JPH0448780B2 - - Google Patents

Description

[Detailed description of the invention]

TECHNICAL FIELD The present invention relates to a method for hydrating olefins, and more particularly to a method for producing a corresponding alcohol by hydrating olefins such as propylene and butene in the presence of a specific solid catalyst and a specific solvent. BACKGROUND ART Although many catalysts for hydration of olefins have been known, attempts have been made to use solid catalysts for ease of separation and recovery from products. Generally speaking, the equilibrium of the hydration reaction of olefins is more favorable at lower temperatures and higher pressures;
Conventionally known solid catalysts, such as silica, alumina,
Silica/alumina, mordenite, zeolite, etc. tend to have lower activity and are not practical. On the other hand, hydration methods using cation exchange resins such as sulfonated styrene-divinylbenzene copolymers as catalysts are also known, and these catalysts have relatively high hydration activity in the presence of liquid water. However, if the reaction temperature is set to 120°C or higher to obtain an industrially desirable reaction rate, the sulfonic acid group will be irreversibly eliminated, greatly reducing the catalytic activity and reducing the sulfonic acid group that was eliminated. can cause corrosion of equipment. Catalysts with such reduced catalytic activity have a problem in that regeneration by calcination, which is often used with ordinary inorganic solid catalysts, cannot be applied. Under these circumstances, a method for hydrating olefin using a specific crystalline aluminosilicate as a catalyst has recently been proposed (U.S. Pat. No. 4,214,107,
(Japanese Patent Application Laid-open No. 70828/1983), but the catalyst activity is insufficient and a practical hydration method has not yet been realized. Furthermore, attempts have been made to perform hydration methods using solid catalysts in the presence of a solvent for the purpose of improving hydration efficiency, and methods using solutions containing sulfone as the solvent are known. (Unexamined Japanese Patent Publication 1973)
-7605, 57-108028). However, the solid catalysts used in these methods essentially use cation exchange resins, and the disadvantages of using cation exchange resins still remain unresolved. SUMMARY OF THE INVENTION OBJECTS OF THE INVENTION An object of the present invention is to provide a hydration method using a solid catalyst that exhibits high catalytic activity, which is not found in conventional methods for hydrating olefins using solid catalysts or solid catalysts and solvents. As a result of intensive research, the present inventors have found that the present invention can be achieved by using a hydration catalyst consisting of hydrogen type mordenite or hydrogen type zeolite Y having a specific silica/alumina ratio in the presence of sulfone. The present invention was completed by discovering that the object can be achieved. SUMMARY OF THE INVENTION That is, the gist of the present invention is to use hydrogen-type mordenite having a silica/alumina (molar ratio) of 20 to 500 and exhibiting the X-ray diffraction diagram shown in Table 1 when producing alcohol by hydrating olefin. Alternatively, there is a method in which olefin is hydrated in the presence of hydrogen type zeolite Y and sulfone, which show the line diffraction diagram shown in Table 2. Hydration Catalyst The catalyst used in the hydration method of the present invention is hydrogen type mordenite or hydrogen type zeolite Y having a specific silica/alumina ratio (hereinafter referred to as hydration catalyst). Mordenite can be synthesized in addition to existing naturally, and its silica/alumina (molar ratio) is 10, as shown by the following formula. 0.5-3.0M2 _{/o 0.Al2O3.10Sio2.0-50H2O} [In the formula, _M is an _alkali metal _or alkaline earth metal, and n is the valence of the metal M. ] The hydration catalyst used in the present invention is a hydrogen type with a silica/alumina (molar ratio) increased to 20 to 500 by treating such mordenite with an appropriate combination of dealkalization, acid extraction, and steam treatment. That is. Dealkalization here means replacing some or all of the alkali metals or alkaline earth metals contained in mordenite with hydrogen ions, resulting in so-called hydrogen-type mordenite. Dealkalization is usually carried out by treating natural mordenite or synthetic mordenite with an aqueous solution of a water-soluble ammonium salt, such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium acetate, etc. to convert the metal cations in mordenite into ammonium ions, and then calcination. This can be achieved by converting the metal cations in mordenite into hydrogen ions, or by treating natural mordenite or synthetic mordenite with an acid, such as an aqueous solution of hydrochloric acid, sulfuric acid, nitric acid, etc., to convert the metal cations in mordenite into hydrogen ions. However, hydrogen-type mordenite is commercially available and can be synthesized, so dealkalization is not necessarily necessary. The acid extraction treatment is to extract alumina in mordenite by bringing it into contact with a mineral acid such as hydrochloric acid, sulfuric acid, nitric acid, or phosphoric acid, or an organic acid such as acetic acid or formic acid. Contact with the above acid is preferably carried out at 20 to 120°C for 1 to 100 hours. The acid extraction treatment may be performed two or more times. Note that this acid extraction treatment can also serve as the above-mentioned dealkalization treatment. 0.1% by weight of alkali metals or alkaline earth metals in mordenite as metal oxides by dealkalization and acid extraction treatment
The following is desirable. Steam treatment, which can be combined with acid extraction treatment, reduces mordenite from 150 to 800 in the presence of steam.
C., preferably 300 to 700.degree. C., for 0.5 to 5 hours, preferably 1 to 30 hours. By the above method, the silica/alumina ratio is adjusted from 20 to 500.
However, a ratio of 30 to 400 is particularly effective in the present invention. The mordenite used in the present invention exhibits the X-ray diffraction pattern shown in Table 1 below.

