JPH07165640A - Catalytic hydration of olefin - Google Patents

Abstract

PURPOSE:To produce an alcohol by contacting an olefin such as ethylene and propylene with water in the presence of a catalyst. CONSTITUTION:An alcohol corresponding to the charged olefin such as ethylene and propylene is produced by charging water and an olefin in a reactor and reacting the raw materials in the presence of a heterogeneous solid catalyst obtained by the coating treatment of a strongly acidic cation exchange resin having sulfonic acid group bonded to an organic polymer matrix with a perfluorocarbon resin such as a polytetrafluoroethylene resin.

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, it relates to a method for producing alcohols by a direct hydration reaction of an olefin, which comprises using a strongly acidic cation exchange resin having improved activity 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. In these production methods by the gas phase reaction, the reaction is generally carried out in a high temperature region, and the conversion rate 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. However, these homogeneous catalysts have a drawback that the separation and recovery from the catalyst and the reaction product (particularly, water, which is one of the raw materials) becomes complicated, and the energy related thereto becomes large. In addition, since these acid catalysts are homogeneously dissolved in the liquid phase, they come into liquid contact with devices such as reactors, which may cause corrosion of the inner walls of the devices, necessitating the use of expensive device materials and making them economical. It can not be said. Therefore, in the liquid phase reaction, a solid heterogeneous catalyst is used to make up for the drawbacks of the homogeneous catalyst. For example, JP-B-44-26656, JP-A-49-117412, JP-A-61-23074
No. 4, JP-B-58-7614, JP-B-63-102121 and the like use a strongly acidic cation exchange resin as a catalyst. Further, JP-A-3-502321, JP-A-3-503175, JP-A-1-246234, JP-A1-246233, JP-A-63-218251.
Etc., a zeolite catalyst is used. The strong acid cation exchange resin catalyst has a lower temperature than the above liquid phase homogeneous catalyst,
It is used under low pressure (around 150 ° C, around 100 atm) reaction conditions and has a relatively high activity. However, since these cation exchange resins have an extremely high affinity with water, when water is present in the reaction system, the catalytic activity itself decreases, and it is difficult to obtain the desired activity. Further, in order to maintain high reaction activity, a reaction temperature of 150 ° C. or higher is required, which causes constant degradation of the catalyst, decomposes and desorbs acidic components such as sulfone groups, and flows out into the reaction solution. Is inevitable. Therefore, the catalytic activity is significantly reduced, and like the liquid phase homogeneous catalyst, there is a risk of equipment corrosion due to the outflowing acidic components, and the reaction equipment must use an expensive material with high corrosion resistance, which is economical. Is disadvantageous to

On the other hand, the zeolite-based heterogeneous catalyst has an insufficient catalytic activity and is not expected to have the catalytic activity as high as that of the strongly acidic cation exchange resin, and is high in order to increase the yield of alcohols. Requires 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.

[0005]

DISCLOSURE OF THE INVENTION The present invention focuses on high productivity such as equilibrium advantage in liquid phase reaction in producing alcohols by direct contact hydration reaction of olefin and water, Moreover, as a result of intensive study to overcome the drawbacks of the strong acid cation exchange resin, which is a conventional liquid phase heterogeneous catalyst, paying attention to the relatively high catalytic activity of the strong acid cation exchange resin catalyst in the liquid phase reaction. In the production of alcohols by catalytic hydration, by using a strongly acidic cation exchange resin having a sulfonic acid group bound to an organic polymer matrix coated with a fluororesin such as Teflon resin as a heterogeneous solid catalyst It suppresses the decrease in the activity of the catalyst due to the presence of water in the reaction system, which was a drawback of conventional strong acid cation exchange resin catalysts, and makes it highly active. At the same time, because dropped enables lowering the reaction temperature, it found to be an inhibiting catalyst desorption decomposition of acidic components by thermal decomposition, and have completed the present invention.

That is, the 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 easily separate a catalyst and a reaction solution, and to activate the catalyst by the presence of water. An object of the present invention is to provide a highly economical method for producing alcohol, which suppresses the decrease. Another object of the present invention is to provide a catalyst capable of carrying out the hydration reaction in a wide temperature range without activity reduction in both gas phase and liquid phase reaction modes.

