JPS60248632A - Preparation of alcohol by hydration method - Google Patents

Abstract

PURPOSE:In preparing an alcohol by catalytic hydration, to obtain the aimed compound in high catalytic activity in high yield, by using crystalline aluminosilicate containing thorium as a catalyst. CONSTITUTION:In preparation of an alcohol by catalytic hydration of an olefin, preferably an olefin containing 2-12C straight-chain or branched structure, especially cyclic olefin having both low hydration reaction rate and equilibrium alcohol concentration, crystalline aluminosilicate containing thorium preferably cation, hydroxide, oxide or metal is used as a catalyst, and the aimed compound is in an extremely higher conversion ratio and selectivity than an existing method and in reactivity to continue for a long time. An amount of thorium contained in the crystalline aluminosilicate is about 0.001-2.5mol/kg, especially 0.002-1.0mol/kg calculated as number of moles of thorium per unit weight of the catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel method for producing alcohol by utilizing olefins.

More specifically, the present invention relates to a method for producing alcohol by water utilization of olefins, which is characterized by using thorium-rich crystalline alumino heptasilicate as a catalyst.

[Convenient Technology J] Conventionally, indirect or direct hydration reactions using mineral acids, especially sulfur, have been known as methods for producing alcohol by olefin water-oxygenation reactions. Another method using aromatic sulfonic acid as a homogeneous catalyst (% publication 43-810
4, Publication No. 43-16123), methods using heteropolyacids such as phosphotungstic acid and phosphomolybdic acid (Patent Publication No. 53-9746), and the like have been proposed.

However, these homogeneous catalysts have the drawback that separation and recovery from the reactants, especially the aqueous layer, is complicated and consumes a large amount of energy.

As a method to remedy these shortcomings, a method using a solid catalyst, for example a method using an ion exchange resin, has been proposed.
-26656).

However, these ion conversion resins have problems such as pulverization of the resin due to mechanical collapse and a decrease in catalytic activity due to insufficient heat resistance, etc., and the disadvantage that stable activity cannot be maintained for a long time. I'm worried.

Furthermore, as a method using a solid catalyst, there is a method using crystalline aluminosilicate. Crystalline aluminosilicate is insoluble in water and has excellent mechanical strength and heat resistance, and is expected to be used as an industrial catalyst, and the following method has been proposed.

That is, an olefin water utilization method (%) using dealkalized mordenite, crimezotyrolite, or faujasite zeolite as a catalyst.

Publication No. 47-45323), olefin water first method (% Publication No. 53-15485), all or part of the ion-convertible cations of specific crystalline aluminosilicate published by Mopil Co., Ltd. of ZSM-5 Temple are hydrogen, group II of the periodic table, group vIIl, or earth group, Method for hydrating olefins using a catalyst substituted with rare earth element ions (Japanese Patent Application Laid-open No. 70828/1982)
, from which a part of the aluminum contained in zeolite has been removed and all or part of the ion-convertible cations have been converted with hydrogen, group ■ or group V of the periodic table, or earth or rare earth element ions. A method for water utilization of olefins using as a catalyst (Japanese Unexamined Patent Publication No. 58-124723).

〔problem〕

However, these methods do not provide industrially sufficient activity, and in order to obtain an industrially satisfactory reaction rate, it is necessary to increase the reaction temperature. However, the water utilization reaction of olefins is generally an exothermic reaction, and the ratio of alcohol to olefin at equilibrium composition decreases as the temperature increases. Therefore, an increase in the reaction temperature results in a decrease in the concentration of the product alcohol, and as a result, a large amount of cost is required to separate and recover the raw material olefin and the product alcohol. On the other hand, an increase in reaction temperature not only increases the water utilization reaction rate of the raw material olefin but also increases the rate of conversion to by-products through reactions such as isomerization, which may reduce the selectivity of the desired reaction. is expected.

As a result of extensive research to solve the above problems, the present inventors have found that by using thorium-containing crystalline aluminosilicate as a catalyst, the water utilization reaction of olefins can be more easily achieved than conventional methods. Furthermore, it was discovered that the reaction progresses with high activity and high selectivity, and that the reactivity is maintained for a long time, and the present invention has been completed.

〔composition〕

That is, the present invention relates to a method for producing alcohol by catalytic hydration of an olefin, which is characterized by using a crystalline aluminone licade containing thorium as a catalyst.

