JPH07242578A - Method for catalytic hydration of olefins - Google Patents

Abstract

(57) [Summary] [Object] To provide a method for producing an alcohol by contacting an olefin such as ethylene or propylene with water in the presence of a catalyst. A partial metal-neutralized salt catalyst of a heteropolyacid in which a part of the protons of the heteropolyacid is substituted with at least one metal cation selected from the group consisting of titanium metal, zirconium metal and tin metal, or these moieties A neutralized salt is dispersed in silica gel derived from a hydrolyzate of silicon alkoxide, and water and olefins such as ethylene and propylene are charged as a raw material into a reactor and reacted in the presence of a silicone-coated solid heterogeneous catalyst. As a result, alcohols corresponding to olefins are produced.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel method for producing alcohols by hydration of olefins. More specifically, the present invention relates to a method for producing alcohols by direct hydration of olefins, which comprises using highly activated heteropolyacid as a catalyst.

[0002]

2. Description of the Related Art Conventionally, as a method for producing an alcohol by a direct hydration reaction of an olefin, a production method by a gas phase reaction and a production method by a liquid phase reaction have been industrially carried out. As a production method by a gas phase reaction, for example, in JP-A-3-207728, a macroporous cation exchange resin is used as a catalyst, and in JP-A-55-124541, an acidic layered clay compound is used as a catalyst. ing. As a more widely industrialized method, JP-A-53-84096,
A catalyst in which phosphoric acid is supported on a carrier as disclosed in JP-A-52-133095 and JP-B-51-44915 is used.

These production methods by gas phase reaction generally carry out the reaction in a high temperature range, and the conversion of propylene is low. Therefore, the amount of alcohols produced per unit volume of the reactor is extremely low, and it is necessary to recycle a large amount of unreacted olefin, which is not an advantageous method in terms of equipment and energy. In addition to this, the method of producing a supported phosphoric acid catalyst which is widely used industrially has a problem that the performance of the catalyst is deteriorated due to scattering of phosphoric acid which is a catalyst component along with the reaction.

Here, as a method for overcoming the drawbacks such as low productivity of alcohols and large-scale circulation of unreacted olefins in the gas phase method, one of the raw materials, water, is brought into contact with olefins in a liquid state, so-called liquid. Phase reactions are also widely known. For example, as a homogeneous catalyst
Aromatic sulfonic acids are described in Japanese Patent Nos. 43-8104 and 43-16123. In addition, Japanese Patent Publication No. 49-166, Japanese Patent Publication No. 50-35
No. 051, JP-B-49-36204, JP-A-53-9746 and the like describe heteropolyacids. In particular, heteropolyacids are industrially used in Japan, and the amount of alcohol produced per unit time is high.

As the solid heterogeneous catalyst, for example, JP-B-44-26656, JP-A-49-117412, JP-A-61-230744.
In Japanese Patent Publication No. 58-7614 and Japanese Patent Publication No. 63-102121, a strongly acidic cation exchange resin is used as a catalyst. Further, in JP-A-3-502321, JP-A-3-503175, JP-A-1-246234, JP-A1-246233, JP-A-63-218251 and the like, a zeolite catalyst is used. Particularly, the cation exchange resin catalyst has a relatively high catalytic activity under relatively low temperature and low pressure conditions, and is used as an industrial catalyst in foreign countries such as Germany.

However, the cation exchange resin catalyst has a heat resistance temperature of substantially 100 ° C. of the resin itself, and it is practically necessary to use the cation exchange resin catalyst at 150 ° C. which is an industrialized condition, because of permanent deterioration of the catalyst. The reaction is progressing with it, and acidic components such as sulfonic acid groups are decomposed and desorbed, and it is unavoidable that the components flow out into the reaction solution. In addition, it is impossible to carry out at a reaction temperature higher than this, and the alcohol production capacity is limited.

On the other hand, the zeolite-based solid heterogeneous catalyst has insufficient catalytic activity, and the catalytic activity as strong as the strongly acidic cation exchange resin cannot be expected. Therefore, in order to increase the yield of alcohols, Requires high reaction temperature.

However, when the zeolite compound is heated to a high temperature in the presence of water in a liquid phase state like the olefin hydration reaction condition, the decomposition of the zeolite is obviously promoted. Therefore, it is practically impossible to produce alcohols at a favorable production rate.

On the contrary, since the above-mentioned heteropolyacid has a high heat resistant temperature, the catalytic reaction between olefin and water is 30
It can be carried out at a temperature close to 0 ° C., which brings about higher productivity than the cation exchange resin, but since it is a homogeneous catalyst, about 75% of the protons of the heteropolyacid are cation-exchanged with an alkali metal (particularly sodium) cation. Partial neutralization suppresses equipment corrosion due to heteropoly acid. Therefore, it is unavoidable that the catalytic activity is significantly reduced as compared with the heteropolyacid which is not partially neutralized.

[0010]

DISCLOSURE OF THE INVENTION The present invention is directed to the production of alcohols by the direct contact hydration reaction of olefin and water, which is stable and has low corrosiveness under high temperature reaction conditions capable of achieving high alcohol productivity. Focusing on the superiority of the heteropolyacid catalyst, the result of diligent study showed that in the method for producing alcohols by catalytic hydration of olefins, some of the protons possessed by the heteropolyacid as a catalyst were converted from titanium, zirconium and tin metal cations. By using a partially neutralized heteropoly acid substituted with at least one metal cation selected from the group consisting of the following, there is no decrease in the activity of a catalyst partially neutralized with an alkali metal cation of a conventional heteropoly acid, but rather improvement in activity. In addition, it made it possible to produce alcohols while suppressing the corrosion of the equipment. Furthermore, by dispersing these heteropolyacids in silica gel derived from the hydrolysis product of silicon alkoxide and further coating this with silicone, by using the immobilized partially neutralized heteropolyacid catalyst,
The inventors have found that the catalyst has stable activity and high activity without decomposing and decomposing an acid component due to thermal decomposition of the catalyst, which has been a drawback of conventional solid heterogeneous catalysts, and has completed the present invention.

