JPH08299790A - Solid base catalyst, its production and production of carbonyl compound derivative using same - Google Patents

Abstract

PURPOSE: To produce a high efficiency solid catalyst having high activity and capable of giving the objective product with high selectivity by incorporating Ba and Ca as constituent elements and specifying the Ba content and the ratio of the Ca content to the Ba content. CONSTITUTION: This solid base catalyst contains Ba and Ca as constituent elements and has 0.09-10wt.% Ba content and the ratio of the Ca content to the Ba content is 6.4-7.93. When this catalyst is used, waste water is not generated at all because the neutralization of a reactive liq. and washing are not required and the objective product can be produced with high efficiency in a high yield. A carbonyl compd. deriv. such as 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate can be obtd. from a carbonyl compd. such as isobutyraldehyde with this catalyst. In this process, 4-8C aldehyde is suitable for use as the carbonyl compd. as starting material.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a solid base catalyst, a method for producing the same, and a method for producing a carbonyl compound derivative using the catalyst. More specifically, it relates to a catalyst composed of a solid substance containing barium and calcium as constituent elements, a method for producing the same, and a method for producing a carbonyl compound derivative using the catalyst.

[0002]

2. Description of the Related Art Alkali metal hydroxides typified by sodium hydroxide are widely used when carrying out a reaction using a base as a catalyst. However, the reaction using an alkali metal hydroxide is a homogeneous reaction, and a large amount of waste water is generated due to neutralization after the reaction, washing with water, and the like. In the method of producing a glycol monoester from an aldehyde, which is one of the reactions using a base as a catalyst, only barium oxide and magnesium oxide are used in the example of JP-B-58-65245 in which an alkaline earth metal oxide is used. Although the reaction using barium oxide has a high catalytic activity, the product selectivity of the glycol monoester is low, and the reaction using magnesium oxide has a low catalytic activity. In a reaction using a carboxylic acid salt as a catalyst, an organic compound other than the reaction system compound is used, so that it may be mixed in the product. In the case of producing diacetone alcohol from acetone, or in the case of producing its dimer aldehyde from aldehyde, it is a known compound and is known as "APPLIED CATALLYSIS, 59".
(1990) 291-309 ”, it was impossible to obtain sufficient catalytic activity when the reaction was carried out using the catalyst. As described above, in the conventional catalyst, a large amount of waste water is generated, or it is difficult to obtain sufficient catalytic activity and product selectivity.

In general, when a heterogeneous solid catalyst is used, the reaction is (1) no operation of neutralizing the catalyst, washing with water or the like, and no or very little waste water, as compared with the homogeneous catalyst reaction. It is known that (2) the catalyst can be reused, and (3) the selectivity is high in many cases. Therefore, it is expected that the use of the heterogeneous solid catalyst will simplify the process as compared with the case where the target product is obtained using the homogeneous catalyst, the cost of the plant will be low, and the target product can be obtained in a high yield. However, as described above, the fact is that no solid catalyst with high activity and high selectivity has been found.

[0004]

The object of the present invention is to provide a highly active solid catalyst which is highly active and capable of obtaining a desired product with high selectivity, and a carbonyl compound derivative using the catalyst. To provide a method.

[0005]

Means for Solving the Problems The present inventors have aimed to achieve high activity and high selectivity by using a specific solid substance containing barium and calcium as constituent elements in specific proportions as a catalyst. The present invention has been completed by discovering that a product of The invention claimed in the present application is as follows.

(1) Containing barium and calcium as constituent elements, the barium content is 0.09 to 10% by weight, and the ratio of the calcium content to the barium content (calcium content / barium content). Amount) is 6.4 to 79
A solid base catalyst characterized in that it is in the range of 3. (2) The solid base catalyst according to the item (1), wherein the solid base catalyst is barium-supported calcium oxide.

(3) One or more salts of barium nitrate, hydroxide or organic acid salt, or an aqueous solution thereof,
After adding calcium hydroxide or calcium oxide or a suspension obtained by dispersing these in water, drying and adding 500
It is obtained by thermal decomposition in a vacuum of up to 1200 ° C, in an inert gas or in the atmosphere, and contains barium of 0.1 to 10
A barium-supported calcium oxide, which is contained in an amount of 1 wt% and has a ratio of calcium content to barium content (calcium content / barium content) in the range of 6.4 to 713. Become a solid base catalyst.

