JP5856841B2 - Method for producing Gerve alcohol - Google Patents

Description

  The present invention relates to a method for producing Gerve alcohol.

When alcohol is dehydrated and condensed in the presence of a base catalyst, one molecule of β-branched alcohol is obtained from two molecules of raw alcohol. This reaction is called a Gerber reaction, and β-branched alcohol obtained by the Gerber reaction is called Gerber alcohol.
Taking the case of using a primary alcohol as the raw material alcohol as an example, it is estimated that the reaction mechanism of the Gerbe reaction consists of the following elementary reactions (1) to (4).
(1) Formation of aldehyde by dehydrogenation of alcohol (2) Formation of α, β-unsaturated aldehyde by aldol condensation of aldehyde (3) Generation of allyl alcohol by reduction of α, β-unsaturated aldehyde (4) Allyl Formation of Gerve Alcohol by Reduction of Alcohol In the conventional method for producing Gerve alcohol, in order to perform the reaction at a high temperature in the presence of a base catalyst, the aldehyde generated by the dehydrogenation of the alcohol of (1) above reacts with the base catalyst As a result, a fatty acid salt (hereinafter, the fatty acid salt may be referred to as “soap”) is produced as a by-product. When the side reaction occurs, the rate of the Gelbe reaction decreases due to consumption of the catalyst, and further, the load in the purification process such as filtration increases due to the by-product of soap.

Many examples using a base catalyst and a zinc compound as a catalyst have been reported for the purpose of improving the reaction rate in the Guerbe reaction and suppressing the by-product of soap. For example, Patent Document 1 discloses a method for producing an alcohol using an organic zinc compound such as potassium hydroxide as a base catalyst and zinc carboxylate or a zinc complex of β-diketone as a zinc compound. Patent Document 2 discloses a method for producing Gerve alcohol using potassium hydroxide as a base catalyst and zinc oxide as a zinc compound.
However, in the methods described in Patent Documents 1 and 2, the reaction rate is improved, but soap by-products cannot be sufficiently suppressed. In the method described in Patent Document 1, it is difficult to separate a zinc carboxylate or a β-diketone zinc complex from Gerve alcohol.
Furthermore, Patent Document 3 discloses a method for producing gerbe alcohol in which an alkaline substance, a dehydrogenation catalyst, and an oxide mainly composed of SiO ₂ are added and reacted. According to this production method, by-product of soap is suppressed, but since a relatively expensive catalyst is essential, development of a cheaper method is desired.

Japanese Patent Laid-Open No. 49-10008 US Pat. No. 5,777,183 JP-A-9-227424

  An object of the present invention is to provide a cheaper production method that can produce gelve alcohol in high yield from an aliphatic alcohol with little soap by-product.

The present inventors have found that the above problem can be solved by reacting an aliphatic alcohol in the presence of a base catalyst and a specific cocatalyst.
That is, the present invention provides a primary and / or secondary aliphatic alcohol in the presence of a base catalyst (A) containing an alkali metal or an alkaline earth metal and a cocatalyst (B) containing a zinc element. A method for producing Gerve alcohol, wherein the cocatalyst (B) is the following (b-1) and / or (b-2).
(B-1) Zinc compound, and solid metal oxide containing one kind of metal element selected from aluminum and metal elements belonging to Group 4, 8, and 10 of the periodic table (long period type) (b-2) Zinc Solid composite metal oxide containing an element, and one or more metal elements selected from aluminum and metal elements belonging to Groups 4, 8, and 10 of the periodic table (long-period type)

  According to the present invention, by using a base catalyst and a specific cocatalyst containing zinc, it is possible to suppress the by-product of soap in the Gerbe reaction, and to produce Gerve alcohol at a low cost and in a high yield.

It is a graph which shows the relationship of the alcohol conversion rate and soap byproduct rate in the comparative example 3.

