JP2005255652A - Method for producing aliphatic saturated carboxylic acid - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an aliphatic saturated carboxylic acid, by which the unsaturated bond of an aliphatic unsaturated carboxylic acid or an aliphatic olefin-based hydrocarbon is cleft by using only a solid oxidation catalyst and a molecular oxygen-containing gas without using a peroxide so as to produce a corresponding aliphatic saturated monocarboxylic acid and aliphatic saturated dicarboxylic acid. <P>SOLUTION: The method for producing an aliphatic saturated carboxylic acid comprises carrying out reaction in a solvent-free condition by using a transition metal skeleton-substituted type zeolite catalyst in oxidatively cleaving an aliphatic unsaturated carboxylic acid or an aliphatic olefin-based hydrocarbon with a molecular oxygen-containing gas to produce a corresponding aliphatic saturated monocarboxylic acid and/or aliphatic saturated dicarboxylic acid. In the production method, the reaction is advanced in a liquid phase or vapor phase under mild conditions of a low temperature and low pressure to produce the objective substance in a high reaction conversion and in high selectivity. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for producing an aliphatic saturated carboxylic acid, and more specifically, by using a transition metal skeleton-substituted zeolite catalyst and a molecular oxygen-containing gas, an aliphatic unsaturated carboxylic acid under mild reaction conditions. The present invention relates to a method for producing an aliphatic saturated monocarboxylic acid and / or aliphatic saturated dicarboxylic acid with high selectivity by oxidative cleavage of a carbon-carbon double bond site in an acid or aliphatic olefinic hydrocarbon. The present invention is useful in the technical field of organic synthesis of aliphatic saturated carboxylic acids useful as synthetic intermediates for organic industrial products such as polyesters and lubricants, for example, ozone, hydrogen peroxide, Various problems associated with the addition and use of peroxides with danger of explosion such as peracetic acid and t-butyl hydroperoxide, heavy metal oxidants harmful to the environment, and other third substances such as organic solvents The present invention is useful for providing a novel method for synthesizing an aliphatic saturated carboxylic acid that can be drastically solved.

  Aliphatic monocarboxylic acids are industrially useful compounds, for example, as lubricating oil raw materials, and aliphatic dicarboxylic acids are, for example, raw materials for plasticizers, nylons, polyesters, hair care products, and the like. As the raw material, aliphatic unsaturated carboxylic acids can be obtained at low cost by hydrolysis of animal or vegetable fats and oils, and industrially, many methods using these aliphatic unsaturated carboxylic acids as raw materials are used. ing. For example, an ozone oxidation method (see Patent Documents 1 to 3) is reported as an industrial production method for obtaining the corresponding aliphatic monocarboxylic acid and aliphatic dicarboxylic acid by oxidative cleavage of double bonds of aliphatic unsaturated carboxylic acids. Has been. However, this type of method requires a large amount of money for the construction of the ozone generator, the ozone used as an oxidizer is expensive, and there is a risk of explosion associated with the generation of ozonide. There are problems to be improved.

  In addition, a method of oxidizing an aliphatic unsaturated carboxylic acid or olefinic hydrocarbon using a heavy metal oxidizing agent such as potassium permanganate or potassium dichromate in an equivalent amount or hypochlorous acid in the presence of a ruthenium tetroxide catalyst. A method using a salt as an oxidizing agent (see Patent Document 4) has been reported. However, this type of method is industrially expensive because these oxidants are expensive, highly toxic, and there are problems in the collection and waste disposal of oxidants and catalysts after completion of the reaction. There is a problem as a manufacturing method of scale.

  In addition, a method has been proposed in which various heteropolyacid compounds (see Patent Documents 5 to 7) and heavy metal salts (see Patent Document 8) are used as catalysts and hydrogen peroxide is used as an oxidizing agent. However, this type of method has a problem that hydrogen peroxide is associated with an explosion risk and is expensive, and a complicated extraction operation is indispensable when separating the reaction product and the catalyst.

