JPH07116072B2 - Method for producing alcohols - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Field of Industrial Application> The present invention relates to a method for producing alcohols, and more specifically, an industrial method for producing alcohols by hydrating olefins using a solid acid as a catalyst. Relates to an improved method.

<Prior Art> Many methods are already known for producing alcohols by hydrating olefins using a solid acid as a catalyst.

For example, ion exchange resins (Japanese Patent Publication No. 38-15619, Japanese Patent Publication No. 44-26656, Japanese Patent Publication No. 60-115542), mordenite, clinoptilolite, or faujasite zeolite (Japanese Patent Publication No. 47- 45323), ZSM type zeolite (JP-A-58-194828), mordenite or zeolite Y (JP-A-59-222431 and JP-A-59).
-222432) is known as a catalyst. Furthermore, many methods using these improved catalysts have been proposed. (JP-A-60-104028-104031, JP-A-
60-248632-248635 JP, JP 61-180735 JP,
Further, there has been proposed a production method in which an acid in an aqueous solution is allowed to coexist with a solid catalyst. (Unexamined-Japanese-Patent No. 60-252437) <Problem which an invention tries to solve> However, in the conventional method, the yield is very low and there is nothing industrially satisfactory.

In view of such circumstances, the present inventors have conducted extensive studies on a method for producing alcohols by hydrating olefins with a solid acid as a catalyst, and as a result, in the presence of fluoroalcohol. It was found that the yield of alcohols was improved by performing hydration, and the present invention was completed.

<Means for Solving Problems> That is, according to the present invention, when a solid acid is used as a catalyst to hydrate an olefin having 2 to 12 carbon atoms to produce an alcohol, the general formula (1) is used. The method for producing alcohols is characterized by hydrating in the presence of fluoroalcohol.

The solid acid used as the catalyst of the present invention may be any of mineral acids, metal salts, ion exchangers, and metal oxides.

Specific examples of the mineral acid type include phosphoric acid, heteropolyacid or a salt thereof supported on diatomaceous earth, silica gel, alumina or activated carbon, and silicic acid. As the metal salt system, Fe, Al, Cr, Co or Cu sulfate, or those obtained by supporting these on silica, B, Al, Cr, Zr, Fe
Alternatively, Mn phosphate or the like may be used. Examples of ion exchangers include sulfonic acid cation exchange resins, acid-treated or ion-exchanged montmorillonite, and the like. Metal oxides include tungsten oxide (WO ₃ , W ₂ O ₅ ) or ZnO, Cr ₂ O ₃ added to this, Al (OH) ₃ , SiO ₂ · Al ₂
O _3, zirconium _{tungstate, MoO 3, ZrO 3, TiO} 2 -SiO
₂ , TiO ₂ —ZnO, NbO ₃ · nH ₂ O and the like. (Catalysis Society,
"Catalyst Lecture Volume 8 (Industrial Catalysis, 2) Industrial Catalysis I", p295 (Tokyo, Kodansha) 1985) Other examples include various zeolites such as mordenite, clinoptilolite, and faujasite. Ferriolite, ZSM, AZ-1 (JP-A-59-128210), TPZ-
3 (JP-A-58-110419), Nu-3 (JP-A-57-8714),
Nu-5 (JP-A-57-129820), Nu-6 (JP-A-57-1238)
17), Nu-10 (JP-A-57-200218) and the like.

The catalyst may have any shape such as powder, granules or a molded body, and a carrier such as alumina or titania may be used when molding.

Examples of the olefins of the present invention include linear, branched, or cyclic olefins having 2 to 12 carbon atoms.

Specifically, as the linear olefin, for example, ethylene,
Propylene, 1-butene, 2-butene, 1-hexene,
2-hexene, 1,5-hexadiene, 1-octene, 2
-Octene, 1,7-octadiene, 1-dodecene and the like. Examples of the branched chain olefin include isobutene, 3-methyl-1-butene, 2,6-dimethyl-
1,7-octadiene and the like can be mentioned. Examples of the cyclic olefin include cyclopentene, cyclohexene,
Cyclooctene, 1,5-cyclooctadiene, cyclododecene, 1,5,9-cyclododecatriene and the like can be mentioned.

R ¹ of the fluoroalcohol of the general formula (1) used in the present invention is hydrogen, halogen, a lower alkyl group or a halogenated alkyl group, or an aryl group or a halogenated aryl group having 6 to 8 carbon atoms, R ² , Each R ³ is independently hydrogen, a lower alkyl group or a halogenated alkyl group, or an aryl group having 6 to 8 carbon atoms or a halogenated aryl group.

Examples of the lower alkyl group include CH _3- , C ₂ H _5- , CH ₃ (C
H ₂ ) _5- (CH ₃ ) ₂ CH-, (CH ₃ ) ₃ C- and the like can be mentioned. As the lower halogenated alkyl group, for example, CH ₂ F-, CHF _2- , CF _3- , C
H ₂ Cl-, CHCl _2- , CCl _3- , CHFCl-, CF ₂ Cl-, C ₂ F _5- , C ₂ F ₄ Cl-, C ₃ F
_{7 -, CH 2 Br (CH} 2) 5 -, CH 2 I (CH 2) 5 -, include _{(CF 3) 2 CF- (CF} 3) 3 C- , and the like.

Examples of the aryl group having 6 to 8 carbon atoms include C ₆ H ₅ —, CH
_{3 C 6 H 4 -, C} 2 H 5 C 6 H 4 -, (CH 3) 2 C 6 H 3 - , and the like. Examples of the halogenated aryl group having 6 to 8 carbon atoms include C ₆ H ₄
F-, C ₆ H ₃ F _2- , C ₆ F _5- , C ₆ H ₄ Cl-, C ₆ H ₄ Br-, C ₆ H ₄ I-, C ₆ H ₃ FCl-C _{6
F 4 Cl-CH 3 C 6} H 3 F-, CH 3 C 6 F 4 -, CF 3 C 6 F 4 -, include _{(CH 3) 2 C 6 H} 2 F- or the like.

