JPS60252437A - Production of alcohol by hydration of olefin - Google Patents

Abstract

PURPOSE:To obtain an alcohol in high yield, proceeding the hydration reaction of an olefin in high activity and selectivity, and keeping the reactivity for a long period, by using a crystalline aluminosilicate as a catalyst in the presence of an acid in the form of an aqueous solution. CONSTITUTION:In the production of an alcohol by the catalytic hydration of an olefin, a crystalline aluminosilicate is used as the catalyst, and the reaction is carried out in the presence of an aqueous solution of an acid (preferably an inorganic compound exhibiting Broensted acidity such as sulfuric acid, nitric acid, tungstic acid, etc., an inorganic compound exhibiting Lewis acidity such as aluminum-group metal halide, etc., an organic carboxylic acid such as formic acid, acetic acid, etc. or an organic sulfonic acid such as benzenesulfonic acid, etc. having a concentration of 0.005-5mol/l, especially 0.01-1mol/l). EFFECT:The rate of reaction can be remarkably improved.

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 utilizing olefin water, which is characterized by using a crystalline aluminosilicate as a catalyst and allowing an acid in a solution state to coexist in the reaction system.

(Prior Art) As a method for producing alcohol by the hydration reaction of olefins, indirect or direct hydration reactions using mineral acids, particularly sulfuric acid, are known. Other homogeneous catalysts include methods using aromatic sulfonic acids (Japanese Patent Publication No. 45-8104 and Japanese Patent Publication No. 43-16123), methods using heteropolyacids such as phosphotungstic acid and phosphomolybdic acid ( Japanese Unexamined Patent Publication No. 53-9746) and the like have been proposed.

However, with these homogeneous catalysts, the acid concentration must be increased to improve the reaction rate, and as a result,
Separation and recovery of reactants from a homogeneous phase becomes complicated and requires a large amount of energy, and disadvantages include an increase in side reactions and the sound of accelerating corrosion of the material of the reactor used.

As a method to improve these drawbacks, a method using a solid catalyst, for example a method using an ion exchange resin, has been proposed (% Publication No. 58-15619, Japanese Patent Publication No. 4
4-26656).

However, these ion-exchange resins have problems such as pulverization of the resin due to mechanical collapse and a decrease in catalytic activity due to heat resistance being opaque, and it is said that stable activity cannot be maintained for a long time. There are drawbacks.

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, a water utilization method for olefins using dealkalized mordenite, clinoptilolite, or faujasite zeolite as a catalyst (Japanese Patent Publication No. 47-4532
(Japanese Patent Publication No. 53-15485), ZSM -5, etc., in which all or part of the ion-exchangeable cations of specific crystalline aluminosilicate published by Mopil are replaced with hydrogen, group ■, group ■ of the periodic table, or earth or rare earth element ions. A method for hydrating olefins as a catalyst (Patent Publication No. 1982-70828), in which a part of the aluminum contained in zeolite is removed, and all or part of the ion-exchangeable cations are replaced with hydrogen, periodic Irrigation method for olefins using catalysts exchanged with Groups ■, ■, or earth or rare earth element ions of the Table of Laws (Japanese Patent Application Laid-Open No. 58-12
4723) etc.

(Problems to be Solved by the Invention) In the method using the crystalline aluminosilicate, sufficient activity cannot be obtained industrially, and in order to obtain an industrially satisfactory reaction rate, the reaction temperature must be increased. It is necessary to do so. 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, resulting in a decrease in the selectivity of the desired reaction. is predicted.

(Means for solving the problem) As a result of intensive research to solve the above problems, the present inventors found that by using crystalline aluminosilicate as a catalyst in the presence of an acid in an aqueous solution state, In the water utilization reaction of olefins, we have discovered that the reaction proceeds with significantly higher activity and selectivity than conventional methods, and that the reactivity lasts for a long time, leading us to complete the present invention. Ta.

That is, the present invention relates to an alcohol production method characterized by using a crystalline aluminosilicate as a catalyst and coexisting an acid in an aqueous solution state in the reaction system when producing alcohol by catalytic water utilization of olefins. .

The feature of the present invention is that while conventional hydration methods using crystalline aluminosilicates as catalysts only show very low yields, the reaction rate is significantly improved by coexisting an acid in an aqueous solution state. However, alcohol can be obtained in substantially good yield.

