KR100651355B1 - Method for preparing ketones on inorganic oxide catalysts modified with cadmium oxide - Google Patents

Abstract

The present invention relates to a carboxylic acid or its derivative in a fixed bed continuous reaction system filled with an inorganic oxide catalyst loaded with cadmium oxide, at a reaction temperature of 200 to 550 ° C., a reaction pressure of 0.1 to 100 psi, and a weight hourly space velocity of 0.1 to 30 h ⁻¹ . (WHSV) to a process for preparing ketones. By using the inorganic oxide catalyst supported on the cadmium oxide according to the above method, it is possible to produce economical ketones having high selectivity.

Cadmium Oxide, Inorganic Oxide, Catalyst, Fixed Bed Continuous Reaction System, Ketone

Description

Method for preparing ketones on inorganic oxide catalysts modified with cadmium oxide}

1 is a graph showing an increase in selectivity for ketone in a cadmium oxide-supported inorganic oxide catalyst.

2 is a graph showing the yield of 3-acetylpyridine according to the reaction time according to the use of the cadmium oxide-supported inorganic oxide catalyst of the present invention.

The present invention relates to a method for preparing a ketone on a cadmium oxide-supported inorganic oxide catalyst, and more particularly to a fixed bed continuous reaction system filled with a cadmium oxide-supported inorganic oxide catalyst as shown in Formulas 1 and 2 below. It relates to a method for producing a ketone represented by the formula (3) by reacting a carboxylic acid or a derivative thereof.                         

Here, R ₁ and R ₃ are the same as or different from each other, alkyl, cycloalkyl, arylalkyl, aryl or heteroaryl group having 1 to 12 carbon atoms, R ₂ is a hydroxy group, a hydrogen atom, a chlorine atom, 1 to 6 carbon atoms Is an alkoxy group or an amino group, and R ₄ is a hydroxy group or a hydrogen atom.

Looking at the prior art for the preparation of ketones, WO 01/15802 describes a process for preparing ketones on alumina or zirconia catalysts carrying ceria or zinc oxide. In this patent, ceria or zinc oxide is supported in monolayer form to increase the catalytic activity for the ketone formation reaction. In the embodiment, a method of preparing methylcyclopropyl ketone by reacting acetic acid and cyclopropanecarboxylic acid is disclosed. Although described, the highest reaction yield for the product ketone was 71%.

U. S. Patent No. 3,966, 822 describes a process for preparing ketones on zirconia catalysts supported with alkali or alkaline earth metal oxides. The patent limited aldehydes to reactants, and the examples describe a process for preparing diisopropylketone from isobutylaldehyde with a peak reaction yield of 85%.

US Pat. No. 4,950,763 describes a process for preparing ketones by reacting carboxylic acid with carboxylic acid or acetone on a titania catalyst. The patent is limited to anatase (Tinata) in the form of anatase supported on Group IA or Group IIA metal oxide catalyst, in the embodiment, methyl nicotinate and acetic acid on a titania catalyst loaded with sodium oxide A method for preparing 3-acetylpyridine is described, but only 54% selectivity for 3-acetylpyridine.

U.S. Patent Nos. 4,528,400 and 4,570,021 describe methods for preparing ketones by reacting pivalic acid with acetone or acetic acid on zirconia, ceria-alumina and thorium oxide-alumina catalysts, but the catalyst used in the patent is expensive It is a radioactive material and the yield was also not satisfactory.

Accordingly, in the present invention, a low-cost catalyst of cadmium oxide-supported inorganic oxide was used to increase the reaction yield and productivity, and also to lower the catalyst deactivation, thereby economically preparing ketones, thereby completing the present invention.

It is therefore an object of the present invention to provide a method for producing ketones with high yield and high productivity and low catalyst deactivation.

