JPH08283186A - Production of alcohols - Google Patents

Abstract

PURPOSE: To efficiently obtain alcohols with markedly improved reactivity by direct hydration of >=8C olefins. CONSTITUTION: In producing alcohols by direct hydration of >=8C olefins in the presence of an acid catalyst, a non-carrying type polyoxoanionic salt of the formula [Mn Hm-n ]<m+> .Z<m-> [M is an alkali metal; Z is a polyoxoanion; (m) is the valence number of Z; (n) is a number satisfying the relationship: 0<(m-n)<(m)] is used as the acid catalyst.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing alcohols, and more specifically, it produces alcohols useful as intermediates for producing surfactants or chemicals such as solvents by direct hydration reaction of olefins. In this case, the present invention relates to a method for producing alcohols in which reactivity is greatly improved by using a polyoxoanion salt as a catalyst.

[0002]

2. Description of the Related Art Conventionally, as a method for producing alcohols having 8 or more carbon atoms, a method of directly hydrating olefins using an acid catalyst has been known. This method is an excellent method because the reaction conditions are mild and selective introduction of hydroxyl groups is possible, as compared with the method of producing alcohols by oxidizing alkanes using a boric acid catalyst or the like. . As acid catalysts used for the direct hydration of olefins, acid type zeolites, cation exchange resins, mineral acids, organic acids and the like have been known so far. However, in general, the reaction rate of the direct hydration reaction is not sufficient for all catalysts, and in particular, in the direct hydration reaction of a long-chain aliphatic olefin such as 1-decene, the water and the olefin are in phase with each other. It had a big defect that it was separated and the contact between the olefin and the catalytic active site was hindered.

For example, (1) a method using a finely divided crystalline aluminosilicate as a catalyst (Japanese Patent Laid-Open No. 60-2
46335, JP-A-63-154633,
(JP-A-63-156736), (2) a method using an acidic ion exchange resin as a catalyst and sulfone as a catalyst (JP-A-53-7605), (3) a heteropolyacid and an aromatic sulfonic acid A method of using an aqueous solution as a catalyst (JP-A-58-112229), (4) a method of using a dispersion of heteropolyacid in silica gel as a catalyst (JP-A-7-118186), (5) an inorganic solid A method has been proposed in which phenol is added as a compatibilizer in the reaction of an acid catalyst (JP-A-62-126141). However, in the methods (1) and (2), the decomposition of the catalyst proceeds at a high temperature of 150 ° C. or higher. Further, in the methods (3) and (4), when an olefin having 8 or more carbon atoms is used, the yield of hydrated alcohol is particularly low due to phase separation. Further, in the method (5), it is necessary to recover the compatibilizer, and a complicated manufacturing process is required. Many studies have been made to solve such problems, but the fact is that they have not been sufficiently solved yet.

[0004]

DISCLOSURE OF THE INVENTION The present invention overcomes the drawbacks of the conventional method for producing alcohols by the direct hydration reaction of olefins, and directly hydrates olefins having 8 or more carbon atoms. It is an object of the present invention to provide a method for further improving the reactivity in the reaction and efficiently producing alcohols.

