JPH083084A - Production of alcohol and catalyst precursor therefor - Google Patents

Abstract

PURPOSE:To produce a saturated alcohol useful as a plasticizer, etc., in high yield, selectivity and thermal efficiency while suppressing the formation of by-products such as esters, ethers and unsaturated alcohols by reacting an aldehyde with hydrogen in gaseous phase in the presence of a specific hydrogenation catalyst. CONSTITUTION:This saturated alcohol is produced by reacting (A) an aldehyde with (B) hydrogen in gaseous phase in the presence of (C) a hydrogenation catalyst obtained by reducing a catalyst precursor composition containing a component of the formula [X is group 8 or group 4A transition metal of the periodic table; (a), (b), (c), (d), (e) and (f) are contents of the components in terms of oxides and are 20-50wt.%, 0-50wt.%, 0-50wt.%, 0.1-5.0wt.%, 0.1-5.0wt.% and 0.01-3.0wt.%, respectively]. The metal X in the formula of the component C is preferably Zr or Ti and the reaction is carried out under 0-10kg/cm<2> pressure at 100-250 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the production of corresponding saturated alcohols in a high yield and with high selectivity while suppressing the formation of undesired by-products during the gas phase hydrogenation reaction of aldehydes. And a catalyst precursor therefor.

[0002]

BACKGROUND OF THE INVENTION Methods for hydrogenating aldehydes to produce the corresponding alcohols are known. For example, in German Patent No. 931827, when an unsaturated aldehyde is reduced in a gas phase in a two-step reaction, first in the first step reaction,
A method is described which uses a copper-nickel catalyst supported on a support and uses a modified copper-support catalyst in a second stage reaction.

Further, in Japanese Patent Laid-Open No. 64-85936, a composition in which a reduced copper oxide-zinc oxide mixture is impregnated with a selectivity enhancer is used as a hydrogenation catalyst to carry out a gas phase hydrogenation reaction of an aldehyde. It describes how to do. Further, also in JP-A-62-116526, a reduced copper oxide-zinc oxide mixed catalyst is used to remove 2
-A method for hydrogenating ethylhexenal is described, but in this case, in order to remove unsaturated alcohol such as 2-ethylhexenol which is produced in a small amount, three-stage hydrogenation reaction under different reaction conditions is carried out. Vessels are used.

[0004]

However, in the method described in German Patent No. 931827, unsaturated alcohol is produced together with the corresponding saturated alcohol, which is very difficult during the distillation purification of the saturated alcohol. Is recognized. Further, according to the method disclosed in JP-A-64-85936, a very small amount of ester is by-produced in the reaction product, and a saturated alcoholic product has not been obtained yet. Further, when the method disclosed in Japanese Patent Laid-Open No. 62-116526 is industrially adopted, there are drawbacks in that the process is complicated and the large number of reactor units leads to an increase in construction cost. .

Examples of the unsaturated alcohol by-produced during the hydrogenation reaction of the aldehyde include 2-ethylhexenol produced during the hydrogenation reaction of 2-ethylhexenal, and the like. Since it has a boiling point close to that of saturated alcohol, it is not easy to industrially carry out purification separation. The main use of saturated alcohols such as 2-ethylhexanol is as a plasticizer. For example, when the unsaturated alcohol is present in 2-ethylhexanol even in a small amount, the obtained phthalic acid is obtained. Di-2-ethylhexyl tends to be colored yellow, making it unsuitable for use as a plasticizer. Therefore, in industrial practice, the reaction is often carried out by carrying out a hydrogenation reaction at a relatively high temperature to completely hydrogenate the unsaturated alcohol, but in this case, the production amount of by-products such as esters is generated. However, there is a problem in that the productivity of saturated alcohol is lowered as a result.

[0006]

Means for Solving the Problems As a result of intensive studies on the above problems, the inventors of the present invention maximized the reaction rate by using a catalyst containing a specific component as a catalyst for alcohol production. It was found that even under high temperature conditions, the formation of undesired by-products such as esters, ethers and unsaturated alcohols can be effectively suppressed, and high yield and high selectivity can be achieved without decreasing the productivity of saturated alcohols. The present invention has been completed by establishing a method for producing alcohol.