The production method of the present invention for achieving the above object is the reaction temperature of 200 to 550 ℃, the carboxylic acid or its derivatives represented by the formula (1) and formula (2) in a fixed bed continuous reaction system filled with a cadmium oxide-supported inorganic oxide catalyst, 0.1 to The reaction is carried out at a reaction pressure of 100 psi and a weight hourly space velocity (WHSV) of 0.1 to 30 h ⁻¹ to prepare a ketone of the following Chemical Formula 3.

Formula 1

Formula 2

Formula 3

Here, R ₁ and R ₃ are the same as or different from each other, alkyl, cycloalkyl, arylalkyl, aryl or heteroaryl group having 1 to 12 carbon atoms, R ₂ is a hydroxy group, a hydrogen atom, a chlorine atom, 1 to 6 carbon atoms Is an alkoxy group or an amino group, and R ₄ is a hydroxy group or a hydrogen atom.

Looking at the present invention in more detail as follows.

As described above, the present invention relates to a method for preparing a ketone of Chemical Formula 3 by reacting carboxylic acid or a derivative thereof in a fixed bed continuous reaction system filled with an inorganic oxide catalyst loaded with cadmium oxide.

According to the present invention, in the method for producing a ketone from carboxylic acid or a derivative thereof, the yield and productivity are improved and the catalyst life is extended by developing and using an inorganic oxide catalyst carrying cadmium oxide. As the carboxylic acid derivative in the reactants, aldehydes, acid chlorides, esters, amides, etc. in which the hydroxy group of the carboxylic acid is substituted with a hydrogen atom, a chlorine atom, an alkoxy group or an amino group can be used.

In addition, the reactant of Formula 1 is selected from the group consisting of aldehyde or carboxylic acid and derivatives thereof, the reactant of Formula 2 is selected from the group consisting of carboxylic acid and derivatives thereof, and Formula 3 is each R ₁ of Formulas 1 and 2 And a ketone consisting of R ₃ .

Cadmium acetate, cadmium chloride, cadmium hydroxide, cadmium nitrate, cadmium sulfate, and the like may be used as precursors of cadmium oxide for producing the cadmium oxide-inorganic oxide catalyst used in the present invention. The precursor solution was impregnated with an inorganic oxide, and then dried and calcined to prepare an inorganic oxide catalyst on which cadmium oxide was supported. At this time, the content of cadmium oxide in the catalyst was 0.05 to 50% by weight, preferably 0.1 to 30% by weight. %to be.

The inorganic oxide is one or more selected from the group consisting of silica, alumina, zirconia, titania, and zinc oxide, preferably alumina or zirconia. On the other hand, the content of cadmium oxide supported on the inorganic oxide is 0.05 to 50% by weight, the selectivity is reduced or the catalyst deactivation rate is increased outside the above range.

In the fixed bed continuous reaction system, the reaction is carried out at a reaction temperature of 200 to 550 ° C., a reaction pressure of 0.1 to 100 psi and a weight hourly space velocity (WHSV) of 0.1 to 30 h ⁻¹ , more preferably of 300 to 500 ° C. The reaction temperature, reaction pressure of 0.1 to 100 psi and weight hourly space velocity (WHSV) of 0.2 to 20 h ⁻¹ are performed.

By using a low-cost catalyst of the inorganic oxide supported on the cadmium oxide of the present invention, ketones can be manufactured by a process of increasing reaction yield and productivity and lowering catalyst deactivation.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to the following Examples.

Comparative Example 1

Zirconium hydroxide (Zirconium hydroxide) is extruded into cylindrical pellets, and dried and calcined to prepare a zirconia catalyst having a specific surface area of 100 m 2 / g and a pore volume of 0.28 cc / g. 35 g of the catalyst prepared in this way were charged to a fixed bed atmospheric reactor and the reactor temperature was raised to 380 ° C. while flowing nitrogen at a flow rate of 20 L / hr. After the temperature inside the reactor was stabilized, 6 g / hr of methyl nicotinate, 36 g / hr of acetic acid, 5.4 g / hr of H ₂ O, and 20 L / hr of nitrogen gas were injected. The analysis was performed by high performance gas chromatography at regular time intervals. At this time, the conversion of methyl nicotinate was 100%, and the selectivity to 3-acetylpyridine was 90%.

