JPS60248635A - Production of alcohol by catalytic hydration of olefin - Google Patents

Abstract

PURPOSE:To produce an alcohol in high yield, by carrying out the catalytic hydration of an olefin in extremely high catalytic activity and selectivity using a catalyst consisting of a crystalline aluminosilicate containing at least one of Ti, Zr and Hf. CONSTITUTION:The production of an alcohol by the catalytic hydration of an olefin is carried out by the use of a catalyst consisting of a crystalline aluminosilicate containing at least one of titanium, zirconium and hafnium, e.g. a catalyst prepared by immersing a crystalline aluminosilicate in an aqueous solution of a compound of titanium, zirconium or hafnium such as titanium halide, titanium nitrate, zirconium sulfate, hafnium sulfate, etc. EFFECT:The reactivity of the catalyst lasts long.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a novel method for producing dialcohols by hydration of 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 containing at least one of titanium, zirconium, and hafnium as a catalyst.

(Prior Art) As a method for producing alcohol by a water utilization reaction of olefins, indirect or direct hydration reactions using mineral acids and sulfuric acid are known. In addition, other homogeneous catalysts include methods using aromatic sulfonic acids (Japanese Patent Publication No. 4B-8104 and Japanese Patent Publication No. 43-16123), methods using heteropolyacids such as phosphotungstic acid and phosphomolybdic acid ( % Publication No. 55-9746) 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 for improving these drawbacks, a method using a solid catalyst, for example a method using an ion exchange resin, has been proposed (4ej Publication No. 58-15619, Japanese Patent Publication No. 44-26656).

However, these ion exchange resins are unable to maintain stable activity for a long period of time due to problems such as pulverization of the resin due to mechanical collapse, a decrease in catalytic activity due to the lack of heat resistance due to isobaric conditions, etc. There is a drawback.

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.The following method has been proposed.

That is, a method for hydrating olefins using dealkalized mordenite, clinoptilolite, or faujasite zeolite as a catalyst (% Publication No. 47-4532)
(Japanese Patent Publication No. 53-15485), ZSM Hydrogen,
A method for water utilization of olefins using catalysts substituted with Groups ■, ■, or earth or rare earth element ions of the periodic table (Japanese Unexamined Patent Publication No. 70828), which removes part of the aluminum contained in zeolite. A method for water utilization of olefins using a catalyst in which all or a part of the ion-exchangeable cations are exchanged with hydrogen, group Ⅰ, group Ⅲ of the periodic table, or earth or rare earth element ions (percent open). 1980-12
4725) 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 extensive research to solve all of the above problems, the present inventors have discovered that by using crystalline aluminosilicate containing titanium, zirconium, and hafnium as a catalyst, olefin In the hydration reaction, the present inventors discovered that the reaction proceeds with significantly higher activity and selectivity than in conventional methods, and that the reactivity lasts for a long time, leading to the completion of the present invention.

That is, the present invention is a method for producing alcohol using t% of crystalline aluminosilicate containing titanium, zirconium, and hafnium as a catalyst when producing alcohol by catalytic hydration of olefin.

A feature of the present invention is that while conventional crystalline aluminosilicate exhibits very low activity, crystalline aluminosilicate containing titanium, zirconium, and hafnium exhibits high activity in this reaction, resulting in a substantial yield. It is possible to obtain alcohol well.

Here, "contained" indicates a state in which titanium, zirconium, and hafnium are physically or chemically bonded to the crystalline aluminosilicate through ionic bonds or other bonds.

This fact is a surprising finding that has not been previously investigated. The reason why crystalline aluminosilicate containing titanium, zirconium, and hafnium exhibits high activity is not clear, but it is thought to be as follows. In the present invention, it is presumed that in the crystalline aluminosilicate containing titanium, zirconium, and hafnium, active sites for the hydration reaction are newly formed in the form of titanium, zirconium, and hafnium. That is,
Generally, crystalline aluminosilicates exchanged with polyvalent metal ions exhibit solid acidity. This is because Brønsted acid sites are developed by polarization of water molecules coordinated to the exchanged polyvalent metal ions [Reference: Takanara et al., "Zeolite", p. 154. Kodansha (1975)). In the treatment containing titanium, zirconium, and hafnium in the present invention, it can be assumed that active sites are developed by a similar process. However, the polyvalent metal ion-exchanged crystalline aluminosilicate of the prior art had the same or lower activity in the olefin water utilization reaction than the corresponding proton-exchanged crystalline aluminosilicate.

