JPH0796517B2 - Method for producing condensate of alicyclic ketone - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing a condensate of an alicyclic ketone, and more specifically, a crystalline aluminosilicate having an effective pore size of 6 Å or more as a catalyst. The present invention relates to a method for producing a bimolecular condensate of an alicyclic ketone used.

(Prior Art) It has long been known that a base or an acid is used as a catalyst for condensing two molecules of alicyclic ketone to obtain bicycloketone. However, the method using an inorganic acid such as sulfuric acid has problems such as neutralization of the reaction solution and wastewater treatment. Regarding the production of 2-cyclohexenyl cyclohexanone by bimolecular dehydration condensation of alicyclic ketone, a method using a solid acid catalyst with a strongly acidic ion exchange resin is disclosed in JP-A-50-111053 and JP-A-50-11053. JP-A-52-91846 discloses a method using an alumina gel.
It is disclosed in the publication.

(Problems to be solved by the invention) However, in these methods, the reaction rate is generally slow, and a relatively large strongly acidic ion exchange resin has a problem in heat resistance, and is usually limited to use at 120 ° C or lower. However, they are not sufficient as industrial production methods such as not being able to obtain a sufficient yield, and they are not at a satisfactory level.

(Means for Solving the Problem) The inventors of the present invention have made earnest studies on a method of obtaining a condensate by bimolecular condensation of an alicyclic ketone in a high yield, and as a result, have found that the catalyst has an effective pore size of 6 Å or more. It has been found that by using a crystalline aluminosilicate, a bimolecular condensate can be obtained with a high reaction rate and a high selectivity.

The alicyclic ketone used in the present invention includes those represented by the following general formula.

In the formula, A represents a saturated carbon chain. Preferably, the carbon number of A is 4 to 6, and the substituent is selected from hydrogen and an alkyl group having 1 to 6 carbons.
However, at least one of the substituents on the α-position carbon is hydrogen.

Specific examples thereof include cyclopentanone, cyclohexanone, cycloheptanone, and alkyl-substituted derivatives of these cyclic ketones (wherein the α-position has at least one hydrogen atom).

Bicycloketone is obtained as a condensate by bimolecular condensation of these alicyclic ketones. For example, 2-cyclopentylidene cyclopentanone is obtained from cyclopentanone, 2-cyclohexenyl cyclohexanone is obtained from cyclohexane, and 2-cycloheptylidene cycloheptanone is obtained from cycloheptanone as a main product by dehydration condensation.

The catalyst used in the present invention is a crystalline aluminosilicate, and zeolites having a large pore size, ie, pores larger than 6Å are preferable. The reaction proceeds even with zeolites having a smaller pore size, but the activity is small. As a typical example of these large pore diameter zeolites, zeolite X, Y,
L, ZSM-12, beta, mordenite, etc. can be mentioned. The pore size is determined from the adsorbed molecule size, and is described in, for example, Brett "Zeolite Molecule Sieve" (Willii Interscience Publishing). Table 1 shows the values described in Koizumi et al., Catalyst, Vol. 25, No. 3, pp. 216-218 as an example of a typical zeolite pore size.

The silica / alumina molar ratio of these zeolites is
A high silica of 20 or more and 1000 or less is preferable because of high activity. The high-silica type zeolite can be obtained by using a known dealumination method or the like. Especially high-silica type Y,
Beta, mordenite can be conveniently used.
Among them, high silica mordenite has a high conversion rate,
It is also advantageous in that there are few by-products such as trimers.

These crystalline aluminosilicates are usually used in the proton form, but polyvalent cations, for example, alkaline earth metals such as magnesium and calcium, lanthanum, rare earth metals such as cerium, chromium, iron, cobalt, nickel, copper,
Those exchanged with metal cations such as zinc, molybdenum, ruthenium, rhodium, platinum, tungsten and rhenium can also be used.

The catalyst may be used in a generally used system such as a suspension system or a fixed bed system.

The alicyclic ketone can be reacted alone or diluted with a solvent inert to the reaction such as benzene, toluene and cyclohexane.

The reaction temperature used in the method of the present invention varies depending on the reaction raw materials, but is usually 50 to 200 ° C, preferably 100 to 150 ° C.
However, the pressure is preferably 10 atm or less.

0.1 as weight space velocity (WHSV) for fixed bed system
When the catalyst is used in a suspended state for about 100 hr ⁻¹ , the catalyst amount is preferably 0.1 to 50% by weight with respect to the raw material ketone.

In addition, it is preferable to remove the produced water from the reaction system during the reaction in terms of further increasing the reaction rate.