[0007]

[Means for Solving the Problems] That is, in the present invention, when an alcohol is produced by a catalytic hydration reaction of an olefin, a fluorocarbon resin is added to a strongly acidic cation exchange resin having a sulfonic acid group bonded to an organic polymer matrix. A method for producing alcohols, which is characterized in that a coated product is used as a catalyst. The fluororesin is preferably a polytetrafluoroethylene resin typified by perfluorocarbon resin and Teflon. Hereinafter, the present invention will be described in detail. 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 have a halogen element, a hydroxyl group, a nitro group,
It may have an amino group, a cyano group, a ketone group, an acetoxy group, an aromatic group, a carboxyl group, a mercapto group, or the like. It is preferably an aliphatic olefin having 2 to 10 carbon atoms. Specifically, straight-chain and branched pentenes such as ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene, 2-methyl-1-butene and 2-methyl-2-butene. Examples thereof include linear and branched hexenes such as 1-hexene, 2-hexene, 3-hexene and methylpentene, and polyolefins such as butadiene, pentadiene and hexadiene. Furthermore, cyclopentene, methylcyclopentene, cyclohexene, methylcyclohexene, cyclooctene, methylcyclooctenes, cyclopentadiene,
It is also possible to use alicyclic olefins such as cyclohexadiene and cyclooctadiene. More preferably, the olefin is at least one selected from the group consisting of lower olefins having 2 to 6 carbon atoms, such as ethylene or propylene. In the present invention, one type or two or more types 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.

In the present invention, alcohols are produced by contacting the above-mentioned olefin and water with a strongly acidic cation exchange resin having a sulfonic acid group bonded to an organic polymer matrix in the presence of a catalyst coated with a fluororesin. The strongly acidic cation exchange resin having a sulfonic acid group bonded to the organic polymer matrix used in the present invention is a huge network and / or gel type cation exchange resin having a sulfonic acid group which is a strongly acidic functional group. In such resins, the sulfonic acid functional groups are attached to the polymer matrix either directly or through one or more carbon atoms or through carbon and heteroatoms such as oxygen, sulfur, etc. It is a base. Specifically, Amberlite-IR-118, IR-120B, IR-1 which is a cation exchange resin manufactured by Rohm and Haas.
22, IR-124, 252, XT-1026, Amberlyst 15, Bayer Revatit-K1131,
K1221, K1411, K2431, K2611, K
2461, K2661 and the like are exemplified as easily available strong acid cation exchange resins. Further, Nafion, which is a heat-resistant cation exchange resin manufactured by DuPont and having a sulfonic acid group bonded to a perfluorocarbon polymer matrix, can also be used in the present invention. Some of these commercially available cation exchange resins are sold as a metal salt type, but the metal salt type is sold in advance.
It is used as a proton type by using sulfuric acid, nitric acid or hydrochloric acid.

In the method of the present invention, these strongly acidic cation exchange resins are further coated with a fluororesin (hereinafter,
It is abbreviated as fluororesin coating. ) Treat and use as catalyst. The catalytic activity is remarkably improved by the fluororesin coating treatment. In carrying out the method of the present invention, the method of coating the strongly acidic cation exchange resin with the fluororesin is not particularly limited, and any method may be used as long as it is a method of carrying the surface or the inner surface on these cation exchange resins. You can do it, but
To give an example of a method that is easy to carry out, a fluororesin spray agent such as Teflon (NORTON) is applied to the surface of the cation exchange resin.
Manufactured by FLUOROGLIDE, etc.) and then dried by heating under reduced pressure or atmospheric pressure to remove the solvent. Fluorine resin dispersion liquid (made by Dupont Co., Ltd.) in a cation exchange resin suspended in water or an organic solvent.
DuPont-Teflon 30, Daikin Neoflon FE
(P dispersion, etc.) is added, and the solvent is removed by heating while stirring and mixing, and the resultant is supported on the surface of the cation exchange resin.

