JP2562641B2 - Olefin hydration method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing an alcohol useful as a chemical raw material by hydration of olefin.

(Prior Art) Conventionally, as a method for producing an alcohol by a hydration reaction of olefin, a method using a mineral acid such as sulfuric acid or a heteropolyacid such as phosphotungstic acid (JP-A-53-9746) has been proposed. ing.

However, in the case of these inorganic acids, there are problems that the apparatus is largely corroded and that a complicated operation of separating and recovering the product from the aqueous layer in which the catalyst is dissolved is required.

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 (Japanese Patent Publication Nos. 38-15619 and 44-26656).
issue).

However, the methods using these ion exchange resins have problems that the resin has a low mechanical strength and is pulverized, and that the heat resistance is insufficient, resulting in a decrease in activity.

Further, a method using a crystalline aluminosilicate (generally called zeolite), which is an inorganic solid acid excellent in heat resistance and mechanical strength, has been proposed as a solid catalyst. For example, in JP-A-57-70828, ethylene using ZSM type zeolite developed by Mobile Oil Co.,
Examples of hydration reaction of propylene and butene are described.
Further, JP-A-58-194828 describes a method for producing a cycloalkanol using a crystalline aluminosilicate having a silica / alumina molar ratio of 20 or more.
No. -104028 describes a method for hydrating cyclic olefins using micronized crystalline aluminosilicates.

Further, there are some reports on a method of improving the activity and selectivity by treating these crystalline aluminosilicates with various metals. For example, JP-A-60-248632 describes an example of a thorium-containing crystalline aluminosilicate obtained by treating a crystalline aluminosilicate with a thorium compound.
-248633 shows an example of a crystalline aluminosilicate containing copper and / or silver, and JP-A-60-248634 shows an example of a crystalline aluminosilicate containing at least one of chromium, molybdenum and tungsten. Has been done.

On the other hand, in the field of zeolites, in recent years, research has been actively conducted on crystalline metallosilicates or crystalline aluminometallosilicates in which a part or all of aluminum in the crystal lattice of zeolite is substituted with another element. For example, JP-A-56-22623 describes an example of a crystalline aluminoferrosilicate containing iron, and JP-A-58-26024 discloses an example of a crystalline borosilicate containing boron. JP-A-58-74521 describes an example of a crystalline titanoaluminosilicate containing titanium, and JP-A-56-59619 discloses a crystalline composition containing chromium. Examples of chromiasilicates are described, and JP-A-59-73420 discloses examples of crystalline gallosilicates containing gallium.

Although it is unknown in what form these foreign elements are included in the crystal lattice, it is known that these metallosilicates differ from crystalline aluminosilicates in terms of acidity. For example, JP-A-60-77124 describes an example of crystalline alumino-ferrosilicate having a structure of zeolite ZSM-11.
It has been shown that the iron entering the crystal reduces the acid strength. Further, JP-A-60-77125 describes an example of a crystalline alumino-ferrosilicate having a structure of zeolite ZSM-12, and it is shown that the acid strength is similarly reduced by the addition of iron. Has been done. It is generally considered that the crystalline aluminometallosilicate has a lower acid strength than the crystalline aluminosilicate having the same crystal structure. These crystalline aluminometallosilicates are
The properties as a catalyst are also expected to be different from that of crystalline aluminosilicates, and many studies on gas phase reactions such as hydrocarbon decomposition, alkylation, disproportionation and isomerization have been conducted. However, there is no example of a hydration reaction of olefin using a crystalline aluminometallosilicate as a catalyst.

(Problems to be Solved by the Invention) The method using crystalline aluminosilicate is certainly highly active and highly selective, and is also excellent in mechanical strength and heat resistance. As a result, it was found that there is a problem that the activity is largely decreased with time during continuous operation for a long time.

(Means for Solving the Problem) In the hydration reaction of olefin, the present inventors have conducted diligent studies in order to find a catalyst with less decrease in activity over time, and as a result, the crystalline aluminometallosilicate was found to be a crystalline aluminosilicate. The inventors have found that the decrease in activity is smaller than that of silicates, and completed the present invention.

