JP3019241B2 - Method for producing cyclododecene - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a process for partially hydrogenating 1,5,9-cyclododecatriene in the presence of a novel catalyst having excellent catalytic activity and cyclododecene selectivity. 1,5,9-cyclododecatriene obtained by trimerization of cyclic oligomers of 1,3-butadiene and the like is subjected to a partial hydrogenation reaction to produce cyclododecene selectively and at a high yield, thereby producing cyclododecene industrially. The present invention relates to a method that can be manufactured in a specific manner. Cyclododecene is a compound which is industrially very useful as an intermediate for the production of dodecadionic acid, 1-epoxy-1, 2-cyclododecanic acid, 12-lactam and the like.

[0002]

2. Description of the Prior Art Known catalysts for the production of cyclododecene by partial hydrogenation of cyclododecatriene include molybdenum and nickel sulfides, reduced nickel, cobalt complexes, palladium black, palladium oxide and the like . Although those supported on various carriers are known, they all have a drawback that the activity of the catalyst and the selectivity of cyclododecene are low.

Examples of the catalyst for producing cyclododecene include (1) a method in which a hydrocarbon such as cyclohexene coexists as a hydrogen-donating compound in the presence of a palladium catalyst (JP-B-41-13984); Method of Using Grade Alcohol as a Hydrogen Donor (British Patent No. 9207)
No. 54), (3) a method of hydrogenating in the presence of nickel sulfide (Berghi Patent No. 634,763), and (4) a method of adding thiophenes and hydrogenating in the presence of a nickel or cobalt catalyst (Japanese Patent Publication No. Sho 42). -19828), (5)
Method using sulfoxides of sulfur compounds (Japanese Patent Publication No. Sho 4
JP-A-8-43114) is known, but the methods (1) and (2) have a low reaction rate and are difficult to selectively hydrogenate, and the method (3) has a high reproducibility with respect to the yield of cyclododecene. And has the disadvantage that the activity of the catalyst is significantly reduced. Method (4) uses thiophenes,
The method (5) uses sulfur compounds such as sulfoxides. However, these methods are not sufficient in the activity of the catalyst and the selectivity of cyclododecene, and are industrially expensive because the above compounds are expensive. This is disadvantageous in terms of economy.

Further, JP-A-49-79990 and the like propose a catalyst for producing cyclododecene in which palladium (or a palladium compound) and cobalt (or a cobalt compound) are supported on a carrier. But,
This known catalyst merely exemplifies cobalt chloride and cobalt acetate as the cobalt component. When the above-mentioned partial hydrogenation reaction is performed using a catalyst using this cobalt chloride or cobalt acetate, a stainless steel-made catalyst is obtained. Even the reaction vessel (SUS vessel) corroded significantly and was not practical in practice.

[0005]

As described above, these known catalysts have problems such as low activity of the catalyst and low selectivity of cyclododecene, and the added compound is expensive. In addition, when chlorides are used as the metal salt to be supported, a reaction vessel made of SUS or the like made of a material of the apparatus is corroded. of course,
There is no problem if the reaction is carried out using a device that does not corrode, but it is unavoidable that the equipment cost is high and is not practical.
That is, an object of the present invention is to solve the above-mentioned drawbacks by finding a novel catalyst supporting compounds other than chlorides and acetates as a catalyst having higher activity and lower selectivity for cyclododecene than conventional catalysts and having low corrosiveness. To solve it.

[0006]

Means for Solving the Problems The present inventors have developed a "method for producing cyclododecene by partial hydrogenation of cyclododecatriene using a catalyst" which can overcome the problems in the conventionally known method for producing cyclododecene. As a result of intensive research to find out, the use of a novel catalyst in which a specific metal sulfate is added to a palladium-based catalyst in which palladium or its compound is supported on a carrier can be used to produce the desired product with extremely high selectivity and high yield. It was found that cyclododecene was obtained, and the present invention was completed. In the present invention, in the partial hydrogenation reaction of cyclododecatriene, a novel catalyst for producing cyclododecene which has high catalytic activity and high selectivity for cyclododecene and does not corrode equipment such as a stainless steel reaction vessel (SUS vessel) is used. It has the advantage that the reaction vessel does not corrode.