[0005]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventor has found that water is not used in the direct hydration reaction of olefins having 8 or more carbon atoms which are phase-separated from water. By using a non-supported partially neutralized polyoxoanion salt that is insoluble and forms fine particles in water, the approach of the olefin to the catalytic active site is promoted, and contact with water becomes effective, so alcohols It has been found that the yield of is significantly improved. The present invention has been completed based on such findings. That is, in the present invention, when an olefin having 8 or more carbon atoms is directly hydrated to produce an alcohol in the presence of an acid catalyst, the acid catalyst is represented by the general formula (I) [M _n H _mn ] ^{m +.} Z ^m -... (I) [In the formula, M represents an alkali metal, Z represents a polyoxoanion, m is a valence of the polyoxoanion, and n is 0 <m-n.
A number satisfying the relation of <m is shown. ] A method for producing alcohols, which comprises using a non-supported polyoxoanion salt represented by In the general formula (I), M is preferably K, Rb or Cs, and the polyatom in the polyoxoanion is W or Mo.
Alternatively, it is preferably V. Further, the above general formula (I)
The polyoxoanion in is preferably a heteropolyoxoanion, and more preferably the heteroatom of the heteropolyoxoanion is P or Si. Hereinafter, the method for producing alcohols of the present invention will be described in more detail.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the method of the present invention, the olefin having 8 or more carbon atoms used as a raw material is not particularly limited, and any of chain olefin, cyclic olefin and aromatic olefin can be used. Here, the chain olefin may have one double bond or two or more double bonds in the molecule, and the double bond may be present at the end or inside. May be.
Further, it may be linear or branched. Examples of such chain olefins include 1-octene; 1,3-octadiene; 1-nonene; 1-decene; 1-undecene; 1-dodecene; 1-tridecene;
1-tetradecene; 1-pentadecene; 1-hexadecene; 1-heptadecene; 1-octadecene; 1-nonadecene; 1-eicosene and the like, and skeleton isomers and double bond position isomers thereof. The cyclic olefin may have one double bond or two or more double bonds in the molecule, and examples thereof include ethylcyclohexene, cyclooctene, cyclododecene, cyclooctadiene and the like. , And those having an appropriate substituent such as an alkyl group introduced on these rings. On the other hand, the aromatic olefin may have one olefinic double bond or two or more olefinic double bonds in the molecule, and the olefinic double bond is present at the end of the chain portion. Or it may exist inside. Examples of such aromatic olefins include styrene, allylbenzene, propenylbenzene, and the like.
And those having an appropriate substituent such as an alkyl group introduced on these rings. In the present invention, when the raw material olefin has less than 8 carbon atoms, the reaction rate decreases, which is not preferable.

In the present invention, these olefins may contain other components as long as they do not interfere with the reaction. In the method of the present invention, by direct hydration of the olefins, but to produce the corresponding alcohols, this time, as the acid catalyst, the general formula (I) [M _n H _mn] ^{m +} · Z ^m- · .. (I) [In the formula, M represents an alkali metal, Z represents a polyoxoanion, m is a valence of the polyoxoanion, and n is 0 <m-n.
A number satisfying the relation of <m is shown. ] An unsupported polyoxoanion salt represented by the following is used. This unsupported polyoxoanion salt is a salt in which the polyoxoanion is partially neutralized and some of the protons remain.

In the above general formula (I), M represents an alkali metal, such as lithium, sodium, potassium,
It may be either rubidium or cesium,
Of these, potassium, rubidium and cesium are preferred. When M is lithium and sodium, the polyoxoanion salt becomes water-soluble, the efficiency of contact with olefins during the hydration reaction decreases, and the catalyst activity is not sufficiently exhibited, which is not preferable. The alkali metal may be contained in the polyoxoanion salt in one kind or in two or more kinds. Z represents a polyoxoanion, and examples of polyatoms in this polyoxoanion include W, Mo, V, Nb, Ta, Co, Ni and F.
e, etc., among them, W, Mo and V are preferable from the viewpoint of catalytic activity and stability. One of these polyatoms may be contained, or two or more of them may be contained as a mixed coordination type. The polyoxoanion may be either an isopolyoxoanion or a heteropolyoxoanion. Examples of the hetero atom in the heteropolyoxoanion include P and S
Examples thereof include i, As and Ge, and of these, P and Si are preferable. These heteroatoms may be contained in one kind or in two or more kinds.