  In addition, a method of oxidizing without using a catalyst using air instead of an expensive oxidant has been reported (see Patent Document 9). In this type of method, a large amount of an aqueous solution containing a phenolic polymerization inhibitor is used. Therefore, there is a problem that a large amount of energy is required for the water concentration operation. As a method using air oxidation, a method using zeolite 5A or zeolite 13X ion-exchanged with cobalt, nickel, or manganese as a catalyst (Non-patent Document 1) has been reported. However, since this type of method requires a high reaction temperature of 240 ° C., there is a problem that aldehydes, which are intermediate products of decarboxylation and oxidation reaction, can be obtained in large quantities as by-products.

  As described above, since the above-mentioned methods proposed so far have many problems, the technical field solves these problems as industrial synthesis of aliphatic saturated carboxylic acids. It has been desired to develop a new manufacturing method that can be used.

Japanese Patent Publication No. 36-4717 US Pat. No. 2,813,111 US Pat. No. 2,813,118 JP-A-56-103132 JP-A-60-34929 JP-A-63-93746 JP-A-5-4938 JP 59-222437 Japanese Patent Publication No.40-12767 H. Shiina et al., Oil Chemistry, 1986, page 349

  Under such circumstances, the present inventors can easily adsorb and desorb aliphatic unsaturated carboxylic acids or aliphatic olefinic hydrocarbons in order to solve the above problems in view of the above prior art. To develop a zeolitic solid catalyst that has a pore structure and only undergoes an oxidative cleavage reaction of a carbon-carbon double bond site when contacted with molecular oxygen gas, and further, a highly selective reaction, As a result of intensive research aimed at developing a method capable of producing an aliphatic saturated carboxylic acid under mild reaction conditions, some elements forming the zeolite framework were converted into a framework using transition metals. By using a transition metal skeleton substitution type zeolite catalyst obtained by substitution, it has been found that the above problems can be solved and the intended purpose can be achieved, and the present invention has been completed based on this finding. .

That is, the present invention overcomes the disadvantages of the conventional synthesis method, uses only a transition metal skeleton-substituted zeolite catalyst and molecular oxygen gas, and under mild reaction conditions without adding other third substances. Provides a highly selective production method of a carboxylic acid and an aliphatic saturated dicarboxylic acid characterized by oxidizing an unsaturated aliphatic carboxylic acid with oxygen to oxidatively cleave the vicinity of a carbon-carbon double bond site in the main chain It is intended to do.
In addition, the present invention can obtain a target product under mild reaction conditions of low temperature and low pressure by accumulating a hydroperoxide compound having a risk of explosion in an extremely simple apparatus and operation without accumulating in the reaction system. In addition, by enabling repeated use of the catalyst and reaction under solvent-free conditions, post-treatment such as industrial waste and industrial waste liquid is not required, and it is extremely low cost and extremely industrially useful. An object of the present invention is to provide a method for producing an aliphatic saturated monocarboxylic acid and / or an aliphatic saturated dicarboxylic acid.