However, the treatment containing titanium, zirconium, and hafnium in the present invention dramatically increases the rate of the desired hydration reaction, even if the crystalline aluminosilicate to be treated is already in the proton form. Improve. In this respect, it is greatly different from the above-mentioned polyvalent metal ion exchange method, and it is thought that additional highly active sites containing titanium, zirconium, and hafnium, which are different from protonic acid sites, are newly formed.

This fact was discovered for the first time in the present invention and cannot be easily deduced from the prior art. Furthermore, when water and organic substances coexist in the reaction system as in the present invention, crystalline aluminosilicate generally preferentially adsorbs water or the alcohol produced, and the adsorption of the second component, that is, the olefin, is reduced. At the same time, the dehydration reaction of alcohol, which is the reverse reaction of water utilization, proceeds, and as a result, the water utilization reaction rate decreases. On the other hand, the heat of adsorption between titanium, zirconium, and hafnium and olefins is much larger than that of other elements. Therefore, in the catalyst used in the present invention, it is presumed that the active sites involving titanium, zirconium, and hafnium promote selective adsorption of olefins onto the catalyst, greatly improving the efficiency of water utilization reactions. be done. Therefore, the catalyst used in the present invention exhibits high activity even under reaction conditions where liquid water is present in the reaction system.

The catalyst used in the present invention can be obtained by a known total treatment of crystalline aluminosilicate. Crystalline aluminosilicates used as catalyst precursors include mordenite, faujazite, clinoptilolite, chabasite, erionite, ferrierite, L-type zeolite,
Examples include ZSM zeolite published by Mopil and other pentasil zeolites.

In the present invention, these crystalline aluminosilicates are used as a crystalline aluminosilicate containing titanium, zirconium, and hafnium, but any method may be used as the method for containing them. For example, immersion methods, i.e. aqueous solutions of titanium, zirconium, hafnium compounds such as titanium halides, titanium nitrates, titanium sulphates, titanates, zirconium halides, zirconium nitrates, zirconium sulphates, hafnium halides, hafnium nitrates, hafnium sulphates, etc. Among them, there is a method of total exchange and/or adsorption of titanium, titanium, zirconium, and hafnium by immersing crystalline aluminosilicate at room temperature or under heating, and a method of evaporation to dryness, that is, a method of completely exchanging and/or adsorbing the titanium, zirconium, and hafnium compounds mentioned above. A method of evaporating to dryness a mixture of an aqueous solution or an aqueous slurry and a crystalline aluminosilicate;
Alternatively, there is a method of treating with titanium, zirconium, or hafnium compounds in an organic solvent.

The concentration of the titanium, zirconium, hafnium compound aqueous solution or aqueous slurry for treating crystalline aluminosilicate according to the present invention is preferably about 0.001 to 20% by weight, preferably 0.01 to 10% by weight. In the case of the immersion method, the processing temperature ranges from room temperature to 1ooch* at normal pressure.
oc is preferable, and the treatment temperature in the case of the evaporation to dryness method is preferably 40 to 100C2, particularly 60 to 100C at normal pressure. Furthermore, it is also effective to perform treatment under 5 pressures and high temperatures. When the above-mentioned treatment is performed in water, the titanium, zirconium, or hafnium compound used may be substantially converted into a different type of titanium, zirconium, or hafnium compound by a reaction such as hydrolysis. Mafc.

After the titanium-, zirconium-, and hafnium-containing treatment described above, it is also possible to perform post-treatments such as ion exchange, water washing, drying, calcination, and reduction.

In the catalyst used in the present invention, the chemical species and existing forms of titanium, zirconium, and hafnium contained are not specified in terms of percentage, but titanium, zirconium,
Those containing hafnium as a cation, hydroxide, oxide or metal are preferred. The amount of titanium, zirconium, and hafnium contained in the crystalline aluminosilicate is approximately 0.002 to 5.0%, expressed as the number of moles of the element per unit weight of catalyst. Omot/kg is preferred, especially 0.004-2. Omot/kl? is preferred. Also,
Although protons or other cations may coexist in the crystalline aluminosilicate after treatment containing titanium, zirconium, and hafnium, all active sites involved in the hydration reaction become active sites involving titanium, zirconium, and hafnium. This is also valid.