[Table] On the other hand, hydrogen-type zeolite Y with a silica/alumina (molar ratio) of 20 to 500, which is one of the hydration catalysts used in the present invention, is produced from zeolite Y, which is a synthetic zeolite based on faugiasite. It is prepared by extracting and removing alkali metals or alkaline earth metals and aluminum contained in Dealalization and dealumination are accomplished, for example, by contacting silicon tetrachloride.
Specifically, zeolite Y is dehydrated at 300 to 500℃,
After drying, it is brought into contact with silicon tetrachloride vapor while raising the temperature from around room temperature. final temperature
The temperature is preferably 400 to 600°C. By doing this, dealkalization and the silica/alumina ratio can be increased, but in order to further increase the silica/alumina ratio, the acid extraction treatment described above may be combined with a steam treatment if necessary. Zeolite Y
The amount of alkali metals or alkaline earth metals in
It is desirable that the amount is 0.1% by weight or less, and silica/
It is desirable to use an alumina ratio of 30 to 400 as a hydration catalyst because it is highly effective. The hydrogen type zeolite Y used in the present invention exhibits an X-ray diffraction diagram shown in Table 2 below.

[Table] Sulfone The sulfone that can be used in the present invention is an acyclic or cyclic sulfone. To illustrate, examples of acyclic sulfones include dimethylsulfone, diethylsulfone, methylethylsulfone, dipropylsulfone, dibutylsulfone, dipynylsulfone, sulfonal, and trional; examples of cyclic sulfones include sulfolane, alkyl-substituted sulfolane, and 2- Examples include methylsulfolane, 3-methylsulfolane, 3-propylsulfolane, 3-butylsulfolane, 2-methyl-4-butylsulfolane, and 3-sulfolene. Most of these sulfones are solid at room temperature and are usually used dissolved in water, but in some cases they are dissolved in methanol,
It may be used after being dissolved in a lower alcohol such as ethanol or the alcohol that is the target of the hydration reaction.
Moreover, two or more types of sulfones may be used. Olefin The olefin that can be hydrated in the present invention is linear, branched, or cyclic, and includes terminal olefins and internal olefins. A suitable olefin has 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms.
monoolefins such as ethylene, propylene, 1-butene, 2-butene, perisobutene, pentenes, hexenes, heptenes, octenes, cyclobutene, cyclopentene, cyclohexene, methylcyclopentene, methylcyclohexene, cyclooctene, styrene. etc. The present invention particularly relates to ethylene, propylene, 1
Linear alphas having 2 to 6 carbon atoms, such as -butene, 2-butene, pentenes, hexenes, and cyclohexene, are particularly advantageous for hydration of internal monoolefins and cyclic monoolefins. The above-mentioned olefins can be used in mixtures, and also in mixtures with non-olefin compounds such as alkanes. Hydration Method In the present invention, an olefin and water are reacted in the presence of a hydration catalyst and a sulfone to produce a corresponding alcohol. The hydration reaction is carried out batchwise or continuously by providing a hydration catalyst in a fixed bed or fluidized bed and supplying olefin and sulfone. The contact ratio of olefin and water is olefin 1
1 to 20 moles of water per mole are suitable. Sulfone is usually used dissolved in water, and in that case the ratio of both is 0.5 to 30 sulfone per 1 volume part of water.
parts by volume, preferably 1 to 20 parts by volume. The reaction temperature is usually 50 to 300°C, preferably 100 to 250°C. The reaction pressure is preferably such that the reaction system maintains a liquid phase or a gas-liquid mixed phase, and is usually 5 to 200 kg/cm ² . In addition, the reaction time is, if the reaction type is batchwise,