That is, an object of the present invention is to produce alcohols in a liquid phase with high efficiency in a direct hydration reaction of an olefin, and to use it stably without decomposing even under high temperature conditions, and to use an apparatus or the like. It is a catalyst that suppresses corrosion substantially completely by making it a solid heterogeneous catalyst with less corrosiveness and high activity, and provides an extremely economical production method for producing alcohols using this catalyst To do.

[0012]

The present invention is a method for producing alcohols by catalytic hydration of olefins, wherein some of the protons of the heteropolyacid are selected from the group consisting of titanium, zirconium and tin metal cations. A method for producing alcohols, which comprises contacting an olefin with water in the presence of a partially neutralized heteropolyacid substituted with at least one metal cation.

More specifically, a partially neutralized heteropoly acid in which a part of the protons possessed by the heteropoly acid is replaced by at least one metal cation selected from the group consisting of titanium, zirconium and tin metal cations is used as a liquid phase homogeneous catalyst. Alternatively, these partially neutralized heteropolyacids are dispersed in silica gel derived from the hydrolysis product of silicon alkoxide, immobilized and silicone-coated, and used as a liquid phase heterogeneous catalyst. It is a method for producing alcohols by hydration.

The present invention will be described in detail below. The olefin used in the present invention is an aliphatic hydrocarbon compound and is a linear or branched monoolefin or polyolefin having at least one carbon-carbon double bond.
Further, these olefins may have a halogen element, a hydroxyl group, a nitro group, an amino group, a cyano group, a carbonyl group, an acetoxy group, an aromatic group, a carboxyl group, a mercapto group or the like as a substituent. It is preferably an aliphatic olefin having 2 to 10 carbon atoms.

Specifically, ethylene, propylene, 1-
Butene, 2-butene, isobutene, 1-pentene, 2-
Penten, 2-methyl-1-butene, 2-methyl-2-
Linear or branched pentenes such as butene, 1-hexene,
2-hexene, 3-hexene, linear or branched hexene such as methylpentene, butadiene, pentadiene,
Examples include polyolefins such as hexadiene. Further, it is also possible to use alicyclic olefins such as cyclopentene, methylcyclopentene, cyclohexene, methylcyclohexene, cyclooctene, methylcyclooctenes, cyclopentadiene, cyclohexadiene, cyclooctadiene. More preferably,
The olefin is at least one selected from the group consisting of lower olefins having 2 to 6 carbon atoms. More preferably, the olefin is ethylene or propylene.

In the present invention, one kind or two or more kinds of them are used in the reaction. Further, the purity of the olefin used in the present invention is not particularly limited, and general reagent purity, industrial purity or olefin diluted with alkane or the like can be used.

The present invention relates to a partially neutralized heteropoly acid obtained by substituting a part of protons contained in the above heteropoly acid with olefin and water by at least one metal cation selected from the group consisting of titanium, zirconium and tin metal cations. The catalyst or these partially neutralized heteropolyacids are dispersed in silica gel and contacted in the presence of an immobilized partially neutralized heteropolyacid catalyst whose surface is coated with silicone to produce alcohols. The alcohols produced by the present invention are olefins to which water is added.

The heteropolyacid used in the present invention is a complex oxide acid composed of two or more different oxide complexes, and has the general formula: H _a (M ₁ ) _b (M ₂ ) _c (O). _d (in the formula, H is a hydrogen atom, M
₁ represents a central atom of the heteropolyacid, M ₂ represents a metal atom constituting the polyacid, and O represents an oxygen atom. Further, a is a positive integer of 10 or less, b is 1 or 2, c is an integer of 10 or more and 30 or less, d is a positive integer of 100 or less, and M ₂ is a group consisting of tungsten, molybdenum, vanadium and antimony. It is at least one metal atom selected from. ) Is a heteropoly acid. In this, M ₁
Is at least one selected from the group consisting of P or Si atoms, M ₂ is W and Mo atoms, and b = 1, c = 1
The general formula is 2: H ₃ PW _n Mo _(12-n) O ₄₀ , H ₄ SiW _n Mo _(12-n) O
₄₀ (In the formula, n is 0 or a positive integer of 12 or less, H
Represents a hydrogen atom, P represents a phosphorus atom, Si represents a silicon atom, Mo represents a molybdenum atom, W represents a tungsten atom, and O represents an oxygen atom. The heteropoly acid represented by) is exemplified as an easily available heteropoly acid. The present invention is not limited to these heteropoly acids.

In the present invention, a part of the protons of these heteropolyacids (H in the above general formula) is replaced with at least one metal cation selected from the group consisting of titanium, zirconium and tin metals: (M ₃ ) _E H _(a-ge) (M ₁ ) _b (M ₂ ) _c (O) _d (wherein H is a hydrogen atom, M ₁ is a central atom of a heteropolyacid, and M ₂ is a metal constituting the polyacid. Represents an atom, M ₃ represents at least one metal atom selected from the group consisting of titanium, zirconium and tin metals, and O represents an oxygen atom.
Is a positive integer of 10 or less, b is 1 or 2, and c is 1
An integer of 0 or more and 30 or less, and d is a positive integer of 100 or less. Further, g represents the metal valence of M ₃ and e is a-
It is a positive number that satisfies (g × e)> 0. ) Is a partially neutralized salt of a heteropoly acid as it is, or these partially neutralized heteropoly acids are dispersed and immobilized in silica gel derived from a hydrolysis product of a silicon alkoxide,
In addition, a silicone-coated immobilized partially neutralized heteropolyacid is used as a catalyst. Preferably, among these partially neutralized salts of heteropolyacids, a compound of the general formula: (M ₃ ) _x H _(3-gx) PW _n Mo _(12-n) O ₄₀ , (M ₃ ) _y H _{(4-gy) SiW n Mo (12-n)} O 40 ( wherein, n is 0 or 12 the following positive integer, H is a hydrogen atom, P
Represents a phosphorus atom, Si represents a silicon atom, Mo represents a molybdenum atom, W represents a tungsten atom, and M ₃ represents at least one metal atom selected from the group consisting of titanium, zirconium and tin metals. O represents an oxygen atom. Furthermore, g is M
And represents the _third metal valency, gx is less than 3 positive number, g
y is a positive number less than 4. The partially neutralized salt of the heteropoly acid represented by (4) is mentioned as an easily available one.