The method for producing Gerve alcohol according to the present invention comprises a primary and / or secondary aliphatic alcohol, a base catalyst (A) containing an alkali metal or an alkaline earth metal, and a cocatalyst containing zinc element ( A method for producing Gerve alcohol to be reacted in the presence of B), wherein the cocatalyst (B) is the following (b-1) and / or (b-2).
(B-1) Zinc compound, and solid metal oxide containing one kind of metal element selected from aluminum and metal elements belonging to Group 4, 8, and 10 of the periodic table (long period type) (b-2) Zinc Solid composite metal oxide containing an element, and one or more metal elements selected from aluminum and metal elements belonging to Groups 4, 8, and 10 of the periodic table (long-period type)

[Primary and / or secondary aliphatic alcohol]
Examples of the aliphatic alcohol used as a raw material in the present invention include primary and / or secondary aliphatic alcohols (hereinafter, also simply referred to as “raw alcohol”). A primary aliphatic alcohol is preferred. Among these, when a primary aliphatic alcohol having 4 to 22 carbon atoms, and further 8 to 18 carbon atoms is used, a purification load due to a soap component by-produced from the alcohol is increased. The effect of suppressing soap by-product, which is one of the problems, is remarkably exhibited.
Specific examples of the primary aliphatic alcohol include 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, 1 -Saturated linear alcohols such as tetradecanol, 1-hexadecanol, 1-octadecanol, 1-eicosanol, 1-docosanol; saturated alicyclic alcohols such as cyclohexanemethanol, cyclohexylethyl alcohol; oleyl alcohol, citronellol, etc. Of unsaturated alcohol.
Specific examples of the secondary aliphatic alcohol include 2-butanol, 2-pentanol, 2-hexanol, 2-heptanol, 2-octanol, 2-nonanol, 2-decanol, 2-undecanol, 2-dodecanol, 2 -Saturated linear alcohols such as tridecanol, 2-tetradecanol, 2-pentadecanol, 2-hexadecanol, 2-heptadecanol, 2-octadecanol, 2-nonadecanol, 2-eicosanol, 2-docosanol Etc.
These raw material alcohols can be used singly or in combination of two or more.

[Base catalyst containing alkali metal or alkaline earth metal (A)]
Examples of the base catalyst (A) containing alkali metal or alkaline earth metal used in the present invention (hereinafter also simply referred to as “base catalyst”) include alkali metals or alkaline earth metals, hydrides thereof, and hydroxides. Products, carbonates, bicarbonates and alkoxides.
Specific examples of alkali metal or alkaline earth metal hydrides, hydroxides, carbonates, bicarbonates include alkali metal hydroxides such as LiOH, NaOH, KOH, RbOH, CsOH, Li ₂ CO ₃ , Na Alkali metal carbonates such as ₂ CO ₃ , K ₂ CO ₃ , Rb ₂ CO ₃ , and Cs ₂ CO ₃ , Alkali metal bicarbonates such as LiHCO ₃ , NaHCO ₃ , KHCO ₃ , RbHCO ₃ , and CsHCO ₃ , Mg (OH ) ₂ and alkaline earth metal hydroxides such as Ca (OH) ₂ . The above base catalyst may be used as a solid such as pellets or as an aqueous solution.
Specific examples of the alkali metal or alkaline earth metal alkoxide include sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium methoxide, potassium ethoxide, potassium t-butoxide and the like.
Among the above basic catalysts, from the viewpoint of reaction rate, alkali metal hydroxides such as LiOH, NaOH, KOH, RbOH and CsOH, which are strong bases, are preferred, and KOH, RbOH and CsOH are more preferred.
A base catalyst (A) can be used individually by 1 type or in combination of 2 or more types.
The amount of the base catalyst (A) used accelerates the Gerve reaction, which is the main reaction, and suppresses the side reaction of soap, which is a side reaction (reaction between the aldehyde generated by the dehydrogenation of alcohol and the base catalyst). From the viewpoint, 0.01 to 15 mol% is preferable with respect to the raw material alcohol, 0.3 to 10 mol% is more preferable, 0.5 to 5 mol% is further preferable, and 1 to 5 mol% is still more preferable. .