Comparative Example 2

Aluminum hydroxide is extrusion molded into cylindrical pellets, transferred to a calcining furnace, and calcined at 550 ° C. for 3 hours in an air atmosphere to prepare an alumina catalyst. 35 g of the catalyst prepared in this way was charged to a fixed bed atmospheric reactor and the reactor temperature was raised to 400 ° C. while flowing nitrogen at a flow rate of 20 L / hr. After the temperature inside the reactor was stabilized, 6 g / hr of methyl nicotinate, 36 g / hr of acetic acid, 5.4 g / hr of H ₂ O and 20 L / hr of nitrogen gas were injected to carry out the reaction. At this time, the conversion of methyl nicotinate was 90%, the selectivity to 3-acetylpyridine was 30%.

Example 1

The zirconia prepared by the method of Comparative Example 1 was loaded with an aqueous solution of cadmium salt and calcined at 500 ° C. to prepare a zirconia-cadmium oxide catalyst having a cadmium oxide content of 5% by weight. 35 g of the catalyst prepared in this way were charged to a fixed bed atmospheric reactor and the reactor temperature was raised to 380 ° C. while flowing nitrogen at a flow rate of 30 L / hr. After the reactor temperature was stabilized, the reaction was carried out by injecting 9 g / hr of methyl nicotinate, 54 g / hr of acetic acid, 8.1 g / hr of H ₂ O, and 30 L / hr of nitrogen gas. 100% and selectivity to 3-acetylpyridine was 97%.

Example 2

The alumina prepared by the method of Comparative Example 2 was loaded with an aqueous solution of cadmium salt and calcined at 500 ° C. to prepare an alumina-cadmium oxide catalyst having a cadmium oxide content of 15% by weight. When the catalyst prepared in this manner was reacted in the same manner as in Comparative Example 2, the conversion of methyl nicotinate was 100%, and the selectivity to 3-acetylpyridine was 92%.

As described above, as a result of supporting cadmium oxide on the inorganic oxide catalyst, selectivity to ketones was increased, and the results are shown in FIG. 1 by comparing the values of the examples and the comparative examples.

Example 3-4                     

Zirconia (ZrO ₂ , Example 3) and zirconia catalyst (2% CdO-ZrO ₂ , Example 4) having a cadmium oxide content of 2% by weight were carried out by the method of Comparative Example 1, The change in selectivity is shown in FIG. 2. As a result of supporting cadmium oxide in the zirconia, the selectivity to ketones was increased and the catalyst life was extended.

Example 5

35 g of a zirconia-cadmium oxide catalyst having a cadmium oxide content of 5% by weight is charged to a fixed bed atmospheric reactor and the reactor temperature is raised to 400 ° C. while flowing nitrogen at a flow rate of 30 L / hr. After the temperature inside the reactor was stabilized, 10 g / hr butyric acid, 60 g / hr acetic acid, 9 g / hr H ₂ O and 30 L / hr nitrogen gas were injected to carry out the reaction. At this time, the conversion of butyric acid was 100%, selectivity to methyl propyl ketone was 94%.

Example 6

35 g of alumina-cadmium oxide catalyst having a cadmium oxide content of 18% by weight was charged to a fixed bed atmospheric reactor, and the reactor temperature was raised to 400 ° C. while flowing nitrogen at a flow rate of 30 L / hr. After the temperature inside the reactor was stabilized, 10 g / hr benzoic acid, 65 g / hr acetic acid, 9 g / hr H ₂ O and 30 L / hr nitrogen gas were injected to carry out the reaction. In this case, the conversion of benzoic acid was 100%, and the selectivity to acetophenone was 91%.

Example 7

35 g of a zirconia-cadmium oxide catalyst having a cadmium oxide content of 5% by weight is charged to a fixed bed atmospheric reactor and the reactor temperature is raised to 390 ° C. while flowing nitrogen at a flow rate of 20 L / hr. After the temperature inside the reactor was stabilized, 6 g / hr of butanamide, 40 g / hr of acetic acid, 5.4 g / hr of H ₂ O and 20 L / hr of nitrogen gas were injected to carry out the reaction. The conversion rate of butanamide was 100%, and the selectivity for methylpropyl ketone was 95%.

Example 8

35 g of a zirconia-cadmium oxide catalyst having a cadmium oxide content of 2% by weight is charged to a fixed bed atmospheric reactor and the reactor temperature is raised to 380 ° C. while flowing nitrogen at a flow rate of 20 L / hr. After the temperature inside the reactor was stabilized, propionaldehyde was reacted by injecting 12 g / hr of propionaldehyde, 5.4 g / hr of H ₂ O, and 20 L / hr of nitrogen gas. In this case, the conversion of propionaldehyde was 100%, and the selectivity for diethyl ketone was 99%.

The conversion and selectivity according to the cadmium oxide content of Example 5-8 at all times are shown in Table 1 below.

catalyst Cadmium oxide content in the catalyst (% by weight) Reactor temperature (℃) % Conversion Selectivity (%) Example 5 Zirconia-Cadmium Oxide 5 400 100 94 Example 6 Alumina-Cadmium Oxide 18 400 100 91 Example 7 Zirconia-Cadmium Oxide 5 390 100 95 Example 8 Zirconia-Cadmium Oxide 2 380 100 99

According to Table 1, a high improvement in conversion and selectivity can be obtained by using an inorganic oxide catalyst carrying cadmium oxide.

As described above, in the present invention, a ketone can be manufactured in a process using a low-cost catalyst of an inorganic oxide on which cadmium oxide is supported to increase reaction yield and productivity, and also have low catalyst deactivation, and thus economical effect is expected.

Claims (7)

In a fixed bed continuous reaction system packed with a cadmium oxide-supported inorganic oxide catalyst, the carboxylic acid or its derivatives represented by the following Chemical Formulas 1 and 2 were subjected to a reaction temperature of 200 to 550 ° C., a reaction pressure of 0.1 to 100 psi, and 0.1 to 30 h ^. Method for preparing a ketone represented by the formula (3), characterized in that the reaction at a weight hourly space velocity (WHSV) of ¹ : Formula 1

Formula 2

Formula 3

Here, R ₁ and R ₃ are the same as or different from each other, alkyl, cycloalkyl, arylalkyl, aryl or heteroaryl group having 1 to 12 carbon atoms, R ₂ is a hydroxy group, a hydrogen atom, a chlorine atom, 1 to 6 carbon atoms Is an alkoxy group or an amino group, and R ₄ is a hydroxy group or a hydrogen atom. The method of claim 1, wherein the cadmium oxide is derived from a cadmium oxide precursor selected from the group consisting of cadmium acetate, cadmium chloride, cadmium hydroxide, cadmium nitrate and cadmium sulfate. The method of claim 1, wherein the inorganic oxide is one or more selected from the group consisting of silica, alumina, zirconia, titania, and zinc oxide. 4. The method of claim 3, wherein the inorganic oxide is alumina or zirconia. The method of claim 1, wherein the content of cadmium oxide supported on the inorganic oxide is 0.05 to 50% by weight. The method of claim 5, wherein the content of cadmium oxide supported on the inorganic oxide is 0.1 to 30% by weight. The method of claim 1, wherein the reaction is performed at a reaction temperature of 300 to 500 ° C., a reaction pressure of 0.1 to 100 psi, and a weight hourly space velocity (WHSV) of 0.2 to 20 h ⁻¹ . .

Images