That is, the present invention, when producing an alcohol by catalytic hydration of olefin, the composition represented by the molar ratio of the oxides of the anhydride is used as a catalyst to use a crystalline aluminometallosilicate represented by the following formula. It is a characteristic method of hydrating olefin.

_{xM 2 / n O · ySiO 2} · Al 2 O 3 · zR 2 / w O ( wherein, M represents at least one cation of valence n, R represents boron, gallium, titanium, chromium, iron, zinc, Represents at least one w-valent metal selected from phosphorus, vanadium, and copper, x = 1.0 ± 0.3, 20 ≦ y ≦ 8
0 and 0 <z ≦ 1.2. ) It is not clear why the activity of crystalline aluminometallosilicates is lower than that of crystalline aluminosilicates, but as mentioned above, crystalline aluminometallosilicates have lower acid strength than crystalline aluminosilicates. Therefore, it is considered that the production of high-molecular-weight products, which is considered to be one factor of the activity reduction of this reaction, is suppressed.

The crystalline aluminometallosilicate used in the present invention has a composition represented by a molar ratio of an oxide of an anhydride and represented by the following formula.

_{xM 2 / n O · ySiO 2} · Al 2 O 3 · zR 2 / w O ( wherein, M represents at least one cation of valence n, R represents boron, gallium, titanium, chromium, iron, zinc, Represents at least one w-valent metal selected from phosphorus, vanadium, and copper, x = 1.0 ± 0.3, 20 ≦ y ≦ 8
0 and 0 <z ≦ 1.2. ) In this formula, M is a cation in the crystalline aluminometallosilicate, preferably proton, IB, II A, II B, III A, III B, IV B, VB, VI in the periodic table.
B, VII B, and VIII metal cations, more preferably protons. R is boron, gallium,
At least one metal selected from titanium, chromium, iron, zinc, phosphorus, vanadium, and copper, and these are
It is a metal that is taken into the crystal during the hydrothermal synthesis of crystalline aluminometallosilicate and does not come out from the crystalline aluminometallosilicate even in the subsequent ion exchange operation. Particularly preferred among these metals is boron,
They are gallium, titanium, chromium and iron.

In this equation, the amount of these metals is represented by z,
z is larger than 0 and is 1.2 or less. When z exceeds 1.2, the acid strength of the crystalline aluminometallosilicate remarkably decreases, resulting in a marked decrease in activity, which is not preferable. The preferable range of z is 0.1 or more and 1.0 or less, and more preferably 0.2 or more and 0.8 or less.

The silica / alumina molar ratio of the crystalline aluminometallosilicate in the present invention is represented by y in the formula, and this value is 20
It is above 80 and below. If y is less than 20,
There is almost no activity in this reaction, and when it exceeds 80, the activity is low and not practical. The preferable range of y is 20 or more and 60 or less, and the more preferable range is 25 or more and 40 or less.

The crystalline aluminometallosilicate in the present invention is
It has a structure similar to crystalline aluminosilicate in its crystal structure, and is preferably zeolite ZSM.
-5, ZSM-11, ZSM-12, zeolite beta, mordenite, and crystalline aluminometallosilicates similar to ferrierite. Particularly preferred are the characteristic X's shown in Table 1.
It is a crystalline aluminometallosilicate similar to ZSM-5 having line diffraction lines.

However, X-ray diffraction analysis is performed using CuKα rays.

The synthesis of the crystalline aluminometallosilicate used in the present invention is carried out by hydrothermal synthesis in the same manner as the usual synthesis of crystalline aluminosilicate. The silica source used at that time is not particularly limited as long as it is used for synthesis of a usual crystalline aluminosilicate, and water glass, silica sol, silica gel and the like can be used.

The alumina source used in the present invention is not particularly limited as long as it is used for the synthesis of a usual crystalline aluminosilicate, and alumina sol, alumina gel, aluminum sulfate, aluminum nitrate, sodium aluminate, etc. are used.