Specific examples are H ₃ PW ₁₂ O ₄₀ , H ₃ PW ₁₁ MoO ₄₀ , H ₃ PW ₁₀ Mo ₂ O ₄₀ and H ₃ PW ₉ Mo in the molecular or rational formula.
₃ O ₄₀ , H ₃ PW ₈ Mo ₄ O ₄₀ , H ₃ PW ₇ Mo ₅ O ₄₀ , H ₃ PW ₆ Mo ₆ O ₄₀ , H ₃ PW ₅ Mo ₇ O ₄₀ , H ₃ PW ₄ Mo
₈ O ₄₀ , H ₃ PW ₃ Mo ₉ O ₄₀ , H ₃ PW ₂ Mo ₁₀ O ₄₀ , H ₃ PWMo ₁₁ O ₄₀ , H ₃ PMo ₁₂ O ₄₀ , H ₄ SiW
₁₂ O ₄₀ , H ₄ SiMo ₁₂ O ₄₀ , H ₄ SiW ₂ Mo ₁₀ O ₄₀ , H ₃ PV ₂ Mo ₁₀ O _40, etc. Part of the protons of the heteropolyacid consists of titanium, zirconium and tin metal cations. Partially neutralized salt of a heteropolyacid substituted with at least one metal cation selected from the group, or these partially neutralized salts of heteropolyacid are dispersed in silica gel derived from a hydrolysis product of silicon alkoxide and fixed. Examples of the catalyst which has been made silicone-coated are used as the catalyst in the present invention.

In the present invention, a partially neutralized salt of a heteropolyacid itself in which a part of the protons of these heteropolyacids is replaced with at least one metal cation selected from the group consisting of titanium, zirconium and tin metal cations, or these At least one selected from the group consisting of a partially neutralized salt of a heteropolyacid dispersed in silica gel derived from a hydrolysis product of a silicon alkoxide, fixed and silicone-coated is used as a catalyst.

The substitution ratio of the proton of the heteropoly acid with at least one cation selected from the group consisting of titanium, zirconium and tin metal cations is not particularly limited, and the proton in the partially neutralized salt of these heteropoly acids is not limited. Is present, but preferably 5 to 95%, more preferably 10 to 90% of the protons possessed by the heteropolyacid are at least one cation selected from the group consisting of titanium, zirconium and tin metal cations. It is recommended to replace it. More specifically, a telopoly acid represented by the general formula: (M ₃ ) _x H _(3-gx) PW _n Mo _(12-n) O ₄₀ , which is a partially neutralized salt of the above-exemplified heteropoly acid, In the partially neutralized salt, the value of gx (gxx) is preferably 0.15 to 2.85, and more preferably 0.3 to 2.7. Therefore, when the metal valence of M ₃ is tetravalent, 4x is preferably 0.15 to 2.85, and 0.3 to
It is more preferably 2.7. However, it goes without saying that the present invention is not limited only to the range of these substitution rates.

Part of the protons of the heteropolyacid is titanium,
The method of substituting with at least one cation selected from the group consisting of zirconium and tin metal cations,
In the present invention, there is no particular limitation, and any method may be used as long as it is a method in which these metal cations and the protons of the heteropolyacid are replaced, but it is exemplified as a method that is easy to carry out. If so, a predetermined amount of heteropolyacid is dissolved in an alcohol solvent in advance, and while stirring, an alcohol solution in which a predetermined amount of titanium, zirconium or tin metal alkoxy compound or acetate compound is dissolved is added and sufficiently reacted to replace. A method for doing so is exemplified. In addition, when a water-labile compound is used, it is preferable to dehydrate the crystal water or structured water of the heteropolyacid in advance and use it as an amorphous water product. Further, when using a water-stable compound, water may be used as a solvent.

At this time, the metal alkoxy compound and the acetate compound used for the substitution are not particularly limited in the present invention, but examples of easily available compounds include titanium isopropoxide, zirconium isopropoxide, Examples thereof include tin acetate.

In the present invention, a partially neutralized heteropoly acid obtained by substituting a part of protons of the heteropoly acid with at least one cation selected from the group consisting of titanium, zirconium and tin metal cations may be used as it is as a homogeneous catalyst. It is possible, but it is also possible to disperse these partially neutralized heteropolyacids in silica derived from the hydrolysis products of silicon alkoxides, to immobilize and to use silicone coatings as the immobilized partially neutralized heteropolyacid catalysts. This is an effective method.

The method of dispersing the partially neutralized heteropolyacid in the silica gel derived from the hydrolysis product of the silicon alkoxide of the partially neutralized heteropolyacid is not particularly limited, and the partially neutralized heteropolyacid is substantially silicon alkoxide. Any method may be adopted as long as it is dispersed in silica gel formed by hydrolysis of, but as a method that can be easily carried out, for example, silicon alkoxide (for example, tetraethoxysilane) is added to alcohol. After quantitatively dissolving, the above partially neutralized heteropolyacid is added to this to be in a dissolved or suspended state, and a predetermined amount of water is added with mechanical stirring to perform hydrolysis. At this time, if necessary, heat treatment may be performed.

