JP2001019657A - Production of alpha-oxocarboxylic acid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To conveniently obtain an α-oxocarboxylic acid in a good yield at a low cost by the gas phase reaction of α-oxoaldehyde and/or α-hydroxyaldehyde with water in the presence of oxygen. SOLUTION: By the gas phase reaction of (preferably 1-5 vol% of) α- oxoaldehyde (e.g. glyoxal, pyruvaldehyde, etc.), and/or α-hydroxyaldehyde (e.g. glycolaldehyde, 2-hydroxypropanal, etc.), with (preferably 5-80 vol% of) water in the presence of (preferably 0.5-10 vol% of) oxygen preferably at 150-500 deg.C, an α-oxocarboxylic acid (e.g. glyoxylic acid, etc.), is obtained. The reaction preferably is conducted in the presence of a catalyst containing at least one of oxide containing at least one of group Ia-IIa elements or the like. Water is reacted in a molar ratio of >=4 based on the α-oxoaldehyde and/or α- hydroxyaldehyde.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing α-oxocarboxylic acid by subjecting α-oxoaldehyde and / or α-hydroxyaldehyde to water and gas phase reaction in the presence of oxygen. Glyoxylic acid, which is a typical α-oxocarboxylic acid, is an industrially useful compound as an intermediate material for various products such as pharmaceutical modifiers, cosmetics, fragrances, and agricultural chemicals.

[0002]

2. Description of the Related Art Heretofore, as a method for producing glyoxylic acid, which is a typical α-oxocarboxylic acid, for example, a method in which liquid phase oxidation of glyoxal using nitric acid, chlorine or hydrogen peroxide as an oxidizing agent (Japanese Patent Publication No. 8018, JP-A-63-83043, etc.) and a method of subjecting glyoxal to liquid phase oxidation in the presence of a catalyst containing, for example, platinum or palladium, and oxygen (Japanese Patent Laid-Open Publication No.
-104652) and the like.

As a method for producing glyoxylic acid using a compound other than glyoxal as a starting material, for example, a method of oxidizing maleic acid with ozone (see Japanese Patent Application Laid-Open No.
9-21644), a method for cathodic reduction of oxalic acid (Japanese Patent Publication No. 53-2440)
6 gazettes) are known.

[0004]

However, among the above-mentioned conventional methods using glyoxal as a starting material, the method using nitric acid or chlorine as an oxidizing agent uses a large amount of nitric acid or chlorine, so that a large amount of by-produced nitrogen is used. There are problems in that treatment of oxides and separation of unreacted strong acids (nitric acid, hydrochloric acid) from products are complicated and costly. In addition, the method using hydrogen peroxide is not economical using expensive hydrogen peroxide, and the operation is complicated, for example, it is necessary to shut off oxygen in the reaction system. Separation also has disadvantages such as complication.

On the other hand, in the above-mentioned conventional method, there are many by-products such as oxalic acid as by-products, and glyoxal must be liquid-phase oxidized under relatively low concentration conditions, resulting in low productivity. In addition, in order to facilitate the progress of the reaction, it is necessary to add an alkali such as sodium hydroxide, or an alcohol such as methanol, which has a disadvantage that post-treatment of these additives after the reaction is complicated. ing.

Further, in the above-mentioned conventional method using a compound other than glyoxal as a starting material, expensive and toxic ozone must be used, and the productivity is low because the reaction step is long.

On the other hand, the above-mentioned conventional method has disadvantages such as the use of expensive oxalic acid and electricity, and the equipment costs of an electrode reaction tank and the like are considerably expensive and not economical.

That is, any of the above-mentioned conventional methods has a problem that glyoxylic acid cannot be produced at low cost.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing α-oxocarboxylic acid simply, with good yield, and at low cost. is there.

[0010]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and have found that α-oxo aldehyde and / or α-hydroxy aldehyde and water are dissolved in the presence of oxygen. The inventors have found that the α-oxocarboxylic acid can be produced inexpensively and efficiently by performing a phase reaction, and have completed the present invention.

That is, in order to solve the above-mentioned problems, the process for producing α-oxocarboxylic acid according to the present invention comprises reacting α-oxoaldehyde and / or α-hydroxyaldehyde with water in the presence of oxygen. It is characterized by a phase reaction.

The above reaction is carried out in groups Ia, IIa, IIIa of the periodic table.
Tribe, IVa, Va, Ib, IIb, IVb, Vb and VIb
A member selected from the group consisting of group elements, iron and nickel
It is preferable to carry out the reaction in the presence of a catalyst containing an oxide containing at least one element.

The molar ratio of water to α-oxoaldehyde and / or α-hydroxyaldehyde is as follows:
It is preferable to carry out the reaction with 4 or more.

The α-oxoaldehyde and / or α-hydroxyaldehyde is represented by the following general formula (1)

[0015]

Embedded image

(Wherein, R represents a hydrogen atom or an organic residue). Gaseous α-oxoaldehyde and / or α-oxoaldehyde obtained by subjecting 1,2-diol represented by the formula:
Preferably it is a hydroxy aldehyde.

Further, the catalyst of the present invention comprises an α-oxoaldehyde and / or an α-hydroxyaldehyde, and water.
A catalyst used when producing an α-oxocarboxylic acid by performing a gas phase reaction in the presence of oxygen, wherein the catalyst is a group Ia, IIa, IIIa, IIIa, IVa, Va group of the periodic table. Ib, IIb
It is characterized by containing an oxide containing at least one element selected from the group consisting of Group IV, IVb, Vb and VIb elements, iron and nickel.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The α-oxo aldehyde used in the present invention is represented by, for example, the following general formula (2)

[0019]

Embedded image

(Wherein, R represents a hydrogen atom or an organic residue). Examples of the organic residue in the formula include, for example, a saturated aliphatic hydrocarbon residue having 1 to 4 carbon atoms,
Examples thereof include an unsaturated aliphatic hydrocarbon residue having 2 to 3 carbon atoms and an aromatic hydrocarbon residue.