[Cocatalyst containing elemental zinc (B)]
In the method for producing Gerve alcohol of the present invention, in addition to the base catalyst (A), a cocatalyst (B) containing a specific zinc element (hereinafter also simply referred to as “cocatalyst”) is used. By using the cocatalyst (B), it is possible to suppress the by-product of soap and to obtain Gerve alcohol in a high yield.

The cocatalyst (B) used in the present invention is the following (b-1) and / or (b-2).
(B-1) Zinc compound, and solid metal oxide containing one kind of metal element selected from aluminum and metal elements belonging to Group 4, 8, and 10 of the periodic table (long period type) (b-2) Zinc A solid composite metal oxide containing an element and one or more metal elements selected from aluminum and a metal element belonging to Group 4, 8, and 10 of the periodic table (long-period type), (b-1), ( b-2) Each will be described. In the following description, “a metal element belonging to Group 4, 8, 10” of the periodic table (long period type) is also simply referred to as “metal element belonging to Groups 4, 8, 10”.

<(B-1) Zinc Compound, and Solid Metal Oxide Containing One Type of Metal Element Selected from Aluminum and Periodic Table (Long Period Type) Metal Elements belonging to Groups 4, 8, and 10>
The component (b-1) used in the present invention is a solid metal oxide containing a zinc compound and one metal element selected from aluminum and a metal element belonging to Groups 4, 8, and 10 (hereinafter simply referred to as “ Co-catalyst combined with “solid metal oxide”. The term “solid” as used herein refers to a substance that is insoluble in the reaction system of the Gerbe reaction described later or that has low solubility and does not dissolve completely uniformly.

(Zinc compound)
Examples of the zinc compound used in the component (b-1) in the present invention include zinc oxide, zinc chloride, zinc acetate, zinc acetylacetonate and the like. From the viewpoint of improving the reaction rate and suppressing soap by-product, oxidation It is preferable to use zinc. As the zinc compound, a commercially available product may be used as it is, or it may be used after usual purification such as washing and drying. Further, the zinc compound may be used in a solid state, or may be a raw material alcohol, or one dissolved or dispersed in a small amount of water or a solvent.
The said zinc compound can be used individually by 1 type or in combination of 2 or more types.

(Solid metal oxide containing one metal element selected from aluminum and metal elements belonging to Groups 4, 8, and 10)
In the present invention, the solid metal oxide used as the component (b-1) contains one metal element selected from aluminum and metal elements belonging to Groups 4, 8, and 10. From the viewpoint of suppressing soap by-product, the metal element is preferably selected from aluminum, titanium, iron and nickel, and more preferably aluminum.
The “solid metal oxide” here does not include a solid composite metal oxide defined as the component (b-2) described later.
Examples of the solid metal oxide containing aluminum include alumina such as α-alumina and γ-alumina, and α-alumina and γ-alumina are preferable because of excellent reaction rate improvement and suppression of soap by-product, γ-alumina is more preferred.
As the solid metal oxide, a commercially available product may be used as it is, or it may be used after usual purification such as washing and drying. Further, the solid metal oxide may be used in a solid state, or may be a raw material alcohol, or one dissolved or dispersed in a small amount of water or a solvent.
The said solid metal oxide can be used individually by 1 type or in combination of 2 or more types.

The molar ratio of zinc compound to solid metal oxide (zinc compound / solid metal oxide) is preferably 10/90 to 90/10 from the viewpoint of suppression of soap by-products, and is preferably 50/50 to 85 / 15 is more preferable, and 60/40 to 80/20 is still more preferable.
Moreover, in the Gerbe reaction mentioned later, there is no restriction | limiting in particular in the order which adds a zinc compound and a solid metal oxide, You may mix and add simultaneously, and may add individually.