After the hydrolysis was completed, the silica gel in which the partially neutralized heteropolyacid was dispersed was filtered and washed, and the filtered solid was dried to remove alcohols and then suspended in water and heated. After washing, it is preferable to filter, dry and dehydrate, and heat-treat in an electric furnace for silicone coating. However, dried and dehydrated silicone may be coated.

The silicon alkoxide used in the present invention has the general formula: (RO) ₄ Si (wherein R is a substituted or unsubstituted hydrocarbon group, which may be the same group or different groups). Is a silicate ester represented by.

At this time, R is preferably an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 15 or less carbon atoms, or an aromatic hydrocarbon group having 15 or less carbon atoms. Further, these R may have an alkyl group, a halogen element, an amino group, a nitro group, an alkoxy group, a cyano group, a hydroxyl group or the like as a substituent.

Specific examples of readily available silicon alkoxides include silicic acid esters such as methyl silicate, ethyl silicate, isopropyl silicate, phenyl silicate and cyclohexyl silicate.

When the hydrolysis is carried out in an alcohol solvent, the alkoxy group (RO) ₄ of the above formula may be substituted in whole or in part with chlorine, bromine or iodine. You can do it. (These react with alcohols to produce (RO) ₄ Si.) Therefore, it is possible to use silicon tetrachloride or the like.

In the present invention, when a partially neutralized heteropolyacid is dispersed in silica gel and coated with silicone to be used as the immobilized partially neutralized heteropolyacid catalyst, the amount of the partially neutralized heteropolyacid dispersed in silica gel is used. Is not particularly limited, but
The weight ratio of partially neutralized heteropolyacid / silica gel is preferably 0.002 to 10.0, and particularly preferably 0.02 to 1.0. If the amount of silica gel is too small, the heteropolyacid will not be substantially dispersed, and if the amount of silica gel is too large, the catalytic action of the heteropolyacid may be impaired.

In the present invention, when the partially neutralized heteropolyacid is used as a solid heterogeneous catalyst, as described above, the partially neutralized heteropolyacid is incorporated into a silica gel derived from a hydrolysis product of a silicon alkoxide. Disperse,
This is further used as a catalyst for the partially neutralized heteropoly acid which has been subjected to silicone coating. Silicone coating is more preferred as a highly active solid heterogeneous catalyst.

The method of silicone coating the partially neutralized heteropolyacid dispersed in silica gel is not particularly limited, and any method can be used as long as it is a method in which the heteropolyacid dispersed in silica gel is supported on the solid surface. However, if the method is easy to carry out, the heteropoly acid dispersed in silica gel is made into a powder, and the necessary amount of the silicone compound used for coating is added to this, and after mixing well, heat treatment is performed. I do. At this time, in order to uniformly perform silicone coating on the heteropolyacid powder dispersed in the silica gel, the silicone compound may be dissolved in an organic solvent such as hexane and mixed with the heteropolyacid powder if necessary. Recommended.

Here, the silicone compound used for the silicone coating will be described. The silicone compound used for silicone coating the partially neutralized heteropolyacid dispersed in silica gel has the general formula:-(OSi (R) ₂ ) _n- (wherein Si is a silicon atom, O is an oxygen atom, R Is a hydrogen atom or a hydrocarbon group, where R is not all hydrogen atoms at the same time, and n is an integer of 5 or more). In the above general formula, R may be the same or different. It is more preferable that part of R is a hydrogen atom, and it is particularly preferable to use an organic polysiloxane compound in which 5 to 50% of R is a hydrogen atom. At this time, polysiloxane in which R is at least one selected from the group consisting of methyl, ethyl, and phenyl groups, or a mixture of these and hydrogen atoms is exemplified as an easily available silicone compound.

Specifically, as a polysiloxane (silicone) in which R is a methyl group and a methyl group is partially replaced by a hydrogen atom, KF which is a silicone oil manufactured by Shin-Etsu Chemical Co., Ltd.
99 etc. are mentioned.

In the present invention, the amount of silicone used for the silicone treatment on the partially neutralized heteropolyacid dispersed in silica gel is not particularly limited, but preferably 0 weight% of the total solid weight of the heteropolyacid dispersed in silica gel. 0.001-2.0 times weight, more preferably 0.0
It is recommended to coat using 1 to 0.5 times weight. If the coating amount is too small, a highly active immobilized partially neutralized heteropolyacid catalyst cannot be obtained, and if the coating amount is too large, the activity of the catalyst itself may be hindered.

In carrying out the present invention, the amount of olefin as a raw material and the amount of water used (amount ratio) are not particularly limited, but the water / olefin molar ratio is preferably in the range of 0.1 to 50, more preferably 0. It is recommended to carry out in the range of 3 to 30. If the amount of water is too small, it is difficult to achieve a high conversion rate of the raw material olefin, and if the amount of water is too large, it is possible to increase the conversion rate of the olefin, but it is necessary to use more water than necessary. This is because the reactor becomes too large and a large amount of water needs to be circulated, so that the reactor cannot be efficiently manufactured.

In carrying out the present invention, the amount of catalyst used is not particularly limited, and any amount may be used, but a preferable amount is the amount of catalyst to the weight of water used in the reaction. 0.00 by weight percent
It is 1 to 300%, more preferably 0.01 to 150%, and further preferably 0.1 to 50%. It is difficult to obtain favorable productivity of alcohol with the use of too small amount of catalyst, and use of the catalyst with too large amount results in sufficiently high reaction rate and extremely high productivity of alcohol, but on the contrary, it is preferable. There is a risk of increased by-products (ethers, polymerized olefins, etc.),
There is a risk of loss of catalyst and loss of economic efficiency.