Preferred among such polyoxoanions
An example of a new one is [PW₁₂O ₄₀]^3-, [PMo₂
W_TenO₄₀]^3-, [PMo_FourW₈O₄₀]^3-, [PW₆Mo
₆O ₄₀]^3-, [PW_FourMo₈O₄₀]^3-, [PW₂Mo_Ten
O₄₀]^3-, [PMo₁₂O₄₀] ^3-, [PVW₁₁O₄₀]^Four-,
[PVMo₁₁O₄₀]^Four-, [P₂VMo₂W_FifteenO₆₂]^7-,
[P₂VMo_FiveW₁₂O₆₂]^7-, [SiW₁₂O₄₀]^Four-,
[SiMo₂W_TenO₄₀] ^Four-, [SiMo_FourW
₈O₄₀]^Four-, [SiW₆Mo₆O₄₀]^Four-, [SiW_FourM
o₈O₄₀]^Four-, [SiW₂Mo_TenO₄₀]^Four-, [SiMo
₁₂O₄₀]^Four-, [SiVW₁₁O ₄₀]^Five-, [SiVMo₁₁O
₄₀]^Five-, [V₃Mo₃O₁₉]^Five-, [V₂Mo
₆O₂₆] ^6-, [V_FourMo₈O₃₆]^Four-, [V₆Mo
₆O₃₆]^6-, [V₈Mo_FourO₃₆]^8-, [V₂Mo₃W₇
O₃₆]^2-And the like. Among these, heteropoly
Oxoanion is more preferred in terms of activity and stability
Especially [PW₁₂O₄₀]^3-, [PW₆Mo₆O₄₀]^3-,
[PMo₁₂O₄₀]^3-, [SiW₁₂O₄₀]^Four-, [SiW₆
Mo₆O₄₀]^Four-And [SiMo₁₂O₄₀]^Four-Is preferred
It These polyoxoanions are used as catalysts.
May be contained in the polyoxoanion salt
However, two or more kinds may be contained.

In the above general formula (I), mn is a number in the range of more than 0 and less than m (valence of polyoxoanion). The preferable range varies depending on the types of the alkali metal and the polyoxoanion and cannot be unconditionally determined, but mn is generally a number in the range of more than 0 and less than 2. In the method of the present invention, one of the above polyoxoanion salts may be used as an acid catalyst,
You may use it in combination of 2 or more type. The amount used is not particularly limited, but from the viewpoint of catalytic activity and economical efficiency, it is 0.01 to 1 with respect to 1 mol of the raw material olefins.
Advantageously, it is used in a proportion of 0,000 g, preferably 0.1 to 1,000 g, more preferably 0.5 to 500 g.

In the present invention, this polyoxoanion salt needs to be used as a non-supported type which is not supported on a carrier, and when used as a catalyst for the hydration reaction, most of it exists in a solid state in the reaction system. Is desirable,
Therefore, it may be used in the form of fine powder or in the form of a molded body such as pellets, or may be used as a mixture of a plurality of forms such as a combination of powder and pellets. On the other hand, when the polyoxoanion salt is used by being supported on various carriers such as activated carbon, silica, alumina, and resin, the carrier interacts with the polyoxoanion salt to lower the acid strength and the catalytic activity is lowered. It is not preferable because it is not fully exhibited. In the method of the present invention, in the presence of the polyoxoanion salt, the olefins are directly hydrated to introduce hydroxyl groups to produce alcohols. At this time, the hydroxyl source is usually water, Alternatively, water prepared by adding an appropriate organic solvent to water is used. The water used at this time may contain impurities as long as it does not interfere with the reaction. The type of the organic solvent is not particularly limited as long as it does not hinder the reaction, but those that contribute to the improvement of the contact efficiency between water and the raw material olefins and the catalyst, and the generated alcohols Those capable of transferring the hydration reaction equilibrium to the production system by the extraction of are preferred. The amount of water used is not particularly limited, but is usually 0.01 to 10000 ml, preferably 0.1 per 1 g of the polyoxoanion salt of the catalyst.
~ 1,000 ml, more preferably 0.5-500
Selected in the milliliter range. Furthermore, when the organic solvent is added to water, the amount thereof is not particularly limited, but it is advantageous to add it in a proportion of usually 70% by volume or less, preferably 50% by volume or less, based on the total amount of water and the solvent. is there. If the amount of the solvent added exceeds 70% by volume, the contact efficiency between water and the catalyst is lowered, and the catalytic activity is not sufficiently exhibited, which is not preferable.