The crystalline aluminosilicate used as a catalyst precursor in the present invention does not particularly specify the composition ratio of silica and alumina, but it should be one in which the molar ratio of silica to alumina is 10 or more, especially the molar ratio of silica to alumina. It is preferable that the ratio 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. .1 μm or less, more preferably 0.05 μm
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.

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

The olefin used in the present invention preferably has 2 carbon atoms.
The above-mentioned linear or branched chain structures of 12 or less are also quaolefins and cyclic olefins. An example of an olefin is
These include ethylene, propylene, 1-butene, 1,2-butene, isobutene, pentenes, hexenes, heptenes, octenes, cyclobutene, cyclopentene, methylcyclopentenes, cyclohexene, methylcyclohexenes, cyclooctene, and cyclododecene. In particular, it is effective for hydrating cyclic olefins, which generally have a slow 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 hydration 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
Usually a range of 50 to 300C is used, preferably 50C.
-250C, especially 60-200C is preferred. Further, the reaction pressure is not particularly limited, and the olefin and water may exist in a gas phase or 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, reducing the rate of the desired reaction, so this reaction is particularly effective in that case. show. The molar ratio of the raw material olefin to water can be varied over a wide range, and 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 and is not practical.

Therefore, in the present invention, the molar ratio of olefin to water is 0.01 to 10 when the process is carried out batchwise, for example.
0 is preferred, - especially 0.06-10.

When this reaction is carried out batchwise, the weight ratio of olefin/catalyst is preferably o, o o s 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 'fr by catalytic hydration of olefin, by using crystalline aluminosilicate containing at least one of titanium zirconium and hafnium as a catalyst, conventional Significantly higher conversion rates and selectivities can be obtained compared to the previous method.

(Example) Example 1 ■ Catalyst preparation (11Q brand sodium silicate 1112p and water 138p
1, aluminum sulfate 32.22, sodium chloride 528 f, concentrated sulfuric acid 92.6 f.

Tetrapropylammonium bromide 139t and water 18
Add a mixture consisting of 96F, mix thoroughly with a high-speed stirring homogenizer, and heat to 150F in an autoclave with stirring.
C.Kept for 4 days. The cooled reaction product was filtered, washed with water, dried at 120C for 8 hours, and then dried at 550C under a stream of air.
It was fired at C for 5 hours. The obtained solid was identified as crystal sb and ZSM-5 by X-ray diffraction method (precursor A).

Precursor A400fi was added to 4 tons of 2M ammonium chloride aqueous solution and maintained at 80C for 2 hours with stirring.

After filtration, the same operation was repeated two more times to perform ion exchange. After washing with water, filtering, and drying, it was calcined at 400C for 2 hours to obtain proton exchange type ZSM-5 (precursor B).

(2) A mixture of 0.38 f of titanium tetrachloride and 100 g of water and 1 Of of precursor A were added, and the mixture was stirred at room temperature for 10 hours. After washing the treated mixture with water and filtering, and drying the solid matter,
Calcinate at 400C for 2 hours under air flow to 7'C (catalyst 1)
.

(3) 250 tons of Precursor B was added to a mixture of 9.52 kg of titanium tetrachloride and 2.51 kg of water, and the mixture was stirred at room temperature for 8 hours.

The treated mixture was washed with water and filtered, and the solid was dried at 80C under nitrogen atmosphere (Catalyst 2).

(4) The catalyst 2 was calcined at 400C for 2 hours under a stream of air (catalyst 3).

(5) The catalyst 5 was heated at 4,000 ℃ for 2 hours under a hydrogen stream (catalyst 4).

The titanium content in the catalyst obtained above was measured by fluorescent X-ray analysis, and the results are shown in the following table.

(2) Water Conservancy Reaction 10 t of the catalyst obtained above, 302 ml of water, and 152 ml of cyclohexene were charged into a stirring autoclave having an internal volume of 100 cm, and reacted with stirring at 120 C for 15 minutes. After the reaction, the entire product was analyzed by gas chromatography.
, 7'c results are shown in the following table.

The product was only cyclohexanol, and no other products were detected.

Comparative Example 1 A hydration reaction was carried out under the same conditions as in Example 1, except that Precursor B was used as a catalyst. As a result, the cyclohexanol concentration in the oil phase was 3.8% by weight.