(4) The solid base catalyst according to item (1), wherein the solid base catalyst is a barium oxide-calcium oxide composite oxide. (5) A compound containing a carbonate ion is added to a solution containing one or more salts of barium nitrate, hydroxide or organic acid salt and one or more salts of calcium nitrate or organic acid salt. The precipitate that sometimes forms is dried to 600-
Obtained by thermal decomposition in a vacuum of 1200 ° C, in an inert gas or in the air, the barium content is 0.09 to 9% by weight, and the calcium content is the ratio of the calcium content to the barium content ( A solid base catalyst comprising a barium oxide-calcium oxide composite oxide contained such that the calcium content / barium content is in the range of 7.2 to 793.

(6) Carbon dioxide is added to a solution containing a solid base catalyst containing one or more salts of barium nitrate, hydroxide or organic acid salt and one or more salts of calcium nitrate or organic acid salt. A precursor containing calcium carbonate having a vaterite structure obtained by drying a precipitate formed when an ion-containing compound is added is pyrolyzed in a vacuum of 600 to 1200 ° C., in an inert gas or in the atmosphere. The content of barium is 0.09 to 9% by weight, and the ratio of calcium content to barium content (calcium content / barium content) is 7.2.
Barium oxide contained to be in the range of
Solid base catalyst composed of calcium oxide complex oxide.

(7) Calcium carbonate is impregnated with a solution of one or more salts of barium nitrate, hydroxide or organic acid salt, dried, and then vacuumed at 600 to 1200 ° C. in an inert gas. Alternatively, it is obtained by thermal decomposition in the atmosphere, contains 0.09 to 9% by weight of barium, and calcium has a ratio of the content of calcium to the content of barium (content of calcium / content of barium). 7.2-
A solid base catalyst comprising barium oxide-calcium oxide composite oxide contained to be in the range of 793.

(8) One or more salts of barium nitrate, hydroxide or organic acid salt, or an aqueous solution thereof,
After adding calcium hydroxide or calcium oxide or a suspension obtained by dispersing these in water, drying and adding 500
When pyrolyzed in a vacuum of up to 1200 ° C, in an inert gas or in the air, and having a barium content of 0.1 to 10% by weight,
A method for producing a solid base catalyst comprising barium-supported calcium oxide, wherein the ratio of calcium content to barium content (calcium content / barium content) is in the range of 6.4 to 713.

(9) Compound containing carbonate ion in a solution containing one or more salts of barium nitrate, hydroxide or organic acid salt and one or more salts of calcium nitrate or organic acid salt The precipitate formed when was added was dried and pyrolyzed in a vacuum at 600 to 1200 ° C., in an inert gas or in the atmosphere, and the barium content was 0.09 to 9
The ratio of the content of calcium to the content of barium (calcium content / barium content) in wt% is 7.2 to
A method for producing a solid base catalyst comprising a barium oxide-calcium oxide composite oxide in the range of 793.

(10) Compound containing carbonate ion in a solution containing one or more salts of barium nitrate, hydroxide or organic acid salt and one or more salts of calcium nitrate or organic acid salt The precursor containing calcium carbonate having a vaterite structure, which was obtained by drying the precipitate formed when the above was added, was pyrolyzed in a vacuum at 600 to 1200 ° C. in an inert gas or in the atmosphere to obtain a barium content. Is 0.0
Solid consisting of barium oxide-calcium oxide composite oxide having a ratio of calcium content to barium content (calcium content / barium content) of 9 to 9% by weight in the range of 7.2 to 793. A method for producing a base catalyst.

(11) Calcium carbonate is impregnated with a solution of one or more salts of barium nitrate, hydroxide or organic acid salt, dried, and dried in a vacuum at 600 to 1200 ° C. in an inert gas. Alternatively, it is pyrolyzed in the atmosphere and has a barium content of 0.09 to 9% by weight and a ratio of the calcium content to the barium content (calcium content / barium content) of 7.2 to 793. Of the barium oxide-calcium oxide composite oxide in the range of 1.

(12) As the catalyst, the above (1) to (7)
Item 10. A method for producing a carbonyl compound derivative from a carbonyl compound, which comprises using the solid base catalyst according to any one of items. (13) The method according to item (12), wherein the carbonyl compound is an aldehyde having 4 to 8 carbon atoms.

(14) The carbonyl compound is isobutyraldehyde and the carbonyl compound derivative is 2,
The production method according to (12) above, which is 2,4-trimethyl-1,3-pentanediol monoisobutyrate. (15) The production method according to (12) above, wherein the carbonyl compound is normal butyraldehyde and the carbonyl compound derivative is 2-ethylhexenal.