In the present invention, the hydration reaction of olefins may be carried out in an inert gas atmosphere consisting of nitrogen, carbon dioxide, argon, helium or the like alone or in a mixture, or as long as the reaction is not hindered. It may be performed in a mixed gas atmosphere with oxygen such as air. When the atmospheric gas contains oxygen, the ratio of oxygen to olefins should be within the explosion limit.

The reaction system is not particularly limited and may be a batch system or a distribution system, and may be a homogeneous system or a heterogeneous system. The reaction system may be a gas, a liquid, a solid, or a mixture of a plurality of states depending on the starting materials, solvent, catalyst, reaction conditions and the like used. When using olefins that are liquid or solid at room temperature and pressure such as dodecene and octadecene as the raw material, liquid phase reaction is generally economical and preferable in terms of utility cost and reactivity. Is also high. When the distribution method is adopted, the flow rate of the raw material olefins in the distribution gas is not particularly limited, but usually 0.
001 to 10000 mmol / hour, preferably 0.01
~ 5,000 mmol / hour, more preferably 0.1 to 1.0
It is selected in the range of 00 mmol / hour. Regarding the reaction temperature in the hydration reaction, in the case of a liquid phase reaction using dodecene, octadecene or the like as the raw material olefin, it is generally selected in the range of 0 to 300 ° C, preferably 50 to 200 ° C. If this temperature is lower than 0 ° C, the reaction rate is too slow to be practical, and if it exceeds 300 ° C, the equilibrium yield of the hydration reaction decreases. Further, the reaction pressure is not particularly limited, and it can be carried out in a wide range from normal pressure to high pressure, but from the viewpoint of economy, it is advantageous to be from normal pressure to 200 kg / cm ² . In this way, the corresponding secondary or tertiary alcohols can be produced from olefins with good reactivity.

[0014]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Preparation Example 1 Preparation of Cs _2.3 H _0.7 PW ₁₂ O ₄₀ Phosphotungstic acid (H ₃ PW ₁₂ O ₄₀ , water content 10.87)
wt%) 31.23 g (9.664 mmol) of water 150 g
Cesium carbonate (Cs ₂ CO _3, purity 99.99%) 3.66339 g (11.2)
An aqueous solution of 5 mmol) dissolved in 150 g of water was added dropwise over 90 minutes while stirring at room temperature. Then, after stirring this mixed solution for 60 minutes, it was transferred to an evaporation dish on a water bath at 100 ° C. and dried for 150 minutes to obtain solid Cs _2.3 H _0.7.
PW ₁₂ O ₄₀ 30.13 g (water content thermal analysis value 3.0 wt%)
I got

Preparation Example 2 Preparation of Cs _2.7 H _0.3 PW ₁₂ O ₄₀ Phosphotungstic acid (H ₃ PW ₁₂ O ₄₀ , water content 10.87)
wt%) 17.82 g (5.515 mmol) of water 100 g
Cesium carbonate (Cs ₂ CO _3, purity 99.99%), 2.4256 g (7.44)
An aqueous solution prepared by dissolving 5 mmol) in 100 g of water was added dropwise over 60 minutes while stirring at room temperature. Then, after stirring this mixed solution for 60 minutes, it was transferred to an evaporation dish on a water bath at 100 ° C. and dried for 160 minutes to obtain solid Cs _2.7 H _0.3.
PW ₁₂ O ₄₀ 17.13 g (water content thermal analysis value 1.5 wt%)
I got