The reaction temperature is not particularly limited, but is preferably in the range of 0 to 500 ° C, more preferably 30 to 300 ° C. If the reaction temperature is extremely low, the conversion rate of the olefin (reaction reagent) is low, in other words, the reaction rate extremely decreases, and the productivity of the reaction product decreases. on the other hand,
When the reaction temperature is 500 ° C. or higher, undesirable side reactions and the like proceed to increase the amount of by-products and the stability of the olefin as a raw material and the stability of alcohols as a product are not preferable, and the reaction selectivity It causes a decline and is not economical.

The reaction can be carried out under any of reduced pressure, increased pressure and normal pressure. From the viewpoint of reaction efficiency (reaction efficiency per unit volume), it is not preferable to carry out at a too low pressure. In addition, it is not preferable to carry out the reaction at an excessively high pressure from the viewpoint of the economical efficiency of the equipment such as a reactor. A generally preferred operating pressure range is 0.5 to 500 atmospheres,
More preferably, it is 1.0 to 300 atm. However, the invention is not limited to only these pressure ranges. From the viewpoint of productivity, it is recommended to carry out the reaction under pressure, as a more economical method.

The reaction can be carried out in any of a liquid phase, a gas-liquid phase and a gas phase, but from the viewpoint of productivity and the scale of the reactor, at least a part of water is in a liquid state. It is preferable to carry out. However, the present invention is not limited to this.

In carrying out the present invention, it is also possible to add a solvent or gas which is inert to the catalyst and the reaction reagent into the reaction system and carry out the reaction in a diluted state. Specifically, methane, ethane, propane, butane, hexane, cyclohexane and other saturated aliphatic hydrocarbons, nitrogen,
Examples thereof include inert gases such as argon and helium.
The present invention can be carried out in any reaction method such as a normal batch reaction, a semi-batch reaction in which a part of raw materials or a catalyst is continuously supplied, or a continuous flow reaction. Further, the order of addition of each component such as the reaction raw material and the catalyst and the addition method are not particularly limited.

Further, various methods such as a fixed bed, a fluidized bed, and a fixed bed of trays are adopted as the catalyst filling method, and any method may be used. When it is carried out as a liquid phase reaction, the catalyst is dissolved in water, and as a homogeneous catalytic reaction, a partially neutralized heteropoly acid is dispersed in silica gel, and a silicone-coated immobilized partially neutralized heteropoly acid catalyst is also used. Is carried out as a heterogeneous catalytic reaction.

The reaction time (residence time or catalyst contact time in flow reaction) is not particularly limited, but is usually 0.
It is 1 second to 30 hours, preferably 0.5 seconds to 15 hours. After the reaction, if necessary, the reaction product can be separated and recovered from the catalyst or the like by a usual separation method such as distillation.

Alcohols, which are the desired products, are subjected to usual separation and purification such as solvent extraction, distillation, alkali treatment, acid treatment and other sequential treatment methods from the above-mentioned separated and recovered substance, or an operation in which these are appropriately combined. It can be isolated and purified by the method. Further, the unreacted raw material can be recovered and recycled to the reaction system for use.

In the case of a batch type reaction, the catalyst recovered by separating the reaction product after the reaction can be used as it is, or after regenerating a part or all thereof, it can be repeatedly used as a catalyst in the reaction again. When carried out in a fixed bed or fluidized bed flow continuous reaction system, by subjecting it to the reaction, a part or all of the catalyst is deactivated or activity-reduced,
After the reaction is interrupted, it can be regenerated and used for the reaction, or a part of the catalyst can be continuously or intermittently withdrawn, regenerated and recycled to the reactor for reuse. Further, fresh catalyst can be continuously or intermittently fed to the reactor. When the reaction is carried out in a moving bed flow continuous reaction or a homogeneous catalyst flow reaction system, the catalyst can be separated, regenerated and reused as in the batch reaction.

[0048]

EXAMPLES The present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples. Preparation of catalyst (1) Partial substitution of a proton of a heteropoly acid with a titanium cation or a zirconium cation In an ethanol solution of a predetermined amount of a heteropoly acid (a heteropoly acid which has been decrystallized and water-dehydrated by heat treatment at 350 ° C. in advance) A predetermined amount of titanium isopropoxide (Ti (O-iPr) ₄ ) or zirconium isopropoxide (Zr (O-iPr) ₄ ) dissolved in ethanol was gradually added to the solution at room temperature with stirring. At the start of addition, precipitation of white precipitate was observed in the ethanol solution. After the addition was completed, the mixture was further stirred at room temperature for 3 hours, liquid components such as ethanol were distilled off under reduced pressure, dried at 80 ° C. under reduced pressure, and further dried at 350 ° C. in an electric furnace.

(2) Partial Substitution of Protons by Tin Cation of Heteropoly Acid A heteropoly acid containing a predetermined amount of crystal water is dissolved in water, and a solution of a predetermined amount of tin acetate (Sn (OAc) ₂ ) dissolved in dilute hydrochloric acid water is prepared. Added with stirring. After the addition was completed, stirring was continued for 3 hours, and then liquid components such as water were distilled off by heating under reduced pressure, and the obtained solid was further reduced under pressure at 80 ° C. and then in an electric furnace.
It was dried at 50 ° C.