(16) The production method according to the above (12), wherein the carbonyl compound is acetone and the carbonyl compound derivative is diacetone alcohol.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The solid base catalyst used in the present invention may be in any solid form such as powder, granules or lumps, but the size is preferably 30 to 450 μm. Although a known method can be considered for the production, in the present invention, the barium-supported calcium oxide is one or more kinds of organic acid salts such as barium nitrate, hydroxide, or acetate, or an aqueous solution thereof, preferably An aqueous solution of barium nitrate or barium hydroxide is added to calcium hydroxide, calcium oxide or a suspension of these in water, preferably calcium hydroxide-water suspension, and then the mixture is dried, , 500 ° C. to 1200 ° C., preferably 600 to 1000 ° C., the solid catalyst contains 0.1 to 10% by weight of barium, and the ratio of calcium content to barium content. The (calcium content / barium content) is preferably set to 6.4 to 713. If the temperature of thermal decomposition is less than 500 ° C, the hydroxide or nitrate will not be completely decomposed, and if the temperature exceeds 1200 ° C, the activity will be extremely reduced due to the sintering of the catalyst. In the present invention, the barium oxide-calcium oxide composite oxide is one or more kinds of organic acid salts such as barium nitrate, hydroxide or acetate, and calcium nitrate,
Alternatively, a precursor that precipitates when a compound containing a carbonate ion is added to a solution with one or more kinds of organic acid salts such as acetate, preferably a precursor containing calcium carbonate having a vaterite structure, or After drying the solid obtained by impregnating calcium carbonate with a solution of one or more salts of organic acid salts such as barium nitrate, hydroxide, or acetate, 600
To 1200 ° C., preferably 800 to 1000 ° C., and the weight of barium in the solid catalyst is 0.09 to 9
The ratio of calcium content to barium content (calcium content / barium content) is 7.2 to 793 in% by weight.
It is preferred that If the temperature of the thermal decomposition is less than 600 ° C, the carbonate is not completely decomposed and sufficient activity cannot be obtained. If the temperature exceeds 1200 ° C, the catalyst activity is extremely high because of the sintering of the catalyst. Fall to.

When the content of barium is 0.09% or less, the selectivity of the desired product is low, and when it exceeds 10% by weight, the catalytic activity is lowered. Ratio of calcium content and barium content (calcium content / barium content)
For example, if the barium content is specified in the barium-supported calcium oxide compound or the barium oxide-calcium oxide compound of the present invention, it can be easily calculated from the value. The ratio of calcium content to barium content (calcium content / barium content) is 6.4 to 793.
If it is larger or smaller than the range, the performance is inferior to the excellent well-balanced performance in high activity and high selectivity as expressed in the present invention.

There is no particular limitation on the atmosphere during thermal decomposition. That is, it can be carried out under reduced pressure, in an inert gas or in air, preferably under reduced pressure. When the production is carried out using the solid catalyst of the present invention, it is preferable that the raw material carbonyl compound contains less acid and water as impurities, but the acid content is 1% by weight and the water content is 5% by weight.
The following can be sufficiently used in the present invention.

The carbonyl compound used in the present invention is an aldehyde, preferably an aldehyde having 4 to 8 carbon atoms, such as isobutyraldehyde, normal butyraldehyde, 2-ethylbutyraldehyde and 2-ethylhexylaldehyde. Acetone is also preferably used, but the present invention is not limited thereto. The catalyst of the present invention is preferably used for producing a carbonyl compound derivative from a carbonyl compound, and particularly, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate is produced from isobutyraldehyde. In this case, when 2-ethylhexenal is produced from normal butyraldehyde, it is more suitable when diacetone alcohol is produced from acetone. Among them, 2,2,4-trimethyl-1,3-pentanediol monoisoate is obtained from isobutyraldehyde. Although the effect is great in producing butyrate, the present invention is not limited thereto.

The catalyst of the present invention can be used in either a fixed bed continuous system or a batch system. The amount of the catalyst of the present invention used is in the range of 0.01 to 100% by weight based on the reaction liquid, but is not limited thereto. The barium-supported calcium oxide can be used in the range of 0.01 to 20% by weight, preferably in the range of 0.05 to 10% by weight, based on the reaction solution in a batch system. The barium oxide-calcium oxide composite oxide can be used in a range of, for example, 0.01 to 20% by weight, preferably 0.05 to 10% by weight, based on the reaction solution.

The reaction temperature when using the catalyst of the present invention is
It can be selected in the range of 10 to 130 ° C. When using barium-supported calcium oxide as a catalyst, for example, in the case of a batch reaction, it is preferable to carry out the mixture of the catalyst and the reaction solution at a temperature of 10 to 130 ° C. for 0.5 to 8 hours. At a temperature of 10 ° C or lower, the reaction rate is not sufficient, and when it exceeds 130 ° C, the selectivity of the product is deteriorated. When the barium oxide-calcium oxide composite oxide is used as a catalyst, for example, in the case of batch reaction, the mixture of the catalyst and the reaction solution is mixed at 10 to 130 ° C.
It is preferable to carry out at the temperature of 0.2 to 3 hours. If the temperature is lower than 10 ° C, the reaction rate is not sufficient, and if it exceeds 130 ° C, the selectivity of the product is deteriorated.