As the metallo source in the present invention, various inorganic compounds and organic metal compounds such as salts of various metals such as sulfates and nitrates, halides such as chlorides and bromides, and oxides can be used.

In the synthesis of the crystalline aluminometallosilicate used in the present invention, an organic template may coexist if necessary. In that case, preferred are urea compounds such as dimethylurea, quaternary ammonium salts such as tetrapropylammonium, diamines such as hexamethylenediamine, and alcohols. However, the crystalline aluminometallosilicate used in the present invention can be synthesized without using an organic substance. In that case, it is preferable to adjust the pH of the raw material to 10 to 12.

The ratio of these alumina source, metallo source and organic template to the silica source is usually expressed in the molar ratio of the oxide, and the following range is recommended. (However, the organic template is represented by a molar ratio.) Alumina / silica = 0.005-0.10 Metal oxide / silica = 0.005-0.05 Organic template / silica = 0-100 Water of crystalline aluminometallosilicate used in the present invention The thermal synthesis conditions are usually such that the temperature is in the range of 70 to 200 ° C., the pressure is the self-generated pressure, and the conditions can be static or stirring.

The crystalline aluminometallosilicate used in the present invention, after hydrothermal synthesis, when an organic template is used,
It is necessary to remove organic substances from the crystals. In that case, as a method for removing organic substances, firing in air at a temperature of 400 ° C. or higher, a liquid-phase oxidation method using an oxidizing agent such as H ₂ O _2, or the like is used. In this way, the crystalline aluminometallosilicate from which the organic matter has been removed is subjected to the same ion exchange operation as that used for a normal crystalline aluminosilicate in order to obtain a desired cation type, and the desired cation is introduced into the crystal. To do. At that time, the metal of the metallo source introduced as a cation into the crystal during hydrothermal synthesis is removed to the outside of the crystal by ion exchange, and it is considered that only the metal tightly bound to the crystal lattice remains in the crystal. To be

The olefin in the present invention preferably has 2 carbon atoms.
And olefins having a linear or branched structure of ˜12. Examples of such olefins include ethylene, propylene, 1-butene, 2-butene,
Examples thereof include isobutene, pentenes, hexenes, heptenes, octenes, cyclobutene, cyclopentene, methylcyclopentenes, cyclohexene, methylcyclohexenes, cyclooctene and cyclododecene.
Of these, cyclohexene is particularly preferable.

The reaction temperature in the present invention varies depending on the olefin used, but is usually in the range of 30 to 300 ° C, preferably 50 to 250 ° C, and more preferably 60 to 200 ° C. Further, the reaction pressure is not particularly limited, and olefin and water may exist as a gas phase or a liquid phase. Especially preferred are equilibrium advantageous liquid phase reactions.

The molar ratio of the raw material olefin and water in the present invention is not particularly limited, but a preferable range of the molar ratio of olefin to water is 0.001 to 100, and a particularly preferable range is 0.01 to 10.

In the present invention, the raw material olefin may be reacted only with water, or may be reacted in the presence of another organic solvent. In that case, examples of usable solvents include saturated saturated hydrocarbons such as hexene and heptane, aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons, alcohols, esters, ketones, and phenols. Can be mentioned. Further, this reaction can be carried out in the presence of an inert gas such as nitrogen, hydrogen, helium, argon, carbon dioxide or the like.

In carrying out the present invention, generally used reaction methods such as a stirred batch system or a continuous system, a fixed bed system and a fluidized bed system are used as the reaction system.

(Effects of the Invention) When the hydration reaction of olefin is carried out using the catalyst of the present invention, it is possible to produce an alcohol with little decrease in activity over time, and with high activity and high selectivity. This is very advantageous for industrial production.

(Examples) Hereinafter, the present invention will be described with reference to Examples.

Examples 1 to 3 1) Synthesis of crystalline aluminometallosilicates Crystalline aluminometallosilicates whose metals are boron, chromium and iron, respectively, were synthesized by the following method.