That is, the gist of the present invention is a method for producing a corresponding saturated alcohol by reacting an aldehyde with hydrogen in a gas phase in the presence of a hydrogenation catalyst, wherein the hydrogenation catalyst is represented by the following general formula (I ) A method for producing alcohol, which comprises using a reduced product of a catalyst precursor composition containing a component represented by

[0008]

Embedded image Cu (a) -Cr (b) -Zn (c) -Mn (d) -Ba (e) -X (f) (I)

(In the formula, X represents a transition metal of Group 8 or Group 4A of the Periodic Table, and a to f represent the contents when each component is converted into an oxide, and have the following values. A: 20 to 50 wt% b: 0 to 50 wt% c: 0 to 50 wt% d: 0.1 to 5.0 wt% e: 0.1 to 5.0 wt% f: 0.01 to Further, the gist of the present invention is the following general formula (I):

[0010]

Embedded image Cu (a) -Cr (b) -Zn (c) -Mn (d) -Ba (e) -X (f) (I)

(In the formula, X represents a transition metal of Group 8 or Group 4A of the Periodic Table, and a to f represent the contents when each component is converted into an oxide, and have the following values. A: 20 to 50 wt% b: 0 to 50 wt% c: 0 to 50 wt% d: 0.1 to 5.0 wt% e: 0.1 to 5.0 wt% f: 0.01 to A catalyst precursor composition for alcohol production containing a component represented by

The present invention will be described in detail below. The catalyst used in the method for producing alcohol of the present invention,
The following general formula (I):

[0013]

Embedded image Cu (a) -Cr (b) -Zn (c) -Mn (d) -Ba (e) -X (f) (I)

A reduced product of the catalyst precursor composition containing the component represented by In the above general formula (I), X represents a transition metal of Group 8 or Group 4A of the Periodic Table, preferably Pd or Ni, or Zr or Ti. Further, a to f represent the contents when each component is converted into an oxide, and a: 20 to 50% by weight b: 0 to 50% by weight c: 0 to 50% by weight d: 0.1 to 5. Values in the range of 0% by weight e: 0.1 to 5.0% by weight f: 0.01 to 3.0% by weight can be arbitrarily combined and selected.

In the above, the content of each component is calculated on the assumption that each component in the composition is converted into an oxide. At this time, Cu is CuO, Cr is Cr ₂ O ₃ , Z
n is ZnO, Mn is Mn ₂ O ₃ , Ba is BaO,
Convert each. Further, the X component is converted into a stable oxide, for example, Pd is PdO and Ni is NiO.
Zr is converted to ZrO ₂ , and Ti is converted to TiO ₂ . Specifically, among the above general formula (I), it is preferable to use the catalyst precursor composition represented by the following general formula (II).

[0016]

Embedded image CuO (a) -Cr ₂ O ₃ (b) -ZnO (c) -Mn ₂ O ₃ (d) -BaO (e) -X ′ (f) (II)

(In the formula, X'is Group 8 or 4A of the periodic table.
Represents a compound of a transition metal of Group III, and a to f represent the contents of the respective components (provided that the X'component is converted to an oxide for calculation) and have the following values. a: 20 to 50% by weight b: 0 to 50% by weight c: 0 to 50% by weight d: 0.1 to 5.0% by weight e: 0.1 to 5.0% by weight f: 0.01 to 3% 0.0% by weight) The conversion of the X'component to the oxide is performed in the same manner as the conversion of the X component.

Further, in the above general formula (I), at least one of b and c is preferably 0.1 to 50% by weight, and further, a precursor of the following general formula (III) or (IV) It is preferred to use the composition.

[0019]

Embedded image Cu (a) -Cr (b) -Mn (d) -Ba (e) -X (f) (III)

(In the formula, a to f represent the contents when the respective components are converted into oxides, and are the values shown below: a: 20 to 50% by weight b: 20 to 50% by weight d: 0 1 to 5.0 wt% e: 0.1 to 5.0 wt% f: 0.01 to 3.0 wt%)

[0021]

Embedded image Cu (a) -Zn (c) -Mn (d) -Ba (e) -X (f) (IV)

(In the formula, a to f represent the contents when each component is converted into an oxide, and are the values shown below: a: 20 to 50% by weight c: 20 to 50% by weight d: 0 1 to 5.0 wt% e: 0.1 to 5.0 wt% f: 0.01 to 3.0 wt%)