Usually, the time is 20 minutes to 20 hours, and in the case of a continuous type, the liquid hourly space velocity (LHSV) is usually 0.1 to 10 volume/hour/volume. This hydration reaction hydrates the olefin to the reacting alcohol, and the present invention is particularly useful for producing isopropanol from propylene, secondary butanol from 1-butene, and/or 2-butene. Effects of the Invention The present invention provides a higher yield of alcohol than the conventional hydration method using an inorganic solid acid as a catalyst, and unlike the hydration method using an ion exchange resin as a catalyst, there is no upper limit to the degree of hydration. Furthermore, the hydration catalyst used in the present invention can be calcined, which is one of the general regeneration methods for inorganic solid acids. It has the following effects: it can be regenerated, almost no side reaction products are produced, and alcohol can be obtained with high selectivity. Examples Hereinafter, the counterinvention will be explained in detail using specific examples.
Note that the percentages in the examples are based on weight unless otherwise specified. Examples 1 to 5 Comparative Examples 1 to 2 Preparation of hydration catalyst Synthetic mordenite (manufactured by Norton, USA, trade name Zeolon 900Na) was heated at 80°C using a 10% ammonium chloride aqueous solution at 15 c.c. per 1 g of the mordenite.
After processing for 1.5 hours, the aqueous solution was removed. The upper air treatment operation was performed three more times to thoroughly wash the mordenite, dry it at 120°C, and then calcinate it in air at 600°C for 3 hours to obtain a solution with Na ₂ O content of 0.1% and silica/alumina (molar ratio). [Hereinafter referred to as S/A. ] 10 hydrogen-type mordenai (catalyst A) were prepared. Catalyst A in the upper air was treated with 12 N hydrochloric acid at 90°C for 20 hours using 15 c.c. per gram of catalyst A to remove the aqueous solution and washed with water until no chlorine ions were detected.
After drying at 120°C, it was further calcined in air at 600°C for 3 hours to prepare hydrogen type mordenite (catalyst B) with a Na2O content of 0.04% and S/A31. Add catalyst A to 15 c.c. of 12N hydrochloric acid per gram of catalyst A.
The aqueous solution was removed by treatment at 90°C for 20 hours. This treatment with hydrochloric acid was repeated again, washed with water until no chlorine ions were detected, dried at 120°C, and then baked in air at 600°C for 3 hours.
A hydrogen-type mordenite (catalyst C) with a Na2O content of 0.03% and S/A50 was prepared. Catalyst C was heated to 700℃ with hot air containing 10% water vapor.
Treated for 3 hours (steam treatment), then treated with 12N hydrochloric acid at 90°C for 20 hours, and then treated with hydrochloric acid once again, washed with water, dried, and calcined in the same manner as the upper air to remove Na. A hydrogen-type mordenite (catalyst D) with ₂ O content of 0.01% and S/A108 was prepared. By repeating the same steam treatment and hydrochloric acid extraction treatment using catalyst D, the silica/alumina ratio was increased and catalyst E (Na ₂ O 0.01%, S/A2
03), Catalyst F (0.003% Na2O, S/A404) and Catalyst G (0.002% Na2O, S/A550) were prepared. All of the hydration catalysts A to G prepared as above showed the same X-ray diffraction patterns as shown in Table 1, indicating that there was no change in the mordenite crystal structure. Hydration reaction of olefin Stainless steel autoclave with stirrer (capacity
500 ml), add 10 ml of hydration catalyst C (6.0
g), add 240ml of sulfolane and 60ml of water, and add 1-
Press 60ml (37g) of butene, 140℃, 40Kg/cm ²
The mixture was stirred for 5 hours to carry out a hydration reaction. After the reaction was completed, the autoclave was rapidly cooled, unreacted 1-butene was removed, and the product was analyzed. As a result, secondary butanol (SBA) was produced at a yield of 7.3 mol%, and the space-time of SBA was The yield was 70 g/-catalyst/hour. In addition, the selectivity of SBA is 99 mol%,
Very small amounts of di-sec-butyl ether and octene were produced as by-products. In addition, hydration reactions of 1-butene were carried out in the same manner as in the case using the respective catalysts obtained in the case of the above process, and the results are shown in Table 3.