This fact is an important and hitherto unexpected finding. That is, the acid in the aqueous solution state used in the present invention can exhibit the effects of the present invention at a concentration that does not exhibit hydration activity by itself, and is only the sum of the respective effects of the crystalline aluminosilicate and the acid in the aqueous solution state. I can't explain it. The reason why crystalline aluminosilicate in which an acid in an aqueous solution coexists exhibits high activity is not clear, but the following possibilities are considered. (11) It is thought that the protons of the acid in the aqueous solution state coordinate with the lone pair of electrons of the oxygen atoms on the surface of the crystalline aluminosilicate, and the acid strength of the crystalline aluminosilicate increases due to the electron-withdrawing effect.

121 In particular, when using an inorganic compound exhibiting Lewis acidity, the effect appears even in a low acidity state as an aqueous solution. Therefore, by direct interaction between the water utilization reaction active sites of the crystalline aluminosilicate and these Lewis acid molecules, new, more highly active hydration reaction active sites are formed, increasing the affinity with olefins, It is surmised that this greatly improves the water utilization reaction activity.

In the present invention, a known crystalline aluminosilicate is used. Examples include mordenite, faujasite, clinoptilolite, chabasite, erionite, ferrierite, L-type zeolite, ZSM zeolite published by Mopil, and other noveltaful zeolites.

The acid used in the present invention is a substance that exhibits acidity when mixed with water, and even if it is denatured during the reaction by hydrolysis, thermal decomposition, etc., as long as the aqueous solution remains acidic in that state. good. Examples include sulfuric acid, nitric acid to hydrochloric acid, molybdic acid, tungstic acid, inorganic compounds exhibiting Bronsted acidity such as heteropolyacid, aluminum group halides, transition metal halides, transition metal sulfate groups,
Inorganic compounds with Lewis acidity such as transition metal complexes, carboxylic acids such as formic acid, acetic acid, propionic acid, trifluoroullic acid, methanesulfonic acid, benzenesulfonic acid, p-
Organic sulfonic acids such as toluenesulfonic acid are used. Furthermore, it is also effective to select two or more of these acids and mix them together for use in the reaction.

The acid exists in the reaction system in the form of an aqueous solution. If the concentration is too high, it becomes very difficult to separate and recover the reactants. Additionally, if the acid concentration is too low, the acid strength as an aqueous solution will be insufficient. Therefore, in the present invention, the concentration of acid varies depending on the type of acid, but is usually 0.001 to 5.
mol-/l range, preferably 41. (d 0.00 s
~2 rnot/l range, more preferably 0.0
It is used in a range of 1 to 1 mO4/l.

Moreover, at the above acid concentration, when only the acid in an aqueous solution state is used as a catalyst without using crystalline aluminosilicate, hardly any water utilization activity is exhibited.

The crystalline aluminosilicate used in the present invention does not particularly specify the composition ratio of silica and alumina, but
Depending on the type and concentration of the acid used, one with a high ratio of silica to alumina is preferable because it has excellent shape stability. Therefore, in the present invention, it is preferable that the ratio of silica to alumina is 10 or more, and particularly, the ratio of silica to alumina is 20 or more.

Further, the particle size of the crystalline aluminosilicate used in the present invention is not particularly defined, but the particle size is usually 0.5 μm or less, preferably 0.5 μm or less, expressed as the particle size of -order particles. .1μm or less, preferably 0.05μm
The following are 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 the type of exchangeable cation species. but,
It is effective to use it after performing proton exchange. It is also effective to use it after performing exchange with polyvalent metal ions.

Crystalline aluminum silica used in the present invention
■ Group A elements such as titanium, zirconium, and hafnium,
■ Group A elements such as chromium, molybdenum, and tungsten; Group ■ elements such as silver, cobalt, nickel, and ruthenium; copper;
Group IB elements such as silver, III such as aluminum, gallium, etc.
Those containing at least one of group B elements, rare earth elements such as yttrium, lanthanum, and cerium, and actinide elements such as thorium are also effective. Here, "contained" refers to a state in which the above-mentioned element is physically or chemically bonded to the crystalline aluminosilicate through an ionic bond or other bond.

In this reaction, the catalyst may have any shape, such as powder, granules, and molded bodies having a specific shape. Furthermore, when a molded body is used, aluminum silica, titania, etc. can also be used as a carrier or binder.

The olefin used in the present invention preferably has 2 carbon atoms.
These are olefins and cyclic olefins having a direct or branched structure of 12 or less. An example of an olefin is
Ethylene, propylene, 1-butene, 2-butene, isobutene, pentenes, hexenes, heptenes, octenes, cyclobutene, cyclopentene, methylcyclopentenes, cyclohexene, methylcyclohexene,
Schiff, octene, cyclododecene, etc. In particular, it is effective for water utilization of cyclic olefins, which generally have a low water utilization reaction rate and a low equilibrium alcohol concentration.

