JPH0676345B2 - Method for producing alcohols - Google Patents

Description

The present invention relates to a method for producing alcohols, more specifically, a method for producing alcohols by hydrating olefins using an inorganic solid acid as a catalyst. The present invention relates to an industrially excellent improvement method.

<Prior Art> A method for producing alcohols by hydrating olefins using an inorganic solid acid as a catalyst is already known.

Japanese Patent Publication No. 47-45323 proposes a method for producing alcohols by hydrating olefins using dealkalized mordenite, clinoptilolite, or faujasite zeolite as a catalyst. According to the description in the specification, in the hydration of ethylene, the conversion rate of the charged water to ethyl alcohol is 0.4 to 8.1%. Calculated from this description, the conversion rate of ethylene to ethyl alcohol is 0.1 to 1.6%. In the hydration of propylene, the conversion rate of the charged water to iso-propyl alcohol is 0.1 to 5.9%. Calculated from this description, the conversion of propylene to iso-propyl alcohol is 0.1-2.
It is 0.7%. In hydration of 1-butene, the conversion rate of the charged water to sec-butyl alcohol is 0.1 to 1.5%. Calculated from this description, the conversion rate of 1-butene to sec-butyl alcohol is 0.1 to 7.0%.

Furthermore, in the hydration of cyclohexene, the conversion rate of the charged water to cyclohexanol is 0.05 to 0.06%.
Calculated from this description, the conversion rate of cyclohexene to cyclohexanol is 0.07 to 0.08%.

According to JP-A-58-194828, cycloalkene is
A method has been proposed for producing a cycloalkanol by catalytically hydrating in the presence or absence of an organic solvent, using a crystalline aluminosilicate having a molar ratio of silica to alumina of 20 or more as a catalyst. There is. According to the description in the specification, cyclohexene catalyzed by ZSM-5 zeolite (molar ratio of silica to alumina of 60 and 25) and ZSM-12 (70) developed by Mobil Oil Co. is used. In hydration, the cyclohexanol yield is 9 to 15%. When 50 g of various organic solvents are added to 10 g of cyclohexene, the cyclohexanol yield is 25 to 32%.

According to JP-A-59-222431, there is proposed a method for producing alcohols by hydrating an olefin in the presence of hydrogen-type mordenite having a silica / alumina (molar ratio) of 20 to 500 or hydrogen-type zeolite Y. Has been done. According to the description therein, the yield of secondary butanol is 1.0 to 11.5% in the hydration of 1-butene. In the hydration of other olefins, the yield of each alcohol is
Ethanol is 6.8%, isopropanol is 18%, secondary butanol is 10%, 2-pentanol is 6.5%, 2-hexanol is 5.6%, and cyclohexanol is 5.1%.

According to JP-A-59-222432, there is disclosed a method for producing an alcohol by hydrating an olefin in the presence of hydrogen type mordenite having a silica / alumina (molar ratio) of 20 to 500 or hydrogen type zeolite Y and sulfone. Proposed.
According to the description therein, in the hydration of 1-butene, the yield of secondary butanol is 16.1% in the presence of dimethyl sulfone. In the hydration of other olefins, the yield of each alcohol is 6.7% for ethanol,
Isopropanol 12.4%, secondary butanol 13.3
%, 2-pentanol 8.8%, 2-hexanol 7.5
%, And cyclohexanol is 8.2%.

According to JP-A-60-104028, a cyclic alcohol is produced by catalytic hydration of a cyclic olefin in a liquid phase using a crystalline aluminosilicate having a ratio of external acid points to total acid points of 0.07 or more. A method has been proposed. According to the description in the specification, in the hydration of cyclohexanol, the concentration of the oil phase after the reaction was 3.5 to 22.8% by weight. Although there is no description about the yield of cyclohexanol, according to the description of Example 4, the cyclohexanol concentration in the oil phase was 22% by weight, and the cyclohexanol concentration in the aqueous phase was 2%. No product was detected. Assuming that the oil phase consists of cyclohexanol and cyclohexene and the aqueous phase consists of cyclohexanol and water, the yield of cyclohexanol is 21.4%.