The activity-reduced catalyst with time recovers its activity by solvent cleaning or regeneration such as air combustion regeneration and can be used repeatedly.

(Effect of the Invention) According to the method of the present invention, it is possible to produce a bicycloketone that is a condensate in a higher yield than an alicyclic ketone. Furthermore, the catalyst is a solid, there is no need for neutralization treatment of the reaction solution, waste acid treatment, etc., and the durability of the catalyst is excellent, and there is no problem of thermal deterioration. The activity can be recovered by regeneration and can be used repeatedly, etc.
The industrial advantage is great.

(Examples) Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

The conversion rate and selectivity used in the present invention are obtained by the following equations.

Example 1 100 g of cyclohexanone and 25 g of dealuminated Y-type zeolite (H type, SiO ₂ / Al ₂ O ₃ = 20) were placed in a 200 cc three-necked flask equipped with a thermometer, a stirrer and a condenser, and placed on an oil bath. heating
The reaction was carried out at 120 ° C for 1 hour. After the reaction, the reaction mixture was cooled, and then the organic phase was analyzed by gas chromatography. As a result, the conversion of cyclohexanone was 20% and the selectivity of 2-cyclohexenylcyclohexanone was 98%.

Example 2 As in Example 1, except that H-type mordenite (SiO ₂ / Al ₂ O ₃ = 30) was used as a catalyst, the condensation reaction of cyclohexanone was carried out. As a result, the conversion rate of cyclohexanone
The selectivity of 23% and 2-cyclohexenylcyclohexanone was 98%.

Example 3 The same procedure as in Example 1 was carried out, except that ultra-stabilized high silica Y-type zeolite (SiO ₂ / Al ₂ O ₃ = 97, manufactured by Tosoh Corporation) was used as a catalyst. As a result, the conversion of cyclohexanone is 40
%, The selectivity of 2-cyclohexenyl cyclohexanone is
It was 97%.

Example 4 Similar to Example 1, but as catalyst, US Pat.
A beta-type zeolite was synthesized according to the method described in No. 8,069. About 6 times this at room temperature using 1N nitric acid
Treated for a long time, filtered, washed with water, dried, and then H-type zeolite (Si
O ₂ / Al ₂ O ₃ = 96) was used. as a result,
The conversion of cyclohexanone was 68% and the selectivity of 2-cyclohexenylcyclohexanone was 85%.

Example 5 As in Example 4, except that the reaction temperature was 100 ° C., 1
Reacted for hours. As a result, the conversion rate of cyclohexanone
The selectivity of 50% and 2-cyclohexenylcyclohexanone was 96.5%.

Examples 6-8 Performed as in Example 1, but using various dealuminated mordenites as catalysts. The results are shown in Table 2.

Example 9 As in Example 1, but with the addition of dealuminated mordenite with a silica / alumina ratio of 96 as the catalyst and a further H ₂ O / N at 650 ° C.
₂ = Steamed for 2 hours in an 8/2 molar atmosphere
It was carried out at a reaction temperature of 145 ° C. using 10 g. As a result, the conversion of cyclohexanone was 47% and the selectivity of 2-cyclohexenylcyclohexanone was 98.2%.

Example 10 10 g of the same catalyst as in Example 9 molded into about 1 mmφ × 3 mm was filled in a stainless steel reaction tube having an inner diameter of 10 mm, heated to 125 ° C., and cyclohexanone was fed at a supply rate of 10 cc / Hr by a metering pump. Ivy. As a result of composition analysis of the distillate 5 hours after the passage, the conversion of cyclohexanone was 48% and the selectivity of 2-cyclohexenylcyclohexanone was 97.8%.

Example 11 The procedure of Example 9 was repeated, except that 3-methylcyclohexanone was used as the starting ketone. As a result, the conversion of methylcyclohexanone was 42% and the selectivity of 2- (methylcyclohexenyl) 3-methylcyclohexanone was 98%.
It was in%.

Example 12 As in Example 4, except that cyclopentanone was used as the starting ketone and the reaction was carried out at a reaction temperature of 130 ° C.
As a result, the conversion of cyclopentanone was 40% and the selectivity of 2-cyclopentylidenecyclopentanone was 90.5%.

Comparative Example 1 As in Example 1, but using alumina gel as the catalyst. As a result, the conversion of cyclohexanone is 15
%, The selectivity of 2-cyclohexenyl cyclohexanone is
It was 93%.

Claims (1)

[Claims] 1. A method for producing an alicyclic ketone condensate, which comprises using a crystalline aluminosilicate having an effective pore size of 6Å or more as a catalyst in producing the alicyclic ketone condensate.