That is, the present invention relates to a method for producing cyclododecene by hydrogenating 1,5,9-cyclododecatriene, comprising palladium or a compound thereof, an alkaline earth metal, an aluminum group element, a manganese group element,
And a salt of sulfuric acid with at least one metal selected from the group consisting of iron and iron group elements (hereinafter also referred to as a metal sulfate) in an atomic ratio of palladium to the metal of 0.1.
The present invention relates to a method for producing cyclododecene, which comprises producing a cyclododecene by subjecting 1,5,9-cyclododecatriene to a partial hydrogenation reaction in the presence of a catalyst supported on a carrier so that the ratio becomes 1 to 4.

[0008] As the carrier used in the catalyst used in the present invention, diatomaceous earth, activated carbon, alumina, carbonates of alkaline earth metals and the like are preferably mentioned. In the preparation of the catalyst, the method of supporting each catalyst component on a carrier is not particularly required and is a method usually performed, that is, an impregnation method, an immersion adsorption method, a kneading method, a deposition method,
Evaporation to dryness, coprecipitation or the like may be used, but in the present invention, it is desirable to prepare by impregnation or evaporation to dryness because it is simple. The above-mentioned loading is preferably carried out using an aqueous solution of each metal compound. In addition, the above-mentioned loading of the catalyst component on the carrier may be carried out simultaneously with each component, or may be carried out sequentially for each component.

The amount of palladium or its compound supported on the carrier is usually 0.1 to 10% by weight, preferably about 0.2 to 5% by weight, in terms of palladium metal, based on the carrier. The metal sulfate used in the catalyst used in the present invention is at least one selected from the group consisting of alkaline earth metals, aluminum group elements (metals), manganese group elements (metals), and iron group elements (metals). It is a salt of a species metal with sulfuric acid.

Examples of the alkaline earth metal include magnesium, calcium, strontium, barium and the like. Examples of the aluminum group metal include aluminum, gallium and indium, and examples of the manganese group metal include: Manganese, rhenium and the like can be mentioned, and as the iron group metal, iron,
Cobalt and nickel can be mentioned. Preferred examples of the metal sulfate include magnesium sulfate, aluminum sulfate, manganese sulfate, ferrous sulfate, cobalt sulfate, nickel sulfate, and the like.

The amount of the metal sulfate is 0.1 to 4 times, preferably 0.2 to 3 times the metal in the metal sulfate per 1 atom of the palladium metal. Quantity. The supported amount of the metal sulfate is 0.1 to 0.1% of the metal in the metal sulfate based on the unit weight of the palladium metal.
It is preferable that the supporting amount is 2.0 times by weight, particularly 0.2 to 1.5 times by weight. In the present invention, if the ratio of the amount of the metal supported in the metal sulfate to the palladium metal is too large, the catalyst may be deactivated, and if the ratio of the supported amount is too small, the present invention may be used. It is not appropriate because it has no effect.

The above-mentioned catalyst may be a powder, a powdery carrier,
Alternatively, it is preferably used as a solid catalyst which is a molded article. The solid catalyst is not particularly limited in terms of its particle size, the stirring conditions in the hydrogenation reaction of cyclododecatriene, the optimal value is set depending on the separation conditions of the reaction solution after the reaction, usually, The particle size of the catalyst may be selected from the range of 100 to 500 mesh, and the surface area of the solid catalyst is desirably about 100 m ² / g or more.

The supporting method of the metal sulfate (catalyst preparation method) is as follows.
A material in which palladium or a compound thereof is previously supported on a carrier is impregnated with an aqueous solution of 1 to 2% by weight of a metal sulfate,
Thereafter, it is preferred that a method of distilling off water, such as by rotary evaporation, may be performed simultaneously carrying the metal sulfate in supporting the palladium or compound thereof on a support by cases.