Example 2 (1) Catalyst Preparation To a mixture of 0.76 g of titanium tetrachloride and 1.0 t of water, 100 p of the precursor B was added, and the mixture was stirred at room temperature for 8 hours.

The treated mixture was washed with water, filtered, dried, and placed under a stream of air for 4
Calcined at 00C for 2 hours (Catalyst 5). The titanium content by X-ray fluorescence analysis was 0.04 mat/kg.

(2) Water Utilization Reaction A hydration reaction was carried out under the same conditions as in Example 1, except that catalyst 5 obtained above was used. As a result, the cyclohexanol concentration in the oil phase was 11.6% by weight.

Example 3 (1) Catalyst preparation To a mixture of 11.62 Tnt of α-titanic acid and 200 Tnt of water,
Precursor B100f'' ((added and heated on a water bath at 100C and evaporated to dryness. After drying at 130C for 8 hours, it was calcined at 400C for 2 hours under a stream of air (catalyst 6).

Titanium content according to fluorescent X-ray analysis is 0.95 mol
It was 1kg.

(2) The hydration degree [Tf, . %Met.

Example 4 Titanium tetrachloride y O, 76f and water 200rnI! , to a mixture of catalyst 3 i 20. f and stirred at room temperature for 8 hours. The treated mixture was washed with water, filtered, and the solid material was dried and calcined at 400 C for 2 hours under a stream of air. The resulting solid was subjected to the titanium-containing treatment described above four more times (Catalyst 7). Titanium content determined by fluorescent X-ray analysis is o.42
It was 9 in mot/.

The water utilization reaction was carried out under the same conditions as in Example 1, except that Catalyst 7 obtained above was used, and as a result, the cyclohexanol concentration in the oil phase was 13.5% by weight.

Example 5 Catalyst 3 with 1001, water 3002 and cyclohexene 1
50 grams were charged into a stirring autoclave having an internal volume of 1 ton, and reacted with stirring at 100 C for 5 hours. The cyclohexanol concentration in the oil phase was 21.8% by weight.

Separate only the oil phase from the reaction mixture by decantation,
While the aqueous slurry phase containing the catalyst was kept in the reaction vessel, the raw material cyclohexene f150 was newly added and the reaction was carried out under the same conditions as above. As a result of repeating this operation a total of 40 times, the final cyclohexanol concentration in the oil phase was 22.1% by weight, with almost no decrease in catalyst activity or selectivity observed. Ta. Further, the color of the catalyst was white, and no changes such as coloring were observed.

Comparative Example 2 The water utilization reaction was repeated under the same conditions as in Example 5 except that Precursor B was used as a catalyst.
% by weight, whereas the concentration of cyclohexanol in the oil phase in the final reaction mixture was 2.6% by weight:)
Ta. Suddenly, the catalyst turned dark brown.

Example 6 ■ Catalyst preparation Synthetic mordenite (TSZ644 manufactured by Toyo Soda Co., Ltd.) Total 2M
After ion exchange with an aqueous ammonium tl chloride solution, the product was calcined to obtain proton exchange type mordenite (precursor C).

The above precursor (:1009) was added to a mixture of 3,785' titanium tetrachloride and 1.0 t of water, and the mixture was kept at 80C for 2 hours while stirring.The treated mixture was washed with water, filtered, dried, and air-filled. Calcined for 2 hours at 40 DC under air flow (Catalyst 8).Fluorescent X
The titanium content according to the line analysis method was 0.14 mot/kg.

(2) Water utilization reaction A hydration reaction was carried out under the same conditions as in Example 1 except that the catalyst 8 obtained above was used and the reaction time was 80 minutes. As a result, the cyclo-xanol concentration in the oil phase was 8. It was 0% by weight. Furthermore, 0.10% by weight of methylcyclopentene, 0.055% by weight of dicyclohexyl ether, and 0.03% by weight of cyclohexene dimer were present.

Comparative Example 5 A water utilization reaction was carried out under the same conditions as in Example 6, except that Precursor C was used as a catalyst. As a result, the cyclohexanol concentration in the oil phase was 4.0% by weight.

In addition, methylcyclopentene is 0.8% by weight, and dicyclohexyl ether is 0.8% by weight.
0.14 weight amount of hexene dimer was present.