Examples of the α-oxoaldehyde include glyoxal; pyruvaldehyde, 2-oxobutanal, 2-oxopentanal, 2-oxohexanal and the like; 2-oxo-3-butenal, 2-oxo -3-pentenal; 2-phenyl-2-oxoethanal and the like.

The α-hydroxyaldehyde used in the present invention is represented by the following general formula (3)

[0023]

Embedded image

(Wherein, R represents a hydrogen atom or an organic residue). Examples of the organic residue in the formula include, for example, a saturated aliphatic hydrocarbon residue having 1 to 4 carbon atoms,
Examples thereof include an unsaturated aliphatic hydrocarbon residue having 2 to 3 carbon atoms and an aromatic hydrocarbon residue.

As the α-hydroxyaldehyde,
Specifically, glycol aldehyde; 2-hydroxypropanal, 2-hydroxybutanal, 2-hydroxypentanal, 2-hydroxyhexanal; 2-hydroxy-3-butenal, 2-hydroxy-3-pentenal; 2-phenyl -2-hydroxyethanal and the like.

The method for obtaining the above-mentioned raw material α-oxoaldehyde and / or α-hydroxyaldehyde is not particularly limited. For example, (i) the following general formula (1)

[0027]

Embedded image

(Wherein R represents a hydrogen atom or an organic residue) 1,2-diol (hereinafter simply referred to as 1,2)
-Diol), or (i)
i) a method of heating an α-oxoaldehyde solution and / or an α-hydroxyaldehyde solution.

The 1,2- used in the above method (i)
Examples of the organic residue of the diol in the general formula (1) include a saturated aliphatic hydrocarbon residue having 1 to 4 carbon atoms, an unsaturated aliphatic hydrocarbon residue having 2 to 3 carbon atoms, and an aromatic hydrocarbon. And a hydrogen residue.

The 1,2-diol may be any one that can be vaporized under normal pressure conditions. The above 1, 2-
Specific examples of the diol include ethylene glycol;
Propylene glycol, 1,2-butanediol, 1,
2-pentanediol, 1,2-hexanediol, 3-
Methyl-1,2-butanediol; 1,2-dihydroxy-3-butene, 1,2-dihydroxy-4-pentene; 1-phenyl-1,2-dihydroxyethane and the like.

The gas phase oxidation reaction of the 1,2-diol is as follows:
It can be carried out according to various known methods for producing α-oxoaldehyde and α-hydroxyaldehyde. For example, a method for producing glyoxal, which is a typical α-oxoaldehyde, includes metal Ag, CuO—ZnO / α
A method is known in which ethylene glycol is vapor-phase oxidized using -Al2O3 or the like as a catalyst. Particularly, in a reaction catalyzed by metal Ag in the presence of a small amount of a phosphorus-containing component, a high yield (84
%) (JP-A-58-59933, etc.).

As the α-oxoaldehyde solution in the method (ii), an α-oxoaldehyde aqueous solution is preferable, and for example, a glyoxal aqueous solution can be used, and it is advantageous because steam can be supplied together with steam by heating. As the α-hydroxyaldehyde solution, an aqueous solution of an α-hydroxyaldehyde dimer, for example, an aqueous solution obtained by dissolving a glycolaldehyde dimer in water can be used.

The method (i) is preferred in that gaseous α-oxoaldehyde and / or α-hydroxyaldehyde can be obtained simply and efficiently.

The oxygen used in the present invention can be supplied using a molecular oxygen-containing gas. As the molecular oxygen-containing gas, ordinary molecular oxygen-containing gas such as oxygen, air, and a mixed gas obtained by diluting them with an inert gas such as nitrogen or helium can be used, but industrially, It is inexpensive and preferable to use air or a mixed gas of air and an inert gas.

The water used in the present invention is preferably 4 or more, more preferably 5 to 25, expressed as a molar ratio to the α-oxoaldehyde and / or α-hydroxyaldehyde.

The composition of the feed gas in the present invention, that is, α-oxoaldehyde and / or α-hydroxyaldehyde, water and oxygen (molecular oxygen) is not particularly limited. α-
The proportions of oxoaldehyde and / or α-hydroxyaldehyde, water and oxygen (molecular oxygen) are, in this order, 1% to 5% by volume, 5% to 80% by volume, and 0.1% by volume.
More preferably, 5% by volume to 10% by volume (the remainder is an inert gas and the total is 100% by volume). In this order, 2% by volume to 5% by volume, 20% by volume to 50% by volume,
And 1 to 8% by volume (same as above). When the composition of the feed gas is out of the above range, there is a possibility that the α-oxocarboxylic acid cannot be produced in a high yield, or when water is added beyond the above range, the raw material α-oxoaldehyde and / or α-oxocarboxylic acid cannot be produced. In addition to reducing the concentration of hydroxyaldehyde to reduce the productivity of α-oxocarboxylic acid, extra operations such as concentration are required, which is wasteful.

Also in the feed gas, ie in a mixed gas containing α-oxoaldehyde and / or α-hydroxyaldehyde, water, oxygen (molecular oxygen) and an inert gas optionally added for dilution. It is not preferable that a substance which inhibits a target reaction, for example, an alcohol or an olefin substantially coexist. This is because alcohols and olefins undergo oxidative esterification and lower the yield of the target α-oxocarboxylic acid. The method for preparing the feed gas is not particularly limited.