As for the reaction mode, commonly used methods such as a fluidized bed method, a stirring batch method, or a continuous method are used. Regarding the reaction temperature, a low temperature is advantageous from the viewpoint of 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. The reaction temperature varies depending on the olefin used, but is usually 50 to 500 C, preferably 50 to 250 C.
, particularly preferably 60 to 200p. Further, the reaction pressure is preferably such that the acid can remain in an aqueous solution state. The olefin may be present as a gas phase;
It may also exist as a liquid phase.

The molar ratio of the raw material olefin to water can be varied over a wide range, and also varies depending on whether the reaction format is continuous or batchwise. However, if the olefin or water is in large excess compared to one of the raw materials, the reaction rate decreases and is not practical. Therefore, in the present invention, the molar ratio of olefin to water is preferably from 0.01 to 100, particularly when carried out batchwise.
03-10 is preferable.

When this reaction is carried out batchwise, the weight ratio of the olefin to the solid catalyst is preferably 0.005 to 100, particularly 0.05.
-10 is preferred. Further, the reaction time is preferably 3 to 300 minutes, particularly preferably 10 to 180 minutes.

In addition to olefin and water, which are reaction raw materials, inert gases such as nitrogen, hydrogen, helium, argon, and carbon dioxide,
Alternatively, aliphatic saturated hydrocarbons, aromatic hydrocarbons, oxygen-containing organic compounds, sulfur-containing organic compounds, halogen-containing organic compounds, etc. may be present in the reaction system.

(Effects of the Invention) According to the present invention, when producing alcohol by catalytic water utilization of olefins, by using crystalline aluminosilicate as a catalyst and coexisting an acid in an aqueous solution state in the reaction system, conventional methods can be improved. Significantly higher conversion rates and selectivities are obtained in comparison.

(Example) Example 1 Q-brand sodium silicate 1112 Rito water 13862
to a mixture of 62°21 aluminum sulfate, 528 f sodium chloride, 92.6 f concentrated sulfuric acid, and 159 g tetrapropylammonium bromide. A mixture consisting of 18962 and 18962 water was added, rigorously mixed using a high-speed stirring homogenizer, and kept in a stirring TK autoclave at 150'C for 4 days. The cooled reaction product was washed with water, dried at 120°C for 8 hours, and then calcined at 550C for 5 hours under a stream of air. The obtained solid was a crystal, and ZS was determined by X-ray diffraction method.
It was identified as M-5 (catalyst ■).

Catalyst I, 4001 was added to 4 tons of ammonium chloride 2M water bath and kept at aoc for 2 hours with stirring.

After filtration, the same operation was repeated two more times to perform ion exchange. After washing with water, filtration, and drying, the product was calcined at 4ooc for 2 hours to obtain proton exchange type ZSM-5 (catalyst ①).

A mixture of water 301 and acid and cyclohexene 152
The catalyst l110fi obtained above was charged into a stirring autoclave having an internal volume of 100 m, and the air in the a1 system was replaced with nitrogen, and then reacted at 118c for 17 minutes with stirring.

After the reaction, the product was analyzed by gas chromatograph 2F method. Table 1 shows the type of acid used, the concentration of its aqueous solution, and the reaction results.

Table 1 Comparative Example 1 The hydration reaction was carried out under the same conditions as in Example 1 except that no acid was added, and the cyclohexanol concentration in the oil phase was 6.
．． There were eight enemies.

Comparative Example 2 A hydration reaction was carried out under the same conditions as in Example 1-A, except that catalyst (1) was not added. As a result, the cyclohexanol concentration in the oil phase was below the detection limit.

Example 2 Except that the reaction temperature was 98C1 and the reaction time was 4.5 hours,
As a result of carrying out the water utilization reaction under the same conditions as in Examples 1-A,
The cyclohexanol concentration in the oil phase was 20.4 times.

Example 3 A water utilization reaction was carried out under the same conditions as in Example 1-A, except that Catalyst I was used as the catalyst, and as a result, the concentration of cyclohegizanol in the oil phase was 6.8% by weight.

Example 4 Synthetic mordenite (T S Z 644 manufactured by Toyo Soda Co., Ltd.)
After ion exchange with an aqueous ammonium 2Mi dihydride solution, proton-exchanged mordenite (catalyst ■) was obtained by calcination.