A feature of the present invention is that, while conventional crystalline aluminosilicates exhibit very low activity, thorium-containing crystalline aluminolaricates exhibit high activity in this reaction.
Alcohol can be obtained in substantially good yield.

Here, "contained" indicates a state in which thorium is physically or chemically bonded to the crystalline aluminosilicate through an ionic bond or other bond.

This fact is a surprising finding that had not been expected until now. The reason why crystalline aluminosilicate rich in thorium gold exhibits high activity is not clear, but it is thought to be as follows. In the present invention, it is presumed that the crystalline aluminosilicate containing thorium is formed in such a way that the active points for the reaction with water are also formed in a form containing thorium.

That is, in general, crystalline aluminosilicate converted with polyvalent Kusunoki ions exhibits solid acidity. This is because the water molecules coordinated to the exchanged polyvalent metal ions become polarized, resulting in the development of Brønsted acid sites (References: Takagi et al.
Zeolite"p, 134゜Koyusha (1975)). A similar process was used in the thorium-containing treatment of the present invention).
However, the polyvalent metal ion or hollow crystalline aluminosilicate of the prior art is less active in the olefin water utilization reaction than the corresponding proton exchange type crystalline aluminosilicate. However, the thorium-containing treatment of the present invention can dramatically speed up the desired water utilization reaction even when the crystalline aluminosilicate to be treated is already in the zoloton type. In this point, it is greatly different from the above-mentioned polyvalent gold J'0'4 ion exchange method, and a highly active site called thorium, which is different from a promine acid site, is formed in Ir:I'c. This fact was discovered for the first time in the present invention, and cannot be easily deduced from the prior art. When they coexist, crystalline aluminosilicate generally preferentially adsorbs water or the produced alcohol [and prevents the adsorption of the second component, that is, olefin, and at the same time prevents the adsorption of alcohol-A, which is the reverse reaction of water utilization. The dehydration reaction proceeds, and the hydration reaction sphere # falls off as a result of condensation.On the other hand, the prefectural PA of thorium and olefin is much larger than that of other elements.Therefore, in the catalyst used in the invention It is presumed that the n(f) point involving thorium promotes the selective adsorption of olefin onto the catalyst, greatly improving the efficiency of the hydration reaction. Therefore, in the present invention, The catalyst used exhibits active activity even in reaction conditions where liquid water is present in the reaction system.

The catalyst used in the invention can be obtained by processing known crystalline aluminosilicates. Crystalline aluminone licades used as catalyst precursors include mordenite, faujasite, clinoptilolite, chabasite, erionite, ferrierite, L-type zeolite,
Examples include ZSM zeolite published by Mopil and other pental zeolites. In the present invention, these crystalline aluminosilicates are treated to form crystalline aluminosilicate containing thorium, but any method may be used for the method of containing thorium.

For example, there is a dipping method in which the crystalline aluminosilicate is immersed in an aqueous solution of a thorium compound such as thorium nitrate, thorium chloride, or thorium sulfate at room temperature or under heating to exchange and/or adsorb the thorium base. There are methods such as evaporating a mixture of an aqueous solution or aqueous slurry of the compound and crystalline aluminosilicate to dryness, or treating it with a thorium compound in a solvent. The concentration of the thorium compound aqueous solution or aqueous slurry used to treat the crystalline aluminosilicate according to the present invention is preferably in the range of about 0.001 to 20% by weight, particularly preferably 0.05 to 10% by weight. In the case of the immersion method, the processing temperature is room temperature to IOO℃ at normal pressure, especially room temperature -80℃.
is preferable, and the treatment temperature in the case of evaporation to dryness method is 40°C at normal pressure.
-100°C, especially 60-100°C7. Furthermore, it is also effective to process at high pressure and high temperature 1. When carrying out the above-mentioned treatment in water, the thorium compound used may be substantially converted into a different type of thorium compound by a reaction such as hydrolysis.

In addition, after the above thorium element-containing treatment, ion exchange,
It is also possible to carry out post-treatments such as washing with water, drying, firing, and reduction. In the catalyst used in the present invention, the chemical type and existence form of thorium contained are not particularly specified, but thorium may be contained in the form of a cation, hydroxide, oxide, or metal oxide. preferable. The amount of thorium contained in the crystalline alumino/licade is preferably from about 0.001 to Z 5 mo p, expressed in moles of thorium per amount of catalyst unit M),
In particular, 9 is most likely to be 0.002 to 1.0 mOμ/.

It is also effective that protons or other cations may coexist in the crystalline alumino hepta-silicate after thorium-containing treatment, or that all active sites involved in water utilization reactions become active sites involving thorium.

The crystalline aluminosilicate used as a catalyst precursor in the present invention does not particularly specify the composition ratio of silica and alumina, but the crystalline aluminosilicate has a molar ratio of silica to alumina of 10 or more, especially a molar ratio of silica to alumina. is preferably 20 or more.

Furthermore, the particle size of the crystalline aluminosilicate used in the present invention is not particularly defined, but expressed in terms of the particle size of secondary particles, the particle size is usually 0.5 μm or less, preferably 0.1 μm or less. more preferably 0.05
A material smaller than μm is used.

Furthermore, secondary particles as an aggregate of primary particles due to aggregation or the like are also effective.

The crystalline aluminosilicate used in the present invention is not limited in its exchangeable cation species. However, it is effective to use it after performing proton exchange.

In this reaction, the shape of the catalyst may be any shape, such as powder, granules, molded bodies with specific shapes, etc. When a molded body is used, alumina may be used as a carrier or binder. , sled force, titania, etc. can also be used.

The olefin used in the present invention is preferably an olefin having a straight chain or branched structure having 2 to 12 carbon atoms, and a cyclic olefin. Examples of olefins include ethylene, zolopyrene, 1-butene, 2-butene, isobutyne, pente/s, hexenes, heptenes, octenes, cyclobutene, cyclopentene, methylcyclopentenes, cyclohexene, methylcyclohexenes, cyclooctene, cyclododecene etc. In particular, it is effective for hydrating round cyclic olefins, which generally have low water utilization reaction rates and have an equilibrium alcohol concentration.

As the reaction mode, commonly used methods such as a fluidized bed method, a stirring method, or a continuous method are used. Regarding the reaction temperature, a low temperature is advantageous from the viewpoint of the equilibrium of the olefin water utilization reaction and from the viewpoint of increasing side reactions, etc., but a high temperature is advantageous from the viewpoint of the reaction rate.
-1 Reaction mixture varies depending on the olefin used, but is usually used in the range of 30 to 300°C, preferably iJ:
The temperature range is preferably from 50 to 250°C, particularly from 60 to 200°C. Further, the reaction pressure is not particularly limited, and the olefin and water may exist as a gas phase or as a liquid phase. In particular, when water becomes a liquid phase, as mentioned above, the vicinity of the active site of the catalyst is generally covered with water, slowing down the desired reaction rate, so this reaction is particularly effective in that case. show. The molar ratio of raw material olefin/water can be varied over a wide range, and also varies depending on whether the reaction is carried out continuously or batchwise. However, if the olefin or water is in large excess compared to other raw materials, the reaction rate decreases, making it impractical. Therefore, in the present invention, the molar ratio of onfin to water is preferably in the range of 0.001 to 100, especially when carried out in a batchwise manner.
The range of 03 to 10 is preferable.

Olefin and catalyst when conducting this reaction batchwise
(7) 畢)i td, 0005~] Oo Ka-i
L<, especially 005 to 10 is preferable. The reaction time is preferably 3 to 300 minutes, particularly preferably 10 to 180 minutes.

- In addition to the olefin and water, which are reaction raw materials, nitrogen and hydrogen 1. Inert residues such as helium, argon, and back oxygen dioxide, aliphatic saturated olohydrocarbons, aromatic hydrocarbons, oxygen-containing organic compounds, sulfur-containing organic compounds, halogen-containing organic compounds, etc. are present in the reaction system. It's okay.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.

Example 1 [1] Catalyst preparation]) 11.12 g of Q ground sodium silicate and 13 g of water
Add a mixture of 32.2 g of aluminum sulfate, 328 g of sodium chloride, 9.2.6 g of concentrated sulfuric acid, 139 g of tetranolopylammonium bromide and 1896 g of water to 86 g of the mixture, and mix thoroughly with a high-speed stirring homogenizer. 1. Keep under stirring at 150°C for 4 days in an autoclave. After filtering and washing the reaction product with water,
It was dried for 8 hours at 120°C and then tested at 550°C under a stream of air. 400 g of Precursor A was added to 4 ml of a 2M aqueous ammonium chloride solution and kept at 80° C. for 2 hours with stirring. After filtration, the same operation was repeated two more times to perform ion exchange, washing with water, filtration, drying, and then baking at 400° C. for 2 hours to obtain proton '4i type ZSM-5 (hereinafter referred to as body B).

2) Thorium nitrate (rV+) 0.72 g and water JOO
aerate 1 g of the precursor A into the mR mixture;
Stirred at room temperature for 8 hours. The treated mixture was washed with water and filtered, and the solid material was dried and then calcined in an air stream at 400° C. for two nights to obtain catalyst 1.

3) To a mixture of 18 g of tric nitrate b, Qv) and water at 25° C., 250 g of the precursor B was added, and the mixture was stirred at room temperature for 12 hours. The treated mixture was washed with water and filtered, and the solid material was dried at 80° C. in a nitrogen atmosphere to obtain catalyst 2 (i1″).

4) Catalyst 2 was calcined at 400° C. for 2 hours under a stream of air to obtain Catalyst 3.

5) The catalyst 3 was heated at 400° C. for 3 hours under a hydrogen stream to obtain a catalyst 4.

6) Thorium nitrate (TV) xa, sg and water 100mj4
50 g of the precursor B was added to the mixture, and the mixture was heated on a 100° C. water bath and evaporated to dryness. Catalyst 5 was obtained by drying at 130°C for 12 hours and calcining at 400°C for 4 hours under a stream of air.

The amount of thorium contained in the catalyst obtained above is
Measured by line analysis method. The results are shown in Table 1.

Table 1 rl ['] Water utilization reaction 10 g of the catalyst obtained above, 30 g of water, and 15 g of cyclohexene were charged into a stirred autoclave with an internal volume of 1 oyal, and after replacing the air in the system with nitrogen, the temperature was kept at 118°C for 14 hours.
The reaction was allowed to take place while stirring for a minute. After the reaction, the product was analyzed by gas chromatography. The results are shown in Table 2. The only product was cyclohexanol, no other products were detected.

Table 2 Comparative Example 1 Example 1 except that Precursor B was used as the catalyst. ! :Water use reaction was carried out under the same conditions. As a result, the cyclohexanol concentration in the oil phase was 3.3% by weight.

Example 2 20 g of catalyst 3 was added to a mixture of 4 g of thorium (IV) nitrate and 200 d of water, and the mixture was stirred at room temperature for 10 hours.

The treated mixture was washed with water, filtered, and the solid material was dried and then calcined at 400° C. for 2 hours under a stream of air. The obtained solid was further subjected to the above-mentioned thorium-containing treatment three times to obtain catalyst 6. The thorium content of catalyst 6 was determined by fluorescent X-ray analysis to be 0.41 moμ/Kr.

A water utilization reaction was carried out under the same conditions as in Example 1 except that the catalyst 6 obtained above was used. As a result, the concentration of cyclohexanol in the oil phase was 13.0% by weight.

Example 3 100g of catalyst 3, 300g of water and cyclohexene 1
50g of the mixture was charged into a stirring autoclave with a content of Table 1, and reacted at 96°C for 5.5 hours with stirring. As a result, the concentration of cyclohexanol in the oil phase was 18.2% by weight.
Met. Only the oil phase was separated from the reaction mixture by decantation, and while the aqueous slurry phase containing the catalyst was kept in the reaction vessel, 150 g of raw material cyclohexene was added, and the reaction was carried out under the same conditions as above. As a result of repeating this operation 40 times in total, the cyclohexanol concentration in the oil phase finally obtained was 18,080% by weight, and almost no decrease in catalyst activity or selectivity was observed.

Comparative Example 2 A water reaction was repeated under the same conditions as in Example 3 except that Precursor B was used as a catalyst. The cyclohexanol concentration in the oil phase in the first reaction mixture was 52% by weight, whereas the cyclohexanol concentration in the oil phase in the final reaction mixture was 23% by weight.

Example 4 Synthetic mordenite (TSZ64j manufactured by Toyo Soda Co., Ltd.) at 2M
After ion exchange with an ammonium chloride aqueous solution, proton exchange type mordenite (hereinafter referred to as precursor C) was obtained by firing.

20 g of the precursor C was added to a mixture of 3.3 g of thorium nitrate (1 v) and 200 d of water, and the mixture was kept at 80° C. for 2 hours while stirring. The treated mixture was washed with water, filtered, dried, and calcined at 400° C. for 2 hours under a stream of air to obtain catalyst 7. The thorium content of this catalyst 7 according to fluorescent X-ray analysis is 0-23
The mail weight was 7Kg.

A reaction was carried out using the catalyst 7 obtained above under the same conditions as in Example 1 except that the reaction time was 65 minutes. As a result, the concentration of cyclohexanol in the oil phase was 1% by weight. Further, 0.066% by weight of methyl cycloenthene, 0.05% by weight of synchlorohexyl ether, and 0.05% by weight of cyclohexene dimer were present.

Comparative Example 3 A water utilization reaction was carried out under the same conditions as in Example 4, except that a catalyst and a 1.7% precursor C were used. As a result, the concentration of cyclohexanol in the oil phase was 3.1% by weight. Also, methylcycloenthene is 0.58% by weight, dicyclohexyl ether is 0.27% by weight, and cyclohexene dimer is 0.
．． It was present at 1.4% by weight.

Example 5 A water utilization reaction was carried out under the same conditions as in Example 1 except that 10 g of propylene and 10 g of catalyst 3 were used as the olefin, the reaction temperature was 186° C., and the reaction time was 35 minutes. As a result, the concentration of 2-pro, o-nol in the aqueous phase is s, aiiji1
%Met.

Example 6 Using 1-butene as the olefin, the reaction temperature was set to 166
Water utilization reaction was carried out under the same reaction conditions as in Example 5 except that the temperature was lowered to 0.degree. C. After cooling, the container was opened and subjected to analysis. As a result, the 2-butanol concentration in the aqueous phase was 3.0% by weight. i
The gas phase component containing unreacted 1-butene contained 5% cis and trans-2-butene.

Comparative Example 4 A reaction was carried out under the same conditions as in Example 6 except that Precursor B was used as a catalyst. As a result, the 2-butanol concentration in the aqueous phase was 1.0 weight, i%. Additionally, 10 cis and trans-2-butenes were present as gas phase components.

Example 7 Isobutyne was used as the olefin, and the reaction temperature was 60°C.
The water utilization reaction was carried out under the same conditions as in Example 6 except for the following. As a result, the concentration of 2-methyl-2-propatol in the aqueous phase was 22.8% by weight.

Comparative Example 5 A water utilization reaction was carried out under the same conditions as in Example 7 except that Precursor B was used as a catalyst. As a result, the concentration of 2-methyl-2-protanol in the aqueous phase was 55% by weight.

Example 8 Using 1-octene as the olefin, the reaction temperature was 12
The reaction was carried out under the same conditions as in Example 5 except that the temperature was 0°C. As a result, the concentration of 2-octatool in the oil phase was 39%.

Example 9 A hydration reaction was carried out under the same conditions as in Example 7 except that an isobutyne-containing hydrocarbon having the following composition was used as the olefin. As a result, 2-methyl-2-pronominol 7bS 1 a2 double ftk was present in the aqueous phase. No other products were observed.

Composition of isobutene-containing hydrocarbon Isobutane 53 Weight ratio n-butane 13.47 Trans-butene 2 6.8 # Isobutene 44.1' Butene 7-125.17 Cis-butene-25,3' Example 10 [I], Catalyst Preparation Q To a mixture of 780 g of brand sodium silicate and 973 g of water was added a mixture consisting of 23.1 g of aluminum sulfate, 232 g of sodium chloride, 65.1 g of sulfuric acid, 98 g of tetraprobyl ammonium odor, and 1340 g of water, and the mixture was heated using a high-speed stirring homogenizer. After thorough mixing, the mixture was kept at 110° C. for 5 days in an autoclave with stirring. The cooled reaction product was filtered, washed, dried, and calcined using the catalyst preparation method of Example 1, and further subjected to ion conversion with an aqueous ammonium chloride solution, followed by filtration, washing, drying, and calcining. Thorium was added to the catalyst precursor obtained above in the same manner as 3) of Example 1, and the mixture was calcined at 400° C. for 2 hours under a stream of air to obtain catalyst 8.

[■], Water utilization reaction A reaction was conducted under the same conditions as in Example 1 except that the catalyst 8 obtained above was used, and then analyzed. As a result, the cyclohexanol concentration in the oil phase was 14.3% by weight.

〔effect〕

According to the present invention, when producing alcohol by catalytic water utilization of olefins, by using crystalline aluminosilicate containing thorium as a catalyst, a significantly higher conversion rate and selectivity can be obtained compared to conventional methods, and Reactivity connects for a long time.

Patent applicant: Asahi Kasei Industries, Ltd.

Claims (1)

[Claims] An alcohol production method characterized by using crystalline aluminosilicate that uses thorium as a catalyst to produce alcohol by catalytic water utilization of olefins.