In the reaction of the present invention, a reaction temperature and a reaction pressure at which the raw material α-oxoaldehyde and / or α-hydroxyaldehyde can maintain a gaseous state are employed. The reaction pressure is usually normal pressure or reduced pressure,
Pressurization is also possible. The reaction temperature depends on the type of the raw material α-oxoaldehyde and / or α-hydroxyaldehyde,
And 150 to 50, depending on other reaction conditions.
It is preferably in the range of 0 ° C, more preferably in the range of 180 to 400 ° C. If the reaction temperature is lower than 150 ° C., the raw material α
The conversion of α-oxoaldehyde and / or α-hydroxyaldehyde is greatly reduced, and if the reaction temperature is higher than 500 ° C., side reactions such as combustion increase, and the selectivity of the target product α-oxocarboxylic acid is significantly reduced. I do. Gaseous raw materials α-oxoaldehyde and / or α-hydroxyaldehyde and gaseous water (steam) are obtained by diluting molecular oxygen-containing gas (oxygen, air, or the like with an inert gas such as nitrogen or helium). Together with a mixed gas) under normal pressure or reduced pressure.

Further, the space velocity (GHSV; a value obtained by dividing the amount of supplied gas per hour (L / hr) by the amount of catalyst (L), which is converted into a standard state (NTP) ) Varies depending on the type of raw materials and other reaction conditions,
is preferably in the range of hr ^-1 ~10,000hr ^-1, 50
More preferably, the range is from ⁰ hr ^{-1 to} 5,000 hr ^-1 .

In the production method of the present invention, the use of the catalyst of the present invention described below is particularly preferable in terms of yield and the like.

The catalyst of the present invention is a catalyst used in the above-mentioned process for producing α-oxocarboxylic acid, and is a compound of the periodic table Ia
Group, IIa, IIIa, IVa, Va, Ib, IIb, IVb
And oxides containing at least one element selected from the group consisting of Group V, Vb and VIb elements, iron and nickel.

Examples of the catalyst include: Group Ia elements such as Li, Na, K, Rb and Cs; Group IIa elements such as Mg, Ca, Sr and Ba; Group IIIa elements such as B and Al, Ga, In, Tl, etc .; Group IVa element such as Si, Ge, Sn, Pb; Group Va element, P,
As, Sb, Bi and the like; Cu, Ag,
Au and the like; as a group IIb element, Zn, Cd, Hg and the like; IVb
Group elements, Ti, Zr, etc .;
Nb, Ta, etc .; Group VIb elements include Cr, Mo, W
And the like. Among them, an oxide catalyst containing phosphorus (P) as an element is preferable.

As raw materials for the catalyst, oxides, hydroxides, halides, salts (nitrates, carbonates, carboxylates, phosphates, sulfates, etc.), metals and the like are used.

The method for preparing the catalyst is not particularly limited, and any conventionally known method can be applied.
For example, (1) a method in which a catalyst material is dissolved or suspended in water, heated and concentrated under stirring, dried, and calcined to obtain a catalyst; In this case, an alkaline precipitant such as aqueous ammonia is used), and the resulting hydrolyzate is filtered, washed, dried and calcined to obtain a catalyst.

The drying and calcination may be performed in an air at a temperature of 100 to 120 ° C., and then in an air at a temperature of 300 to 1000 ° C., depending on the type and composition of the oxide catalyst. More preferably, the calcination is performed in air at a temperature in the range of 400 to 800 ° C. Further, if necessary, it is more preferable to carry out molding or pretreatment for adjusting the particle diameter.

The catalyst may be a known carrier (eg, silica, alumina, titania, zirconia, niobium oxide,
Diatomaceous earth, silicon carbide, or the like).

The oxide catalyst containing phosphorus, which is a preferable catalyst, will be described in more detail. The phosphorus-containing oxide catalyst is not particularly limited, but among them, a metal phosphate and a phosphorus-containing heteropolyacid are preferable.

Examples of the metal of the metal phosphate include those forming a phosphate, groups Ia, IIa, IIIa, IVa, and IVa of the periodic table.
Elements of the Va, Ib, IIb, IVb, Vb and VIb groups,
There is no particular limitation as long as it is at least one element selected from the group consisting of iron and nickel. For example, alkali metals, alkaline earth metals, B, Al, Sn, Pb, Sb,
Bi, Ti, Zr, V, Nb, Ta, Cr, Mo, W,
Examples include Fe, Ni, Cu, Ag, and Zn. The metal of the metal phosphate may be not only one kind but also a combination of two or more kinds. That is, a metal phosphate containing two or more metals can be used.

The metal phosphate may be a mixture of two or more metal phosphates containing different metals. Further, when the metal phosphate is charged into the reactor as a catalyst layer, different metal phosphates may be charged (laminated) on the gas inlet side and the gas outlet side.

The molar ratio of metal to phosphorus in the above metal phosphate may be different from the stoichiometric ratio of orthophosphate, and specifically, the metal / P = 1 / 0.5 to 1/2 Range.