The catalyst precursor composition used in the present invention can be produced by any method suitable for producing a catalyst substance, for example, a coprecipitation method or an impregnation method. Specifically, components other than X in the general formula (I) are coprecipitated as a mixture from an aqueous solution of a metal compound, for example, a metal salt, and the mixture is converted (decomposed) into a corresponding oxide.
To produce a metal oxide, and further to impregnate the metal oxide with an aqueous solution of a salt of the component X, for example, a nitrate aqueous solution, and calcinate (decompose) in air to produce the metal oxide. The X component in the catalyst precursor composition is a transition metal of Group 8 or Group 4A of the Periodic Table, and is present in the form of a suitable compound such as an oxide. Usually, the catalyst precursor composition of the present invention is mainly in the form of an oxide, but regardless of the form of the composition, it may be a composition containing a specific amount of each component represented by the general formula (I). .

The catalyst precursor composition produced by the above method may optionally contain a small amount of a modifier,
For example, it can be pelletized by a known method such as tablet molding or extrusion molding. The catalyst precursor composition,
Before being used in the hydrogenation reaction of aldehydes, in the presence of a reducing agent such as hydrogen, the temperature is 150 to 350 ° C, preferably 170 ° C.
It is reduced by heating for several hours while adjusting the temperature range to 300 ° C. It is not preferable to apply an excessive temperature of about 350 ° C. or higher during the reduction because it will cause a decrease in the activity of the catalyst.

The reducing agent used may preferably be a dilute hydrogen flow containing 1 to 10% hydrogen in the diluent gas, and nitrogen gas is preferably used as the diluent gas. As the raw material aldehyde, a linear or branched saturated or unsaturated aldehyde having 3 to 22 carbon atoms is usually used, which can be used as a single product or as a mixed aldehyde, and may contain a small amount of impurities. Good.

Specifically, propionaldehyde, isobutyraldehyde, n-butyraldehyde, n-valeraldehyde, isovaleraldehyde, 2-methylvaleraldehyde, 2-ethylhexanal, 2-ethylbutyraldehyde, methyl-n-propyl. Acetaldehyde, capronaldehyde, isocapronaldehyde, capryl aldehyde, n-nonyl aldehyde, isononyl aldehyde, 2-propylheptenal, 2-propyl-4-methylhexenal, n-decanal, dodecanal, tridecanal, myristinaldehyde, penta Examples include decanal, palmitin aldehyde, stearaldehyde, acrolein, methacrolein, ethacrolein, 2-ethyl-3-propylacrolein and crotonaldehyde. That.

The starting aldehyde used is the oxo process (hydroformylation), ie the reaction of an olefin with carbon monoxide and hydrogen in the presence of a catalyst to add a formyl group to one of the carbon atoms of the olefinic group. It is also possible to use either some or all of the reaction mixture of the reaction. Examples of the raw material aldehyde obtained from the oxo process include a mixture of isobutyraldehyde and n-butyraldehyde, isononyl aldehyde, and the like.

The starting aldehyde can also be obtained by a process different from the oxo process, such as an olefin or saturated hydrocarbon oxidation reaction or aldol condensation. Examples of the raw material aldehyde obtained from the aldol condensation include 2-ethylhexenal, a mixture of 2-propylheptenal and 2-propyl-4-methylhexenal, and the like.

In the present invention, an aldehyde is reacted with hydrogen in the gas phase in the presence of a hydrogenation catalyst. As hydrogen, substantially pure hydrogen gas can be used alone, but it can also be supplied by mixing with, for example, aldehyde and other gas inert to the catalyst. Inert gases suitable for mixing with hydrogen include nitrogen, methane and the like.

The concentration of hydrogen in the reaction zone is not critical, but usually there should be a stoichiometric excess of hydrogen relative to the aldehyde to be reduced. Normal,
The molar ratio of hydrogen to aldehyde is about 3-400, preferably about 5-200. For aldehydes containing 2 to 12 carbon atoms, the molar ratio of hydrogen to aldehyde is about 3 to 3
It is preferably in the range of 0.

The temperature of the hydrogenation reaction is usually 100 to 250.
It is carried out at a temperature in the range of 150 to 200 [deg.] C. in order to most effectively utilize the selectivity of the hydrogenation catalyst of the present invention. The reaction pressure is usually 0 to 10 kg.
/ Cm ² G range. When a pressure exceeding 10 kg / cm ² G is used, there is no problem in reaction selectivity, but it is not advantageous because a large amount of energy is required to completely vaporize the aldehyde.