(3) Silicone coating catalyst of partially neutralized heteropolyacid dispersed in silica gel In ethanol in which a predetermined amount of ethyl silicate was dissolved,
After adding a predetermined amount of a partially neutralized salt of the heteropoly acid prepared by the above-mentioned preparation method (1) or (2), which is partially substituted with a titanium cation, a zirconium cation or a tin cation, and after stirring at 40 ° C. for 1 hour Then, pure water was added dropwise at a molar ratio of 3 times that of the ethyl silicate charged at this temperature. After the completion of dropping, the temperature of the solution was raised to 80 ° C., and stirring was further performed at this temperature for 48 hours. As a result, the solution became agar and lost fluidity. After heating this under reduced pressure to remove the solvent, the residual solid was further dried at 100 ° C. The dried solid was washed in pure water at 80 ° C. for 9 hours with stirring and filtered to obtain a solid separated by filtration. This solid at 100 ℃
After dehydration in, it was heat-treated at 300 ° C. in an electric furnace.

10 g of the heat-treated solid was mixed with a predetermined amount of silicone oil (KF-99, manufactured by Shin-Etsu Chemical Co., Ltd.) in 20 m of hexane.
It was suspended in a solution dissolved in 1 and thoroughly stirred and contacted. Then, hexane was removed at room temperature under reduced pressure, and the solid was dried, and then the solid was subjected to heat treatment in an electric furnace at 200 ° C. for 3 hours to obtain a silicone coating catalyst of partially neutralized heteropolyacid dispersed in silica gel. did. This catalyst was used as a solid catalyst in the reaction.

(4) Calculation of Replacement Ratio of Protons of Heteropoly Acid with Titanium Cation and Zirconium Cation Total amount of protons of the heteropoly acid used for substitution (A
Milligram atom: For example, dodecatungstophosphoric acid (H ₃ PW
_In the case of ₁₂ O ₄₀ ) a mmol, the total number of titanium or zirconium atoms contained in the titanium or zirconium isopropoxide used for substitution for A = 3a) (B milligram atom, B in the case of the used metal isopropoxide b mmol). = B) × 4, and calculated by the following formula. Therefore, the substitution rate is based on the total amount of protons, and it is assumed that the substitution is performed with protons of 4 atoms per atom of titanium or zirconium cation. Therefore, the substitution rate was calculated by the following formula. Calculation formula: substitution rate (%) = 100 × (4B / A)

(5) Calculation of Substitution Ratio of Protons of Heteropoly Acid with Tin Cations Total amount of protons contained in the heteropoly acid used for substitution (A
Milligram atom: For example, dodecatungstophosphoric acid (H ₃ PW
_In the case of ₁₂ O ₄₀ ) a mmol, the total number of tin atoms contained in the tin acetate used for substitution for A = 3a) (B milligram atom, in the case of tin acetate used, B = b) × 2
Was calculated by the following formula. Therefore, the substitution rate is based on the total amount of protons, and is 2 per tin cation.
It is supposed to replace the atom's proton. Therefore, the substitution rate was calculated by the following formula. Calculation formula: substitution rate (%) = 100 × (2B / A)

(6) Quantification of reaction product The reaction product was reacted at a predetermined temperature for a predetermined period of time, cooled, and then depressurized to normal pressure. It was analyzed and quantified by the Tograph method. still,
All product yields were calculated based on the starting olefins used in the reaction. Table 1 shows the catalysts prepared by the above methods (1) and (2), and Table 2 shows the catalysts prepared by the method (3).

[0055]

[Table 1] Table 1 ──────────────────────────────────── Heteropoly acid Substituted metal phosphoron catalyst (substitution Previous) Ion substitution rate (%) ──────────────────────────────────── H ₃ PW ₁₂ O ₄₀ − 0.0 Catalyst 1 H ₃ PW ₁₂ O ₄₀ Na ⁺ 83.3 Catalyst 2 H ₃ PW ₁₂ O ₄₀ Cs ⁺ 83.3 Catalyst 3 H ₃ PW ₁₂ O ₄₀ Ti ⁴⁺ 83.3 Catalyst 4 H ₃ PW ₁₂ O ₄₀ Zr ⁴⁺ 83.3 Catalyst 5 H ₃ PW ₁₂ O ₄₀ Sn ²⁺ 83.3 Catalyst 6 H ₃ PW ₁₁ MoO ₄₀ − 0.0 Catalyst 7 H ₃ PW ₁₁ MoO ₄₀ Ti ⁴⁺ 83.3 Catalyst 8 H ₃ PMo ₁₂ O ₄₀ − 0.0 Catalyst 9 H ₃ PMo ₁₂ O ₄₀ Sn ²⁺ 50.0 catalyst 10 H ₄ SiW ₁₂ O ₄₀ − 0.0 catalyst 11 H ₄ SiW ₁₂ O ₄₀ Ti ⁴⁺ 50.0 catalyst 12 H ₄ SiW ₁₂ O ₄₀ Na ⁺ 50.0 catalyst 13 ──────────── ─────────────────────────

[0056]

[Table 2] Table 2 ──────────────────────────────────── Heteropolyacid Substituted Fluorone Silica / Heteropolyacid Silicone / Solid catalyst (before substitution) Ion substitution rate (%) Weight ratio (#) Weight ratio (##) ────────────────────────── ─────────── H ₃ PW ₁₂ O ₄₀ Ti ⁴⁺ 83.3 1 / 0.110 0.05 / 1 catalyst 14 H ₃ PW ₁₂ O ₄₀ Ti ⁴⁺ 83.3 1 / 0.110 0.1 / 1 catalyst 15 H ₃ PW ₁₂ O ₄₀ Ti ⁴⁺ 83.3 1 / 0.110 0.2 / 1 catalyst 16 H ₃ PW ₁₂ O ₄₀ Zr ⁴⁺ 83.3 1 / 0.113 0.1 / 1 catalyst 17 H ₃ PW ₁₂ O ₄₀ Sn ²⁺ 83.3 1 / 0.131 0.1 / 1 catalyst 18 H ₃ PW ₁₂ O ₄₀ Ti ⁴⁺ 50.0 1 / 0.121 0.1 / 1 catalyst 19 H ₃ PW ₁₁ MoO ₄₀ Ti ⁴⁺ 83.3 1 / 0.146 0.1 / 1 catalyst 20 H ₃ PMo ₁₂ O ₄₀ Sn ²⁺ 83.3 1 / 0.122 0.1 / 1 catalyst 21 H ₄ SiW ₁₂ O ₄₀ Ti ⁴⁺ 50.0 1 / 0.132 0.1 / 1 catalyst 22 H ₄ SiMo ₁₂ O ₄₀ Ti ⁴ + 50.0 1 / 0.106 0.1 / 1 catalyst 23 ────────── ──────────────────── ────── (#) Weight comparison of the heteropoly acid by weight and the silica after cation replacement. (##) Weight ratio of each silica-dispersed heteropolyacid and the silicone oil used for the coating treatment.