<(B-2) Solid composite metal oxide containing zinc element and one or more metal elements selected from aluminum and metal elements belonging to Group 4, 8, 10>
In the present invention, the solid composite metal oxide used for the component (b-2) (hereinafter also simply referred to as “(b-2) component” or “solid composite metal oxide”) is composed of zinc element, aluminum and It is a composite metal oxide containing one or more metal elements selected from metal elements belonging to Groups 4, 8, and 10 as essential components.
One or more metal elements selected from aluminum and metal elements belonging to Groups 4, 8, and 10 are made of aluminum, titanium, iron, and nickel in the same manner as (b-1) from the viewpoint of suppressing soap by-product. At least one selected from the above is preferable, and aluminum is more preferable.
Specific examples of the component (b-2) include Zn—Al—O, Zn—Ti—O, Zn—Fe—O, and Zn—Ni—O. The said solid complex metal oxide can be used individually by 1 type or in combination of 2 or more types.
In the component (b-2), the molar ratio (zinc element / metal element) between the zinc element and one or more metal elements selected from aluminum and metal elements belonging to Groups 4, 8, and 10 is the reaction rate. From the viewpoint of improvement and suppression of soap by-products, it is preferably 40/60 to 95/5, more preferably 50/50 to 90/10, and further preferably 60/40 to 80/20. preferable.

The solid composite metal oxide which is the component (b-2) used in the present invention can be prepared by a known method such as a precipitation method or an impregnation method.
In the precipitation method, a soluble precursor of the other metal is hydrolyzed and precipitated in the presence of zinc or aluminum and an oxide of one of the metals of Group 4, 8, and 10. , Zinc and aluminum, and soluble precursors of Group 4, 8, 10 metals are hydrolyzed and precipitated. In the impregnation method, an oxide powder of one of zinc or aluminum and a metal of Group 4, 8, or 10 is impregnated with a solution of a soluble precursor of the other metal, and then a solvent. The desired solid composite metal oxide particles can be obtained by distilling off.
The above-mentioned “soluble precursor of metal” refers to a compound containing zinc, aluminum, a metal element belonging to Groups 4, 8, and 10, which is soluble in an organic solvent such as methanol or a solvent such as water, Examples of the compound include inorganic metal salts such as nitrates of the metal, organic complexes of metals or metal oxides, and the like.

As the cocatalyst (B) in the present invention, either one of the above (b-1) and (b-2) may be used, or (b-1) and (b-2) may be used in combination. Good. It is preferable to use (b-1) from the viewpoint of improving the reaction rate and suppressing soap by-product, and it is preferable to use (b-2) from the viewpoint of handleability.
The amount of the cocatalyst (B) used is preferably 0.001 to 1% by mass, and 0.005 to 0.5% by mass with respect to the raw material alcohol, from the viewpoint of improving the reaction rate and suppressing soap by-product. %, Preferably 0.01 to 0.2% by mass.
The cocatalyst (B) does not require a carrier, but activated carbon, silica, clay mineral, etc. may be used as a carrier as necessary.

  The mass ratio [(B) / (A)] of the cocatalyst (B) to the base catalyst (A) is preferably 0.005 to 10 from the viewpoint of improving the reaction rate and suppressing soap by-product, More preferably, it is 0.01-5, and it is still more preferable that it is 0.01-1.

[Guerbe reaction]
In the method for producing Gerve alcohol of the present invention, primary and / or secondary aliphatic alcohols are subjected to dehydration condensation in the presence of a base catalyst (A) and a cocatalyst (B) (Gerbe reaction).
The reaction temperature in the Guerbe reaction is preferably 150 ° C. or higher, and more preferably 180 ° C. or higher, from the viewpoint of favoring the alcohol dehydrogenation reaction. On the other hand, the reaction temperature is preferably 280 ° C. or lower, more preferably 250 ° C. or lower, from the viewpoint of suppressing soap by-product.
The pressure during the reaction may be any of reduced pressure, normal pressure and increased pressure. In order to efficiently remove the water produced as a by-product by the dehydration condensation reaction and advance the dehydration condensation efficiently, the pressure during the reaction is preferably 100 kPa or less, more preferably 30 kPa or less, and more preferably 10 kPa or less. More preferably it is. On the other hand, when a low-boiling point alcohol is used as the raw material alcohol, the reaction is preferably carried out in a pressurized state from the viewpoint of maintaining a liquid phase state at a reaction temperature suitable for the Gerve reaction. From the viewpoint of ease of operation, normal pressure is preferred.
Although there is no restriction | limiting in particular in the lower limit of the pressure at the time of reaction, It is preferable that it is more than the pressure at which raw material alcohol boils at the temperature at the time of reaction. In addition, it is not necessary to maintain a constant pressure from the initial stage to the late stage of the reaction.