At this time, it is recommended that the cation exchange resin used for the fluororesin coating be used after removing water before the coating, for example, by spraying or impregnating and supporting in an organic solvent. In the method of the present invention, the amount of the fluororesin used for the fluororesin coating of the cation exchange resin is not particularly limited, but is preferably 0.0005 to 2.0 times the solid weight of the cation exchange resin, and more preferably 0. It is recommended to coat using 005 to 0.2 times weight. If the coating amount is too small, the effect of the coating will be practically insignificant, and if the coating amount is too large, the activity of the catalyst itself may be hindered.

The alcohols produced by the present invention are alcohols obtained by adding water to olefins and corresponding to olefins. 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 a water / olefin molar ratio is preferably in the range of 0.1 to 50, more preferably 0.3 to It is recommended to carry out a range of 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 so that the reaction This is because the vessel becomes too large and a large amount of water needs to be circulated, so that it cannot be manufactured efficiently.

The reaction temperature is not particularly limited, but is preferably in the range of 0 to 200 ° C, more preferably 30 to 170 ° 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,
If the reaction temperature is 200 ° C. or higher, undesirable side reactions and the like proceed to increase the amount of by-products and the stability of the olefins as raw materials and the alcohols as products, which is not preferable and the reaction selectivity It causes a decline and is not economical.

The amount of the catalyst used is not particularly limited in the method of the present invention, but when it is carried out in a batch reaction, it is preferably 0.0 based on the weight of the charged water.
1 to 100% by weight, more preferably 0.1 to 30% by weight
Is the range. If it is too small, the reaction becomes extremely slow and inefficient, and if it is too large, the reaction proceeds sufficiently fast, but process troubles such as deterioration of liquid fluidity may occur.

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.

In carrying out the present invention, it is also possible to add a solvent or gas which is inactive to the catalyst and the reaction reagent into the reaction system and carry out 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 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 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.

The present invention can be carried out in any reaction method of ordinary batch reaction, semi-batch reaction in which a part of raw materials or catalysts are continuously supplied, or 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, as the catalyst filling method, a fixed bed, a fluidized bed, a suspension bed,
Various methods such as a fixed shelf can be adopted, and any method may be used, but it is preferable to use a fixed bed.

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 the reaction product is needed,
It can be separated and recovered from the catalyst and the like by a usual separation method such as filtration separation, extraction and distillation.

Alcohols, which are the desired products, are subjected to ordinary 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 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 of it, it can be repeatedly used as a catalyst in the reaction again.

When the reaction is carried out in a fixed bed or fluidized bed continuous reaction system, the catalyst, which is partially or wholly deactivated or reduced in activity by being subjected to the reaction, is regenerated after interruption of the reaction and then used in the reaction. Alternatively, a part of the catalyst may be continuously or intermittently withdrawn, regenerated, recycled to the reactor, and reused. 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.

[0023]

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 Fluorine resin coating of cation exchange resin: A Fluoro was added to 10 g of dehydrated and dried cation exchange resin.
After spraying the glide as uniformly as possible, the resin was dried under reduced pressure at 150 ° C. until the weight of the resin became constant, and this was used as a catalyst. The weight of the fluororesin relative to the ion exchange resin is shown in Table 1. Fluorine resin coating of cation exchange resin: B The dehydrated and dried cation exchange resin was suspended in water, DuPont-Teflon 30 suspension was added with stirring, and the mixture was heated and dried under reduced pressure with sufficient mixing, This was used as a catalyst by drying until the resin weight became constant. The weight of fluororesin relative to the ion exchange resin is shown in Table 1. At this time, the weight of the fluororesin adhering to the ion exchange resin was a calculated value from the weight difference between the charged ion exchange resin and the weight of the resin after the fluororesin treatment. Alcohol Yield In all the examples and comparative examples, the analysis was carried out by a gas chromatographic method for the reaction solution, and the yield was expressed based on the charged olefin.

[0025]

[Table 1] Table 1 ──────────────────────────────────── Catalyst Cation exchange resin Coating method Fluorine Resin / exchange resin weight ratio ──────────────────────────────────── Catalyst 1 Amberlyst 15 A 0. 01 Catalyst 2 Amberlyst 15 A 0.031 Catalyst 3 Amberlyst 15 A 0.053 Catalyst 4 Amberlyst 15 B 0.028 Catalyst 5 Revatit K 2611 A 0.030 Catalyst 6 Revatit K 2661 A 0.029 Catalyst 7 Revatit K 2431 A 0.031 Catalyst 8 Amberlite IR-120B A 0.027 Catalyst 9 Amberlite XT-1026 A 0.032 ──────────────────────── ─────────── ─

Examples 1 to 9 After one of the catalysts 1 to 9 was charged in an autoclave of 70 ml in an amount of 3.0 g in terms of the weight of the ion exchange resin alone, and further, 24.0 g (1.33 mol) of water was charged. , 12.0 g (0.285 mol) of propylene were press-fitted, and the mixture was heated and stirred at 140 ° C. for 2 hours to carry out a reaction. 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, as shown in Table 2, it was confirmed that isopropyl alcohol was produced in good yield. At this time, in all of the examples, formation of isopropyl ether as a by-product was not confirmed. Furthermore, the catalyst after the reaction is
All were settled at the bottom of the reaction vessel and could be easily separated.

Comparative Example 1 Reaction and analysis were carried out under the same conditions as in Example 1 except that 3.0 g of Amberlyst 15 which was not subjected to the fluororesin coating treatment was used in Example 1. As shown in Table 2, the yield of isopropyl alcohol was lower than that of Example 1. This shows that the fluororesin coating treatment in the method of the present invention is extremely effective.

[0028]

[Table 2] Table 2 ──────────────────────────────────── Catalyst isopropyl alcohol yield (%) ──────────────────────────────────── Example 1 Catalyst 1 20.3 Example 2 Catalyst 2 21 .7 Example 3 Catalyst 3 19.0 Example 4 Catalyst 4 20.9 Comparative Example 1 Underlist 15 (no coating) 14.1 Example 5 Catalyst 5 22.1 Example 6 Catalyst 6 21.5 Example 7 Catalyst 7 20.3 Example 8 Catalyst 8 21.0 Example 9 Catalyst 9 19.8 ────────────────────────────── ───────

Example 10 The reaction was carried out under the same conditions as in Example 2 except that the reaction temperature was 150 ° C. As a result, isopropyl alcohol and isopropyl ether were 33.6% and 1.4%, respectively, based on the charged propylene.

Example 11 The reaction was carried out under the same conditions as in Example 2, except that the amount of water charged was 36.0 g. As a result, the yield of isopropyl alcohol was 31.0%, and formation of diisopropyl ether as a by-product was not observed.

Examples 12 to 13 Reactions were carried out under the same conditions as in Example 10 except that ethylene or 1-butene was used instead of propylene and 0.285 mol of each was charged. As shown in Table 3, the yield was good with each olefin, and alcohols were produced. All the yields in Table 3 are based on the charged olefin. The alcohols produced are ethanol from ethylene and 2-butanol from 1-butene.

[0032]

[Table 3] Table 3 ──────────────────────────────────── olefin alcohol yield (%) ──────────────────────────────────── Example 12 Ethylene 30.2 Example 13 1-Butene 35 4 ─────────────────────────────────────

[0033]

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 with 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. (3) It is possible to produce industrially important alcohols significantly in terms of safety, process, and economy. (4) By using a Teflon resin-treated catalyst, alcohols can be produced in an extremely high yield as compared with conventional cation exchange resin catalysts. (5) It is possible to provide a heterogeneous solid catalyst for producing alcohols by a direct hydration reaction of an extremely highly active olefin. INDUSTRIAL APPLICABILITY As described above, the present invention can provide an industrially excellent method for producing alcohols by hydration of olefins.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C07C 31/125 9159-4H // C07B 61/00 300

Claims (5)

[Claims] 1. When producing alcohols by catalytic hydration of olefins, a strong acid cation exchange resin having a sulfonic acid group bonded to an organic polymer matrix coated with a fluororesin is used as a catalyst. And a method for producing alcohols. 2. The method according to claim 1, wherein the fluororesin is a perfluorocarbon resin. 3. The method according to claim 1, wherein the fluororesin-coated product is a strongly acidic cation exchange resin impregnated with a polytetrafluoroethylene resin or spray-treated so as to adhere to the surface thereof. 4. 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. 5. The method according to claim 4, wherein the olefin is ethylene or propylene.