In the hydrogenation reaction of the present invention, the vaporized aldehyde vapor stream is combined with a hydrogen-containing gas at a desired temperature and pressure to obtain a catalyst precursor composition represented by the above general formula (I). It is achieved by bringing it onto the reduced product, and is preferably carried out in a flow (continuous) mode such as a fixed catalyst bed reactor. In addition, the hydrogenation reaction
It can be carried out by either a constant temperature method or an adiabatic method, and particularly in the present invention, the reaction heat can be circulated in the hydrogenation reaction as a useful heat source by, for example, generating high-pressure steam.

Unreacted hydrogen and aldehyde recovered from the hydrogenation reaction product can be recycled and used in the hydrogenation reaction zone. Further, the obtained crude alcohol product may be further purified by fractional distillation or the like, but normally, it can be sufficiently used as a product as it is without particular purification operation.

[0034]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. In addition, Example 1
In 4 and Comparative Examples 1 to 3, the catalyst precursor composition having the following composition prepared by a known coprecipitation method was used. The content of each component represents% by weight.

Example 1 (Catalyst A) An aqueous solution of manganese nitrate was added to an aqueous solution of cupric nitrate trihydrate [Cu (NO ₃ ) ₂ .3H ₂ O] to prepare a solution containing copper and manganese. On the other hand, ammonium dichromate [(NH ₄ ) ₂ Cr ₂ O ₇ ] was dissolved in an aqueous ammonia solution to prepare a chromium-containing solution.

A solution containing the above copper and manganese was added to the solution.
After heating to 0 ° C., the above chromium-containing solution was added dropwise to the solution while stirring at the same temperature. This time,
Although a precipitate was partially formed, dilute nitric acid was added to further adjust the pH, and stirring was continued to complete the formation of the precipitate. After this, the precipitate was filtered off, and the filtered precipitate was washed thoroughly with water. The precipitate thus obtained is 1
After drying for 2 hours, a powder composed of copper, chromium and manganese was obtained. Add this powder to barium hydroxide [Ba (OH) ₂ .8H
₂ O] A liquid for warm water was added and evaporated to dryness with stirring.

Copper, chromium, and manganese thus obtained,
Add an aqueous solution of nickel nitrate to powder consisting of barium 1
The mixture was stirred and mixed at 00 ° C and evaporated to dryness. The obtained powder containing copper chromium-manganese-barium-nickel was calcined in air at a temperature of 350 ° C. for 3 hours to obtain an A catalyst shown below.

[0038]

Embedded image CuO (39.4) -Cr ₂ O ₃ (41.9) -Mn ₂ O ₃ (1.5) -Ba0 (1.7) -NiO (1.0)

(When this A catalyst is represented by the general formula (I), it is Cu (31.5) -Cr (28.7) -Mn (1.0) -Ba (1.5) -Ni (0.8).) Example 2 (B Catalyst) By the method according to Example 1, the B catalyst shown below was prepared.

[0040]

Embedded image CuO (39.4) -Cr ₂ O ₃ (41.9) -Mn ₂ O ₃ (1.5) -Ba0 (1.7) -PdO (0.1)

(This B catalyst is represented by the general formula (I): Cu (31.5) -Cr (28.7) -Mn (1.0) -Ba (1.5) -Pd (0.09).) Example 3 (C Catalyst) By the method according to Example 1, the following C catalyst was prepared.

[0042]

Embedded image CuO (39.4) -Cr ₂ O ₃ (41.9) -Mn ₂ O ₃ (1.5) -Ba0 (1.
7) -ZrO ₂ (1.0)

(This C catalyst is represented by the general formula (I): Cu (31.5) -Cr (28.7) -Mn (1.0) -Ba (1.5) -Zr (0.7)) Example 4 (D Catalyst) By the method according to Example 1, the following D catalyst was prepared.

[0044]

Embedded image CuO (40.2) -ZnO (35.9) -Mn ₂ O ₃ (1.5) -Ba0 (1.7) -NiO (1.0)

(When this D catalyst is represented by the general formula (I), it is Cu (32.1) -Zn (28.8) -Mn (1.0) -Ba (1.5) -Ni (0.8).) Comparative Example 1 (E Catalyst) The following E catalyst was prepared by a method similar to that in Example 1.