In the above catalyst preparation method, when palladium or a compound thereof is supported on a carrier and then a metal sulfate (aqueous solution) is supported, the palladium compound supported on the carrier is supported prior to the support of the metal sulfate. Is preferably reduced in a liquid phase or a gas phase. This is because, in the above-described catalyst preparation method, when the sulfate is loaded after the palladium component is loaded, the loaded palladium compound may be dissolved and the palladium component may be reduced from the catalyst. In the present invention, the catalyst usually prepared as described above is used as it is in the partial hydrogenation reaction, but if necessary, the catalyst obtained by the above-mentioned catalyst preparation method is subjected to a reduction treatment again. May be used after use.

In the present invention, the partial hydrogenation reaction of cyclododecatriene may be carried out by thoroughly stirring the reaction solution and suspending the catalyst and the reaction solution uniformly, and the reaction may be performed in a batch process or a semi-batch process. It is possible to carry out the reaction by a process or by a continuous process. In the present invention, a solvent is not particularly necessary, but a saturated hydrocarbon such as cyclohexane may be used as a solvent.
To 180 ° C., particularly preferably 130 to 160 ° C., and the reaction pressure is 5 kg / cm ² (gauge pressure).
Hereinafter, the hydrogen partial pressure is preferably about 0.5 to 1.5 kg / cm ² .

In the present invention, if the reaction temperature is too high, it is not preferable because the selectivity is lowered due to the formation of cyclododecane and hydrogenated products, and if the hydrogen pressure is too high, the hydrogenation The formation of a compound having an excessively high reaction becomes remarkable, and the selectivity of cyclododecene decreases, which is not preferable.

In the production method of the present invention, a special additive (for example, thiophene, sulfoxide or alcohol) is used during the partial hydrogenation reaction as in the known production method of cyclododecene.
Since it is not necessary to use palladium, it is industrially or industrially advantageous, and after the completion of the partial hydrogenation reaction, there is no need to remove these special additives, and palladium or its compound and a metal sulfate are not required. The above-mentioned partial hydrogenation reaction can be carried out in the presence of a catalyst in which is carried on a carrier (in the absence of other additives). In this case, the intended product cyclododecene is separated from the reaction solution and purified. It becomes easy to do.

[0018]

EXAMPLES The present invention will be described more specifically with reference to examples.
The present invention is not limited to this. Next, Examples and Comparative Examples of the present invention will be described. Example 1 A catalyst having 5% by weight of Pd supported on activated carbon (NE Chemcat Corporation, P
d / C), and then an aqueous solution of cobalt sulfate (aqueous metal sulfate solution) prepared by dissolving 0.48 g of cobalt sulfate (heptahydrate) in 25 ml of water. The mixture was stirred well at 50 ° C. for 30 minutes and mixed. Thereafter, water is substantially removed from the mixed solution in the flask by evaporation using a rotary evaporator, and the contents are dried to prepare a catalyst in which cobalt sulfate is further supported on palladium-supported activated carbon (Pd / C). did.

Next, the catalyst 0.1 prepared as described above was used.
4 g, 1,5,9-cyclododecatriene 20 g and cyclohexane (solvent) 60 g were charged into a 200 ml stainless steel autoclave with a stirrer (SUS autoclave) and purged with N ₂ , and then placed in a pre-heated oil bath. I put it. While stirring the reaction solution in the SUS autoclave at 750 rpm, the temperature of the reaction solution was set to 1
The temperature was raised to 50 ° C., and further, H ₂ gas was charged until the pressure (gauge pressure) in the autoclave became 4.7 kg / cm ² , and the autoclave was heated at 1,5, The partial hydrogenation of 9-cyclododecatriene was started.

In the above-mentioned partial hydrogenation reaction, the autoclave was immediately cooled and stopped when about 2 moles of hydrogen was absorbed with respect to 1,5,9-cyclododecatriene as a raw material. The reaction solution in the autoclave where the reaction was stopped was taken out, the catalyst was separated by filtration, and the filtrate (reaction solution) was analyzed by gas chromatography to find that cyclododecene was formed. According to the above analysis, the conversion of 1,5,9-cyclododecatriene was 99.5% and the selectivity of cyclododecene was 96.5%. In addition, corrosion of the SUS autoclaim was hardly observed.