According to JP-A-60-104029, a cyclic olefin is catalytically hydrated using a mordenite, faujasite or ferriolite type zeolite having a silica to alumina molar ratio of at least 20 as a catalyst to produce a cyclic alcohol. The method of doing is proposed. According to the description in the specification, the yield of cyclohexanol is 8.5 to 14.2%.
Is.

According to JP-A-60-104030, the general formula M ₂ O ・ Al ₂ O ₃・ XSi
O ₂ (In the formula, M represents at least one of an alkali metal ion, an ammonium ion and a hydrogen ion, and X is 10 to 10
Part of the alkali metal ion and / or ammonium ion of the crystalline aluminosilicate having a composition corresponding to 1000) and characterized in the X-ray diffraction pattern by a certain diffraction angle (2θ) and relative intensity. Or using a catalyst in which all are replaced with hydrogen ions,
A method of hydrating a cycloolefin to produce a cycloalkanol has been proposed. According to the description in the specification, the conversion of cyclohexene is 6.8 to 12.3% and the selectivity of cyclohexanol is 90 to 100%. Calculated from this description, the yield of cyclohexanol is 6.1-12.3%.

According to JP-A-60-104031, a part of aluminum contained in the zeolite is removed as a catalyst, silicon from an external source is further arranged at the position of the skeleton structure, and the molar ratio of silica to alumina is at least 20. In addition to the above, a method for producing a cyclic alcohol by catalytically hydrating a cyclic olefin using a zeolite having a reduced content of defect sites in the crystal structure has been proposed. According to the description therein, the yield of cyclohexanol was 7.8.
~ 12.7%.

<Problems to be Solved by the Invention> In the method for producing alcohols by hydrating olefins, in order to recover alcohols produced from the mixture after the reaction, unreacted olefins and water are removed. There must be. Since the removal of olefins and water is performed by distillation or the like, a large amount of heat is required and it is expensive. Therefore, it is preferable that the amount of unreacted olefins and water is small, in other words, the yield of alcohols is preferably high.

However, in the conventional method, the yield is very low, and nothing is industrially satisfactory.

An object of the present invention is to improve the yield and to find an industrially advantageous method.

<Means for Solving Problems> In view of such circumstances, the inventors of the present invention have keenly studied a method of producing an alcohol in a high yield by using an inorganic solid acid as a catalyst to hydrate an olefin. As a result of repeated studies, it was found that the yield of alcohols was improved by performing hydration in the presence of phenols, and the present invention was completed.

That is, the present invention is a method for producing alcohols, which comprises hydrating olefins using an inorganic solid acid as a catalyst to produce alcohols, and performing hydration in the presence of phenols. .

The inorganic solid acid used as a catalyst in the method of the present invention is
Any of a mineral acid type, a metal salt type, an ion exchanger and a metal oxide type may be used. Specifically, examples of the mineral acid type include phosphoric acid, heteropolyacid or a salt thereof supported on diatomaceous earth, silica gel, alumina, activated carbon, and silicic acid. As a metal salt system, sulfates of Fe, Al, Cr, Co, Cu or those supporting these on silica, B, Al, Cr, Zr, F
e, Mn phosphate, etc. Ion exchangers include montmorillonite treated with acid or ion exchange. As a metal oxide system, tungsten oxide (WO ₃ , W ₂ O
₅ ) or ZnO, Cr ₂ O ₃ added to this, Al (OH) ₃ , Si
O ₂ · Al ₂ O ₃ , zirconium tungstate, MoO ₃ -ZrO ₂ , Ti
There are O ₂ —SiO ₂ , TiO ₂ —ZnO, NbO ₃ · nH ₂ O, and the like. (Cited documents,
The Catalyst Society of Japan, "Catalyst Lecture Volume 8 (Industrial Catalysis, 2) Industrial Catalysis I", p295 (Tokyo, Kodansha) 1985) Other specific examples include various zeolites such as mordenite,
Clinoptilolite, faujasite, ferriolite, ZSM, AZ-1 (JP-A-59-128210), TPZ-3 (JP-A-58-
110419), Nu-3 (JP-A-57-3714), Nu-5 (JP-A-57-12)
9820), Nu-6 (JP-A-57-123817), Nu-10 (JP-A-57-2)
00218) and the like.