Examples 1 to 3 In three 70 ml autoclaves, 2.0 g of catalyst 4, 5 or 6 and 24.0 g of water (1.33 m) were added.
ol) and then propylene 12.0 g
(0.285 mol) was press-fitted at 140 ° C. for 5
The reaction was carried out by heating and stirring for a period of time. After completion of the reaction, the autoclave was cooled and the pressure was released, and the reaction solution was analyzed by gas chromatography. As a result, it was confirmed that isopropyl alcohol was produced in good yield as shown in Table 3. At this time, in all of the examples, formation of isopropyl ether as a by-product was not confirmed.

Comparative Examples 1 to 3 are the same as Catalyst 1, Catalyst 2 or Catalyst 3 in Table 1.
The reaction was carried out under exactly the same conditions as in Example 1 except that 0 g was used. As shown in Table 3, the dodecatungstophosphoric acid catalyst substituted with a Ti, Zr or Sn cation showed superior catalytic activity to the unsubstituted heteropolyacid. Furthermore, Na or Cs ion-substituted dodecatungstophosphoric acid markedly decreased the catalytic activity as compared with the unsubstituted one.
From this, it can be seen that the catalyst of the present invention is a very effective catalyst.

Example 4 The reaction was carried out under exactly the same conditions as in Example 1 except that 2.0 g of catalyst 8 in Table 1 was used. The results are shown in Table 3, and a high yield of isopropyl alcohol was obtained.

Comparative Example 4 The reaction was carried out under exactly the same conditions as in Example 4 except that the catalyst 7 in Table 1 was changed to 2.0 g. As shown in Table 3, this result indicates that the H ₃ PW ₁₁ MoO ₄₀ catalyst is a catalyst in which a part of the protons is replaced with Ti ions.
It is clear that the catalytic activity is lower than that of the heteropolyacid in the present invention, and the partial substitution of the heteropolyacid with the Ti cation in the present invention exhibits extremely high catalytic activity.

Example 5 2.0 g of catalyst 10 which is a catalyst in which 50% of protons of dodecamolybdophosphoric acid are replaced with Sn cations as a catalyst
The reaction was carried out under exactly the same conditions as in Example 1 except for the use. As a result, as shown in Table 3, the production of isopropyl alcohol was observed in good yield.

Comparative Example 5 The reaction was carried out under exactly the same conditions as in Example 5 except that 2.0 g of dodecamolybdophosphoric acid (catalyst 9 in Table 1) was used as the catalyst. As a result, the yield of isopropyl alcohol was the value shown in Table 3. From this, it became clear that the catalyst in which a part of the protons of dodecamolybdophosphoric acid was replaced by Sn cations showed high catalytic activity even though the amount of protons retained decreased.

Example 6 The catalyst was treated with 50% of the protons of dodecatungstosilicic acid as T.
The direct hydration reaction of propylene was carried out under exactly the same conditions as in Example 1 except that 2.0 g of the catalyst substituted with i cation (Catalyst 12 in Table 1) was used. As a result, as shown in Table 3, the production of isopropyl alcohol was confirmed in good yield.

Comparative Examples 6 to 7 The catalyst is dodecatungstosilicic acid (catalyst 1 in Table 1).
1) or 50% of the protons of dodecatungstosilicic acid
In which is replaced by Na cation (Catalyst 1 in Table 1
The reaction was carried out under the same conditions as in Example 6 except that 2.0 g of 3) was used. The results are shown in Table 3. From this, dodecatungstosilicic acid has almost no decrease in its catalytic activity even if a part of the proton is replaced by a Ti cation for corrosion inhibition, but by replacing it with a Na cation like a conventional catalyst, The catalytic activity is extremely reduced, and it is clear that the catalyst of the present invention is excellent.

[0065]

[Table 3] Table 3 ──────────────────────────────────── Catalyst iPA yield (%) ─ ─────────────────────────────────── Example 1 Catalyst 4 11.8 Example 2 Catalyst 5 10. 3 Example 3 Catalyst 6 10.7 Comparative Example 1 Catalyst 1 7.1 Comparative Example 2 Catalyst 2 3.9 Comparative Example 3 Catalyst 3 5.7 Example 4 Catalyst 8 11.4 Comparative Example 4 Catalyst 7 7.3 Implementation Example 5 Catalyst 10 15.6 Comparative Example 5 Catalyst 9 14.0 Example 6 Catalyst 12 11.3 Comparative Example 6 Catalyst 11 12.0 Comparative Example 7 Catalyst 13 2.5 ──────────── ───────────────────────── iPA = Isopropyl alcohol; Yield is based on propylene fed. Yield is a by-product in all Examples and Comparative Examples. Generation of isopropyl ether was observed.

Example 7 The reaction was carried out under the same conditions as in Example 1 except that the reaction temperature was 160 ° C. As a result, isopropyl alcohol and isopropyl ether were 22.1% and 0.6%, respectively, based on the charged propylene.

Example 8 The reaction was carried out under the same conditions as in Example 7, except that the amount of water charged was 36.0 g. As a result, the yield of isopropyl alcohol was 34.2%, and the production of by-product diisopropyl ether was 0.3%.