After the reaction, to obtain the desired product from the reaction solution, the desired solution is obtained by filtering the reaction solution from the catalyst and distilling it by a known method.

[0025]

EXAMPLES The effects of the present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Example 1 Calcium hydroxide (Ca (OH) 2, manufactured by Kanto Kagaku) 3
8.5 g is suspended in 100 ml of pure water. 1.5 g of barium nitrate (Ba (NO3) 2, manufactured by Wako Pure Chemical Industries, Ltd.) in pure water 200
It was dissolved in ml, added to the above calcium hydroxide suspension, mixed and dried. The white solid (4.0 g) thus obtained was calcined in vacuum at 900 ° C. for 1 hour and then cooled to room temperature. As a result, 3.7 g of a catalyst containing 3% by weight of barium was obtained. The whole amount of the obtained catalyst was transferred to a reactor, 200.0 g of isobutyraldehyde was added and stirred,
The reaction was carried out at 110 ° C for 1 hour. After the reaction, the reaction solution was filtered off and the filtrate was analyzed by gas chromatography.
The results are shown below. Conversion of isobutyraldehyde 90.7% Selectivity of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (hereinafter abbreviated as CS-12)
89.8% CS-12 yield 81.4%

Example 2 Calcium hydroxide (Ca (OH) 2, manufactured by Kanto Kagaku) 3
7.7 g was suspended in 100 ml of pure water. 2.5 g of barium nitrate (Ba (NO3) 2, Wako Pure Chemical Industries, Ltd.) was added to pure water 200
It was dissolved in ml, added to the above calcium hydroxide suspension, mixed and dried. The white solid (4.0 g) thus obtained was calcined in vacuum at 900 ° C. for 1 hour and then cooled to room temperature. As a result, 3.9 g of a catalyst containing 5% by weight of barium was obtained. The whole amount of the obtained catalyst was transferred to a reactor, 200.0 g of isobutyraldehyde was added and stirred,
The reaction was carried out at 110 ° C for 1 hour. After the reaction, the reaction solution was filtered off and the filtrate was analyzed by gas chromatography.
The results are shown below. Conversion of isobutyraldehyde 91.4% Selectivity of CS-12 89.1% Yield of CS-12 81.4%

Example 3 Calcium hydroxide (Ca (OH) 2, manufactured by Kanto Kagaku) 3
8.9 g was suspended in 100 ml of pure water. 1.1 g of barium nitrate (Ba (NO3) 2, manufactured by Wako Pure Chemical Industries) was added to pure water 200
It was dissolved in ml, added to the above calcium hydroxide suspension, mixed and dried. The white solid (4.0 g) thus obtained was baked in vacuum at 700 ° C. for 1 hour and then cooled to room temperature. As a result, 3.7 g of a catalyst containing 2% by weight of barium was obtained. The whole amount of the obtained catalyst was transferred to a reactor, 200.0 g of isobutyraldehyde was added and stirred,
The reaction was carried out at 110 ° C for 1 hour. After the reaction, the reaction solution was filtered off and the filtrate was analyzed by gas chromatography.
The results are shown below. Conversion of isobutyraldehyde 92.4% Selectivity of CS-12 84.0% Yield of CS-12 77.4%

Example 4 Calcium hydroxide (Ca (OH) 2, manufactured by Kanto Kagaku) 3
9.2 g was suspended in 100 ml of pure water. 0.5 g of barium nitrate (Ba (NO3) 2, manufactured by Wako Pure Chemical Industries) was added to 200 parts of pure water.
It was dissolved in ml, added to the above calcium hydroxide suspension, mixed and dried. The white solid (4.0 g) thus obtained was baked in vacuum at 700 ° C. for 1 hour and then cooled to room temperature. As a result, 3.9 g of a catalyst containing 1% by weight of barium was obtained. The whole amount of the obtained catalyst was transferred to a reactor, 200.0 g of isobutyraldehyde was added and stirred,
The reaction was carried out at 110 ° C for 1 hour. After the reaction, the reaction solution was filtered off and the filtrate was analyzed by gas chromatography.
The results are shown below. Isobutyraldehyde conversion 90.9% CS-12 selectivity 83.8% CS-12 yield 76.2%