In the method of the present invention, the olefin used as a raw material is preferably a linear, branched or cyclic olefin having 12 or less carbon atoms. Examples of the linear olefin include 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, and 2,6-dimethyl-1,7-octadiene. Examples of cyclic olefins include cyclopentene, cyclohexene, cyclooctene, 1,5-cyclooctadiene, cyclododecene, and 1,5,9-cyclododecatriene.

Phenols used in the method of the present invention are phenol and substituted phenols, which are compounds having one or more hydroxyl groups directly substituted on the benzene ring.

Specific examples of the phenols used in the method of the present invention are compounds of the following formula.

In the formula, R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are each independently hydrogen, lower alkyl group, phenyl group, substituted phenyl group, halogen, hydroxyl group, lower alkoxyl group, lower alkoxycarbonyl group, carboxyl group. , Nitro group, mercapto group,
Examples include lower alkylthio groups and sulfonic acid groups. Also R ¹
It is also possible to form a benzene ring with any two adjacent ones of R to R ⁵ and the carbon atom of the benzene ring to which these two are bonded.

Examples of phenols include phenol, cresol, xylenol, trimethylphenol, ethylphenol, i-propylphenol, t-butylphenol,
Phenylphenol, toluylphenol, chlorophenol, bromphenol, iodophenol, pyrocatechol, resorcin, hydroquinone, pyrogallol, hydroquinone monomethyl ether, methyl salicylate, salicylic acid, 4-hydroxybenzoic acid, nitrophenol, mercaptophenol, methylthio, phenol, phenol Examples thereof include sulfonic acid, 1-naphthol, 2-naphthol and sulfosalicylic acid.

The amount of phenols is about 0.01 to 10 mol per mol of olefin.

The amount of water in the method of the present invention is usually about 1 to 100 mol per mol of olefin.

The reaction temperature in the method of the present invention is 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. Further, if the reaction temperature is 200 ° C or higher, the chemical equilibrium tends to the olefin side, which is disadvantageous.

The reaction pressure in the method of the present invention is preferably not less than the pressure required to keep the olefin in the liquid phase under the reaction conditions. However, the pressure may be such that 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 method of 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 Present Invention> According to the present invention, when an olefin is hydrated using an inorganic solid acid as a catalyst to produce an alcohol, hydration is performed in the presence of a phenol to give an alcohol The yield is significantly improved over the conventional method.

<Example> In order to describe the method of the present invention more specifically, the following examples will be described, 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 (Synthesis of catalyst ZSM-5) First, a raw material liquid having the following compositions was prepared.

Liquid A Water 433g H ₂ SO ₄ 44.8g Al ₂ (SO ₄ ) ₃・ 17H ₂ O 15.5g (n-Pr) ₄ NBr 54.3g Liquid B Water 320g Sodium No. 3 Silica 498g Liquid C Water 754g NaCl 172g Above C Liquid A and liquid B were simultaneously added dropwise to the liquid and mixed. At this time, vigorous stirring was performed while maintaining the pH in the system at 9-11.
(A few drops of 48% NaOH aqueous solution were added for pH adjustment.) The pH at the end of mixing was 9.5. The mixture was placed in a SUS autoclave (1) and stirred at 160 ° C for 20 hours (350
Hydrothermal synthesis was performed. After cooling, the mixture was filtered, washed thoroughly with a large amount (~ 7 l) of distilled water, and filtered repeatedly. 120
After drying at ℃ for 15 hours, it was baked at 530 ℃ for 3 hours under air flow to obtain white powdery crystals. This was identified as ZSM-5 by X-ray diffraction measurement. As a result of analysis by an atomic absorption method, the SiO ₂ / Al ₂ O ₃ mole ratio was 64.