The present invention for solving the above-described problems comprises the following technical means.
(1) An aliphatic unsaturated carboxylic acid or aliphatic olefinic hydrocarbon having 6 to 30 carbon chains having one or more unsaturated bonds in the carbon chain of the reaction substrate, using a molecular oxygen-containing gas, Transition metal skeleton substitution type in which a part of the skeletal structure is substituted with a transition metal as a catalyst in the oxidative cleavage reaction by oxidative cleavage reaction to produce the corresponding aliphatic saturated monocarboxylic acid and / or aliphatic saturated dicarboxylic acid A method for producing an aliphatic saturated carboxylic acid, comprising using a zeolite catalyst.
(2) The transition metal skeleton substitution type zeolite catalyst has a general formula (R ₄ N ⁺ ) (OH ⁻ ) (H ₂ O) _x [Al ₁₂ P ₁₂ O ₄₈ ] (wherein R ₄ N ⁺ is a quaternary AlPO-5 zeolite represented by ammonium salt, x is an integer), or general formula Na _n (H ₂ O) ₁₆ [Al _n Si _96-n O ₁₉₂ ] (wherein n is 0 ≦ n <27) The transition metal skeleton-substituted zeolite having a structure corresponding to the MFI-based zeolite represented by a certain integer), wherein a part of the skeleton structure is substituted with another transition metal. A method for producing an aliphatic saturated carboxylic acid.
(3) The transition metal skeleton substitution zeolite catalyst in which the transition metal to be subjected to skeleton substitution is at least one selected from cobalt, manganese, iron, nickel, vanadium, molybdenum, chromium, niobium, and tantalum is used (1 The manufacturing method of the aliphatic saturated carboxylic acid as described in).
(4) The transition metal to be subjected to skeleton substitution is cobalt or manganese, and a transition metal skeleton substitution type zeolite catalyst having a content of 0.1 to 5% by weight with respect to the zeolite catalyst is used. A method for producing an aliphatic saturated carboxylic acid.
(5) In the above (1), a transition metal skeleton substitution type zeolite catalyst in which the amount of the transition metal used for skeletal substitution is 0.2 to 20% by weight with respect to the starting zeolite is used. The manufacturing method of carboxylic acid of description.
(6) A transition metal skeleton substitution type zeolite catalyst in which a transition metal introduced into a zeolite skeleton is activated to a higher oxidation electronic state by calcination at 200 to 700 ° C. in an oxygen atmosphere. The manufacturing method of the aliphatic saturated carboxylic acid as described in said (1) used.
(7) A transition metal skeleton substitution-type zeolite catalyst, an aliphatic unsaturated carboxylic acid or an aliphatic olefinic hydrocarbon, and molecular oxygen gas are contacted by a liquid phase reaction under a temperature condition of 10 to 150 ° C. The manufacturing method of the aliphatic saturated carboxylic acid as described in said (1).
(8) The method for producing an aliphatic saturated carboxylic acid according to (1) above, wherein the amount of the transition metal skeleton substitution type zeolite catalyst used is 0.1 to 50% by weight based on the reaction substrate. .

Next, the present invention will be described in more detail.
The present invention uses a transition metal skeleton-substituted zeolite catalyst and molecular oxygen gas to effectively utilize the advanced recognition ability for the chemical structure of olefins based on the shape selectivity effect derived from the pore structure of the catalyst. And oxidative cleavage from an aliphatic unsaturated carboxylic acid or aliphatic olefinic hydrocarbon to the corresponding aliphatic saturated carboxylic acid by the following reaction.

The constitution of the transition metal skeleton substitution type zeolite catalyst used in the present invention will be described. The zeolite catalyst of the present invention is, for example, the general formula (R ₄ N ⁺ ) (OH ⁻ ) (H ₂ O) _x [Al ₁₂ P ₁₂ O ₄₈ ] (wherein R ₄ N ⁺ is a quaternary ammonium salt, x is an integer), or a general formula Na _n (H ₂ O) ₁₆ [Al _n Si _96-n O ₁₉₂ ] (where n is an integer satisfying 0 ≦ n <27) and a transition metal in which a part of the skeleton structure is substituted with another transition metal Examples of the framework substitution type zeolite are shown below. These transition metal skeleton substitution type zeolites are known methods (for example, Verifyed Synthesis of Zeolitic Materials 2nd Revised Edition, Ed. Can be manufactured. As long as these zeolite catalysts are transition metal skeleton substitution type zeolites, the production method and composition thereof are not particularly limited. For example, an aqueous solution containing alumina, transition metal, quaternary ammonium, etc. is autoclaved. It is produced by hydrothermal treatment.