128 g of sodium silicate (water glass No. 3) was dissolved in 120 g of water (solution A). _{Al 2 (SO 4) 3 ·} 18H 2 O3.9g and concentrated sulfuric acid 4g water 4
It was dissolved in 0 g (solution B). 20 g of 1,3-dimethylurea 80 g of water
g (solution C). 1.2 mmol of the metal source shown in Table 2 was dissolved in 20 g of water (solution D). Using a homogenizer, solution A was mixed with solutions B, C, and D with vigorous stirring, and stirring was continued for 1 hour. The obtained gel was heated and crystallized at 150 ° C. for 40 hours while stirring at a stirring peripheral speed of 2 m / sec.

The resulting product was washed with water, washed with water, dried at 120 ° C. for 5 hours, and then calcined in air at 500 ° C. for 5 hours to remove organic substances. Then, this product is subjected to ion exchange in 1N sulfuric acid for 8 hours, filtered, washed, and dried at 120 ° C. for 6 hours to remove H 2
A crystalline aluminometallosilicate of the type was obtained.

The X-ray diffraction pattern of the obtained product is shown in FIG. 1 (Example 1), FIG. 2 (Example 2) and FIG. 3 (Example 3). This X-ray diffraction pattern was found to be almost the same as the diffraction pattern shown in Table 1. Further, the composition expressed in the oxide form of these anhydrides was determined from the amount of acid determined by fluorescent X-ray analysis and the adsorption method of pyridine.
The results are shown in Table 3.

2) Cyclohexene Hydration Reaction Using the three types of crystalline aluminometallosilicates obtained in 1) as catalysts, a circulation experiment of cyclohexene hydration reaction was conducted for 200 hours continuously under the following conditions.

Reactor: 300cc internal volume autoclave of stainless steel Holdup amount in the reaction tank Oil: 120cc Slurry: 80cc Slurry concentration: 80% by weight of water, 20% by weight of catalyst Cyclohexene supply: 27g / hr Reaction temperature: 125 ° C Upper part of the reaction vessel The oil was continuously extracted from the overflow nozzle under stirring conditions such that an oil-only phase was formed, and the water consumed by the reaction was pumped in pulses every 12 hours.

FIG. 4 shows the time-dependent change in the cyclohexanol concentration in the spilled oil up to 200 hours after the start of the reaction.

It has been found that the reduction in activity of these crystalline aluminometallosilicates is relatively small.

Comparative Example 1 A crystalline aluminosilicate was synthesized in the same manner as in Examples 1 to 3 without using a metal source.

The product obtained was found to be a zeolite as a result of X-ray diffraction analysis.
It was identified as ZSM-5. Further, the composition expressed in the form of an oxide of an anhydride was as follows.

_{0.98H 2 O · 30SiO 2 · Al} 2 O 3 by using the H-ZSM-5 as the catalyst, Examples 1 to 3
Hydration reaction of cyclohexene was carried out under the same conditions as above. The results are shown in FIG. 4 for comparison.

As is clear from FIG. 4, it was found that the activity of crystalline aluminosilicate decreases faster than that of crystalline aluminometallosilicate.

Examples 4 to 8 A crystalline aluminometallosilicate similar to zeolite ZSM-5 was synthesized by the following method without using an organic substance.

1) Synthesis of seed slurry Q brand silicate aqueous solution (Na ₂ O 8.9% by weight, SiO ₂ 28.9% by weight, H ₂ O 62.2% by weight) 5.3 kg was added with NaOH 26 g and H ₂ O ₂ kg to obtain a uniform solution. It was This solution was charged into a stainless steel autoclave (internal volume 50), and while stirring, H ₂ O15k
An aqueous solution in which 0.4 kg of Al ₂ (SO ₄ ) ₃ · 18H ₂ O and 0.3 kg of concentrated sulfuric acid were dissolved in g was pumped in at room temperature for 1 hour. After that, the temperature is raised to 180 ° C and 10
Crystallized for a time. Then, the synthesized slurry was extracted, partially filtered, washed, dried, and then subjected to X-ray diffraction analysis. As a result, it was found to be ZSM-5 having a crystallinity of 60%.