Example 5 122.6 g of calcium nitrate tetrahydrate (Ca (NO3) 2.4H2O, manufactured by Wako Pure Chemical Industries) and barium nitrate (Ba (NO
3) 2, 1.7 g of Wako Pure Chemical Industries, Ltd. was dissolved in 500 ml of pure water, and ammonium carbonate ((NH4) 2CO3,
A solution prepared by dissolving 60.6 g of Wako Pure Chemical Industries, Ltd. in 300 ml of pure water is added. The generated precipitate was filtered, washed with water, and dried to obtain a white solid vaterite structure precursor. 7.3 g of the obtained white solid is calcined in vacuum at 900 ° C. for 1 hour, transferred to a reactor, 200.0 g of isobutyraldehyde is added, and the mixture is stirred and reacted at 60 ° C. for 0.5 hour. After the reaction,
The reaction solution was filtered off and the filtrate was analyzed by gas chromatography. The results are shown below. Conversion of isobutyraldehyde 98.8% Selectivity of CS-12 93.8% Yield of CS-12 92.7%

Example 6 84.8 g of calcium carbonate (CaCO3, manufactured by Wako Pure Chemical Industries, Ltd.)
Is suspended in 200 ml of pure water. Barium nitrate (Ba
(NO3) 2, manufactured by Wako Pure Chemical Industries, Ltd.) (4.8 g) is dissolved in 150 ml of pure water, added to a suspension of calcium carbonate, mixed and dried. 7.3 g of the obtained white solid is calcined in vacuum at 900 ° C. for 1 hour, transferred to a reactor, 200.0 g of isobutyraldehyde is added, and the mixture is stirred and reacted at 60 ° C. for 0.5 hour. After completion of the reaction, the reaction solution was filtered and the filtrate was analyzed by gas chromatography. The results are shown below. Conversion of isobutyraldehyde 95.4% CS-12 selectivity 89.7% CS-12 yield 85.6%

Example 7 52.0 g of calcium carbonate (CaCO3, manufactured by Wako Pure Chemical Industries)
Is suspended in 200 ml of pure water. Barium nitrate (Ba
1.7 g of (NO3) 2, manufactured by Wako Pure Chemical Industries, Ltd. is dissolved in 100 ml of pure water, added to a suspension of calcium carbonate, mixed and dried. 7.3 g of the obtained white solid is calcined in vacuum at 900 ° C. for 1 hour, transferred to a reactor, 200.0 g of isobutyraldehyde is added and stirred, and reacted at 90 ° C. for 0.6 hour. After completion of the reaction, the reaction solution was filtered and the filtrate was analyzed by gas chromatography. The results are shown below. Conversion of isobutyraldehyde 97.6% Selectivity of CS-12 87.0% Yield of CS-12 84.9%

Example 8 The reaction crude liquid obtained in Example 5 was filtered by a known method to obtain 150 g of a liquid, which was then purified by ordinary rectification. The results are shown below. Yield of CS-12 135.2 g Fractional efficiency 97.2%

Example 9 7.3 g of a white solid obtained in the same manner as in Example 5 was calcined in vacuum at 900 ° C. for 2 hours, transferred to a reactor and added with 600.0 g of isobutyraldehyde and stirred at 80 ° C. 1 in C
React for hours. After completion of the reaction, the reaction solution was filtered and the filtrate was analyzed by gas chromatography. The results are shown below. Conversion of isobutyraldehyde 95.4% Selectivity of CS-12 95.3% Yield of CS-12 90.9%

Example 10 7.3 g of a white solid obtained in the same manner as in Example 5 was calcined in vacuum at 950 ° C. for 3 hours, transferred to a reactor and added with 600.0 g of isobutyraldehyde and stirred to 80 ° C. 2 in C
React for hours. After completion of the reaction, the reaction solution was filtered and the filtrate was analyzed by gas chromatography. The results are shown below. Conversion of isobutyraldehyde 89.3% Selectivity of CS-12 95.2% Yield of CS-12 85.0%

Example 11 7.3 g of a white solid obtained in the same manner as in Example 5 was calcined in nitrogen at 1000 ° C. for 2 hours, transferred to a reactor and added with 600.0 g of isobutyraldehyde and stirred at 80 ° C. React at C for 1.2 hours. After the reaction is completed, the reaction solution is filtered off,
The filtrate was analyzed by gas chromatography. The results are shown below. Conversion of isobutyraldehyde 95.2% CS-12 selectivity 94.8% CS-12 yield 90.3%

