JPS62269749A - Catalyst composition for oxidation reaction - Google Patents

Abstract

PURPOSE:To improve the oxidation efficiency of the title catalyst composition by depositing a platinum group element as the first component, an element such as Sn as the second component, and an element such as Ce as the third component on an inorg. carrier, and specifying the ratios of the first component to the second and third components. CONSTITUTION:(a) One or more kinds of elements selected from platinum group elements, (b) >=1 kind of element selected from a group consisting of Sn, Bi, and Sb, and (c) >=1 kind of element selected from Ce, Sn, and Te [excluding Sn when Sn is used as the (b) component] are deposited on an inorg. carrier to obtain the catalyst composition. In this case, the atomic ratio (b/a) of the (a) component to the (b) component is controlled to 0.01-5, and the atomic ratio (c/a) of the (a) component to the (c) component is adjusted to 0.001-5. Besides, 0.1-20wt% (a) component, 0.1-20wt% (b) component, and 0.01-20wt% (c) component are deposited. The catalyst is used when a carboxylic or ketonic compd. is produced by oxidizing a hydroxy or aldehydric compd. (excluding saccharides).

Description

Detailed Description of the Invention 3. Detailed Description of the Invention [Field of Industrial Application] The present invention provides a catalyst composition for an oxidation reaction used when oxidizing a hydroxy compound or an aldehyde compound to produce a carboxyl compound or a ketone compound. In more detail, we have made the platinum-based noble metal catalyst multi-elementized, that is, added two or more elements as catalyst components to the platinum group element, which is the main catalyst element, and created a composite catalyst component, which has never been done before. The present invention relates to a catalyst composition for oxidation reactions having high activity and high selectivity.

[Conventional technology and problems]

Conventionally, hydroxy compounds and aldehyde compounds are catalytically oxidized in the presence of noble metal catalysts such as palladium carbon (Pd/C) and platinum carbon (Pt/C) to produce the corresponding carboxyl compounds (or their alkali metal salts) and A method of converting it into a ketone compound is known. However, in this case, the following problems arise.

That is, when a pd/lpt/c catalyst is used in an oxidation reaction,
The reaction progresses smoothly from the early stage to the middle stage, but
Particularly at the end of the reaction, a phenomenon is observed in which the reaction rate drops significantly or the reaction stops without being completed. Although the degree of this phenomenon varies depending on the structure of the object to be oxidized, it is generally observed in oxidation reactions using noble metal catalysts.

For example, JP-A-53-141218 describes a method of oxidizing polyoxyethylene alkyl ether using a 5χPd/C catalyst to convert it into the corresponding carboxylic acid salt. However, in this method, the reaction stops at about 80% yield.

In addition, J. Catal, 67, 1 (1981) describes the oxidation reaction of glucose to sodium gluconate using a 2ZP t/C catalyst, but in this case too, the yield was about 90%. The reaction stops at this point.

As described above, oxidation reactions using platinum-based noble metal catalysts generally have the problem that the reaction stops midway and is not completed.

On the other hand, there have been several patents that have attempted to add a second catalyst component to noble metal catalysts for oxidation reactions, such as Pt/C and Pd/C, to improve their catalytic activity as two-way catalysts. It will be done.

For example, JP-A-54-132547 describes a method for producing aromatic carboxylic acids using a lead-added Pt/C or Pd/C catalyst. Also, Japanese Patent Application Publication No. 1973
Japanese Patent No. 138886 describes a catalyst composition containing lead, tin, indium, and tellurium.

Furthermore, JP-A-57-163376 describes a method for producing diacetone-2-keto L-gulonic acid using a Pt/C or Pd/C catalyst to which bismuth or lead is added. In addition, the specification of BP-1070 contains platinum-based elements (
platinum, palladium, rhodium, ruthenium, rhenium)
describes a method for producing pyruvic acid using the addition of silver, tellurium, tin, lead, and indium, all of which claim to improve yield.

However, even in the methods described in the specifications of these patents, the reaction was not completed and the yield was not satisfactory.

[Means for solving problems]

Therefore, in order to solve the problems of platinum-based precious metal catalysts in oxidation reactions as described above, the present inventors conducted intensive research on the mechanism and found that the incomplete reaction phenomenon observed when precious metal catalysts are used in oxidation reactions. It was discovered that this is mainly due to the high oxygen adsorption power of platinum and palladium, which are the main catalytic elements.