The combination of temperature and pressure during the reaction can be easily removed from the reaction system by azeotropic boiling with the raw alcohol or solvent used as necessary from the viewpoint of water removal and suppression of soap by-products. It is preferable to select such a combination of temperature and pressure. The raw alcohol and solvent azeotroped with water can be returned to the reaction system after being separated.
The reaction is preferably carried out in an inert gas atmosphere from the viewpoint of preventing degradation due to oxidation or the like of the generated Gerve alcohol, and from the viewpoint of removing by-product water, the inert gas is preferably distributed as a carrier. .
As the inert gas, nitrogen, argon, carbon dioxide gas or the like is preferably used.
The inert gas can be circulated by a method of circulating the reaction solution above or a method of bubbling in the reaction solution. There is no particular limitation on the flow rate of the inert gas, but it is desirable to adjust the flow rate appropriately so that by-product water can be efficiently removed and loss due to entrainment is prevented. From the above viewpoint, the flow rate of the inert gas is preferably 0.1 to 5 V / min, more preferably 0.5 to 2 V / min with respect to the volume V of the reactor.

Although there is no restriction | limiting in particular in the preparation order of raw material alcohol, a base catalyst (A), and a cocatalyst (B), When performing cross-reaction using 2 or more types of alcohol as raw material alcohol, it is hard to produce a gel reaction independently. It is preferable that the alcohol is charged first and the reaction is carried out while dripping the alcohol that tends to cause a Gelbe reaction alone.
Although reaction time is not specifically limited, The shorter one is preferable, 1 to 20 hours are preferable and 1 to 10 hours are more preferable.

  In the method for producing Gerve alcohol of the present invention, a reaction solvent may be used as necessary in order to control the viscosity of the reaction solution or to facilitate water removal. When the reaction solvent is used, the amount used is not particularly limited, but is preferably 10 to 500% by mass, more preferably 20 to 200% by mass with respect to the raw material alcohol.

After the reaction, the yield of Gerve alcohol can be improved by further reducing the aldehyde group and unsaturated bond of the intermediate product.
After the reaction, purified Gerve alcohol is obtained through normal purification steps such as filtration, washing with water, distillation and recrystallization. According to the method of the present invention, since there is little by-product of soap, high-purity Gerve alcohol can be obtained only by a simple refining operation such as passing through a cartridge type small filtration filter.

[Preparation Examples 1 to 6: Preparation of zinc compound and solid composite metal oxide]
A zinc compound and a solid composite metal oxide used for the cocatalyst were prepared by the methods described in Preparation Examples 1 to 6 below. In addition, the zinc element / metal element molar ratio (hereinafter referred to as “Zn / M ratio”) of the solid composite metal oxide Zn—MO (M: metal element) containing zinc element in Preparation Examples 2 to 6 .) Was determined by ICP emission spectroscopy.

(Preparation Example 1) Preparation of ZnO particles by precipitation method 89 g of zinc nitrate hexahydrate (manufactured by Kanto Chemical Co., Inc.) is put in a 500 mL beaker, and 368 g of ion-exchanged water is added and dissolved to obtain 0.75 mol / L. An aqueous zinc nitrate solution was prepared. Next, 64 g of sodium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) was put in a 2 L beaker, and 600 mL of ion exchange water was added and dissolved to prepare a 1.0 mol / L sodium carbonate aqueous solution.
The zinc nitrate aqueous solution was added dropwise to the sodium carbonate aqueous solution at room temperature over 30 minutes. After completion of dropping, the precipitated white precipitate was filtered under reduced pressure, and the resulting cake was washed with 300 mL of ion-exchanged water. The cake was reslurried, filtered and washed twice with water, then dried at 120 ° C. for one day, and further calcined at 400 ° C. for 3 hours to obtain ZnO particles.