  The type of transition metal used for skeletal substitution is not particularly limited as long as it is a transition metal belonging to Group 3 to Group 14 in the periodic table of elements, but preferably cobalt, manganese, iron , Nickel, vanadium, molybdenum, chromium, niobium, tantalum, and the like, transition metals that easily change their oxidation number by oxidation or reduction reaction and can take a higher oxidation electronic state are desirable, particularly preferably cobalt and Manganese is exemplified.

  In the production of the zeolite of the present invention, the transition metal is used in an amount of 0.2 to 20% by weight based on the starting zeolite. By adjusting the amount charged, the content of cobalt, manganese, etc. in the catalyst raw material finally obtained can be arbitrarily adjusted between 0.1 and 10% by weight. However, when the amount charged is large, in addition to the skeleton-substituted transition metal, transition metal oxides are formed not only on the surface of the pores but also in the pores, not only inhibiting the selective oxidative cleavage reaction, but also formed. Since the decarboxylation reaction of carboxylic acid is promoted, the range of 0.1 to 5% by weight is preferable as the amount to be charged. In the present invention, it is preferable to use a quaternary ammonium salt such as triethylamine, tetrapropylammonium bromide, tetraethylammonium hydroxide, etc. as a template compound.

  In the present invention, using a zeolite raw material composition containing an aluminum raw material, a transition metal raw material, a quaternary ammonium raw material, etc., for example, by a hydrothermal reaction in an autoclave, preferably at a temperature of 150 to 250 ° C., Under the reaction conditions of a reaction time of 24 to 240 hours, the zeolite of the present invention is synthesized. The obtained transition metal skeleton substitution type zeolite is calcined under a high temperature condition to burn and remove an organic compound such as quaternary ammonium used as a template compound, and the transition metal introduced into the zeolite skeleton, It is preferable to activate to a higher oxidation electronic state. By performing this calcination treatment, the transition metal skeleton-substituted zeolite is induced into an active catalyst in which only the oxidative cleavage reaction can mainly occur when contacting with the molecular oxygen gas. The firing temperature condition is 200 to 700 ° C., preferably 500 to 600 ° C. in an oxygen atmosphere.

  The transition metal skeleton substitution type zeolite catalyst thus obtained is used in the form of a powder or kneaded with a third substance and granulated or molded. It is also possible to form a thin film on another carrier and use it as a catalyst. The amount of the catalyst used is 0.1 to 50% by weight, preferably 2 to 20% by weight, based on the aliphatic unsaturated carboxylic acid or aliphatic olefinic hydrocarbon compound as the reaction substrate. The

  Next, the aliphatic unsaturated carboxylic acid used as a raw material in the present invention is not particularly limited as long as it is an aliphatic unsaturated carboxylic acid having 6 to 30 carbon chains and having one or more unsaturated bonds in the carbon chain. Preferably, for example, oleic acid, erucic acid, linoleic acid, linolenic acid or ricinoleic acid alone or a mixture thereof is exemplified. Further, mixed unsaturated fatty acids obtained by hydrolyzing substances containing these unsaturated carboxylic acids, for example, vegetable oils such as palm oil, rapeseed oil, soybean oil, olive oil, and animal oils such as beef tallow and fish oil It is also possible to use. It is also possible to use a compound that is easily derived from an aliphatic unsaturated carboxylic acid, such as an ester, nitrile, or amide compound. Moreover, it is also possible to use an aliphatic olefin hydrocarbon compound as a raw material used in the present invention, and the product in this case is only an aliphatic saturated monocarboxylic acid.

Examples of the molecular oxygen-containing gas used as an oxidizing agent in the present invention include pure oxygen, ordinary air, industrial exhaust gas, or other inert gases such as pure oxygen and helium, nitrogen, argon, carbon dioxide, etc. Are mixed at an arbitrary ratio. In order to shorten the reaction time, pure oxygen is desirable. The reaction pressure is suitably in the range of 0.1-50 atm, more preferably 0.5-10 atm.