2) Main Synthesis Crystalline aluminometallosilicates whose metals are boron, gallium, titanium, chromium and iron were synthesized by the following method.

A homogeneous solution of 30 g of NaOH and 2.2 kg of water added to 5.7 kg of Q brand silicate solution, and 10.5 kg of seed slurry of 1) were charged into a stainless steel autoclave, and 16 kg of water was Al ₂ (SO ₄ ) ₃
An aqueous solution in which 0.42 kg of 18H ₂ O and 0.3 kg of concentrated sulfuric acid were dissolved was pumped in over 1 hour while stirring. Furthermore, Table 4
A solution prepared by dissolving 0.13 mol of the metal source shown in 2 in 2 kg of water was pumped in. The pH of this raw material gel was 11.5. Then, the temperature was raised to 155 ° C., and crystallization was performed while stirring.

The resulting slurry was extracted, filtered and washed with a centrifugal dehydrator, and then the cake was ion-exchanged in 1N nitric acid 20 for 5 hours at room temperature. The slurry was washed with a centrifugal dehydrator, washed, and then dried at 120 ° C. for 10 hours. The product thus obtained was found by X-ray diffraction analysis to show almost the same diffraction pattern as zeolite ZSM-5. Also,
Composition of each metal oxide obtained by fluorescent X-ray analysis, and liquid phase ion exchange-alkali titration method (Fifth Internat
Table 5 shows the composition expressed as an oxide of the cation based on the acid amount obtained from the ional conference on Zeolites, 1980, P335).

3) Hydration reaction of cyclohexene Using 5 kinds of crystalline aluminometallosilicate obtained in 2) as a catalyst, a circulation experiment of hydration reaction of cyclohexene was conducted for 500 hours continuously under the following conditions.

Reactor: Autoclave made of stainless steel with an internal volume of 300 cc Holdup amount in the reaction tank Oil: 80 cc Slurry: 80 cc Slurry concentration: 73 wt% water, 27 wt% catalyst Cyclohexene supply rate: 37 g / hr Reaction temperature: 120 ° C Upper part of the reactor The oil was continuously withdrawn from the overflow nozzle under stirring conditions such that an oil-only phase was formed, and the water consumed by the reaction was pumped in pulses every 24 hours.

FIG. 5 shows the time-dependent change in the cyclohexanol concentration in the spilled oil up to 500 hours after the reaction was started.

It can be seen that the decrease in activity of these crystalline aluminometallosilicates is relatively small.

Comparative Example 2 A crystalline aluminosilicate was synthesized in exactly the same manner as in Examples 4 to 8 without using a metal source.

The product obtained was found to be a zeolite as a result of X-ray diffraction analysis.
It was identified as ZSM-5. Further, the composition expressed in the form of an oxide of an anhydride was as follows.

0.99H ₂ O · 29SiO ₂ · Al using ₂ O ₃ The H-ZSM-5 as a catalyst, KoTsuta cyclohexene hydration reaction under the same conditions as in Example 4-8. The results are shown in FIG. 5 for comparison.

As is clear from FIG. 5, it was found that the activity of crystalline aluminosilicate decreases faster than that of crystalline aluminometallosilicate.

Examples 9 to 12 1) Synthesis of crystalline aluminometallosilicates Crystalline aluminometallosilicates whose metals are zinc, phosphorus, vanadium and copper were synthesized by the following method.

72 g of sodium silicate (water glass No. 3) was dissolved in 35 g of water (solution A). _{Al 2 (SO 4) 3 ·} 18H 2 O5.2g and concentrated sulfuric acid 1.2g
Was dissolved in 20 g of water (solution B). 5 g of 1,3-dimethylurea in water
It was dissolved in 40 g (solution C). 1.0 mmol of the metal source shown in Table 6 was dissolved in 20 g of water (solution D). A using a homogenizer
The liquids B, C and D were mixed while vigorously stirring the liquid. The obtained gel was heated at 110 ° C. for 3 days while stirring at a stirring peripheral speed of 1.0 m / sec, and then at 160 ° C. for 10 hours.