(Preparation Example 2) Preparation of Zn—Al—O composite oxide particles by impregnation method 3.5 g of aluminum nitrate nonahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was placed in a 500 mL eggplant flask, and 100 g of ion-exchanged water was added. In addition, it was completely dissolved. To this, 3.0 g of the ZnO particles of Preparation Example 1 was added, and concentrated using a rotary evaporator until no liquid was left. It was dried at 120 ° C. for one day and further calcined at 400 ° C. for 3 hours to obtain Zn—Al—O particles as a solid composite metal oxide. The obtained Zn—Al—O particles had a Zn / Al ratio (molar ratio) of 80/20.

Preparation Example 3 Preparation of Zn—Ti—O Composite Oxide Particles by Impregnation Method Into a 500 mL eggplant flask, 1.8 g of tetraisopropyl orthotitanate was added, and 100 g of dehydrated methanol was added and completely dissolved. To this, 2.0 g of the ZnO particles of Preparation Example 1 was added, and then concentrated using a rotary evaporator until there was no liquid. It was dried at 120 ° C. for one day and further calcined at 400 ° C. for 3 hours to obtain Zn—Ti—O particles as a solid composite metal oxide. The obtained Zn—Ti—O had a Zn / Ti ratio (molar ratio) of 80/20.

(Preparation Example 4) Preparation of Zn—Fe—O composite oxide particles by impregnation method 3.7 g of iron nitrate nonahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was placed in a 500 mL eggplant flask, and 100 g of ion-exchanged water was added. In addition, it was completely dissolved. To this, 3.0 g of the ZnO particles of Preparation Example 1 was added, and then concentrated using a rotary evaporator until the liquid disappeared. It was dried at 120 ° C. for one day and further calcined at 400 ° C. for 3 hours to obtain a solid composite metal oxide Zn—Fe—O. The obtained Zn—Fe—O had a Zn / Fe ratio (molar ratio) of 80/20.

(Preparation Example 5) Preparation of Zn—Ni—O composite oxide particles by impregnation method 2.68 g of nickel nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was placed in a 500 mL eggplant flask, and 100 g of ion-exchanged water was added. In addition, it was completely dissolved. To this, 3.00 g of the ZnO particles of Preparation Example 1 was added, and then concentrated using a rotary evaporator until there was no liquid. It was dried at 120 ° C. for one day and calcined at 400 ° C. for 3 hours to obtain Zn—Ni—O which is a solid composite metal oxide. The obtained Zn—Ni—O had a Zn / Ni ratio (molar ratio) of 80/20.

Preparation Example 6 Preparation of Zn—Al—O Composite Oxide Particles by Impregnation Method 9.22 g of aluminum nitrate nonahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) and 3.00 g of ZnO particles of Preparation Example 1 Except for this, Zn—Al—O particles, which are solid composite metal oxides, were obtained in the same manner as in Preparation Example 2. The obtained Zn—Al—O particles had a Zn / Al ratio (molar ratio) of 60/40.

[Examples 1-6 and Comparative Examples 1-3]
In the following Examples and Comparative Examples, the alcohol conversion rate, Gerve alcohol yield, soap byproduct rate, and soap byproduct rate difference were determined by the following methods.

<Measurement of alcohol conversion rate and Gerve alcohol yield>
In the examples and comparative examples, the solutions after completion of the reaction were diluted with hexane, followed by gas chromatography [column: Ultra-alloy-1 (HT) capillary column 30.0 m × 250 μm (manufactured by Fronter LAB), detector: FID. Injection temperature: 300 ° C., detector temperature: 350 ° C., He flow rate: 19.0 mL / min. The product was quantified.
The alcohol conversion rate and Gerve alcohol yield were calculated by the following formulas, respectively.
Alcohol conversion rate (%) = ([feed amount of raw material alcohol (mol)] − [amount of residual alcohol (mol)]) / [feed amount of raw material alcohol (mol)] × 100
Gerve alcohol yield (%) = [Amount of generated Gerve alcohol (mol)] × 2 / [Feed amount of raw material alcohol (mol)] × 100

<Measurement of soap byproduct rate>
In Examples and Comparative Examples, the soap production rate (%) at the end of the reaction was calculated according to the following formula by obtaining the acid value before and after the reaction by the neutralization titration method.
Soap byproduct rate (%) = ([acid value at the start of reaction (mg-KOH / g)] − [acid value at the end of reaction (mg-KOH / g)]) / [acid value at the start of reaction ( mg-KOH / g)] × 100
The above-mentioned soap by-product rate represents the amount of soap actually generated as a percentage with respect to the theoretical amount when soap of the same amount as the added base is generated.