Example 12 36.5 g of a white solid obtained in the same manner as in Example 5 was calcined in the air at 1000 ° C. for 2 hours, transferred to a reactor and added with 600.0 g of isobutyraldehyde and stirred at 80 ° C. C
React for 3 hours. After completion of the reaction, the reaction solution was filtered and the filtrate was analyzed by gas chromatography. The results are shown below. Conversion of isobutyraldehyde 96.1% Selectivity of CS-12 93.1% Yield of CS-12 89.5%

Example 13 7.3 g of a white solid obtained in the same manner as in Example 5 was calcined in vacuum at 800 ° C. for 3 hours, transferred to a reactor and added with 200.0 g of normal butyraldehyde and stirred to give 80. ° C
React for 2 hours. After completion of the reaction, the reaction solution was filtered and the filtrate was analyzed by gas chromatography. The results are shown below. Normal butyraldehyde conversion 70.4% 2-Ethylhexenal selectivity 89.2% 2-Ethylhexenal yield 62.8%

Example 14 7.3 g of a white solid obtained in the same manner as in Example 7 was calcined in vacuum at 800 ° C. for 3 hours, transferred to a reactor, and 200.0 g of normal butyraldehyde was added and stirred to obtain 80. ° C
React for 2 hours. After completion of the reaction, the reaction solution was filtered and the filtrate was analyzed by gas chromatography. The results are shown below. Normal butyraldehyde conversion 76.9% 2-Ethylhexenal selectivity 85.2% 2-Ethylhexenal yield 65.5%

Example 15 3.6 g of a white solid obtained in the same manner as in Example 5 was calcined in vacuum at 800 ° C for 3 hours, transferred to a reactor and added with 200.0 g of acetone and stirred at 50 ° C. React for 2 hours. After completion of the reaction, the reaction solution was filtered and the filtrate was analyzed by gas chromatography. The results are shown below. Acetone conversion 9.3% Diacetone alcohol selectivity 90.9% Diacetone alcohol yield 8.5%

Example 16 3.6 g of a white solid obtained in the same manner as in Example 7 was calcined in vacuum at 800 ° C for 3 hours, transferred to a reactor and added with 200.0 g of acetone and stirred at 50 ° C. React for 2 hours. After completion of the reaction, the reaction solution was filtered and the filtrate was analyzed by gas chromatography. The results are shown below. Acetone conversion 12.6% Diacetone alcohol selectivity 87.1% Diacetone alcohol yield 11.0%

Example 17 The reaction crude liquid obtained in Example 14 was filtered by a known method to obtain 150 g of the liquid, which was then purified by ordinary rectification.
The results are shown below. Yield of diacetone alcohol 15.8g Fractionation efficiency 95.8%

Comparative Example 1 Magnesium oxide (MgO, manufactured by Wako Pure Chemical Industries, Ltd.) (4.0 g) was calcined in vacuum at 700 ° C. for 1 hour and then cooled to room temperature. The whole amount of this compound was transferred to a reactor, 200.0 g of isobutyraldehyde was added, and the mixture was stirred and reacted at 110 ° C for 15 hours. After the reaction, the reaction solution was filtered off and the filtrate was analyzed by gas chromatography. The results are shown below. Conversion of isobutyraldehyde 0.1% Selectivity of CS-12 90.5% Yield of CS-12 0.009%

Comparative Example 2 Barium oxide (BaO, Wako Pure Chemical Industries, Ltd.) 4.0 was placed in a reactor.
g, 200.1 g of isobutyraldehyde are added and stirred,
Incubate at 110 ° C for 1 hour. After the reaction, the reaction solution was filtered off and the filtrate was analyzed by gas chromatography.
The results are shown below. Conversion of isobutyraldehyde 98.6% CS-12 selectivity 20.8% CS-12 yield 20.5%

Comparative Example 3 3.7 g of calcium carbonate (CaCO3, manufactured by Wako Pure Chemical Industries, Ltd.) was baked in vacuum at 900 ° C for 1 hour, transferred to a reactor, and 200.0 g of isobutyraldehyde was added and stirred at 60 ° C. And react for 2.6 hours. After the reaction, the reaction solution was filtered off and the filtrate was analyzed by gas chromatography. The results are shown below. Conversion of isobutyraldehyde 94.5% Selectivity of CS-12 56.2% Yield of CS-12 53.1%