Example 2 1,5,9-Cyclododecatriene was prepared in the same manner as in Example 1 except that the reaction temperature in the partial hydrogenation reaction was 130 ° C. and the reaction pressure was 3.2 kg / cm ^2. A partial hydrogenation reaction produced cyclododecene. The reaction solution in the autoclave where the reaction was stopped was taken out, the catalyst was separated by filtration, and the filtrate (reaction solution) was analyzed by gas chromatography to find that cyclododecene was formed. According to the analysis, the conversion of 1,5,9-cyclododecatriene was 99.5.
% And the selectivity for cyclododecene was 94.0%.

Example 3 As an aqueous solution of metal sulfate, nickel sulfate (hexahydrate) was used.
A catalyst having nickel sulfate supported on palladium-supported activated carbon was prepared in the same manner as in Example 1, except that an aqueous solution prepared by dissolving 24 g in 25 ml of water was used. 1,5,9-Cyclododecatriene was partially hydrogenated to produce cyclododecene in the same manner as in Example 1, except that the catalyst prepared as described above was used for the partial hydrogenation reaction. The reaction solution in the autoclave where the reaction was stopped was taken out, the catalyst was separated by filtration, and the filtrate (reaction solution) was analyzed by gas chromatography to find that cyclododecene was formed. According to the analysis, the conversion of 1,5,9-cyclododecatriene was 99.5% and the selectivity of cyclododecene was 95.5%.

Example 4 Aluminum sulfate (anhydrous) was used as an aqueous solution of metal sulfate.
A catalyst in which aluminum sulfate was supported on palladium-supported activated carbon was prepared in the same manner as in Example 1, except that an aqueous solution prepared by dissolving 0.63 g in 25 ml of water was used. 1,5,9-Cyclododecatriene was partially hydrogenated to produce cyclododecene in the same manner as in Example 1, except that the catalyst prepared as described above was used for the partial hydrogenation reaction. The reaction solution in the autoclave where the reaction was stopped was taken out, the catalyst was separated by filtration, and the filtrate (reaction solution) was analyzed by gas chromatography to find that cyclododecene was formed. According to the analysis, 1,5,9-
The cyclododecatriene conversion was 99.5% and the cyclododecene selectivity was 95.5%.

Example 5 As an aqueous solution of metal sulfate, magnesium sulfate (anhydrous) was used.
A catalyst in which magnesium sulfate was supported on palladium-supported activated carbon was prepared in the same manner as in Example 1, except that an aqueous solution prepared by dissolving 0.50 g in 25 ml of water was used. 1,5,9-Cyclododecatriene was partially hydrogenated to produce cyclododecene in the same manner as in Example 1, except that the catalyst prepared as described above was used for the partial hydrogenation reaction. According to the analysis, the conversion of 1,5,9-cyclododecatriene was 99.5% and the selectivity of cyclododecene was 96.5%.

Example 6 Ferrous sulfate (heptahydrate) 0.5 as a metal sulfate aqueous solution
A catalyst having ferrous sulfate supported on palladium-supported activated carbon was prepared in the same manner as in Example 1, except that an aqueous solution prepared by dissolving 0 g in 25 ml of water was used. 1,5,9-Cyclododecatriene was partially hydrogenated to produce cyclododecene in the same manner as in Example 1, except that the catalyst prepared as described above was used for the partial hydrogenation reaction. According to the analysis, the conversion of 1,5,9-cyclododecatriene was 98.5% and the selectivity of cyclododecene was 9%.
It was 4.0%.

Comparative Example 1 1,5,9-Cyclododecatriene was prepared in the same manner as in Example 1 except that a catalyst (Pd / C, manufactured by NE Chemcat) supporting 5% of Pd on activated carbon was used as it was. A partial hydrogenation reaction produced cyclododecene. The reaction solution in the autoclave where the reaction was stopped was taken out, the catalyst was separated by filtration, and the filtrate (reaction solution) was analyzed by gas chromatography to find that cyclododecene was formed. According to the analysis, the conversion of 1,5,9-cyclododecatriene was 99.5% and the selectivity of cyclododecene was 83.5%.
Met.