[0046]

Embedded image CuO (39.4) -Cr ₂ O ₃ (41.9) -Mn ₂ O ₃ (1.5) -Ba0 (1.7)

(This E catalyst is represented by the general formula (I): Cu (31.5) -Cr (28.7) -Mn (1.0) -Ba (1.5).) Comparative Example 2 (F catalyst) Example 1 The following F catalyst was prepared by a method according to

[0048]

Embedded image CuO (37.8) -Cr ₂ O ₃ (36.1) -Mn ₂ O ₃ (1.8)

(When this F catalyst is represented by the general formula (I), it becomes Cu (30.2) -Cr (24.7) -Mn (1.3).) Comparative Example 3 (G catalyst) A method according to Example 1 was used. The following G catalyst was prepared.

[0050]

[Chemical 21] CuO (49.3) -ZnO (45.1)

(This G catalyst is represented by the general formula (I): Cu (39.4) -Zn (36.2).) Examples 5-8 and Comparative Examples 4-6 Inner diameter about 2.4 cm (1 inch) Approximately 10 cc of each catalyst was charged into a stainless steel single-tube reactor having a reactor, and nitrogen gas was supplied into the reactor to raise the internal temperature of the reactor to 170 ° C. Subsequently, the nitrogen gas was switched to a nitrogen gas containing 10% by volume of hydrogen, and the reactor internal temperature was set to 2 to 250 ° C.
After raising the temperature at a rate of 3 ° C./min, each catalyst was reduced for about 3 hours. Further, the temperature inside the reactor was raised to 300 ° C. at a rate of 2 to 3 ° C./min, and then the catalyst was reduced for about 2 hours.

After completion of the reduction, the temperature inside the reactor was set to 180 ° C., the nitrogen gas was switched to nitrogen gas containing 90% by volume or more of hydrogen, and the pressure in the reaction system was 4.6 kg / cm.
Maintained at ² G. 2-Ethylhexenal (hereinafter referred to as EPA) having a purity of 99% or more obtained by the hydroformylation reaction of propylene with a rhodium-containing catalyst and the aldol condensation with a caustic soda catalyst is completely vaporized, and the above-mentioned hydrogen-containing gas is transferred to the reactor. Supplied.

The above-mentioned EPA supply rate is 15 on a liquid basis.
cc / hr, and the supply rate of the hydrogen-containing gas is hydrogen / E
The PA was adjusted and supplied so that the molar ratio was about 22.
The obtained reaction product was collected in a condenser and analyzed by gas chromatography. The results are shown in Table 1.

[0054]

[Table 1]

As is clear from the results shown in Table 1, in the hydrogenation reaction according to the method of the present invention, the by-product of unsaturated alcohol is effectively suppressed, so that the obtained alcohol is used as a corresponding plasticizer. The coloring test performance is greatly improved when

[0056]

EFFECTS OF THE INVENTION By carrying out a gas phase hydrogenation reaction of an aldehyde using a reduced product of a specific catalyst precursor composition of the present invention, by-products such as esters, ethers and unsaturated alcohols can be obtained even under high temperature conditions. It is possible to suppress the formation of the above and to produce the corresponding saturated alcohol with high yield and high selectivity. Further, according to the present invention, the heat of reaction generated during hydrogenation can be effectively used as a heat source, which has a high industrial utility value.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location C07C 31/02 9155-4H

Claims (13)