The water utilization reaction was carried out under the same conditions as in Example 1-A, except that the above catalyst (1) was used and the reaction time was 70 minutes. As a result, the cyclohexanol concentration in the oil phase was 7.8% by weight. . Still, 0.06% by weight of dicyclohexyl ether,
As a result of the water utilization reaction of cyclohexene dimer,
The cyclohexanol concentration in the oil phase was 5.9% by weight. In addition, dicyclohexyl ether is o, 4o weight i%
, 0.18% by weight of cyclohexene dimer was present.

Example 5 Using propylene as the olefin, the reaction temperature was 188
C. The water utilization reaction was carried out under the same conditions as in Example 1-A, except that the reaction time was 60 minutes. As a result, the concentration of 2-propanol in the aqueous phase was 4.1% by weight.

Example 6 Using 1-butene as the olefin, the reaction temperature was 168
A hydration reaction was carried out under the same conditions as in Example 5, except that the sample was designated as C. After cooling, the package was opened and subjected to analysis.

The concentration of 2-butanol in the aqueous phase was 2.8% by weight. - Also, 6% of cis and trans-2-butene were present in the gas phase containing unreacted 1-butene.

Comparative Example 4 A hydration reaction was carried out under the same conditions as in Example 6 except that no acid was added. As a result, the 2-butanol concentration in the aqueous phase was 1.
．． It was 0% by weight. In addition, 10% of gas phase components and [7] cis and trans 2-butenes were present.

Example 7 A water utilization reaction was carried out under the same conditions as in Example 5, except that isobutyne was used as the olefin and the reaction temperature was 62C. As a result, the concentration of 2-methyl-2-propatol in the aqueous phase was 26.7. % by weight.

Comparative Example 5 A water utilization reaction was carried out under the same conditions as in Example 7, except that no acid was added. As a result, the concentration of 2-methyl-2-gummypanol in the aqueous phase was 5.3% by weight.

Example 8 Using 1-octene as the olefin, the reaction temperature was 12D.
The hydration reaction was carried out under the same conditions as in Example 5, except that C was used, and as a result, the concentration of 2-octatool in the oil phase was 2.0% by weight.

Example 9 To a mixture of 0.40 r of titanium tetrachloride and 100 m of water was added 1 oy of catalyst (1), and the mixture was stirred at room temperature for 8 hours. The treated mixture was washed with water, filtered, and dried for 40 minutes under a stream of air.
00 for 3 hours (catalyst ■). The titanium content determined by X-ray fluorescence analysis was 0.15 moz/ki expressed in moles per unit weight of catalyst.

The water utilization reaction was carried out under the same conditions as in Example 1-A, except that catalyst (1) was used as the catalyst, and the cyclohexanol concentration in the oil phase was 15.8% by weight.

Example 10 A water utilization 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, and as a result, 18. 3 weight - present. Moreover, no other products were observed.

Composition of inbutylene-containing hydrocarbons Inbutane 5.3% by weight n-butane 15,4I Trans-butene-26,8z Isobutyne 44.1 # Butene-1 25,1 y Cis-butene-25,! l z Example 11 To a mixture of Q brand sodium silicate 7761 and water 9741, consisting of 22.1 f aluminum sulfate, 226 p sodium chloride, 64.5 f concentrated sulfuric acid, 57" tetyl bromide 96 f lobylammonium and 15181 water The mixture was added and mixed rigorously in a high-speed stirring homogenizer and then kept at 110 C in an autoclave under stirring for 5 days.The cooled reaction product was filtered, washed with water, and dried in the same manner as the catalyst preparation in Example 1. , calcination, ion exchange with ammonium chloride aqueous solution, filtration, washing with water, drying,
Firing was performed. The solid obtained is fine crystals, and
It was identified as ZSM-5 by line diffraction method (Catalyst V).

The reaction was carried out under the same conditions as in Example 1-A except that the catalyst obtained above was used, and concentrated sulfuric acid was added thereto, followed by analysis. As a result, the cyclohexanol concentration in the oil phase was 14.1% by weight.
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Claims (1)

[Claims] (11) A method for producing alcohol, which comprises using a crystalline aluminosilicate as a catalyst and coexisting an acid in an aqueous solution state in the reaction system when producing alcohol by catalytic water utilization of olefins. (2) The method according to claim 1, wherein the acid is an inorganic compound having Bronsted acidity or Lewis acidity. 13) The method according to claim 1, wherein the acid is an organic carboxylic acid or an organic sulfonic acid. Method.