  There is no particular limitation on the method of bringing the transition metal skeleton substitution type zeolite catalyst into contact with the aliphatic unsaturated carboxylic acid or aliphatic olefinic hydrocarbon compound and molecular oxygen gas, and both liquid phase and gas phase methods can be used. However, preferably, a liquid phase reaction is used from the viewpoint of suppressing a decarboxylation reaction under a high temperature condition. In the liquid phase reaction, the reaction temperature is usually 10 to 150 ° C., but the reaction rate decreases at a low temperature of 60 ° C. or lower, and the decarboxylation reaction proceeds at a high temperature of 120 ° C. or higher. Therefore, it is preferably in the range of 60 to 120 ° C.

  The reaction of the present invention results from the allyl peroxy radical species obtained by the reaction of the molecular oxygen gas with the double bond site in the aliphatic unsaturated carboxylic acid or aliphatic olefinic hydrocarbon compound. Therefore, for example, when a solvent is used for the reaction, it does not generate peroxide under the reaction conditions, does not deteriorate due to oxygen oxidation reaction, and does not contain a radical trapping agent (polymerization inhibitor). There is no restriction | limiting in particular, For example, benzene, toluene, n-hexane, n-octane, acetic acid, propionic acid etc. are illustrated. However, if the polymerization inhibitor is contained in the solvent in a slight amount, the oxidative cleavage reaction of the present invention is remarkably hindered. For example, it is necessary to purify the solvent by a method such as distillation.

  The transition metal skeleton substitution type zeolite catalyst used in the method of the present invention has high lipophilicity, a high specific surface area, and an optimum pore diameter for reaction. For this reason, even under solvent-free conditions, the hydrophobic long chain carbon moiety in the aliphatic unsaturated carboxylic acid or aliphatic olefinic hydrocarbon compound can be easily adsorbed in the pores, and the carbon-carbon double bond moiety Since the oxidative cleavage reaction proceeds smoothly, a reaction under solvent-free conditions is also possible.

  In addition, aliphatic unsaturated carboxylic acids are known to undergo rapid polymerization reaction by high-temperature heating in the presence of oxygen, and this method is used as an industrial production method of dimer acid ( Ulmann, Encyclopa "dieder Technich Chemical., Bd7, 1996, p. 538.) However, in the present invention, the reaction field is limited to the fine pores in the zeolite, and therefore a molecule that requires a large reaction field. The production of dimer acid due to the inter-reaction has the advantage of being suppressed under heating conditions in the presence of oxygen.

  In the present invention, the reaction time varies depending on, for example, the amount of the catalyst added, the raw material compound, and the like, but is usually in the range of 1 to 120 hours, preferably 6 to 24 hours.

  The reaction mixture obtained according to the present invention can be obtained by subjecting the transition metal skeleton substitution type zeolite catalyst to filtration fractionation, and the desired mixture of aliphatic saturated monocarboxylic acid and aliphatic dicarboxylic acid can be obtained. It is possible. In addition, the reaction product can be fractionated and purified after extraction with hot water, using an operation such as distillation or recrystallization. In addition, the zeolite catalyst separated by filtration can be reused as it is, but when the catalytic activity is reduced by long-term use, by treating in a temperature range of 500 to 600 ° C. in an oxygen atmosphere, Can be played repeatedly and reused.

  The zeolite catalyst used in the method of the present invention adsorbs molecular oxygen gas in its pores, and also has a double bond of an aliphatic unsaturated carboxylic acid or aliphatic olefinic hydrocarbon incorporated into the pores. By reacting the site with molecular oxygen promptly, an unsaturated aliphatic carboxylic acid-based allyl peroxy radical or an aliphatic olefin-based allyl peroxy radical is generated as a precursor of the oxidative cleavage reaction.

  On the other hand, in the oxygen oxidation reaction of cycloolefins using a transition metal skeleton substitution type zeolite solid catalyst, it is known that a cycloolefin peroxy radical having explosive properties is generated as a reaction precursor. Further, by passing through this cycloolefin peroxy radical, for example, in the case of cyclohexene, enols and enones such as 2-cyclohexen-1-ol and 2-cyclohexen-1-one can be used. In some cases, cyclooctene oxide is formed.