[Table] Examples 6 to 10, Comparative Example 3 Preparation of hydration catalyst Zeolite Y (manufactured by Union Showa Co., Ltd., trade name SK-
40, Na ₂ O content 7.7%, S/A4) was filled into a quartz tube, dried at 380° C. for 2 hours in a stream of dry nitrogen, and then cooled to room temperature. Nitrogen gas saturated with silicon tetrachloride at room temperature is placed over the zeolite into a quartz tube.
While feeding at a rate of 250ml per minute per 10g of Y, 4
The temperature was raised from room temperature at a heating rate of °C/min. Even after the temperature reached 500°C, the gas containing silicon tetrachloride was supplied for another hour at that temperature. Next, while supplying nitrogen gas to the quartz tube, zeolite Y was cooled, washed with water until no chlorine ions were detected, and incubated at 200°C for 8
By drying for hours, hydrogen type zeolite Y (catalyst I) with 0.06% Na ₂ O and S/A29 was prepared. On the other hand, in the preparation method of upper air catalyst I, except that the silicon tetrachloride treatment time at 500°C was 1 hour 40 minutes (Example 7) or 2 hours 20 minutes (Example 8) Similarly, Na2O0.05%, S/A46
of hydrogen-type zeolite Y (catalyst J) and Na ₂ O0.02
%, S/A 97 hydrogen type zeolite Y (catalyst K) was prepared. Catalyst K, 1N hydrochloric acid, Catalyst K1g
After treatment at ₈₀ ℃ for 8 hours using 20 c.c. Y (catalyst L) was prepared. After subjecting catalyst L to the same hydrochloric acid treatment as for the upper air three times, washing with water,
By drying, hydrogen type zeolite Y (catalyst M) containing 0.005% Na ₂ O and S/A425 was prepared. Catalyst M was treated twice with 1N hydrochloric acid at 80°C for 8 hours, washed with water and dried in the same manner as above.
Hydrogen type zeolite Y with Na ₂ O 0.004%, S/A547
(Catalyst N) was prepared. Furthermore, zeolite Y used as a raw material for catalyst preparation was subjected to dealkalization treatment and water washing in the same manner as the preparation method of catalyst A in Example 1 using a 10% ammonium chloride aqueous solution at 15 c.c. per gram of zeolite. Dry and calcinate to reduce Na ₂ O content
0.2%, S/A4 hydrogen type zeolite Y (catalyst H)
was prepared. Since the catalysts H to N obtained above all exhibit the X-ray diffraction patterns shown in Table 2,
It was found that the crystal structure of zeolite Y was maintained. Olefin hydration method Using each catalyst prepared above as a hydration catalyst,
The hydration reaction of 1-butene was carried out in the same manner as in Example 2. The results are shown in Table 4.