Comparative Example 2 Example 1 was repeated except that the amount of cobalt sulfate used was changed to 2 g.
In the same manner as in, a catalyst in which cobalt sulfate was supported on palladium-supported activated carbon was prepared. 1,5,9-Cyclododecatriene was partially hydrogenated to produce cyclododecene in the same manner as in Example 1, except that the catalyst prepared as described above was used for the partial hydrogenation reaction.

The reaction solution in the autoclave where the reaction was stopped was taken out, the catalyst was separated by filtration, and the filtrate (reaction solution) was analyzed by gas chromatography to find that cyclododecene was formed. According to the analysis, the conversion of 1,5,9-cyclododecatriene was 75.2% and the selectivity of cyclododecene was 80.3%.

Comparative Example 3 In the same manner as in Example 1 except that an aqueous solution prepared by dissolving 0.41 g of cobalt chloride (hexahydrate) in 25 ml of water was used, cobalt chloride was supported on palladium-supported activated carbon. A catalyst was prepared. 1,5,9-Cyclododecatriene was partially hydrogenated to produce cyclododecene in the same manner as in Example 1, except that the catalyst prepared as described above was used for the partial hydrogenation reaction.

The reaction solution in the autoclave where the reaction was stopped was taken out, the catalyst was separated by filtration, and the filtrate (reaction solution) was analyzed by gas chromatography to find that cyclododecene was formed. According to the analysis, the conversion of 1,5,9-cyclododecatriene was 99.5% and the selectivity of cyclododecene was 94.5%. The corrosion of the SUS autoclave (reactor) after the completion of the reaction was remarkably corroded due to a large amount of iron rust.

Comparative Example 4 Cobalt acetate was supported on palladium-supported activated carbon in the same manner as in Example 1, except that an aqueous solution prepared by suspending 0.42 g of cobalt acetate (tetrahydrate) in 25 ml of water was used. A catalyst was prepared. 1,5,9-Cyclododecatriene was partially hydrogenated to produce cyclododecene in the same manner as in Example 1, except that the catalyst prepared as described above was used for the partial hydrogenation reaction. According to that analysis,
The 1,5,9-cyclododecatriene conversion was 99.5% and the cyclododecene selectivity was 83.9%.

[0032]

According to the production method of the present invention, palladium or a compound thereof and at least one metal selected from the group consisting of alkaline earth metals, aluminum group metals, manganese group metals and iron group metals are provided. And a sulfuric acid metal salt obtained in a specific ratio supported on a carrier at a specific ratio to carry out a partial hydrogenation reaction of 1,5,9-cyclododecatriene to achieve a selective and highly selective reaction. Cyclododecene is obtained in yield. The present invention provides a method for performing a partial hydrogenation reaction of 1,5,9-cyclododecatriene with a cyclododecene selectivity of 10% compared to a case where a catalyst in which only palladium containing no metal sulfate is supported on a carrier is used.
% Or more, and SUS autoclave (reactor)
Corrosion has an effect that iron rust and the like are substantially eliminated and corrosion is significantly reduced as compared with the case where a catalyst supporting a metal chloride or a metal acetate is used.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-61-11145 (JP, A) JP-A-49-79990 (JP, A) JP-B-50-5185 (JP, B1) JP-B-49 24472 (JP, B1) JP 48-43114 (JP, B1) JP 48-13109 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 13/275 C07C 5 / 05 C07B 61/00 300

Claims (1)

(57) [Claims] 1. A method for producing cyclododecene by hydrogenating 1,5,9-cyclododecatriene, comprising palladium or a compound thereof and an alkaline earth metal, an aluminum group element, a manganese group element, and an iron group element. In the presence of a catalyst comprising at least one metal sulfate selected from the group supported on a carrier such that the atomic ratio of palladium to the metal is 0.1 to 7, 1,5,
A method for producing cyclododecene, comprising producing cyclododecene by subjecting 9-cyclododecatriene to a partial hydrogenation reaction.