  However, in the method of the present invention, the unsaturated aliphatic carboxylic acid-based allyl peroxy radical or aliphatic olefin-based allyl peroxy radical generated as a reaction precursor is different from the above-described oxidation reaction of the cycloolefin compound, and is a skeleton substitution type. In the pores of the zeolite catalyst, it undergoes a rapid oxidative cleavage reaction, leading to the desired aliphatic saturated monocarboxylic acid and / or aliphatic saturated dicarboxylic acid. Therefore, in the present invention, the above-mentioned by-products such as enols, enones, epoxy compounds and hydroperoxy compounds are hardly confirmed. In addition, since no aliphatic compound is produced by the decarboxylation reaction and only the oxidative cleavage reaction proceeds preferentially, it has a characteristic that a high reaction selectivity of the target aliphatic saturated carboxylic acid can be obtained.

  According to the present invention, (1) only the oxidative cleavage reaction proceeds preferentially even under mild reaction conditions, and the corresponding aliphatic saturated monocarboxylic acid and / or aliphatic aliphatic olefinic hydrocarbon and / or Aliphatic saturated dicarboxylic acids can be produced with high reaction selectivity and almost no by-products. (2) Risk of explosion of ozone, hydrogen peroxide, peracetic acid, t-butyl hydroperoxide, etc. An aliphatic saturated monocarboxylic acid and / or an aliphatic saturated dicarboxylic acid can be produced without using a peroxide. (3) The catalyst can be used repeatedly and can be reacted in a solvent-free condition. Therefore, there is an extraordinary effect that processing of industrial industrial waste and industrial waste liquid is not necessary, and the cost is extremely low.

  EXAMPLES Next, although this invention is demonstrated concretely based on an Example, this invention is not limited at all by the following Examples.

Production Example 1
In this production example, a Co-ALPO-5 zeolite catalyst was synthesized by the following method.
11.55 g of orthophosphoric acid (manufactured by Nacalai Tax Co., Ltd., reagent special grade) was added to 31.3 g of ion-exchanged water and stirred until it was completely dissolved. This was cooled with ice water (0 ° C.), and 2.33 g of cobalt nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, reagent special grade) was added and stirred until it was completely dissolved. Next, 6.25 g of pseudo boehmite (Catapal Alumina, SCC-30, 75% alumina) was added and stirred until completely dissolved. Furthermore, 7.2 g of triethylamine (made by Kokusan Kagaku Co., Ltd., reagent grade) was slowly added dropwise and stirred until it was completely dissolved. All operations during this time were performed while cooling with ice water (0 ° C.).

  The slurry solution thus obtained had a pH of 3.0. This slurry was transferred to an autoclave with a Teflon (registered trademark) inner cylinder and hydrothermally treated at 200 ° C. for 36 hours while rotating the autoclave. After the hydrothermal treatment, the contents are taken out from the autoclave and separated into solid and liquid, and then the solid is sufficiently washed with ion-exchanged water, dried at 100 ° C. for 20 hours, and calcined at 550 ° C. for 6 hours to obtain a reaction catalyst. It was. The Co content of this catalyst by ICP analysis was 2.9 wt%.

Production Example 2
In this production example, a Co-MFI zeolite catalyst was synthesized by the following method.
After dissolving 1.2 g of solid sodium hydroxide in 150 g of distilled water, colloidal silica aqueous solution (catalyst chemical industry Co., Ltd., CATALOID SI-30, SiO ₂ 30%, Na ₂ O 0.38% while stirring) ) 60.0 g was added. Next, a solution in which 1.5 g of cobalt chloride hexahydrate was dissolved in 25 g of distilled water was added. Further, 799 g of tetrapropylammonium bromide was added as an organic structure-directing agent, and water with a pH of 11.9 was added. A slurry for thermal synthesis was obtained. Tetraethylammonium hydroxide was added to the resulting slurry to adjust the pH to 13.4, and the mixture was reacted at 170 ° C. for 4 days in an autoclave having a Teflon (registered trademark) inner cylinder, followed by filtration and washing. . The obtained Na-type Co-MFI was treated with 0.1N hydrochloric acid overnight, and calcined at 550 ° C. for 22 hours to remove organic substances, and used as a reaction catalyst.