The method for preparing the metal phosphate catalyst is not particularly limited. For example, a coprecipitation method of coprecipitating a metal phosphate from an aqueous solution obtained by mixing and dissolving a metal salt and a phosphoric acid source. Kneading method in which a metal salt and a phosphoric acid source are mixed to form a slurry, and then kneaded to obtain a metal phosphate; Examples of the metal salt include, but are not particularly limited to, metal nitrates, carbonates, oxalates, hydroxides, and chlorides. One of these metal salts may be used alone, or two or more thereof may be used in combination. Specific examples of the phosphoric acid source include phosphates such as orthophosphoric acid, ammonium phosphate, ammonium monohydrogen phosphate, and ammonium dihydrogen phosphate, but are not particularly limited. One of these phosphate sources may be used alone, or two or more thereof may be used in combination. Furthermore, the combination of the metal salt and the phosphoric acid source is not particularly limited, and various combinations can be adopted.

Depending on the type and composition of the metal phosphate, the metal phosphate is dried in air at a temperature of 100 to 120 ° C., and then dried at a temperature of 300 to 1000 ° C. In air, more preferably at a temperature of 400 to 800 ° C.
It is more preferable to perform calcination in air within the range described above, and further to perform pretreatment for forming or adjusting the particle diameter as necessary. The metal phosphate can be used as a catalyst without performing the above pretreatment.

More preferably, the metal phosphate is used as a catalyst in the state of a mixture to which an inorganic oxide has been added. As the inorganic oxide, specifically, for example,
Examples include silica, titania, zirconia, niobium oxide, and diatomaceous earth, but are not particularly limited. The above titania may be of an anatase type or a rutile type. One kind of these inorganic oxides may be used, or two or more kinds may be used in combination. The amount of the inorganic oxide added to the metal phosphate depends on the type and composition of the metal phosphate and the type of the inorganic oxide, but the proportion of the inorganic oxide in the total amount of both is 1% by weight to 90% by weight. %
, More preferably in the range of 10% by weight to 60% by weight. The metal phosphate is
Even if it is not in the state of the above mixture, it can be used as it is as a catalyst.

The phosphorus-containing heteropolyacid is not particularly limited, but has the following general formula (4):

[0055]

Embedded image

(Wherein M represents at least one element selected from the group consisting of tungsten, molybdenum and vanadium, a is a numerical value determined by M, and n is 0 or a positive number). Heteropolyacids are particularly preferred because of their excellent catalytic performance.

Further, some or all of the hydrogen atoms constituting the Keggin-type heteropolyacid may belong to Group Ia, IIa or IIIa of the periodic table.
Tribe, IVa, Va, Ib, IIb, IVb, Vb and VIb
Selected from the group consisting of elements of the group III, iron and nickel
A compound replaced by at least one kind of element, that is, a compound represented by the following general formula (5):

[0058]

Embedded image

(Wherein M represents one or more elements selected from the group consisting of tungsten, molybdenum and vanadium, M ′ represents a metal atom such as an alkali metal atom, an alkaline earth metal atom, and a transition metal atom; a is a numerical value determined by M, b is any numerical value that satisfies 0 <b ≦ a, and n is 0 or a positive number). The method for preparing the Keggin-type heteropolyacid or heteropolyacid salt, that is, the method for preparing the phosphorus-containing heteropolyacid is not particularly limited, and various known methods can be employed.

The phosphorus-containing heteropolyacid depends on the type and composition of the phosphorus-containing heteropolyacid, but it is preferable to perform a pre-treatment after drying in air and baking in air at a temperature higher than the reaction temperature. The phosphorus-containing heteropolyacid can be used as a catalyst without performing the above pretreatment.

The phosphorus-containing heteropolyacid is more preferably used in a state of being supported on a carrier. The carrier is not particularly limited, but may be any substance that does not adversely affect the reaction and is stable to the phosphorus-containing heteropolyacid. Specific examples include silica, titania, zirconia, niobium oxide, and diatomaceous earth, but are not particularly limited. The above titania may be of an anatase type or a rutile type. One kind of these inorganic oxides may be used, or two or more kinds may be used in combination.

The supporting method for supporting the phosphorus-containing heteropolyacid on the carrier is not particularly limited, but specifically, a kneading method or an impregnating supporting method can be adopted. The phosphorus-containing heteropolyacid can be used as a catalyst without being supported on a carrier.

In the production method of the present invention, any fixed bed flow type or fluidized bed type reactor can be used as long as it can be carried out by a gas phase reaction.

[0064]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. The product was analyzed by liquid chromatography and gas chromatography. Further, the conversion, selectivity, and yield in the examples were in accordance with the following definitions.

[0065]

(Equation 1)

[0066]

(Equation 2)

[0067]

(Equation 3)

[0068]

(Equation 4)

[0069]

(Equation 5)

[0070]

(Equation 6)

Example 1 In the following Examples 1 to 11, glyoxal (hereinafter referred to as GLO) as gaseous α-oxoaldehyde was obtained by gas phase oxidation of ethylene glycol (hereinafter referred to as EG) as 1,2-diol. ) And / or glycolaldehyde as α-hydroxy aldehyde (hereinafter referred to as GAL), and then the gaseous GLO and GAL were mixed with water vapor and molecular oxygen-containing gas, and then reacted under the reaction conditions described below. And supplied to the catalyst layer to carry out a reaction.

(Preparation of Gaseous GLO and GAL by Gas Phase Oxidation of EG) Gaseous GLO and GAL were obtained by oxidative dehydrogenation of EG.
A SUS pipe having an inner diameter of 5.2 mm was used as a reaction tube (reactor), and 0.6 g of metal Ag (electrolytic silver manufactured by Yokohama Metal Co., Ltd.) having a particle size of 20 to 30 mesh was filled in the reaction tube as a catalyst. Further, an evaporator for heating a gas (EG, molecular oxygen-containing gas) supplied to the reaction tube to a predetermined temperature was attached to the gas inlet side of the reaction tube. Furthermore, a heat insulating material was first wound around the outside of the reaction tube, and an electric heater was wound thereon, thereby controlling the temperature of the catalyst layer. The composition of the supplied gas was 4.2% by volume of EG and 4.8% by volume of oxygen (the remainder was nitrogen gas, and the total was 100% by volume, hereinafter referred to as nitrogen gas balance). Note that triethyl phosphite as a phosphorus-containing compound was added to the supply gas such that the ratio of phosphorus to EG was 60 ppm.

The space velocity (SV) of the supply gas is 45,000.
0 hr ^-1 and supplied to the reaction tube, and the reaction temperature,
That is, the temperature of the catalyst layer was controlled at 530 ° C., and the reaction was performed at normal pressure. When the components of the obtained reaction gas were analyzed, EG
Was 100%, the yield of GLO was 83%, and the yield of GAL was 1%.

(Catalyst preparation) Reagent ferric phosphate (FePO
40 g of 4.4H2O (Katayama Chemical) was conditioned with 40 g of water, placed in a stainless steel vat, dried in air at 120 ° C. for 20 hours, and fired in air at 490 ° C. for 3 hours.
The solid obtained after the calcination was adjusted to a particle size of 9 to 20 mesh and used as a catalyst. The ratio between iron and phosphorus is 1: 1.

(Vapor-phase oxidation reaction of GLO and GAL)
ml of a stainless steel reaction tube having an inner diameter of 10 mm (the above 1, 1).
(Connected to a 2-diol gas-phase oxidation reactor), immersed in a molten salt bath at 220 ° C., and placed in the reaction tube a reaction gas obtained by the gas-phase oxidation of the 1,2-diol. (Including GLO, GAL, generated water, molecular oxygen-containing gas, etc.) and the catalyst layer inlet gas composition is 2.5% by volume in total of GLO and GAL, 3% by volume of molecular oxygen, 30% by volume of steam (nitrogen (Gas balance). That is, the additional oxygen quantifies the oxygen contained in the reaction gas obtained by the gas phase oxidation of the 1,2-diol, and the additional steam is
The amount of water produced was calculated from the reaction results obtained by the gas phase oxidation of 2-diol, and the shortage was supplied to the reaction tube. The supply gas was supplied to the reaction tube at a space velocity (SV) of 1,200 hr ^-1 and reacted at normal pressure. When the components of the obtained reaction gas were analyzed, the total conversion of GLO and GAL was 100%, and glyoxylic acid (hereinafter referred to as GOA)
Was 55%, and the GOA yield based on EG was 46%.

Example 2 (Preparation of Gaseous GLO and GAL by Gas Phase Oxidation of EG) Example 1
Performed under the same conditions as

(Catalyst preparation) Reagent ferric phosphate (FePO
40 g of 4.4H2O, manufactured by Katayama Chemical Co., Ltd. and 12 g of anatase type titanium dioxide (TiO2, manufactured by Wako Pure Chemical Industries) are kneaded and adjusted with 40 g of water, put in a stainless steel vat, and dried in air at 120 ° C. for 20 hours. It was calcined at 490 ° C. for 3 hours in air. The solid obtained after the calcination was adjusted to a particle size of 9 to 20 mesh and used as a catalyst. The ratio between iron and phosphorus is 1: 1. The amount of titanium dioxide was adjusted to be about 50% by weight based on the total amount of the finished catalyst.

(Vapor-phase oxidation reaction of GLO and GAL) Using this catalyst, the reaction was carried out under the same reaction conditions as in Example 1 except that steam was changed to 40% by volume and the reaction temperature was changed to 230 ° C. When the components of the obtained reaction gas were analyzed, the total conversion of GLO and GAL was 100%, the selectivity of GOA was 59%, and the yield of GOA based on EG was 49%.

Example 3 (Preparation of gaseous GLO and GAL by gas phase oxidation of EG) Example 1
Performed under the same conditions as

(Catalyst preparation) Iron (III) nitrate nonahydrate (Fe (NO
3) 3.9H2O (Wako Pure Chemical) 97 g was dissolved in 200 g of water, and 85% phosphoric acid aqueous solution (H3PO4, Wako Pure Chemical) was dissolved therein.
An aqueous solution obtained by diluting 33.2 g into 30 g of water was added. While stirring this solution, anatase type titanium dioxide (TiO 2)
(2, manufactured by Wako Pure Chemical Industries, Ltd.) 45 g. After the addition, heating was started and the mixture was stirred under reflux for 22 hours. After the resulting milky white slurry was naturally cooled to room temperature, 25% aqueous ammonia (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise. When the pH of the solution reached 7, the addition was completed. The obtained slurry was concentrated on a hot water bath, dried and calcined in the same manner as in Example 1 to obtain a catalyst having a uniform particle diameter. The ratio between iron and phosphorus is 1: 1.2. The amount of titanium dioxide was adjusted to be about 50% by weight based on the total amount of the finished catalyst.

(Vapor-phase oxidation reaction of GLO and GAL) Using this catalyst, the reaction was carried out under the same reaction conditions as in Example 1 except that steam was changed to 10% by volume and the reaction temperature was changed to 250 ° C. When the components of the obtained reaction gas were analyzed, the total conversion of GLO and GAL was 100%, the selectivity of GOA was 52%, and the yield of GOA based on EG was 43%.

Example 4 (Preparation of gaseous GLO and GAL by gas phase oxidation of EG) Example 1
Performed under the same conditions as

(Preparation of catalyst) Reagent potassium hydroxide (KOH,
1 g of Wako Pure Chemicals is dissolved in 40 g of water, and this solution is mixed with a reagent ferric phosphate (FePO4.4H2O, Katayama Chemical) 40
g, knead well and put in a stainless steel vat,
After drying in air at 120 ° C. for 20 hours, it was calcined in air at 490 ° C. for 3 hours. The solid obtained after the calcination was adjusted to a particle size of 9 to 20 mesh and used as a catalyst. The ratio of iron to phosphorus and potassium is 1: 1: 0.1.

(Gaseous gas phase oxidation reaction of GLO and GAL) Using this catalyst, the reaction conditions were the same as in Example 1 except that the space velocity (SV) was changed to 1,400 hr ^-1 and the reaction temperature was changed to 210 ° C. Reacted. When the components of the obtained reaction gas were analyzed, GL
The total conversion of O and GAL was 100%, the selectivity for GOA was 57%, and the yield of GOA based on EG was 47%.

Example 5 (Preparation of gaseous GLO and GAL by gas phase oxidation of EG) Example 1
Performed under the same conditions as

(Catalyst preparation) Iron (III) nitrate nonahydrate (Fe (NO
3) 97 g of 3.9H2O, manufactured by Wako Pure Chemical and 9 g of aluminum nitrate (Al (NO3) 3.9H2O, manufactured by Wako Pure Chemical) are dissolved in 200 g of water, and an 85% phosphoric acid aqueous solution (H3PO4, Wako Pure Chemical) is dissolved therein. Aqueous solution (27.7 g) diluted with 50 g of water was added.
While stirring this solution, 28% aqueous ammonia (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise to form a precipitate. The dropping was completed when the pH of the solution reached 7. The obtained precipitate was concentrated on a hot water bath, dried and calcined in the same manner as in Example 1 to obtain a catalyst having a uniform particle diameter. The ratio of iron, phosphorus and aluminum is 1: 1: 0.1.

(Vapor-phase oxidation reaction of GLO and GAL) Using this catalyst, the reaction was carried out under the same reaction conditions as in Example 1 except that the reaction temperature was changed to 230 ° C. When the components of the obtained reaction gas were analyzed, the total conversion of GLO and GAL was 100%,
The selectivity of GOA is 53%, and the yield of GOA based on EG is 44%.
%Met.

Example 6 (Preparation of Gaseous GLO and GAL by Gas Phase Oxidation of EG) Example 1
Performed under the same conditions as

(Preparation of catalyst) 11-molybdovanasolinic acid
(H4PMo11VO40 · nH2O, manufactured by Nippon Inorganic Chemical Industry) was dissolved in water. Spherical silica (Fuji Silysia Co., trade name: Caracto Q-50) was used as a catalyst carrier.
The particle size was adjusted to 0 mesh. This silica carrier was added to the above heteropolyacid aqueous solution, concentrated and supported on a hot water bath, and further dried at 120 ° C. in air to obtain a silica-supported 11-molybdovanadophosphoric acid catalyst. Heteropolyacid loading rate is 29
% By weight (in terms of anhydride).

(Vapor-phase oxidation reaction of GLO and GAL) Using this catalyst, the reaction conditions were the same as in Example 1 except that the space velocity (SV) was changed to 2,000 hr ^-1 and the reaction temperature was changed to 200 ° C. Reacted. When the components of the obtained reaction gas were analyzed, GL
The total conversion of O and GAL was 100%, the selectivity for GOA was 46%, and the yield of GOA based on EG was 38%.

Example 7 (Preparation of gaseous GLO and GAL by vapor phase oxidation of EG) Example 1
Performed under the same conditions as

(Preparation of catalyst) Iron (III) nitrate nonahydrate (Fe (NO
3) 3.9H2O (manufactured by Wako Pure Chemical Industries) 97g and silver nitrate (AgNO
3. Dissolve 32.6 g of Wako Pure Chemicals in 200 g of water, and add an 85% phosphoric acid aqueous solution (H3PO4, Wako Pure Chemicals).
An aqueous solution obtained by diluting 3 g into 50 g of water was added. While stirring this solution, 28% aqueous ammonia (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise to form a precipitate. The dropping was completed when the pH of the solution reached 7. The obtained precipitate was concentrated on a hot water bath, dried and calcined in the same manner as in Example 1 to obtain a catalyst having a uniform particle diameter. The ratio of iron, phosphorus and silver is 1: 2: 0.8.

(Vapor-phase oxidation reaction of GLO and GAL) The same reaction conditions as in Example 1 except that the space velocity (SV) was changed to 2,000 hr ^-1 and the reaction temperature was changed to 210 ° C. using this catalyst. Reacted. When the components of the obtained reaction gas were analyzed, GL
The total conversion of O and GAL was 100%, the selectivity for GOA was 41%, and the yield of GOA based on EG was 34%. Example 8 (Preparation of gaseous GLO and GAL by vapor phase oxidation of EG) Example 1
Performed under the same conditions as

(Preparation of catalyst) In a solution of 7.7 g of an aqueous solution of ammonium metatungstate (50% by weight as WO3, manufactured by Nippon Inorganic Chemical Industry) in 50 g of water, spherical silica gel (Carrieract, trade name, manufactured by Fuji Silysia Ltd.) 30 g (Q-30, particle size 9-20 mesh) was immersed for 2 hours. After that, it is dried by heating in a hot water bath at 120 ° C. in air.
The catalyst was dried for 0 hour and calcined in air at 500 ° C. for 2 hours to obtain a catalyst. The ratio of silica to tungsten is 30: 1.

(Vapor-phase oxidation reaction of GLO and GAL) Using this catalyst, the reaction conditions were the same as in Example 1 except that the space velocity (SV) was changed to 1,000 hr ^-1 and the reaction temperature was changed to 240 ° C. Reacted. When the components of the obtained reaction gas were analyzed, GL
The total conversion of O and GAL is 95% and the selectivity of GOA is 2
The yield of GOA based on 4% and EG was 19%.

Example 9 (Preparation of gaseous GLO and GAL by vapor phase oxidation of EG) Example 1
Performed under the same conditions as

(Preparation of catalyst) 40 g of zinc oxide (ZnO, manufactured by Wako Pure Chemical Industries) was conditioned with 30 g of water, and then dried and calcined in the same manner as in Example 1 to obtain a catalyst having a uniform particle diameter.

(Vapor phase oxidation reaction of GLO and GAL) Using this catalyst, the reaction was carried out under the same reaction conditions as in Example 1 except that the reaction temperature was changed to 280 ° C. When the components of the obtained reaction gas were analyzed, the total conversion of GLO and GAL was 93%.
The selectivity of A is 21% and the yield of GOA based on EG is 20%
Met.

Example 10 (Preparation of gaseous GLO and GAL by gas phase oxidation of EG) Example 1
Performed under the same conditions as

(Catalyst preparation) Reagent tricalcium phosphate (Ca
3 (PO4) 2, manufactured by Kishida Chemical Co., Ltd.) was conditioned with 30 g of water, dried and calcined in the same manner as in Example 1 to obtain a catalyst having a uniform particle diameter. The ratio of calcium to phosphorus is 1: 0.67.

(Vapor phase oxidation reaction of GLO and GAL) Using this catalyst, the reaction was carried out under the same reaction conditions as in Example 1 except that the reaction temperature was changed to 290 ° C. When the components of the obtained reaction gas were analyzed, the total conversion of GLO and GAL was 87%.
The selectivity of A is 19%, and the yield of GOA based on EG is 14%.
Met.

Example 11 (Preparation of gaseous GLO and GAL by vapor phase oxidation of EG) Example 1
Performed under the same conditions as

(Preparation of catalyst) 40 g of a reagent nickel phosphate heptahydrate (Ni3 (PO4) 2.7H2O, manufactured by Yoneyama Chemical Industry Co., Ltd.) was conditioned with 30 g of water, dried and calcined in the same manner as in Example 1. , And the particle size was adjusted to be a catalyst. Incidentally, the ratio of nickel to phosphorus is 1: 0.67.

(Vapor phase oxidation reaction of GLO and GAL) Using this catalyst, the reaction was carried out under the same reaction conditions as in Example 1 except that the reaction temperature was changed to 280 ° C. When the components of the obtained reaction gas were analyzed, the total conversion of GLO and GAL was 94%.
The selectivity of A is 27%, and the yield of GOA based on EG is 21%.
Met.

Embodiment 12 In this embodiment, a gaseous GLO is produced by gas phase oxidation of EG.
Instead of obtaining GAL and GAL, gaseous GLO obtained by heating the GLO solution was mixed with water vapor and a molecular oxygen-containing gas, and supplied to the catalyst layer under the following reaction conditions to carry out the reaction.

(Gas Phase Oxidation Reaction of GLO) As the GLO solution, a commercially available 40% glyoxal aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) was used. 35 ml of the catalyst of Example 1 was used with an inner diameter of 10 m.
m, and immersed in a molten salt bath at 230 ° C. to supply a mixed gas of GLO and steam obtained by heating an aqueous GLO solution into the reaction tube. The volume was adjusted to be 4% by volume of molecular oxygen, and 30% by volume of steam (nitrogen gas balance). The GLO aqueous solution diluted with water was heated and evaporated so as to have the set steam amount. The supply gas was supplied to the reaction tube at a space velocity (SV) of 1,200 hr ^-1 and reacted at normal pressure. When the components of the obtained reaction gas were analyzed, the conversion of GLO was 100% and the selectivity of GOA was 45%.

Embodiment 13 In this embodiment, a gaseous GLO is produced by gas phase oxidation of EG.
Instead of obtaining GAL and GAL, gaseous GAL obtained by heating the GAL solution was mixed with water vapor and a molecular oxygen-containing gas, and supplied to the catalyst layer under the reaction conditions described below to perform a reaction.

(Gas Phase Oxidation Reaction of GAL) As a GAL solution, an aqueous solution of glycolaldehyde prepared by dissolving a commercially available glycolaldehyde dimer (manufactured by Wako Pure Chemical Industries, Ltd.) in water was used. After filling 35 ml of the catalyst of Example 1 into a stainless steel reaction tube having an inner diameter of 10 mm, the catalyst was immersed in a molten salt bath at 230 ° C., and a GAL aqueous solution obtained by heating a GAL aqueous solution in the reaction tube was obtained.
A mixed gas of AL and steam was supplied, and the gas composition at the inlet of the catalyst layer was adjusted to 3% by volume of GAL, 4% by volume of molecular oxygen, and 30% by volume of steam (nitrogen gas balance). The supply gas was supplied to the reaction tube at a space velocity (SV) of 1,200 hr ^-1 and reacted at normal pressure. When the components of the obtained reaction gas were analyzed, the conversion rate of GAL was 100
%, And the selectivity of GOA was 46%.