[Claims] 1. A method for producing a corresponding saturated alcohol by reacting an aldehyde with hydrogen in a gas phase in the presence of a hydrogenation catalyst, wherein a component represented by the following general formula (I) is used as the hydrogenation catalyst. A method for producing alcohol, which comprises using a reduced product of a catalyst precursor composition contained therein. ## STR00001 ## Cu (a) -Cr (b) -Zn (c) -Mn (d) -Ba (e) -X (f) (I) (wherein, X is a group 8 of the periodic table or It represents a transition metal of Group 4A, a to f represent the contents when each component is converted into an oxide, and are the following values: a: 20 to 50% by weight b: 0 to 50% by weight c : 0 to 50 wt% d: 0.1 to 5.0 wt% e: 0.1 to 5.0 wt% f: 0.01 to 3.0 wt%) 2. A method for producing a corresponding saturated alcohol by reacting an aldehyde with hydrogen in a gas phase in the presence of a hydrogenation catalyst, wherein the hydrogenation catalyst has the following general formula (I
The method for producing alcohol according to claim 1, wherein a reduced product of the catalyst precursor composition represented by I) is used. Embedded image CuO (a) -Cr ₂ O ₃ (b) -ZnO (c) -Mn ₂ O ₃ (d) -BaO (e) -X ′ (f) (II) (wherein X ′ Represents a compound of a transition metal of Group 8 or Group 4A of the Periodic Table, and a to f represent the content of each component (however, the X'component is calculated by converting it to an oxide), and the values shown below. A: 20 to 50% by weight b: 0 to 50% by weight c: 0 to 50% by weight d: 0.1 to 5.0% by weight e: 0.1 to 5.0% by weight f: 0.0. 01-3.0% by weight) 3. At least one of b and c is 0.1 to 50.
The method for producing alcohol according to claim 1 or 2, wherein the alcohol content is% by weight. 4. The method for producing alcohol according to claim 1, wherein the hydrogenation catalyst is a reduced product of a catalyst precursor composition containing a component represented by the following general formula (III). ## STR00003 ## Cu (a) -Cr (b) -Mn (d) -Ba (e) -X (f) (III) (In the formula, a to f are when each component is converted to an oxide. It represents the content and has the following values: a: 20 to 50% by weight b: 20 to 50% by weight d: 0.1 to 5.0% by weight e: 0.1 to 5.0% by weight f: 0.01-3.0% by weight) 5. The method for producing alcohol according to claim 1, wherein the hydrogenation catalyst is a reduced product of a catalyst precursor composition containing a component represented by the following general formula (IV). ## STR00004 ## Cu (a) -Zn (c) -Mn (d) -Ba (e) -X (f) (IV) (where a to f are the components converted to oxides) It represents the content and has the following values: a: 20 to 50% by weight c: 20 to 50% by weight d: 0.1 to 5.0% by weight e: 0.1 to 5.0% by weight f: 0.01-3.0% by weight) 6. The X component is Pd or Ni.
6. The method for producing alcohol according to any one of 5 above. 7. The X component is Zr or Ti.
6. The method for producing alcohol according to any one of 5 above. 8. The reaction is carried out under the conditions of a pressure of 0 to 10 kg / cm ² G and a temperature of 100 to 250 ° C.
The method for producing alcohol according to any one of 1. 9. The following general formula (I): embedded image Cu (a) -Cr (b) -Zn (c) -Mn (d) -Ba (e) -X (f) (I) ( In the formula, X represents a transition metal of Group 8 or Group 4A of the Periodic Table, a to f represent the contents when each component is converted into an oxide, and are the following values: a: 20 -50% by weight b: 0-50% by weight c: 0-50% by weight d: 0.1-5.0% by weight e: 0.1-5.0% by weight f: 0.01-3.0% by weight %) A catalyst precursor composition for producing alcohol, which contains a component represented by 10. The following general formula (II): embedded image CuO (a) -Cr ₂ O ₃ (b) -ZnO (c) -Mn ₂ O ₃ (d) -BaO (e) -X ′ ( f) (II) (wherein X'represents a compound of a transition metal of Group 8 or Group 4A of the Periodic Table, and a to f are each component (provided that the X'component is converted to an oxide to be calculated. The following values are given: a: 20 to 50% by weight b: 0 to 50% by weight c: 0 to 50% by weight d: 0.1 to 5.0% by weight e: 0 1 to 5.0 wt% f: 0.01 to 3.0 wt%), The catalyst precursor composition for alcohol production according to claim 9. 11. At least one of b and c is 0.1-5.
The catalyst precursor composition according to claim 9 or 10, which is 0% by weight. 12. The following general formula (III): embedded image Cu (a) -Cr (b) -Mn (d) -Ba (e) -X (f) (III) (wherein a to f represents the content when each component is converted into an oxide, and is a value shown below: a: 20 to 50% by weight b: 20 to 50% by weight d: 0.1 to 5.0% by weight e : 0.1 to 5.0 wt% f: 0.01 to 3.0 wt%) The catalyst precursor composition according to any one of claims 9 to 11, containing a component represented by the formula: 13. The following general formula (IV): embedded image Cu (a) -Zn (c) -Mn (d) -Ba (e) -X (f) (IV) (wherein a to f represents the content when each component is converted into an oxide, and is a value shown below: a: 20 to 50% by weight c: 20 to 50% by weight d: 0.1 to 5.0% by weight e : 0.1 to 5.0 wt% f: 0.01 to 3.0 wt%) The catalyst precursor composition according to any one of claims 9 to 11, containing a component represented by the formula: