JP2004002485A - Method for producing tertiary alcohol - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for economically and highly actively producing tert-butanol at a high yield by hydrating isobutene, and to provide a catalyst therefor. <P>SOLUTION: The method comprises performing, by using a strong-acid cation exchange resin, ion exchange of a polystyrenesulfonate to obtain polystyrene sulfonic acid, producing the tert-butanol from isobutene by using the polystyrenesulfonic acid and separating the product into two layers i.e. a catalyst-containing layer and a catalyst-nucontaining layer to obtain the tert-butanol. <P>COPYRIGHT: (C)2004,JPO

Description

The present invention relates to ion exchange of a polymer having a sulfonic acid group soluble in water and / or olefin, for example, polystyrene sulfonic acid from a sulfonic acid salt of the polymer using a porous strong acid cation exchange resin. And a method for industrially producing a tertiary alcohol using a polymer having a sulfonic acid group as a catalyst.

Tertiary alcohols are used as industrial chemicals and solvents, and are also important as various industrial raw materials. For example, tert-butyl alcohol is used in large quantities as a raw material for producing methyl-tert-butyl ether and methyl methacrylate. .

Conventionally, tertiary alcohols are produced by hydration of olefins using a catalyst. The conventional production method is usually carried out by a liquid phase reaction, and is divided into a heterogeneous catalyst method using a solid catalyst and a homogeneous catalyst method using an acidic catalyst aqueous solution.

(4) As a heterogeneous catalyst method, a method using a strongly acidic ion exchange resin as a catalyst is known (for example, see Patent Document 1). In this method, the catalyst is an insoluble solid resin, and the substrate olefin and water are generally inhomogeneous, so that the contact is insufficient and the activity is low. Therefore, in order to homogenize the liquid phase and increase the rate of the hydration reaction, a method is used in which a large amount of an organic acid such as acetic acid is added to the liquid phase to form a uniform phase. However, in this method, the formed tertiary alcohol and organic acid often easily form an organic acid ester in the presence of a strongly acidic ion exchange resin. Therefore, an extra ester separation / recovery step is required, and it is difficult to avoid complication of the process. In this method, the ion exchange resin is usually suspended and used in a batch reaction system. Therefore, the olefin hydration reaction proceeds only up to the chemical equilibrium conversion, and it is difficult to obtain a high olefin conversion.

On the other hand, as the homogeneous catalyst method, sulfuric acid, heteropolyacid (for example, see Patent Document 2), p-toluenesulfonic acid (for example, see Patent Document 3) and the like are disclosed as catalysts. Each of these catalysts has excellent catalytic activity, but since it is a homogeneous catalyst, the reaction product and the catalyst form a homogeneous phase. Therefore, it is necessary to separate the generated tertiary alcohol and the aqueous catalyst solution. Normally, the tertiary alcohol is separated and recovered by distillation. At that time, a reverse reaction or generation of by-products is caused, and the yield is reduced.

Therefore, in the homogeneous catalyst method, a separation method other than the distillation method has been proposed as a method for separating the tertiary alcohol as a product from the catalyst. For example, using a heteropolyacid as a catalyst, using an olefin containing a hydrocarbon inert to a hydration reaction as a raw material, adding a large amount of a tertiary alcohol to the reaction system, or adding a specific inorganic salt to the reaction system. A method of separating an organic phase containing a tertiary alcohol and an aqueous phase containing a catalyst is disclosed (for example, see Patent Document 4). However, this method requires that an olefin containing a hydrocarbon inert to the hydration reaction be used as a raw material, and that a large amount of a tertiary alcohol be previously added to the reaction system. Therefore, olefins that can be used as raw materials are limited, and a large amount of tertiary alcohol needs to be added in advance, so that the reaction rate tends to decrease due to the reverse reaction and the amount of tertiary alcohol recycled increases. This causes inconvenience. In addition, since a specific inorganic salt is added to the reaction system, the reaction system becomes complicated, and the problem of corrosion occurs.

On the other hand, a polymer having a sulfonic acid group has been conventionally obtained by ion exchange of a polymer having a sulfonic acid salt. However, the polymer has a large molecular weight and low diffusivity, so that the polymer cannot be sufficiently contacted with an ion exchange resin, and there is a problem that ion exchange does not easily proceed in producing a catalyst. For example, an example using a gel-type or porous-type cation exchange resin (Amberlite IR-120B) having a crosslinking degree of 2 to 20% as an ion exchange resin is disclosed (for example, see Patent Document 5). . In the disclosed embodiment, the time required for ion exchange is long, and a large amount of ion exchange resin is required. As a result, the cost is inevitably increased. This method also has a problem that it is difficult to obtain a polymer having a high exchange rate of metal cations of a sulfonic acid salt of the polymer and having a high concentration of sulfonic acid groups.

JP-B-56-22855

JP-B-58-39806 JP-B-62-12208 JP-B-58-39806 JP-A-60-15408

The present invention has been made in view of the above prior art, and has as its object a method for economically producing a tertiary alcohol by hydration of an olefin in a high activity, a high yield, and a catalyst for use in the method. It is to provide a manufacturing method.

The present inventors have conducted intensive studies to solve the above-mentioned problems. As a result, when a polymer having a sulfonic acid group soluble in water and / or olefin is used as a catalyst, the hydration reaction of the olefin proceeds efficiently and at a high yield. Was separated by a simple operation, and it was found that a desired tertiary alcohol was obtained, thereby completing the present invention.

That is, the present invention provides a method for obtaining a polymer having a sulfonic acid group by ion-exchanging a polymer having a sulfonic acid salt, the method comprising using a porous strong acid cation exchange resin having a sulfonic acid group. This is a method for producing a polymer. Further, the present invention is a method for producing a tertiary alcohol, comprising hydrating an olefin using a polymer having a sulfonic acid group soluble in water and / or olefin as a catalyst. Hereinafter, the present invention will be described in more detail.

First, a method for producing a polymer having a sulfonic acid group, which is the first invention of the present application, will be described. In the present invention, a polymer having a sulfonic acid salt is subjected to ion exchange using a porous strong acid cation exchange resin to obtain a polymer having a sulfonic acid group.

Examples of the polymer having a sulfonate as a raw material in the present invention include polystyrene sulfonate, polynaphthalene sulfonate, polyvinyl sulfonate, styrene sulfonate-maleic anhydride copolymer, naphthalene sulfonate-formalin Copolymers and the like can be exemplified. In these polymers having a sulfonate, a part of the skeleton of the polymer is substituted with an alkyl group, an alkoxy group, a halogen group, a carboxyl group, an ester group, a nitrile group, a nitro group, an N-alkylamide group, or the like. You may. The polymer having these sulfonates is more preferably a polystyrene sulfonate, a polyvinyl sulfonate or a mixture thereof.

Examples of the cation of the sulfonate include lithium, sodium, potassium, cesium, magnesium, calcium, beryllium, aluminum, nickel, copper, zinc, cobalt, tellurium, vanadium, titanium, iron, chromium, manganese, ammonium, and silver. But more preferably sodium and potassium.

Usually, a polymer having a sulfonic acid salt as a raw material is handled as an aqueous solution. Although the concentration is not particularly limited, the concentration of the aqueous solution is increased at a high concentration, and a concentration operation is required at a low concentration. If necessary, other organic solvents soluble in the aqueous polymer solution, such as alcohols, ketones and ethers, can be added.

The ion exchange resin used in the catalyst preparation of the present invention is, for example, a porous strongly acidic cation exchange resin having a styrene-divinylbenzene copolymer or the like as a base, and examples of the exchange group include a sulfonic acid group. Can be Generally, strongly acidic ion exchange resins are classified into a gel type and a porous type according to a physical porous state. The gel type is an ion exchange resin having only micropores, which are pores generated by swelling, and the porous type is an ion exchange resin having macropores, which are physical pores that do not disappear even in a dry state in addition to micropores. . As the porous ion exchange resin, MP type (macroporous type resin), MR type (resin having a huge network structure), and the like are further known (for example, Peterok P23, Vol. 10, No. 12, 1987). .

製 The porous strongly acidic cation exchange resin used in the present invention is not particularly limited in its production method. For example, it can be produced by sulfonating a granular copolymer of styrene and divinylbenzene with a base resin using sulfuric acid. Above all, the resin used as the base of the MP type or the MR type is characterized by the solvent used in the production. That is, the MP-type resin is produced by adding a water-insoluble organic solvent which sufficiently dissolves the monomer and sufficiently swells the produced polymer, for example, an aromatic hydrocarbon such as benzene or toluene to the polymerization system. Further, the MR type resin is produced by adding a water-insoluble organic solvent which does not swell the monomer but dissolves the produced polymer, for example, a secondary alcohol.

Commercially available porous cation exchange resins usable in the present invention include, for example, Amberlyst 15E (manufactured by Organo Co., Ltd.) as the MR type and Diaion PK220 (manufactured by Mitsubishi Kasei Co., Ltd.) as the MP type. And Duolite C-264 (manufactured by Sumitomo Chemical Co., Ltd.).

強 Porous type strongly acidic ion exchange resin has many macropores which are physical pores which do not disappear even in a dry state. Therefore, when a porous strong acid ion exchange resin is used, even a high molecular weight polymer electrolyte such as polystyrene sulfonate easily diffuses into the ion exchange resin through many macropores, and the ion exchange resin contains It is presumed that the exchange group can be effectively used and ion exchange can be performed in a short time and with a small amount of ion exchange resin.

球状 Further, the ion exchange resin used in the present invention is suitably a spherical one having a particle diameter of about 0.3 to 1.0 mm.

れ ば According to the present invention, the ion exchange method is not particularly limited, and can be carried out by a usual method. For example, a method of directly adding a required amount of a porous strongly acidic cation exchange resin to a solution of a polymer having a sulfonate and stirring for a predetermined time, or pre-filling the column with the ion exchange resin, and then adding the sulfonate A method of flowing a predetermined amount of a solution of the polymer. The temperature at this time can be usually carried out at room temperature, but if necessary, it can be heated to around 120 ° C. Further, if necessary, a polymer having a sulfonic acid group can be obtained at a higher ion exchange rate by repeating the ion exchange reaction. Thus, a solution of a polymer having a desired sulfonic acid group can be obtained.

ス ル ホ ン In the polymer having a sulfonic acid group as a catalyst, a sulfonic acid salt may remain in a part thereof. The proportion of the sulfonic acid salt remaining in the polymer having a sulfonic acid group as a catalyst is preferably 80% or less. Above this range, the activity of the olefin hydration reaction is significantly reduced, which is not preferred.

ポ ー The porous strongly acidic cation exchange resin used in the present invention can be repeatedly used because it is easily regenerated by a method usually used after use, for example, by flowing an aqueous solution of hydrochloric acid or sulfuric acid into the resin.

Next, the hydration reaction of olefin according to the second invention of the present application will be described. In the present invention, the polymer having a sulfonic acid group produced by the first invention of the present application can be used as a catalyst, but a polymer having a sulfonic acid salt is obtained by another method, for example, a known polymerization or copolymerization method. Thereafter, a polymer having a sulfonic acid group may be produced by a general method such as ion exchange or electrophoresis. Further, a polymer having no sulfonic acid group and then introducing a sulfonic acid group may be used.

The olefin used as a reaction raw material in the present invention is isobutene, α-methylstyrene, isoprene and / or a mixture thereof. These olefins may contain a hydrocarbon mixture that is inert to the hydration reaction. For example, isobutene may be a mixture optionally containing a C4 saturated or unsaturated hydrocarbon such as 1-butene, cis-2-butene, trans-2-butene, n-butane, isobutane, and the like. Further, α-methylstyrene may contain aromatic hydrocarbons such as benzene, toluene, xylene, cumene and the like. Examples of these olefins containing a hydrocarbon inert to the hydration reaction include, for example, a C4 fraction by-product of a fluid catalytic cracking reaction of petroleum, a catalytic dehydrogenation fraction of n-butane, and the like containing isobutene. Can be Further, among the naphtha decomposition products, so-called spent BB obtained after removing butadiene from a fraction having 4 carbon atoms can be mentioned.

The polymer having a sulfonic acid group must be soluble in water or an olefin, and those having a weight average molecular weight of 500 to 5,000,000 can be used. More preferably, the molecular weight is suitably from 1,000 to 1,000,000. The concentration of the polymer having a sulfonic acid group used as a catalyst is not particularly limited, but it can be used within a range from 5% by weight or more to a saturation solubility. At this time, the solvent of the polymer is preferably water, which is also a reaction substrate. If necessary, a polymer having a sulfonic acid group and an olefin, a solvent inert to water, for example, dioxane, acetone or the like may be added, and a tertiary alcohol as a product may be added. No problem.

The reaction temperature is not particularly limited, but the reaction is carried out in the range of 10 to 120 ° C, preferably 30 to 100 ° C. If the temperature is higher than 120 ° C., the equilibrium conversion of the olefin hydration reaction is extremely low, and the amount of tertiary alcohol produced is extremely reduced. The amount decreases.

反 応 In the present invention, the reaction pressure is normal pressure to 30 KG. The olefin is supplied to the reaction system as a gas or liquid. More preferably, in consideration of the hydration reaction rate of the olefin, the reaction pressure at which the olefin exists as a liquid is desirable. In this case, if necessary, the pressure can be controlled using an inert gas such as nitrogen, argon, or carbon dioxide.

As an embodiment of the present invention, any of a stirring type reactor, an external circulation type reactor, a column type reactor, a tubular type reactor and the like can be used, and a batch type, a semi-batch type, and a continuous type may be used. . Considering a process for obtaining an olefin at a high conversion and a desired tertiary alcohol with high purity and high productivity, a countercurrent multistage continuous operation is desirable.

In the present invention, since a polymer having a sulfonic acid group soluble in water and / or olefin is used as a catalyst, a two-phase separation occurs when the reaction solution after the reaction is allowed to stand, and a layer containing the catalyst and a layer not containing the catalyst. And separated into The temperature of the two-phase separation operation is 0 to 130 ° C, preferably 20 to 100 ° C. If a large amount of the tertiary alcohol is formed, it is easily separated into two phases even at room temperature. However, if it is difficult to separate into two phases, it can be separated into two phases by heating. The temperature at this time may be heated to 60 ° C. or higher, and in some cases, to 80 ° C. or higher. The operation pressure is not particularly limited, but it is desirable to operate at the same pressure as the olefin hydration reaction pressure in the process.

層 The layer not containing the catalyst is separated from the layer containing the catalyst by a decanter or the like. The tertiary alcohol is easily purified from the catalyst-free layer by a conventional method, for example, a distillation method. On the other hand, the layer containing the catalyst can be circulated and reused as an aqueous catalyst solution as it is. In this two-phase separation operation, if necessary, a suitable solvent inert to the reaction system may be added. Examples of these solvents include butanes, pentanes, hexanes, cyclohexane, benzene, toluene, xylene, and alcohols.

分離 Separation of the tertiary alcohol produced by the reaction from the catalyst is not limited to two-phase separation, but may be filtration using a separation membrane, since the catalyst is a polymer soluble in water and / or olefin. Microfiltration, ultrafiltration, reverse osmosis and the like are available as a method of filtration.

こ と Being able to separate the produced tertiary alcohol from the catalyst by two-phase separation or filtration as described above is advantageous in the following three points.

(1) A layer containing a tertiary alcohol obtained by two-phase separation or filtration does not contain a catalyst, and does not cause a reduction in yield due to dehydration or a side reaction of a tertiary alcohol, which has been a problem in a conventional process.

(2) Since the tertiary alcohol is distilled and purified by separating the aqueous layer containing the catalyst, the vacuum distillation performed in the conventional process can be avoided, and the distillation and purification at normal pressure can be performed. Further, the throughput in the distillation step can be significantly reduced, and the size of the distillation apparatus can be reduced.

(3) Since the catalyst is separated before distillation, the catalyst is not easily deteriorated by heat, and the catalyst phase can be recycled and used as it is.

In the present invention, the filtration / two-phase separation step is not always necessary. For example, the tertiary alcohol may be directly separated from the reaction solution by distillation under reduced pressure.

Next, an example of a specific method of the present invention will be described with reference to the drawings. An olefin as a raw material is introduced into a reactor 1 through a line 4. On the other hand, a catalyst aqueous solution (line 7) to be separated and reused in the decanter 2 and a make-up amount of the catalyst aqueous solution (line 3) are combined and introduced into the reactor 1 to cause a countercurrent reaction. The reaction liquid is withdrawn from the line 5 and led to the decanter 2, where it is separated into a layer containing the catalyst and a layer not containing the catalyst. The layer containing the tertiary alcohol without the catalyst is sent from line 8 to a purification tower such as distillation. The layer containing the catalyst separated in the decanter 2 is recycled to the reactor 1 through the line 7. The remaining olefin after the reaction is transferred from the line 6.

According to the present invention, a tertiary alcohol can be obtained in a high yield and economically from an olefin by a hydration reaction. According to the present invention, the catalyst used at that time has a high ion exchange rate from the sulfonic acid salt to the sulfonic acid group, so that a very high quality catalyst can be obtained.

The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

(Catalyst preparation)
Examples 1-4
200 g of an aqueous solution of sodium polystyrene sulfonate having a different molecular weight (resin content: 20 wt%) and 130 g (dry weight) of Amberlyst 15E (manufactured by Organo) were mixed and stirred for 1 hour. After removing Amberlyst 15E by filtration, the amount of sodium in the filtrate was measured to determine the ion exchange rate of polystyrenesulfonic acid. Table 1 shows the results.

Ion exchange rate (%) = 100− (amount of sodium sulfonate in filtrate) / (amount of sulfonic acid group and sodium sulfonate in filtrate) * 100
Examples 5 and 6
After mixing 200 g of an aqueous solution of sodium polystyrene sulfonate having a different molecular weight (resin content: 20 wt%) and 100 g (dry weight) of Amberlyst 15E (manufactured by Organo Co., Ltd.) and stirring for 1 hour, the Amberlyst 15E was removed by filtration. Thereafter, the filtrate was subjected to ion exchange again using 50 g of Amberlyst 15E. Table 1 shows the ion exchange ratio of the obtained aqueous solution of polystyrene sulfonic acid.

Comparative Example 1
The ion exchange reaction was carried out for 24 hours under the same conditions as in Example 1 except that the type of the ion exchange resin was Amberlite IR-120 (manufactured by Organo), which was a gel-type cation exchange resin. Table 1 shows the ion exchange rates.

　表から明らかなように、ポーラス型の強酸性陽イオン交換樹脂を用いた場合、ゲル型の陽イオン交換樹脂を用いた場合と比べて、ポリスチレンスルホン酸塩の分子量の大小にかかわらず、短時間で少量の樹脂を用いて、高いイオン交換率でポリスチレンスルホン酸を得ることができ、さらにイオン交換反応を繰り返すことにより、より高いイオン交換率を達成することができる。

As is evident from the table, when using the porous strongly acidic cation exchange resin, compared with the case using the gel type cation exchange resin, regardless of the molecular weight of the polystyrene sulfonate, it is shorter. Thus, polystyrenesulfonic acid can be obtained at a high ion exchange rate using a small amount of resin, and a higher ion exchange rate can be achieved by repeating the ion exchange reaction.

Examples 7 to 10
The catalyst was obtained by performing ion exchange in the same manner as in Example 1 except that the type of the polymer and the amount of the ion exchange resin were changed as shown in Table 2.

　（イソブテンの水和反応）
　反応生成物は、内部標準物質としてジメトキシエタンを用い、試料をか性ソーダで中和し、ガスクロマトグラフィーにより分析した。また実施例中ではｔｅｒｔ−ブチルアルコールをＴＢＡと略す。

(Hydration reaction of isobutene)
The reaction product was analyzed by gas chromatography using dimethoxyethane as an internal standard substance, neutralizing the sample with caustic soda. In the examples, tert-butyl alcohol is abbreviated as TBA.

Examples 11 to 13
The autoclave was charged with 5 g of isobutene and 150 ml of a 10 wt% aqueous solution of various polystyrenesulfonic acids, sealed, heated to 70 ° C., and reacted for 2 hours with stirring. In any of Examples 11 to 13, by-products such as diisobutene and triisobutene were not detected, and the selectivity was 100%.

　実施例１４
　原料をイソブテンからスペントＣ４（組成は表５の通り）１６．８ｇ（イソブテン５ｇ含有）に変えた以外は実施例１１と同じ条件で反応を行った。副生のジイソブテン、セカンタリーブタノールは検出されず、８０％のイソブテン反応率、選択率１００％でＴＢＡが得られた。

Example 14
The reaction was carried out under the same conditions as in Example 11 except that the raw material was changed from isobutene to 16.8 g of Spent C4 (composition is as shown in Table 5) (containing 5 g of isobutene). By-product diisobutene and secondary butanol were not detected, and TBA was obtained with an isobutene conversion of 80% and a selectivity of 100%.

Example 15
Using 50 ml of an aqueous solution of polystyrene sulfonic acid having a hydrogen ion concentration of 0.2 N (molecular weight: 10,000, sodium exchange rate in sulfonic acid group: 63.5%) as a catalyst, 10 g of isobutene was reacted at 60 ° C. for 30 minutes. The TBA generation rate per gram of the catalyst was 0.470 g / hr · g-catalyst.

Comparative Example 2
The reaction was carried out under the same conditions as in Example 15 using an aqueous solution of silicotungstic acid having a hydrogen ion concentration of 0.2 N as a catalyst. The TBA production rate per gram of the catalyst was 0.253 g / hr · g-catalyst.

Example 16
An autoclave was charged with 20 g of an aqueous solution obtained by concentrating the catalyst obtained in Example 7 to a hydrogen ion concentration of 1.2 N and 5 g of raw material isobutene, and reacted at 70 ° C. for 3 hours. After the reaction, the pressure was returned to normal pressure, and unreacted isobutene was purged. The reaction solution was transferred to a separating funnel, kept at 25 ° C., and separated into two phases. The upper layer and the lower layer were separated and analyzed, and the isobutene reaction rate and the TBA partition rate were determined. Incidentally, by-products such as diisobutene and triisobutene were not detected, and the selectivity was 100%.