Example 14 In this example, gas-phase oxidation of propylene glycol (hereinafter referred to as PG) as a 1,2-diol and pyruvaldehyde (hereinafter referred to as PAL) as gaseous α-oxoaldehyde were carried out. And / or after obtaining lactaldehyde (2-hydroxypropanal, hereinafter referred to as HPAL) as α-hydroxyaldehyde, the gaseous PAL and HPAL are subsequently mixed with water vapor and a molecular oxygen-containing gas,
The reaction was carried out by supplying to the catalyst layer under the reaction conditions described below.

(Preparation of gaseous PAL and HPAL by gas phase oxidation of PG) Gaseous PAL and HPAL were obtained by oxidative dehydrogenation of PG. A SUS pipe having an inner diameter of 5.2 mm was used as a reaction tube (reactor).
Metal mesh Ag (electrolytic silver manufactured by Yokohama Metal Co., Ltd.) 0.8
g. Further, an evaporator for heating a gas (PG, molecular oxygen-containing gas) supplied to the reaction tube to a predetermined temperature was attached to the gas inlet side of the reaction tube. Furthermore, a heat insulating material was first wound around the outside of the reaction tube, and an electric heater was wound thereon, thereby controlling the temperature of the catalyst layer. The composition of the supplied gas is as follows: PG is 5.0% by volume, oxygen is 7.0% by volume (the rest is nitrogen gas, and the total is 100% by volume.
Nitrogen gas balance). Note that triethyl phosphite as a phosphorus-containing compound was added to the supply gas so that the ratio of phosphorus to PG was 60 ppm.

The space velocity (SV) of the supplied gas is 70,00
0 hr ^-1 and supplied to the reaction tube, and the reaction temperature,
That is, the temperature of the catalyst layer was controlled at 540 ° C., and the reaction was performed at normal pressure. When the components of the obtained reaction gas were analyzed, PG
Conversion is 100%, PAL yield is 80%, HPAL
Was 0.5%.

(Gas Phase Oxidation Reaction of PAL and HPAL) After filling 35 ml of the catalyst of Example 1 into a stainless steel reaction tube having an inner diameter of 10 mm (connected to the PG gas phase oxidation reactor), 240 ° C. Immersed in a molten salt bath of
A reaction gas (including PAL, HPAL, generated water, molecular oxygen-containing gas, etc.) obtained by gas phase oxidation of PG is supplied, and the gas composition at the catalyst layer inlet is a total of 4% by volume of PAL and HPAL, a molecular oxygen of 5%.
It was adjusted to be 40% by volume (nitrogen gas balance) and 40% by volume of steam. That is, additional oxygen determines the amount of oxygen contained in the reaction gas obtained by the gas phase oxidation of the PG, and the additional water vapor calculates the amount of water generated from the reaction results obtained by the gas phase oxidation of the PG. Was supplied to the reaction tube. The space velocity (SV) of the supply gas is 1,200 hr ^-1
And the reaction was carried out at normal pressure. When the components of the obtained reaction gas were analyzed, the total conversion of PAL and HPAL was 86%, and the selectivity of pyruvic acid was 37%.
%, The yield of pyruvic acid based on PG was 25%.

[0113]

As is apparent from the above embodiment, α
By carrying out a gas phase reaction of -oxoaldehyde and / or α-hydroxyaldehyde with water in the presence of oxygen, α-oxocarboxylic acid can be produced simply and with good yield. Therefore, it can be said that the method of the present invention is excellent as a method for industrially producing α-oxocarboxylic acid.

As is clear from the above-described embodiment,
When the gas phase reaction of α-oxo aldehyde and / or α-hydroxy aldehyde with water in the presence of oxygen, the catalyst of the present invention is used to easily produce α-oxo carboxylic acid in good yield. be able to.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H006 AA02 AA05 AC45 AC46 BA02 BA05 BA06 BA07 BA08 BA10 BA11 BA12 BA13 BA15 BA19 BA21 BA29 BA30 BA35 BA37 BA55 BA75 BB61 BC10 BC11 BC18 BC31 BC38 BE30 BE60 BQ10 BR10 BS10

Claims (5)

[Claims] (1) α-oxoaldehyde and / or α-oxoaldehyde
A method for producing α-oxocarboxylic acid, comprising reacting hydroxyaldehyde with water in the gas phase in the presence of oxygen. 2. The method according to claim 1, wherein the reaction is carried out in groups Ia, IIa, III of the periodic table.
a, IVa, Va, Ib, IIb, IVb, Vb and VI
The method for producing α-oxocarboxylic acid according to claim 1, wherein the method is carried out in the presence of a catalyst containing an oxide containing at least one element selected from the group consisting of group b elements, iron and nickel. . 3. The method according to claim 1, wherein the molar ratio of water to α-oxoaldehyde and / or α-hydroxyaldehyde is 4
The method for producing α-oxocarboxylic acid according to claim 1 or 2, which is as described above. 4. The α-oxoaldehyde and / or α-hydroxyaldehyde represented by the following general formula (1): (Wherein, R represents a hydrogen atom or an organic residue) is a gaseous α-oxo aldehyde and / or α-hydroxy aldehyde obtained by gas phase oxidation of 1,2-diol represented by the following formula: The α- according to any one of claims 1 to 3.
A method for producing oxocarboxylic acid. 5. An α-oxo aldehyde and / or α-oxo aldehyde
A catalyst used for producing α-oxocarboxylic acid by subjecting hydroxyaldehyde and water to a gas phase reaction in the presence of oxygen, wherein the catalyst is a group Ia, IIa or Ia of the periodic table.
IIa, IVa, Va, Ib, IIb, IVb, Vb and
A catalyst for producing α-oxocarboxylic acid, comprising an oxide containing at least one element selected from the group consisting of group VIb elements, iron and nickel.