Comparative Example 4 63.2 g of calcium nitrate tetrahydrate (Ca (NO3) 2.4H2O, manufactured by Wako Pure Chemical Industries) and barium nitrate (Ba (NO
3) 2, 25.6 g of Wako Pure Chemical Industries, Ltd. was dissolved in 500 ml of pure water, and ammonium carbonate ((NH4) 2CO was added to the solution.
(3, Wako Pure Chemical Industries, Ltd.) 42.1 g was dissolved in 300 ml of pure water, and a solution was added. The resulting precipitate is filtered, washed with water, dried,
It is used as a catalyst precursor. 6.2 g of the obtained white solid was baked in vacuum at 900 ° C. for 1 hour, transferred to a reactor, 200.0 g of isobutyraldehyde was added, and the mixture was stirred and reacted at 60 ° C. for 0.5 hour. After the reaction is completed, the reaction solution is filtered off,
The filtrate was analyzed by gas chromatography. The results are shown below. Conversion of isobutyraldehyde 0.1% Selectivity of CS-12 70.3% Yield of CS-12 0.1%

Comparative Example 5 Barium Nitrate (Ba (NO3) 2, Wako Pure Chemical Industries, Ltd.) 52.2
g is dissolved in 300 ml of pure water, and calcium oxide (Ca
O, manufactured by Wako Pure Chemical Industries, Ltd.) 44.8 g, mixed and dried at 140 ° C. Obtained white solid (5.9 g) in air (850 g)
The mixture is calcined at 6 ° C for 6 hours, the whole amount is transferred to a reactor, 200.0 g of isobutyraldehyde is added, and the mixture is stirred and reacted at 80 ° C for 6 hours. After completion of the reaction, the reaction solution was filtered and the filtrate was analyzed by gas chromatography. The results are shown below. Conversion of isobutyraldehyde 0.6% Selectivity of CS-12 83.2% Yield of CS-12 0.5%

Comparative Example 6 Barium Nitrate (Ba (NO3) 2, Wako Pure Chemical Industries, Ltd.) 52.2
g is dissolved in 300 ml of pure water, and calcium oxide (Ca
O, manufactured by Wako Pure Chemical Industries, Ltd.) 44.8 g, mixed and dried at 140 ° C. Obtained white solid (5.9 g) in air (850 g)
Bake for 6 hours at ℃, transfer the whole amount to a reactor and add acetone 20
Add 0.0 g and stir to react at 80 ° C for 6 hours.
After completion of the reaction, the reaction solution was filtered and the filtrate was analyzed by gas chromatography. The results are shown below. Acetone conversion 1.1% Diacetone alcohol selectivity 55.2% Diacetone alcohol yield 0.6%

Comparative Example 7 Barium Nitrate (Ba (NO3) 2, Wako Pure Chemical Industries, Ltd.) 52.2
g is dissolved in 300 ml of pure water, and calcium oxide (Ca
O, manufactured by Wako Pure Chemical Industries, Ltd.) 44.8 g, mixed and dried at 140 ° C. Obtained white solid (5.9 g) in air (850 g)
The mixture is calcined at 6 ° C. for 6 hours, the whole amount is transferred to a reactor, 200.0 g of normal butyraldehyde is added, and the mixture is stirred and reacted at 80 ° C. for 6 hours. After completion of the reaction, the reaction solution was filtered and the filtrate was analyzed by gas chromatography. The results are shown below. Normal butyraldehyde conversion rate 1.1% 2-Ethylhexenal selectivity 80.3% 2-Ethylhexenal yield 0.8%

[0049]

EFFECTS OF THE INVENTION The use of the catalyst of the present invention eliminates the need for neutralization of the reaction solution and washing with water as compared with the case of using a known catalyst, so that no waste water is generated and high efficiency is obtained. It is possible to simultaneously achieve a high level of performance that cannot be achieved by conventional catalysts, that is, the target product can be produced in high yield. The present invention makes it possible to provide such a catalyst, a method for producing the same, and a method for producing a carbonyl compound derivative using the same, which is industrially significant.

Claims (16)