Examples 17 and 18
The reaction was carried out under the same conditions as in Example 16 except that the raw materials were changed to isobutene amounts of 10 g and 20 g. After purging the unreacted isobutene after the reaction, the results of two-phase separation at 25 ° C. are shown in Table 4. In both Examples 17 and 18, by-products such as diisobutene and triisobutene were not detected, and TBA was obtained with a selectivity of 100%.

Examples 19 and 20
The catalyst obtained in Example 8 was charged into an autoclave as 20 g of an aqueous solution concentrated to a hydrogen ion concentration of 1.2 N and isobutene as 5 g and 10 g, respectively, and reacted at 70 ° C. for 3 hours. After purging the unreacted isobutene after the reaction and separating the two phases at 25 ° C., the results are as shown in Table 4. In both Examples 19 and 20, by-products such as diisobutene and triisobutene were not detected, and the selectivity was 100%.

Example 21
An autoclave was charged with 20 g of an aqueous solution obtained by concentrating the catalyst prepared in Example 1 to a hydrogen ion concentration of 1.2 N and 10 g of isobutene, and reacted at 70 ° C. for 3 hours. After purging the unreacted isobutene after the reaction and separating the two phases at 82 ° C., the results are as shown in Table 4. By-products such as diisobutene and triisobutene were not detected, and the selectivity was 100%.

Example 22
The reaction was carried out under the same conditions as in Example 16 except that the raw material was changed from isobutene to 16.8 g of Spent BB (composition is as shown in Table 5) (containing 5 g of isobutene). After purging the unreacted spent BB after the reaction, the results of two-phase separation at 25 ° C. are shown in Table 4. By-product diisobutene and secondary butanol were not detected, and TBA was obtained with a selectivity of 100%.

Example 23
The reaction was carried out under the same conditions as in Example 17 except that the catalyst obtained in Example 9 was used. After purging the unreacted isobutene after the reaction, the results of two-phase separation at 25 ° C. are shown in Table 4. By-products such as diisobutene and triisobutene were not detected, and TBA was obtained with a selectivity of 100%.

Example 24
The reaction was carried out under the same conditions as in Example 17 except that the catalyst obtained in Example 10 was used. After the reaction, unreacted isobutene was purged, and the results of two-phase separation at 25 ° C. are shown in Table 4. By-products such as diisobutene and triisobutene were not detected, and TBA was obtained with a selectivity of 100%.

Comparative Examples 3 and 4
The reaction was carried out under the same conditions as in Example 1 using an aqueous solution of silicotungstic acid and p-toluenesulfonic acid having a hydrogen ion concentration of 1.2 N as a catalyst. After the reaction, a homogeneous solution was formed, and no two-phase separation was observed even when the temperature was raised to 90 ° C. or sodium was added as a cation. Table 4 shows the results of the analysis of the homogeneous solution. Further, by-products such as diisobutene and triisobutene were not detected, and the selectivity was 100%.

It is explanatory drawing which showed an example of the process of the hydration reaction of an olefin.

Explanation of reference numerals

DESCRIPTION OF SYMBOLS 1 Reactor 2 Decanter 3 Line for transferring makeup aqueous solution of catalyst 4 Line for introducing raw olefin 5 Line for transferring reaction liquid 6 Line for transferring remaining olefin 7 Line for transferring aqueous catalyst solution to be reused 8 Alcohol-containing Line to transfer phase to purification tower

Claims (6)

A method for producing a tertiary alcohol, comprising subjecting an olefin to a hydration reaction using a polymer having a sulfonic acid group soluble in water and / or olefin as a catalyst. The method of claim 1, wherein the olefin is isobutene and the tertiary alcohol is tert-butanol. The method according to claim 1, wherein the polymer having a sulfonic acid group is polystyrene sulfonic acid or polyvinyl sulfonic acid. The method according to claim 1, wherein the olefin hydration reaction is carried out by a countercurrent reaction. The method according to claim 1, wherein the reaction solution after the hydration reaction is separated into two layers into a layer containing a catalyst and a layer not containing a catalyst. The production method according to claim 1, wherein the reaction solution after the hydration reaction is separated into a layer containing a catalyst and a layer not containing a catalyst by filtration.

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