  In this production example, it was confirmed by an X-ray diffraction pattern and an electron microscope that no Co-MFI zeolite was produced and no metal oxide was precipitated after firing. The Co content in Co-MFI was confirmed by analysis of a Cs ion exchange sample and a proton type sample after acid treatment. The Co content of the proton type sample was 1.07 wt%.

Production Example 3
In this production example, a Mn-MFI zeolite catalyst was synthesized by the following method.
After dissolving 1.2 g of solid sodium hydroxide in 150 g of distilled water, colloidal silica aqueous solution (catalyst chemical industry Co., Ltd., CATALOID SI-30, SiO ₂ 30%, Na ₂ O 0.38% while stirring) ) 60.0 g was added. Next, a solution prepared by dissolving 1.2 g of manganese chloride tetrahydrate in 25 g of distilled water was added, and further, 7.99 g of tetrapropylammonium bromide was added as an organic structure-directing agent, and pH 11.9 hydrothermal A slurry for synthesis was obtained. Tetraethylammonium hydroxide is further added to the resulting slurry to adjust the pH to 13.4, and after reacting at 170 ° C. for 4 days in an autoclave having a Teflon (registered trademark) inner cylinder, filtration and washing are performed. went. The obtained Na-type Mn-MFI was further treated with 0.1N hydrochloric acid overnight, and calcined at 550 ° C. for 22 hours to remove organic substances, thereby obtaining a reaction catalyst.

  It was confirmed by X-ray diffraction pattern and electron microscope that Mn-MFI was produced and no metal oxide was precipitated after firing. The content of Mn in Mn-MFI was confirmed by analysis of a Cs ion exchange sample and a proton type sample after acid treatment. The Mn content of the proton type sample was 0.57 wt%.

  Only 100 g of the Co-AlPO-5-based zeolite catalyst obtained in Production Example 1 and 1.0 g of oleic acid (manufactured by Tokyo Chemical Industry, purity 99%) were equipped with a 100 ml pressure-resistant glass container equipped with an oxygen inlet at 1 atm. In addition, the mixture was heated and stirred at 80 ° C. for 24 hours while supplying oxygen gas under solvent-free conditions. After completion of the reaction, the reaction solution and the catalyst were separated by filtration. The obtained reaction solution was subjected to ethyl esterification and then analyzed using gas chromatography to determine the reaction conversion rate of oleic acid and the reaction selectivity to aliphatic saturated monocarboxylic acid and aliphatic saturated dicarboxylic acid. It was. The results are shown in Table 1.

  Using 0.05 g of the Co-MFI zeolite catalyst obtained in Production Example 2, the oxidation reaction and analysis of oleic acid were carried out in the same manner as in Example 1. The results are shown in Table 1.

  Using 0.05 g of the Mn-MFI zeolite catalyst obtained in Production Example 3, the oxidation reaction and analysis of oleic acid were carried out in the same manner as in Example 1. The results are shown in Table 1.

  As described above in detail, the present invention provides an aliphatic unsaturated carboxylic acid or aliphatic olefinic hydrocarbon by subjecting an unsaturated bond to an oxidative cleavage reaction using a molecular oxygen-containing gas, thereby producing a corresponding aliphatic saturated carboxylic acid. The present invention relates to a method for producing an aliphatic saturated carboxylic acid characterized by using a transition metal skeleton substitution type zeolite catalyst in producing an acid. Conventionally, in the technical field of producing aliphatic saturated carboxylic acids, Although reaction conditions are necessary, expensive, not easy to handle, and the use of peroxides that can explode is unavoidable, the present invention drastically overcomes these problems. It is possible to solve the problem.