<Calculation method of difference in soap byproduct rate>
The difference between the soap byproduct rate when using the base catalyst and the cocatalyst and the soap byproduct rate when using only the base catalyst was determined as “soap byproduct rate difference”.
Since the soap by-product rate increases with the progress of the reaction, it is necessary to compare at the same alcohol conversion rate.
Therefore, the reaction was carried out in the same manner as in Example 1 described later except that only the base catalyst was used without using the cocatalyst (Comparative Example 3), and the same alcohol conversion was performed based on the soap byproduct rate in this case. The rate was compared with the soap byproduct rate of Examples 2 to 6, and this difference was determined as “soap byproduct rate difference”. Specific calculation methods are as follows (i) to (iv).
(I) Except that only the base catalyst was used, the reaction was carried out in the same manner as in Example 1 described later (Comparative Example 3), and sampling was performed as appropriate to determine the soap byproduct rate at a plurality of alcohol conversion rates.
(Ii) The values of alcohol conversion and soap by-product obtained in (i) were second-order approximated by the least square method to obtain the following formula (1). In addition, the approximate curve represented by Formula (1) is as having shown in FIG.
[Soap byproduct rate (%)] = 0.008 × [conversion rate (%)] ² + 0.0744 × [conversion rate (%)] + 19.497 (1)
(Iii) The value of the alcohol conversion obtained in each example was substituted into the above formula (1), and the soap byproduct rate [A ₀ (%)] in Comparative Example 3 corresponding to the alcohol conversion from here. Asked.
(Iv) The difference [A ₁ −A ₀ ] between the soap by-product rate [A ₁ (%)] obtained in each example and the soap by-product rate obtained in the above (iii) was determined, and this was calculated. The difference in soap byproduct rate (%) was used.

Example 1 ((b-1) a zinc compound and a solid metal oxide are used as a cocatalyst)
In a 100 mL flask with a stirrer, 56 g (0.30 mol) of 1-dodecanol (product of Kao Corporation, product name: Calcoal 2098) which is a raw material alcohol, potassium hydroxide (manufactured by Kishida Chemical Co., Ltd., pellet form) ) 0.50 g (3.0 mol% with respect to the raw material alcohol), 0.024 g (raw material alcohol) of a mixture of the ZnO particles of Preparation Example 1 which is a cocatalyst and Al ₂ O ₃ (manufactured by STREM, γ-alumina) 0.043% by mass, ZnO / Al ₂ O ₃ = 80/20 (molar ratio)) was added to the system while bubbling nitrogen into the system at 240 ° C. with stirring (nitrogen flow rate: 50 mL / min.). ), And the reaction was performed at normal pressure for 5 hours.
The alcohol conversion was 94%, the Gerve alcohol yield was 87%, and the soap byproduct rate was 54%. Production conditions and results are shown in Table 1.

Comparative Examples 1-3
The reaction was performed in the same manner as in Example 1 under the production conditions shown in Table 1. In addition, all the raw material alcohol used was 1-dodecanol (0.30 mol), and potassium hydroxide (Kishida Chemical Co., Ltd., pellet form) 0.50g (3.0 mol with respect to raw material alcohol) as a base catalyst. %) And a cocatalyst (total amount of zinc compound and solid metal oxide) 0.024 g (0.043% by mass relative to the raw material alcohol) were used. Production conditions and results are shown in Table 1.