Next, the Na-type ZSM-5 obtained above was subjected to ion exchange with 200 g of 5% ammonium chloride water at 65 ° C. for 2 hours four times and then passed. The washing with 200 g of distilled water was repeated 5 times, and the washing was repeated. After drying at 120 ° C. for 10 hours, it was baked at 500 ° C. for 3 hours under air flow to obtain white powdery crystals.

Example 1 In a glass ampoule tube having an internal volume of 10 ml, 0.6 g of "ZSM-5" obtained in Reference Example 1, 0.9 g of cyclohexene, 1.8 g of water and 0.9 g of phenol were put. The ampoule tube was sealed and reacted at 100 ° C. for 8 hours. Then, after cooling, the ampoule tube was opened, the contents were taken out, and 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 41.9%.

Example 2 An experiment was conducted in the same manner as in the method of Example 1, except that salicylic acid was used instead of phenol. As a result, the yield of cyclohexanol was 38.9%.

Example 3 An experiment was conducted in the same manner as in Example 1 except that 1-naphthol was added instead of phenol.
As a result, the yield of cyclohexanol was 32.6%.

Example 4 An experiment was performed in the same manner as in the method of Example 1, except that the reference catalyst "JRC-Z-HM20" of the Japan Catalysis Society was added in place of "ZSM-5" and the reaction was carried out at 130 ° C. As a result, the yield of cyclohexanol was 17.9%.

Example 5 An experiment was performed in the same manner as in the method of Example 1, except that the reference catalyst "JRC-Z-HM15" of the Society of Catalysis of Japan was added instead of "ZSM-5" and the reaction was carried out at 130 ° C. As a result, the yield of cyclohexanol was 15.8%.

Example 6 In a glass autoclave having an internal volume of 100 ml, 5 g of "ZSM-5" obtained in Reference Example 1, 7.5 g of cyclohexene, 15 g of water and 7.5 g of phenol were placed. Autoclave sealed and 100 ° C
And reacted for 4 hours with stirring. After cooling and opening, the oil phase was taken out and found to be 13.9 g. Cyclohexanol was quantified by gas chromatography. As a result, the concentration of cyclohexanol was 19.8% by weight. The concentration of cyclohexanol in the aqueous phase was 1.6% by weight. Therefore, the yield of cyclohexanol was 32.9%.

Comparative Example 1 An experiment was conducted in the same manner as in Example 6 except that phenol was not added. As a result, the oil phase is 8.
There was 2 g, and the cyclohexanol concentration was 8.0% by weight. The concentration of cyclohexanol in the water phase is 1.9% by weight.
Met. Therefore, the yield of cyclohexanol is 10.1.
%Met.

Reference Example 2 First, a raw material liquid having the following compositions was prepared.

Liquid 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 Liquid B Water 198g Sodium silicate No. 3 159g Above liquid B Then, the solution A was mixed. The mixture was placed in a SUS autoclave (1) and heated at 120 ° C for 72 hours and then at 160 ° C for 5 hours.
Hydrothermal synthesis was carried out while stirring for hours (600-700 rpm).
After cooling, the mixture was filtered, washed sufficiently with a large amount (~ 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 powder 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 four times with 100 g of 5% aqueous ammonium chloride at 60 ° C. for 1 hour, filtered, and washed with distilled water.

After drying at 120 ° C for 16 hours, it was baked at 500 ° C for 3 hours in an air atmosphere to obtain white powdery crystals.

Example 5 In a glass ampoule tube having an internal volume of 10 ml, 0.6 g of "ZSM-5" obtained in Reference Example 2, 0.9 g of cyclohexene, 1.8 g of water, m-
0.3 g of cresol 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 28.2%.

Examples 6 to 13 The procedure of Example 5 was repeated, except that the phenols shown in Table 1 were used instead of m-cresol. The results are shown in Table 1.

Comparative Example 2 The procedure of Example 5 was repeated except that m-cresol was not added. As a result, the yield of cyclohexanol was 12.4%.

Claims (1)

[Claims] 1. A method for producing alcohols, which comprises hydrating olefins to produce alcohols using an inorganic solid acid as a catalyst, wherein hydration is performed in the presence of phenols.