Preparation Example 3 Cs_2.5H_0.5PW₁₂O₄₀Key of
Phosphotungstic acid (H₃PW₁₂O₄₀, Water content 10.87
wt%) 19.39 g (6,000 mmol) 100 g of water
Cesium carbonate was added to the aqueous solution that was dissolved in and stirred for 10 minutes.
(Cs₂CO_3,Purity 99.99%) 2.4436 g (7.50)
(0 mmol) in 100 g of water was added to room temperature.
And added dropwise over 45 minutes with stirring. Then this mix
After stirring the liquid for 60 minutes, evaporating dish on water at 100 ° C
And dried for 160 minutes to give solid Cs_2.5H_0.5
PW₁₂O₄₀ 18.38 g (water content thermal analysis value 1.2 wt%)
Got Preparation Example 4 Cs_2.5H_0.5PW₁₂O₄₀(10wt%) /
SiO₂Preparation of phosphotungstic acid (H₃PW₁₂O₄₀, Water content 8.1wt
%) 5.00 g (1.60 mmol) was dissolved in 100 g of water.
Highly pure silica gel (commercial
Product name: Sylstar BP, manufactured by Nippon Kagaku Kogyo Co., Ltd.)
Addition was continued for 10 minutes. For this suspension,
Cesium carbonate (Cs₂CO_3,Purity 99.99%) 0.649
An aqueous solution prepared by dissolving 5 g (1.99 mmol) in 50 g of water.
Was added dropwise over 30 minutes with stirring at room temperature. Next
Then, after stirring this mixed solution for 60 minutes, water at 100 ° C.
Transfer to an evaporating dish for melting, dry for 90 minutes, and₂Up
To Cs _2.5H_0.5PW₁₂O₄₀ 10 wt% was carried
Solid (Cs_2.5H_0.5PW₁₂O₄₀(10 wt
%) / SiO₂) 54.95 g were obtained.

Cs was prepared in the same manner as in Preparation Examples 1 to 3.
_2.5H_0.5PMo₁₂O₄₀, Cs_3.5H _0.5SiW₁₂O₄₀
And Cs₃PW₁₂O₄₀Also prepared. Example 1 Cs in 10 g of 1-dodecene and 24 g of water_2.3H_0.7PW₁₂
O₄₀ 4g added in suspension was autoclaved.
Placed in a tube, 100 kg at 8 kg / cm²G nitrogen pressurization
After reacting under 5 hours, 2-dodecanol 0.57
Mmol was produced. In addition, per unit time of catalyst standard
The amount of 2-dodecanol produced (reaction rate) is 0.029 mi.
Limol / g-catalyst · hr. Table 1 shows the reaction conditions
The results are shown in Table 2.

Examples 2 to 14 Using 1-dodecene as the olefin, the hydration reaction was carried out in the same manner as in Example 1 under the reaction conditions shown in Table 1.
The results are shown in Table 2. Examples 15 to 17 The hydration reaction was carried out in the same manner as in Example 1 except that the olefins shown in Table 1 were used instead of 1-dodecene. The results are shown in Table 2.

[0020]

[Table 1]

[0021]

[Table 2]

[0022]

[Table 3]

Comparative Example 1 10 g of 1-dodecene and 24 g of water were mixed with zeolite (H-MF).
I07146-55, manufactured by UOP, Si / Al weight ratio of about 38) 4 g was added in a suspension state, charged into an autoclave, and reacted at 100 ° C. under a pressure of 8 kg / cm ² G nitrogen for 5 hours. By the way, 2-dodecanol 0.19
Mmol was produced. The amount of 2-dodecanol produced per unit time (reaction rate) on the basis of the catalyst was 0.010 mmol / g-catalyst · hr. The reaction conditions are shown in Table 3 and the results are shown in Table 4. Comparative Example 2 1-dodecene (1.7 g), water (10 g), and phosphotungstic acid (H ₃ PW ₁₂ O ₄₀ , water content 8.1 wt%) 11.1 g and p-
Toluenesulfonic acid (1.9 g) was added to the autoclave to prepare a homogeneous solution, which was then heated at 100 ° C to 8 kg /
The reaction was carried out under a pressure of cm ² G nitrogen for 5 hours. The reaction conditions are shown in Table 3 and the results are shown in Table 4.