That is, at the beginning of the reaction, the concentration of the oxidizable material is high and oxygen is consumed at a supply rate-limiting rate, but at the end of the reaction, when the concentration of the oxidizable material decreases and the oxygen concentration in the reaction system becomes excessive, Excessive adsorption of oxygen occurs on the catalyst surface, and as a result, adsorption of unreacted oxidized substances onto the catalyst surface is suppressed, and the reaction is stopped midway. This effect is particularly noticeable in pressurized systems.

Therefore, the present inventors continued research to alleviate or suppress this phenomenon, and as a result, completed the present invention.

That is, the present invention uses 1 selected from platinum group elements (palladium, platinum, ruthenium, rhodium) as the first catalyst component.
one or more elements selected from the group consisting of tin, bismuth, and antimony as a second catalyst component;
and as a third component of the catalyst, one or more elements selected from selenium, tin, and tellurium (excluding tin when the second component is tin) are supported on an inorganic carrier, and the first component of the catalyst is The ratio R1 (second component/first component) of the second catalyst component is 0.01 to 5.0 in atomic ratio, and the ratio R2 (third component/first component) of the first catalyst component and the third catalyst component is 1st component)
A catalyst composition for an oxidation reaction used when producing a carboxyl compound or a ketone compound by oxidizing a hydroxy compound or an aldehyde compound (excluding Group I!), characterized in that the atomic ratio is 0.001 to 5. It is something that provides something.

In the oxidation reaction catalyst composition of the present invention, it is important to simultaneously use one or more of the first catalyst component, one or more of the second component, and one or more of the third component.

The ratios of the second and third components to the first catalyst component, which is the main catalyst element, R1 and R2 are each 0.01 in atomic ratio.
-5.0.001-5, preferably 0.05-3.0.005-3, particularly preferably 0.08-2.0.01-1.5, respectively. It is important that

Further, the catalyst of the present invention is used as a supported catalyst supported on an inorganic carrier. Generally known carriers are used as the carrier. Examples include activated carbon, asbestos, alumina, silica gel, activated clay, and diatomaceous earth, among which activated carbon is particularly preferred.

The first component, the second component, and the third component of the catalyst used in the present invention
The supported amounts of the components are usually 0.1 to 20% by weight and 0.1 to 20% by weight, respectively.
The range is 1 to 20% by weight, 0.01 to 20% by weight,
Preferably 1 to 15% by weight, 0.5 to 15% by weight, 0.05 to 15% by weight, particularly preferably 2 to 15% by weight, respectively.
~13% by weight, 0.75-10% by weight, 0.10-10
Weight%.

In addition, the catalyst of the present invention may contain alkaline earth elements, zinc, transition metals, etc., if necessary, in order to improve the durability of the catalyst or the hue of the reaction product when the catalyst of the present invention is used in an oxidation reaction. Compounds can be added.

In X-ray diffraction measurements of the catalyst of the present invention, for example, the diffraction peak of palladium, which is the first component of the catalyst, is significantly broadened. That is, in the catalyst of the present invention, it can be said that the first catalyst component, which is the main catalyst element, is in a highly dispersed state.

Raw materials for the first catalyst component include palladium chloride, palladium iodide, palladium nitrate, palladium oxide, chloroplatinic acid, iodoplatinic acid, platinum nitrate, platinum oxide, platinum chloride,
Platinum cyanide, platinum iodide, or intramolecular complexes such as palladium acetate or palladium acetylacetone, or palladium selenide or tellurium formed between a pre-prepared platinum carbon catalyst, palladium carbon catalyst, or a third catalyst component. Examples include compounds such as rhodium chloride,
Particularly preferred are palladium chloride, chloroplatinic acid, pre-prepared platinum carbon catalysts, and palladium carbon catalysts.

Ruthenium chloride, rhodium chloride, and rhodium nitrate also serve as raw materials for the first catalyst component.

Raw materials for the second catalyst component include tin tetrachloride, tin tetrabromide, tin iodide, tin oxide, antimony oxide, antimony oxychloride, antimony pentachloride, bismuth chloride, bismuth oxychloride, bismuth oxypromide, and bismuth tartrate. , bismuth hydroxide, or compounds formed between the catalyst and the third component of the catalyst, such as bismuth selenide and tellurium selenide.

Raw materials for the third catalyst component include tellurium tribromide, tellurium dichloride, tellurium oxide, tellurium tetrachloride, tellurium tetrabromide, tellurium tetraiodide, telluric acid and its alkali metal salts, tellurite and its alkali metals. salts or selenium oxides, selenite, selenate, selenium chloride, alkali metal salts of selenite or selenate, hydrogen selenide, or compounds formed between the first or second catalyst component, e.g. Examples include compounds such as bismuth chloride, bismuth telluride, palladium selenide, rhodium selenide, rhodium telluride, and platinum selenide.

The catalyst of the present invention is prepared by known methods. In preparing the catalyst, an aqueous solution of the first, second and third components of the catalyst is prepared and adsorbed onto, for example, activated carbon in ion-exchanged water. At this time, if an aqueous solution of the catalyst component cannot be prepared, it is solubilized with hydrochloric acid or the like and adsorbed. After adsorption, the catalyst components are reduced using a reducing agent such as formalin, hydrogen, hydrazine, or sodium borohydride. After reduction, the catalyst of the present invention is obtained by washing the catalyst with water and separating it by filtration. Although the catalyst usually has a water content of 50 to 60%, it can be used in the oxidation reaction without drying. Other catalysts of the invention can be prepared in a similar manner. Although the catalysts of the present invention are reusable, some may be re-reduced to maintain high levels of activity. The catalyst composition for oxidation reactions of the present invention is particularly effective for oxidizing -grade hydroxyl groups or aldehyde groups to the corresponding carboxyl groups (or alkali metal salts of carboxyl groups). It is also effective in the synthesis of ketones by dehydrogenation such as

Hydroxy compounds or aldehyde compounds to be oxidized in carrying out the present invention (excluding Group Ii) include aliphatic primary or secondary alcohols, aliphatic aldehydes,
Polyoxyalkylene alkyl ether, polyoxyalkylene alkylaryl ether, polyoxyarylphenyl ether, polyalkylene glycol, ethylene glycol, diethylene glycol, polyols such as glycerin, alkylene oxide adducts of amines or amides, aromas such as benzyl alcohol, anise alcohol, etc. Examples include group alcohols, aromatic aldehydes such as benzaldehyde, alicyclic alcohols such as cyclohexanol, and lactic acid. It is not limited to these compounds.

The reaction is generally carried out in an aqueous solution system, but if the oxidized substance is water-insoluble, the reaction can be promoted by adding a water-soluble solvent or a surfactant.

When carrying out an oxidation reaction using the catalyst of the present invention, the reaction temperature is preferably 0 to 100°C, preferably 20 to 80°C.
The reaction pressure is preferably up to 10 atm, particularly normal pressure.

In addition, the oxidizing agents used specifically for oxidation reactions include oxygen gas,
Alternatively, oxygen-containing gas such as air may be used.

〔Example〕

The present invention will be explained in detail by giving examples below.

Example 1 (Preparation of 2χTe/4χBi/10χPd/C catalyst) 8
．． 4 g of activated carbon is immersed in 100 m of ion-exchanged water (1.66 g of palladium chloride is dissolved in a 7% hydrochloric acid aqueous solution 22- as a raw material for the first catalyst component.
As a raw material for the component, 0.6 g of bismuth chloride is dissolved in a 12% aqueous hydrochloric acid solution 28+nj.

0.25g of tellurium oxide was added as a raw material for the third component of the catalyst.
Dissolve in 361 nl of 6% aqueous hydrochloric acid solution.

A hydrochloric acid solution of these three catalyst components is added to the previously prepared activated carbon to perform an adsorption treatment. Thereafter, 48 g of 48% caustic soda and 24 g of a 37% formalin aqueous solution were added to reduce the catalyst components.

The reduced catalyst is washed with ion-exchanged water, and the catalyst is filtered off. The resulting catalyst was a 2χTe/
It is a 4χBi/10χPd/C catalyst. The catalyst can be used in the oxidation reaction without drying.

R1 of 2χTe/4χ old/10χPd/C catalyst is 0.1
7. R2 is 0.20.

Example 2 (Preparation of 2XBi15χ5n15χPd/C catalyst)8.
8 g of activated carbon is immersed in 100 mZ ion exchange water. As a raw material for the first catalyst component, 0.83 g of palladium chloride is dissolved in 4% aqueous hydrochloric acid solution 221117. 0.3g of bismuth chloride as a raw material for the second catalyst component
% aqueous hydrochloric acid solution (24 m7).

1.1g of tin tetrachloride was added to 20% of the raw material for the third component of the catalyst.
Dissolve in v1 ion exchange water.