Examples 9 to 12 The reaction was carried out under the same conditions as in Example 8 except that the amount of propylene charged was 6 g and the reaction temperature and reaction time were changed as shown in Table 4. As a result, the yields of isopropyl alcohol and diisopropyl ether were produced as shown in Table 4.

[0069]

[Table 4] Table 4 ──────────────────────────────────── Reaction temperature Reaction time Yield (propylene Standard) (° C.) (hour) iPA DiPE ───────────────────────────────────── Example 9 160 3.0 40.3 0.4 Example 10 180 1.0 1.0 47.6 0.5 Example 11 200 0.5 58.8 0.5 Example 12 250 0.1 80.1 1.2 --- ────────────────────────────────── iPA = isopropyl alcohol; DiPE = diisopropyl ether

Examples 13 to 14 Reactions were carried out under the same conditions as in Example 7, except that ethylene or 1-butene was used instead of propylene and 0.285 mol of each was charged. As shown in Table 5, the yield was good and the alcohols were produced with each olefin. All the yields in Table 5 are based on the charged olefin. The alcohols produced are ethanol from ethylene and 2-butanol from 1-butene.

[0071]

[Table 5] Table 5 ──────────────────────────────────── Olefins Alcohol yield (%) ──────────────────────────────────── Example 13 Ethylene 17.6 Example 14 1-Butene 25 1 ─────────────────────────────────────

Examples 15-24 Catalysts 14 to 14 listed in Table 2 in a 70 ml autoclave
Except for the weight of silica and the weight of silicone, any of 23 was partially substituted with Ti, Sn, or Zr metal cations. And the reaction was performed under the same conditions as in Example 1. The results are as shown in Table 6.
The production of isopropyl alcohol was confirmed with good reaction results. Further, formation of by-product isopropyl ether was not observed.

[0073]

[Table 6] Table 6 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Catalyst YPA yield (%) ━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example 15 Catalyst 14 15.2 Example 16 Catalyst 15 17. 6 Example 17 Catalyst 16 14.3 Example 18 Catalyst 17 15.9 Example 19 Catalyst 18 16.8 Example 20 Catalyst 19 15.1 Example 21 Catalyst 20 19.7 Example 22 Catalyst 21 18.4 Implementation Example 23 Catalyst 22 17.0 Example 24 Catalyst 23 12.3 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━ iPA = isopropyl alcohol

[0074]

According to the present invention, the following effects can be obtained. (1) The olefin can be directly hydrated to produce alcohols with good yield and selectivity. (2) Compared to the conventional method, alcohols can be directly hydrated even under mild conditions of low temperature and low pressure. In addition, it can be carried out under the condition that the reactor or the like is hardly corroded. Furthermore, it becomes an effective catalyst as a solid heterogeneous catalyst as well as a liquid phase homogeneous catalyst. (3) It is possible to produce industrially important alcohols significantly in terms of safety, process, and economy. (4) The thermal decomposition of the catalyst can be prevented, and alcohols can be stably produced even under high temperature reaction conditions without deteriorating the activity of the catalyst. It was possible to provide a method for producing alcohols by an excellent olefin hydration reaction.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C07C 31/10 9155-4H // C07B 61/00 300 C07C 31/12 9155-4H

Claims (9)

[Claims] 1. A method for producing alcohols by catalytic hydration of an olefin, wherein a part of protons of a heteropolyacid is replaced with at least one metal cation selected from the group consisting of titanium, zirconium and tin metal cations. A method for producing alcohols, which comprises contacting an olefin with water in the presence of the partially neutralized heteropolyacid. 2. A partially neutralized heteropoly acid in which a part of the protons possessed by the heteropoly acid is replaced by at least one metal cation selected from the group consisting of titanium, zirconium and tin metal cations, and a hydrolysis product of a silicon alkoxide is produced. The method according to claim 1, which is an immobilized partially neutralized heteropolyacid dispersed in silica gel derived from a substance and further coated with silicone. 3. The heteropolyacid has the general formula: Ha (M ₁ ) b (M ₂ ) c (O) d (wherein H is a hydrogen atom and M is a hydrogen atom).
₁ represents a central atom of the heteropolyacid, M ₂ represents a metal atom constituting the polyacid, and O represents an oxygen atom. Further, a is a positive integer of 10 or less, b is 1 or 2, c is an integer of 10 or more and 30 or less, d is a positive integer of 100 or less, and M ₂ is a group consisting of tungsten, molybdenum, vanadium and antimony. It is at least one metal atom selected from. ) The method according to claim 1, wherein 4. The heteropolyacid has the general formula: H ₃ PW _(n) Mo _(12-n) O ₄₀ , H ₄ SiW _(n) Mo _(12-n).
O ₄₀ (In the formula, n is 0 or a positive integer of 12 or less,
H is a hydrogen atom, P is a phosphorus atom, Si is a silicon atom, Mo
Represents a molybdenum atom, W represents a tungsten atom, and O represents an oxygen atom. The method according to claim 1, wherein the method is at least one selected from the group consisting of heteropolyacids represented by 5. The method according to claim 1, wherein the catalytic hydration reaction of the olefin is carried out under the condition that water exists in a liquid state. 6. The method according to claim 1, wherein the olefin is at least one selected from the group consisting of lower olefins having 2 to 6 carbon atoms. 7. The method according to claim 6, wherein the olefin is ethylene or propylene. 8. The method of claim 2 wherein the silicone coating is surface depositing a silicone compound on a partially neutralized heteropolyacid dispersed in silica gel derived from a hydrolysis product of a silicon alkoxide. 9. The method according to claim 8, wherein the silicone compound is an organopolysiloxane compound having a partial silicon-hydrogen bond.