Specific examples of the fluoroalcohol include CF ₃ CH ₂ OH, C
F ₃ CH (CH ₃ ) OH, CF ₃ C (CH ₃ ) ₂ OH, (CF ₃ ) ₂ CHOH, (CF ₃ ) ₃ COH, C ₃ F ₇
CH ₂ OH, C ₃ F ₇ CH (C ₃ H ₇ ) OH, (C ₃ F ₇ ) ₂ CHOH (C ₃ F ₇ ) ₃ COH, CHF ₂ CH ₂
OH, CF ₂ ClCF ₂ CH ₂ OH, (C ₆ H ₅ ) CH- (CF ₃ ) OH, C ₆ H ₅ CF ₂ CH ₂ OH, C ₆ F
₅ CF ₂ CH ₂ OH, etc.

Fluoroalcohol is about 0.01-10 per mole of olefin.
Used in moles. If it is less than about 0.01 mol, the effect is lost and it is not preferable.

The amount of water used in the present invention is usually about 1 per mol of olefin.
~ 100 mol. If the amount is less than 1 mol, the conversion rate of the olefin will be low, and if it is more than 100 mol, the separation of the alcohol will be disadvantageous.

In the batchwise reaction, the amount of the catalyst used is usually in the range of about 0.01 to 200, preferably 0.1 to 200 by weight with respect to the olefin.
Used in the range of up to 20.

The reaction is carried out at about 50 to 200 ° C, preferably 70 to 150 ° C.
When the reaction temperature is 50 ° C or lower, the reaction rate is slow and not practical.
If the reaction temperature is 200 ° C. or higher, the chemical equilibrium tends to the olefin side, which is not preferable.

The reaction pressure in the present invention is preferably at least the pressure required to keep the olefin in the liquid phase under the reaction conditions.
However, a low pressure may be used as long as the olefin is sufficiently dissolved in the reaction solution. The pressure can also be adjusted with an inert gas such as nitrogen gas.

The reaction system in the present invention may be either a batch system or a continuous system, and the continuous system may be a catalyst-filled continuous flow system or a stirring tank flow system.

<Effects of the Invention> According to the present invention, when hydrating olefins using a solid acid as a catalyst to produce alcohols, hydration is carried out in the presence of fluoroalcohol, so that the yield of alcohol is conventionally reduced. Significantly improved over the law.

<Examples> The present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto.

The alcohol yield used in the description is a value calculated using the following equation.

Reference Example 1 A catalyst was synthesized as follows.

First, a raw material liquid having the following composition was prepared.

(Solution A) Water 271g H ₂ SO ₄ 13.2g Al ₂ (SO ₄ ) ₃ / 16-18H ₂ O 4.6g (n-Pr) ₄ NBr 19.9g NaCl 46.9g (Solution B) Water 198g Sodium silicate No. 3 159g Next, the above-mentioned solution B was mixed with solution A. Mix 1 SuS
Prepared in an autoclave made for 72 hours at 120 ° C, then 160
Hydrothermal synthesis was carried out while stirring at 600C for 5 hours (600-700 rpm). After cooling, the mixture was filtered, washed sufficiently with a large amount (about 3 l) of distilled water, and filtration was repeated. After drying at 120 ° C for 15 hours, it was baked at 550 ° C for 3 hours in an air atmosphere to obtain white powdery crystals.

This was identified as ZSM-5 by X-ray diffraction measurement.

Next, 10 g of the Na-type ZSM-5 obtained above was ion-exchanged 4 times with 100 g of 5% ammonium chloride water at 60 ° C. for 1 hour, then filtered, and washed with distilled water. After drying at 120 ° C. for 16 hours, it was calcined in an air atmosphere at 550 ° C. for 3 hours to obtain a white powdery catalyst in which Na was replaced with hydrogen ions.

Example 1 In a glass ampoule tube having an internal volume of 10 ml, 0.6 g of the catalyst obtained in Reference Example 1, 0.9 g of cyclohexene, 1.8 g of water, 1,1,1,3,
0.3 g of 3,3-hexafluoro-2-propanol was added. The ampoule tube was sealed and reacted at 120 ° C. for 2 hours. Then, after cooling, the ampoule tube was opened and the contents were taken out. Then, n-propanol was added thereto to make the oil phase and the aqueous phase a uniform phase, and cyclohexanol was quantified by gas chromatography. As a result, the yield of cyclohexanol was 27.2%.

Example 2 Example 1 was repeated except that 2,1,2,2-trifluoroethanol was added instead of 1,1,1,3,3,3-hexafluoro-2-propanol.

As a result, the yield of cyclohexanol was 16.7%.

Comparative Example 1 Example 1 was repeated except that 1,1,1,3,3,3-hexafluoro-2-propanol was not added. As a result, the yield of cyclohexanol was 12.4%.

Claims (3)

[Claims] 1. A solid acid as a catalyst having 2 to 12 carbon atoms.
In producing alcohols by hydrating olefins of formula (1) And a method for producing alcohols, which comprises hydrating in the presence of a fluoroalcohol. 2. The olefins are cyclopentene, cyclohexene or cyclooctene.
The method for producing an alcohol according to the item. 3. The method for producing alcohols according to claim 1, wherein the fluoroalcohol is 1,1,1,3,3,3-hexafluoro-2-propanol.