INDUSTRIAL APPLICABILITY The present invention is useful industrial intermediates such as lubricants, plasticizers, nylons, polyesters, etc. under mild reaction conditions such as low temperature and low pressure using a very simple apparatus and operation with little risk of explosion. It is possible to provide a method for producing an aliphatic saturated monocarboxylic acid and an aliphatic saturated dicarboxylic acid with high selectivity. In addition, the present invention can repeatedly use the catalyst, can be reacted in a solvent-free condition, does not require treatment of industrial industrial waste or industrial waste liquid, and has advantages such as extremely low cost, It is possible to provide a method for producing aliphatic saturated carboxylic acids having high industrial utility value.

Claims (8)

  Oxidative cleavage of an aliphatic unsaturated carboxylic acid or aliphatic olefinic hydrocarbon having 6 to 30 carbon chains with one or more unsaturated bonds in the carbon chain using a molecular oxygen-containing gas. Transition metal skeleton-substituted zeolite catalyst in which a part of the skeleton structure is substituted with a transition metal as a catalyst in an oxidative cleavage reaction for reacting to produce a corresponding aliphatic saturated monocarboxylic acid and / or aliphatic saturated dicarboxylic acid A process for producing an aliphatic saturated carboxylic acid, characterized in that The transition metal skeleton substitution type zeolite catalyst has the general formula (R ₄ N ⁺ ) (OH ⁻ ) (H ₂ O) _x [Al ₁₂ P ₁₂ O ₄₈ ] (wherein R ₄ N ⁺ represents a quaternary ammonium salt, x is an integer) or an AlPO-5-based zeolite represented by the general formula Na _n (H ₂ O) ₁₆ [Al _n Si _96-n O ₁₉₂ ] (wherein _n is an integer satisfying 0 ≦ n <27) The aliphatic saturated carboxylic acid according to claim 1, which is a transition metal skeleton-substituted zeolite having a structure corresponding to the MFI-based zeolite represented by the formula, wherein a part of the skeleton structure is substituted with another transition metal. Acid production method.   2. The transition metal skeleton substitution type zeolite catalyst according to claim 1, wherein the transition metal that performs skeleton substitution is at least one selected from cobalt, manganese, iron, nickel, vanadium, molybdenum, chromium, niobium, and tantalum. A method for producing an aliphatic saturated carboxylic acid.   The aliphatic saturated carboxylic acid according to claim 1, wherein the transition metal to be subjected to skeleton substitution is cobalt or manganese, and the transition metal skeleton substitution type zeolite catalyst having a content of 0.1 to 5 wt% with respect to the zeolite catalyst is used. Acid production method.   2. The carboxylic acid according to claim 1, wherein a transition metal skeleton substitution type zeolite catalyst in which the amount of transition metal used for skeletal substitution is 0.2 to 20 wt% with respect to zeolite as a starting material is used. Manufacturing method.   A transition metal skeleton substitution type zeolite catalyst in which a transition metal introduced into a zeolite skeleton is activated to a higher oxidation electronic state by calcination under a temperature condition of 200 to 700 ° C. in an oxygen atmosphere is used. Item 2. A process for producing an aliphatic saturated carboxylic acid according to Item 1.   The transition metal skeleton substitution-type zeolite catalyst, the aliphatic unsaturated carboxylic acid or aliphatic olefinic hydrocarbon, and the molecular oxygen gas are contacted by a liquid phase reaction under a temperature condition of 10 to 150 ° C. The manufacturing method of aliphatic saturated carboxylic acid as described in any one of. The method for producing an aliphatic saturated carboxylic acid according to claim 1, wherein the amount of the transition metal skeleton substitution type zeolite catalyst used is 0.1 to 50% by weight based on the reaction substrate.