[Claims] 1. Barium and calcium are contained as constituent elements, the barium content is 0.09 to 10% by weight, and the ratio between the calcium content and the barium content (calcium content / barium content). ) Is 6.4 to 793
The solid base catalyst is characterized in that 2. The solid base catalyst according to claim 1, wherein the solid base catalyst is barium-supported calcium oxide. 3. After adding one or more salts of barium nitrate, hydroxide or organic acid salt or an aqueous solution thereof to calcium hydroxide or calcium oxide or a suspension obtained by dispersing these in water, Dried, 500-1
Obtained by thermal decomposition in a vacuum of 200 ° C. in an inert gas or in the air, 0.1 to 10 wt% of barium is contained, and calcium is a ratio of the content of calcium to the content of barium ( A solid base catalyst comprising barium-supported calcium oxide contained such that the calcium content / barium content) is 6.4 to 713. 4. The solid base catalyst according to claim 1, wherein the solid base catalyst is a barium oxide-calcium oxide composite oxide. 5. A solution containing one or more salts of barium nitrate, hydroxide or organic acid salt and one or more salts of calcium nitrate or organic acid salt with a compound containing carbonate ion. The precipitate formed when added is dried,
Obtained by thermal decomposition in a vacuum of 600 to 1200 ° C., in an inert gas or in the atmosphere, and barium content of 0.0
Barium oxide containing 9 to 9% by weight and containing calcium such that the ratio of calcium content to barium content (calcium content / barium content) is in the range of 7.2 to 793. A solid base catalyst consisting of a calcium oxide complex oxide. 6. A solution containing one or more salts of barium nitrate, hydroxide or organic acid salt and one or more salts of calcium nitrate or organic acid salt with a compound containing a carbonate ion. It is obtained by thermally decomposing a precursor containing calcium carbonate having a vaterite structure obtained by drying a precipitate formed when added, in a vacuum of 600 to 1200 ° C., in an inert gas, or in the atmosphere. Is contained in an amount of 0.09 to 9% by weight, and calcium is contained such that the ratio of the content of calcium to the content of barium (calcium content / barium content) is in the range of 7.2 to 793. A solid base catalyst comprising a barium oxide-calcium oxide composite oxide. 7. A calcium carbonate is impregnated with a solution of one or more salts of barium nitrate, hydroxide or organic acid salt, followed by drying and then in a vacuum at 600 to 1200 ° C.
Obtained by thermal decomposition in an inert gas or in the air, the barium content is 0.09 to 9% by weight, and the calcium is the ratio of the calcium content to the barium content (calcium content / barium content). Content) is 7.2-79
A solid base catalyst comprising barium oxide-calcium oxide composite oxide contained to be in the range of 3. 8. After adding one or more salts of barium nitrate, hydroxide or organic acid salt or an aqueous solution thereof to calcium hydroxide or calcium oxide or a suspension obtained by dispersing these in water, Dried, 500-1
It is pyrolyzed in a vacuum of 200 ° C, in an inert gas or in the air, and has a barium content of 0.1 to 10% by weight, and the ratio of the calcium content to the barium content (calcium content / A method for producing a solid base catalyst comprising barium-supported calcium oxide having a barium content of 6.4 to 713. 9. A solution containing one or more salts of barium nitrate, hydroxide or organic acid salt and one or more salts of calcium nitrate or organic acid salt with a compound containing carbonate ion. The precipitate formed when added is dried,
It is pyrolyzed in a vacuum of 600 to 1200 ° C, in an inert gas or in the air, and has a barium content of 0.09 to 9% by weight and a ratio of the calcium content and the barium content (calcium content. Amount / barium content) is 7.2 to 79
A method for producing a solid base catalyst comprising a barium oxide-calcium oxide composite oxide in the range of 3. 10. A solution containing one or more salts of barium nitrate, hydroxide or organic acid salt and one or more salts of calcium nitrate or organic acid salt with a compound containing a carbonate ion. A precursor containing calcium carbonate having a vaterite structure obtained by drying a precipitate formed when added was thermally decomposed in a vacuum of 600 to 1200 ° C. in an inert gas or in the atmosphere, and the barium content was reduced. 0.09 ~
At 9% by weight, the ratio of calcium content to barium content (calcium content / barium content) was 7.2.
Barium oxide contained to be in the range of
A method for producing a solid base catalyst comprising a calcium oxide complex oxide. 11. A solution of one or more salts of barium nitrate, hydroxide or organic acid salt is impregnated into calcium carbonate and dried, and then dried in a vacuum at 600 to 1200 ° C. in an inert gas or It is pyrolyzed in the atmosphere and has a barium content of 0.09 to 9% by weight and a ratio of calcium content to barium content (calcium content / barium content) of 7.2 to 793. A method for producing a solid base catalyst comprising a barium oxide-calcium oxide composite oxide in a range. 12. A method for producing a carbonyl compound derivative from a carbonyl compound, which comprises using the solid base catalyst according to any one of claims 1 to 7 as a catalyst. 13. The method according to claim 12, wherein the carbonyl compound is an aldehyde having 4 to 8 carbon atoms. 14. The carbonyl compound is isobutyraldehyde and the carbonyl compound derivative is 2,2,4-
The production method according to claim 12, which is trimethyl-1,3-pentanediol monoisobutyrate. 15. The method according to claim 12, wherein the carbonyl compound is normal butyraldehyde and the carbonyl compound derivative is 2-ethylhexenal. 16. The carbonyl compound is acetone,
The production method according to claim 12, wherein the carbonyl compound derivative is diacetone alcohol.