butene, 2-methyl-2-butene or a mixture thereof.   The method for producing tertiary pentanol according to any one of claims 1 to 3, wherein the phenol is phenol, catechol, 4-chlorophenol, 2,4-xylenol, 2-naphthol, 4-nitrophenol or t-butylcatechol.