A hydrochloric acid solution of these three catalyst components is added to the previously prepared activated carbon to perform an adsorption treatment. Thereafter, 24 g of 48% caustic soda and 18 n7 of a 37% formalin aqueous solution were added to reduce the catalyst components.

The reduced catalyst is washed with ion-exchanged water, and the catalyst is filtered off. The resulting catalyst contains 2χB11 containing approximately 50% water.
5χ5n15χPd/C catalyst. The catalyst can be used in the oxidation reaction without drying.

2χB115χ5n15χPd/C catalyst R1 is 0.2
0, R2 is 0.90.

Examples 3-4 Other catalysts of the present invention were prepared in the same manner (Table 1).

Wipe armpit ■POII! (6) A 20% aqueous solution of lauryl alcohol (number of moles of ethylene oxide added: 6) was used as the oxidized substance, and the activity of the catalyst of the present invention and the conventional catalyst were compared.

1 with oxygen gas inlet, gas outlet, thermometer, sampling port and stirrer! Into a flask, add 500 g of a 20% aqueous solution of the oxidizable material, and add caustic soda (1.05 g to the oxidizable material).
mol) and 10 g of the catalyst of the present invention (water content 50%) were charged, and the temperature was raised to 75° C. while stirring. After reaching 75° C., normal pressure oxygen gas is bubbled into the flask at a flow rate of 31/hour. During the reaction, the reaction temperature is stabilized with appropriate cooling. After 3 hours, it is cooled and the catalyst is filtered off.

The oxidation product, the corresponding sodium carboxylate, is neutralized with hydrochloric acid to give the free carboxylic acid, which is extracted with chloroform.

The yield of the extract is determined by removing the solvent under reduced pressure and measuring the acid value and hydroxyl value. The results are shown in Table 1.

Table 1 From Table 1, the catalyst of the present invention is superior to the existing Pd/C catalyst in terms of yield as well as the two-way catalyst previously announced by the present inventors (
It can be seen that this catalyst is superior to catalyst 5) in Table 1.

In addition, it was found that when Sn was added (catalysts 2 and 4), the filtration rate (time required to filter 500 af of the reaction product) of the obtained carboxylate was high and the hue was also good. Ru.

Furthermore, the amount of unreacted substances was also significantly reduced, indicating that the multiplicity of catalyst components was effective. This is interpreted to be based on the suppression of self-poisoning of the catalyst by oxygen as described above.

Broad and narrow IL Various compounds shown in Table 2 were oxidized using the catalyst of the present invention. However, in Table 2, R is a linear alkyl group having 11 carbon atoms, EO is ethylene oxide, and n is 5.

The amount of caustic soda added was 1.05 times the molar amount of each compound, and the reaction time was 5 hours. Other reaction conditions were exactly the same as in Test Example 1.

The reaction results are shown in Table 2, and the reaction product is the corresponding sodium salt of the carboxylic acid. However, in the case of sodium lactate, it becomes sodium pyruvate. It can be seen from Table 2 that the catalyst of the present invention is extremely excellent.

Table 2

Claims (1)

[Scope of Claims] 1 The first catalyst component is one or more elements selected from platinum group elements (palladium, platinum, ruthenium, rhodium), and the second catalyst component is selected from the group consisting of tin, bismuth, and antimony. one or more elements selected from selenium, tin, and tellurium as the third catalyst component;
The catalyst is made by supporting at least one element (excluding tin when the second component is tin) on an inorganic carrier, and the ratio R1 (second component/first component) of the first catalyst component and the second catalyst component is ) is 0.01 to 5.0 in atomic ratio, and the ratio R2 (third component/first component) of the first catalyst component to the third catalyst component is 0.001 to 5 in atomic ratio. A catalyst composition for an oxidation reaction used in producing a carboxyl compound or a ketone compound by oxidizing a hydroxy compound or an aldehyde compound (excluding sugars), characterized by: 2. The catalyst composition for oxidation reactions according to claim 1, wherein the first catalyst component is palladium. 3 Content of the first catalyst component in the catalyst composition is 0.1 to 2
The catalyst composition for oxidation reactions according to claim 1, wherein the content is 0% by weight. 4 Content of the second catalyst component in the catalyst composition is 0.1 to 2
The catalyst composition for oxidation reactions according to claim 1, wherein the content is 0% by weight. 5 Content of the third catalyst component in the catalyst composition is from 0.01 to
The catalyst composition for oxidation reactions according to claim 1, wherein the content is 20% by weight.