The resulting product was washed with water, washed with water, dried at 120 ° C. for 5 hours, and further calcined in air at 500 ° C. for 5 hours. This product was further ion-exchanged in 1N nitric acid for 8 hours,
After being washed with water and dried at 120 ° C. for 10 hours, an H-type crystalline aluminometallosilicate was obtained.

The product thus obtained was found by X-ray diffraction analysis to show almost the same diffraction pattern as zeolite ZSM-5. Table 7 shows the composition expressed in the form of its anhydrous oxide.

2) Cyclohexene Hydration Reaction Using the four types of crystalline aluminometallosilicates obtained in 1) as catalysts, a circulation experiment of cyclohexene hydration reaction was conducted for 200 hours continuously under the following conditions.

Reactor: 300cc internal volume autoclave of stainless steel Holdup amount in reaction tank Oil: 40cc Slurry: 160cc Slurry concentration: 73% by weight of water, catalyst 27% by weight Cyclohexene supply: 74g / hr Reaction temperature: 110 ℃ The oil was continuously withdrawn from the overflow nozzle under a stirring condition such that an oil-only phase was formed, and the water consumed by the reaction was pumped in pulses every 12 hours.

FIG. 6 shows the time-dependent change in the concentration of siccohexanol in the spilled oil up to 200 hours after the start of the reaction.

Example 13 Using the H-type crystalline aluminoborosilicate obtained in Example 4 as a catalyst, the hydration reaction of isobutene was carried out under the following conditions.

Amount of catalyst: 20ml (9-16 mesh molded product) Reaction temperature: 120 ° C Pressure: 10kg / cm ² Water / isobutene molar ratio: 1.0 LHSV: 1.0hr ^-1 2 hours, 10 hours, 30 hours after starting the reaction Is shown in Table 8.

[Brief description of drawings]

1 is an X-ray diffraction pattern of the product obtained in Example 1, 2
The figure is an X-ray diffraction diagram of the product obtained in Example 2, FIG. 3 is the X-ray diffraction diagram of the product obtained in Example 3, and FIG. 4 is the X-ray diffraction diagram of Examples 1 to 3 and Comparative Example 1. In the hydration reaction of cyclohexene, a graph showing the time-dependent change in the cyclohexanol concentration in the effluent oil up to 200 hours after the start of the reaction, and FIG. 5 shows the hydration reaction of cyclohexene in Examples 4 to 8 and Comparative Example 2, After starting the reaction, a graph showing the change with time of the cyclohexanol concentration in the spilled oil up to 500 hours,
FIG. 6 is a graph showing changes in the cyclohexanol concentration in the effluent oil up to 200 hours after the start of the reaction in the cyclohexene hydration reaction of Examples 9 to 12.

Claims (4)

(57) [Claims] 1. A crystalline aluminometallosilicate having a composition represented by the following formula represented by the following molar ratio as an oxide of an anhydride is used as a catalyst when an alcohol is produced by catalytic hydration of olefin. The method of hydration of olefin. _{xM 2 / n O · ySiO 2} · Al 2 O 3 · zR 2 / w O ( wherein, M represents at least one cation of valence n, R represents boron, gallium, titanium, chromium, iron, zinc, Represents at least one w-valent metal selected from phosphorus, vanadium, and copper, x = 1.0 ± 0.3, 20 ≦ y ≦ 8
0 and 0 <z ≦ 1.2. ) 2. The method for hydrating olefin as claimed in claim 1, wherein the crystalline aluminometallosilicate has a characteristic diffraction line shown in Table 1. However, the X-ray diffraction analysis is performed using CuKα rays. 3. R is boron, gallium, titanium, chromium,
The method for hydrating olefin as claimed in claim 1, wherein the olefin is at least one metal selected from iron. 4. The method for hydrating olefin as claimed in claim 1, wherein the olefin is cyclohexene.