Example 7 (1) Preparation of catalyst Precursor B 50 tf was added to a mixture of 4.291 g of zirconium nitrate tetrahydrate and 50 g of water, and the mixture was stirred at room temperature for 8 hours. The treated mixture was washed with water, filtered, dried, and then calcined at 400C for 2 hours under a stream of air (Catalyst 9). The zirconium content determined by fluorescent X-ray analysis is 0.18 mol/
It was kg.

(2) Hydration reaction A hydration reaction was carried out under the same conditions as in Example 1 except that the catalyst 9 obtained above was used. As a result, the cyclohexanol concentration in the oil phase was 10.9% by weight and 0%. Example 8 (1) Catalyst Preparation A catalyst was prepared in the same manner as in Example 7, except that 3.702 hafnium sulfate was used in place of zirconium nitrate (catalyst 10). According to the fluorescent X-ray analysis method, the funium content is 0.16 mol/with fc.

(2) A water utilization reaction was carried out under the same conditions as in Example 1, except that catalyst 10 obtained in the permanent sum reaction was used, and as a result, the cyclohexanol concentration in the oil phase was 8.6% by weight.

Example 9 10 ye of 1-butene was used as the olefin, and 1
The water utilization reaction was carried out under the same conditions as in Example 1, except that the reaction temperature was 170[1:1] and the reaction time was 30 minutes. After cooling, the container was opened and subjected to analysis. 2-butanol was present as product in the aqueous phase in an amount of 6.2% by weight. Also,
Cis and trans-2-butenes were present in an amount of 4% in the gas phase component containing unreacted 1-butene.

Comparative Example 4 A water utilization reaction was carried out under the same conditions as in Example 9, except that the precursor Bfc was used as a catalyst. As a result, the 2-butanol concentration in the aqueous phase was 1.1% by weight. Additionally, 11% of cis and trans-2-butenes were present in the gas phase components.

Example 10 Using isobutyne as the olefin, reaction temperature 1601
:: The hydration reaction was carried out under the same conditions as in Example 9, except that 24.1% by weight of 2-methyl-2-globanol was present in the aqueous phase.

Comparative Example 5 A hydration reaction was carried out under the same conditions as in Example 10, except that Precursor B was used as a catalyst. As a result, 2-methyl-
The 2-propertool concentration was 5.1% by weight.

Example 11 Using propylene as the olefin, the reaction temperature was 190
All water utilization reactions were carried out under the same conditions as in Example 9, except for C. As a result, 5.7 wt.
It existed.

Example 12 Same as Example 1 except that 15fi of 1-octene was used as the olefin, 102 was used as catalyst 5, and the reaction time was 50 minutes in total.
As a result of the hydration reaction under the same conditions as 2-
The concentration of Octatool was 4.5% by weight.

Example 15 ■ Catalyst preparation Q brand sodium silicate 778f and water 970t fi
All parts, aluminum sulfate 22.5? , a mixture consisting of 23 Of salt 1'C sodium, 64.82 of concentrated sulfuric acid, 972 of tetrapropylammonium bromide and 16501 of water was added, mixed rigorously in a high-speed stirring homogenizer, and then heated to 110 C in an autoclave under stirring. I kept it for days. Filter the cooled reaction product in the same manner as in the catalyst preparation of Example 1.

Washing with water, drying, and calcination were performed, and after ion exchange with an aqueous ammonium chloride solution, filtration, washing with water, drying, and calcination were performed. (3) of Example 1 was added to the catalyst precursor obtained above.
Titanium was added in the same manner as above, and 400
C. for 2 hours (Catalyst 11).

(2) The reaction was conducted under the same conditions as in Example 1, except that the catalyst obtained above was used, and then analyzed. As a result, the cyclohexanol concentration in the oil phase was 15.3% by weight.

Example 14 A hydration reaction was carried out under the same conditions as in Example 10, except that an isobutyne-containing hydrocarbon having the following composition was used as the olefin. As a result, 2-methyl-2-propanol was present in the water phase. There were 18.5 wt. Moreover, no other products were observed.

Composition of inbutylene-containing hydrocarbons Isobutane 5.5 Weight - 〇-Flynn 134〃 Transbutene-2 68 1 Isobutine 441 I Butene-1251# Cis-butene-2 53 l

Claims (1)

[Claims] A method for producing alcohol, which comprises using a crystalline aluminosilicate containing at least one of titanium, zirconium, and hafnium as a catalyst when producing alcohol by catalytic hydration of olefin.