【table】

[Table] Comparative Example 5 Preparation of Hydration Catalyst Crystalline aluminosilicate (ZSM-5) was prepared according to the method described in US Pat. No. 3,965,207. That is, 7.4 parts of aluminum sulfate was dissolved in 195 parts of pure water, and further 26.5 parts of sulfuric acid,
An aluminum sulfate solution was prepared by adding 17.8 parts of tetrapropylammonium bromide and 86 parts of sodium chloride. This aluminum sulfate solution was added to and mixed with a mixed solution of 142 parts of water and 281 parts of No. 3 water glass (9.5% Na ₂ O, 28.6% SiO ₂ ) with stirring. The resulting mixture was transferred to a stainless steel autoclave and heated at 160 °C with stirring.
The mixture was heated and held at ℃ for 20 hours. The crystallized solid product was washed with water, dried at 110°C, and then heated at 600°C for 3
Baked in air for an hour. When the obtained solid was analyzed by X-ray, it was found that it had the crystal structure of ZSM-5. Next, this ZSM-5 was broken down at 90°C for 10 hours using a 1N ammonium chloride aqueous solution, and then
After drying at 110°C, hydrogen type ZSM-5 (HZSM-5) with 0.01% Na ₂ O and S/A111 was prepared by baking in air at 600°C for 3 hours. Hydration reaction of olefin When the hydration reaction of 1-butene was carried out in the same manner as in Example 2 using HZSM-5 obtained in the upper atmosphere as a hydration catalyst, the yield of secondary butanol was 0.8.
Only a mol % and a space-time yield of 8 g/-catalyst/hour were obtained. Comparative Example 6 A hydration reaction of 1-butene was carried out in the same manner as in Example 2 using Union Showa Co., Ltd. molecular sieve 10X (calcium X) as a hydration catalyst, and the yield of secondary butanol was It was 0.1 mol% or less. Comparative example 7 Silica alumina (manufactured by JGC Corporation, product name N632−
When the hydration reaction of 1-butene was carried out in the same manner as in Example 2 using HN (75% silica/25% alumina) as a hydration catalyst, the yield of secondary butanol was 0.2 mol%. . Comparative Example 8 Catalyst D10 was added to the motorclave used in Example 2.
ml (6.0g), water 100ml, 1-butene 60ml (37g)
was added and stirred at 140°C for 5 hours to perform a hydration reaction. Analysis of the reaction product revealed that the yield of secondary butanol was 5.3 mol%, and the space-time yield was 50 g/-catalyst/
time, the selectivity was 95% mol%. Comparative Example 9 A hydration reaction similar to Comparative Example 8 was carried out except that Catalyst J was used instead of Catalyst D. As a result, the yield of secondary butanol was 5.1 mol%, and the space-time yield was 50 g/-
Catalyst/hour, selectivity was 96 mol%. Examples 11 to 17 Olefin hydration reactions were carried out by changing the types of olefin, sulfone, and hydration catalyst, and by changing the reaction conditions. The results are shown in Table 5.

【table】

Claims (1)

[Claims] 1 When producing alcohol by hydrating olefin, the silica/alumina (molar ratio) is 20 to 500.
A method of hydrating olefin in the presence of hydrogen-type mordenite exhibiting the X-ray diffraction characteristics shown in Table 1 or hydrogen-type zeolite Y and sulfone exhibiting the X-ray diffraction characteristics shown in Table 2.