  From Table 1, Example 1 using a mixture of zinc oxide and γ-alumina as a base catalyst and a cocatalyst is more than Comparative Examples 1 and 2 using only either zinc oxide or γ-alumina as a cocatalyst. It can also be seen that the alcohol conversion rate and the yield of Gerve alcohol are improved, and that the soap by-product rate is significantly lower than that of Comparative Example 1 using only zinc oxide as a cocatalyst. Moreover, in Example 1, compared with the comparative example 3 which used only a base catalyst, the alcohol conversion rate and the yield of Gerve alcohol improved greatly, and the soap byproduct rate also fell 15%.

Examples 2 to 6 ((b-2) using a solid composite metal oxide as a cocatalyst)
The reaction was performed in the same manner as in Example 1 under the production conditions shown in Table 2. In addition, all the raw material alcohol used was 1-dodecanol (0.30 mol), and potassium hydroxide (Kishida Chemical Co., Ltd., pellet form) 0.50g (3.0 mol with respect to raw material alcohol) as a base catalyst. %), 0.024 g (0.043 mass% based on the raw material alcohol) of the solid composite metal oxide obtained in Preparation Examples 2 to 6 was used as a cocatalyst. Production conditions and results are shown in Table 2.

From Table 2, when the solid composite metal oxide is used as the cocatalyst (B), compared with the case where only the base catalyst (A) is used (Comparative Example 3 in Table 1), there is a difference in the rate of soap by-products. It turns out that it becomes a negative value.
Moreover, it was found from a comparison between Example 2 and Example 6 that the soap by-product rate decreased as the aluminum content in (b-2) the solid composite metal oxide increased.

  According to the present invention, it is possible to produce soap alcohol at a low cost and in a high yield by suppressing the by-product of soap in the Gerber reaction. Gerve alcohol obtained by the production method of the present invention is used as cosmetics such as emollients, resin additives such as plasticizers, various process agents such as oils, etc. It is useful as an excellent surfactant. In addition, it has advantages such as low cost, few impurities such as soap, and less odor.

Claims (9)

The primary aliphatic alcohols of 8 to 18 carbon atoms, Guerbet alcohols are reacted in the presence of a co-catalyst containing a basic catalyst (A), and zinc element containing an alkali metal or alkaline earth metal (B) a method of manufacturing, co catalyst (B) is (b-1) below and / or (b-2) shown der is, aluminum and the periodic table (long-period type) to the group 4, 8, 10 metal element selected from belongs metal elements, aluminum, titanium, Ru chosen iron, and nickel, a manufacturing method of Guerbet alcohols.
(B-1) Zinc compound, and solid metal oxide containing one kind of metal element selected from aluminum and metal elements belonging to Group 4, 8, and 10 of the periodic table (long period type) (b-2) Zinc Solid composite metal oxide containing an element, and one or more metal elements selected from aluminum and metal elements belonging to Groups 4, 8, and 10 of the periodic table (long-period type) The amount of base catalyst (A) is 0.01 to 15 mol% based on the total amount of primary aliphatic alcohols, the production method of Guerbet alcohols according to claim 1. The amount of cocatalyst (B) is from 0.001 to 1 mass% based on the total amount of primary aliphatic alcohols, the production method of Guerbet alcohols according to claim 1 or 2. The method for producing Gerve alcohol according to any one of claims 1 to 3 , wherein a mass ratio [(B) / (A)] of the cocatalyst (B) to the base catalyst (A) is 0.005 to 10. In (b-1), the gel ratio in any one of Claims 1-4 whose molar ratio (zinc compound / solid metal oxide) of a zinc compound and a solid metal oxide is 10 / 90-90 / 10. A method for producing alcohol. In (b-1), the manufacturing method of Gerve alcohol in any one of Claims 1-5 whose zinc compound is a zinc oxide. In (b-1), the manufacturing method of the Gerve alcohol in any one of Claims 1-6 whose solid metal oxide is an alumina. In (b-2), the molar ratio of zinc element to one or more metal elements selected from aluminum and metal elements belonging to Groups 4, 8, and 10 of the periodic table (long-period type) (zinc element / metal element) ) Is 40/60 to 95/5, the method for producing Gerve alcohol according to any one of claims 1 to 4 . The method for producing Gerve alcohol according to any one of claims 1 to 8 , wherein the reaction temperature is 180 to 250 ° C.

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