Comparative Example 3 Water was used in the same manner as in Comparative Example 1 except that 4 g of an acidic ion exchange resin (sulfonated styrene-divinylbenzene copolymer ion exchange resin) was used in place of the catalyst zeolite in Comparative Example 1. A sum reaction was performed. The reaction conditions are shown in Table 3 and the results are shown in Table 4. Comparative Example 4 The hydration reaction was performed in the same manner as in Comparative Example 2 except that 5 g of ferric trifluoromethanesulfonic acid was used in place of the combination of phosphotungstic acid and p-toluenesulfonic acid as the catalyst in Comparative Example 4. Carried out. The reaction conditions are shown in Table 3,
The results are shown in Table 4. Comparative Example 5 The hydration reaction was carried out in the same manner as in Example 1 except that Cs ₃ PW ₁₂ O ₄₀ was used in place of the catalyst Cs _2.3 H _0.7 PW ₁₂ O ₄₀ in Example 1. The reaction conditions are shown in Table 3,
The results are shown in Table 4. Comparative Example 6 In Comparative Example 5, Cs _2.5 H _0.5 PW ₁₂ O ₄₀ (10) prepared in Preparation Example 4 was used instead of Cs ₃ PW ₁₂ O ₄₀ of the catalyst.
wt%) / SiO ₂ except that 40 grams of Comparative Example 5 was used.
A hydration reaction was carried out in the same manner as in. The reaction conditions are shown in Table 3 and the results are shown in Table 4. Comparative Example 7 The hydration reaction was carried out in the same manner as in Comparative Example 3 except that cyclohexane was used instead of 1-dodecene in Comparative Example 3. The reaction conditions are shown in Table 3 and the results are shown in Table 4. Comparative Example 8 The hydration reaction was carried out in the same manner as in Example 1 except that 1-butene was used instead of 1-dodecene. The reaction conditions are shown in Table 3 and the results are shown in Table 4.

[0025]

[Table 4]

Note 1) Zeolite: H-MFI 071
46-55, manufactured by UOP, Si / Al weight ratio of about 38 2) PTSA: p-toluenesulfonic acid 3) acidic ion exchange resin: sulfonated styrene-divinylbenzene copolymer ion exchange resin

[0027]

[Table 5]

[0028]

[Table 6]

[0029]

INDUSTRIAL APPLICABILITY According to the present invention, when an alcohol is produced by a direct hydration reaction of an olefin having 8 or more carbon atoms, a non-supported polyoxoanion salt is used as a catalyst to significantly improve the reactivity. Can be improved to
Alcohols can be efficiently produced.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical indication location B01J 27/186 B01J 27/186 X 27/188 27/188 X 27/19 27/19 X C07C 29 / 04 9155-4H C07C 29/04 // C07B 61/00 300 C07B 61/00 300

Claims (5)

[Claims] 1. When an olefin having 8 or more carbon atoms is directly hydrated in the presence of an acid catalyst to produce an alcohol, the acid catalyst has the general formula (I) [M _n H _mn ] ^{m +} · Z. ^m -... (I) [In the formula, M represents an alkali metal, Z represents a polyoxoanion, m is a valence of the polyoxoanion, and n is 0 <m-n.
A number satisfying the relation of <m is shown. ] The manufacturing method of alcohols characterized by using the unsupported polyoxoanion salt represented by these. 2. The method for producing an alcohol according to claim 1, wherein in the general formula (I), M is K, Rb or Cs. 3. The method for producing alcohols according to claim 1, wherein in the general formula (I), the polyatom in the polyoxoanion is W, Mo or V. 4. The method for producing alcohols according to claim 1, wherein the polyoxoanion in formula (I) is a heteropolyoxoanion. 5. The method for producing alcohols according to claim 4, wherein the hetero atom of the heteropolyoxoanion is P or Si.