JP2798878B2 - Method for producing (meth) acrylonitrile - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing (meth) acrylonitrile by subjecting at least one kind of saturated hydrocarbon selected from the group consisting of propane and isobutane to gas phase catalytic ammoxidation with molecular oxygen and ammonia. Things.

[0002]

2. Description of the Related Art (Meth) acrylonitrile is a synthetic fiber,
It has been manufactured in large quantities as an intermediate raw material for various industrial products, mainly synthetic resins.However, the conventional method has been to produce olefin raw materials, such as propylene and isobutene, in the presence of a catalyst using molecular oxygen and ammonia in the gas phase. A method for performing catalytic ammoxidation is generally known.

On the other hand, as the price of olefins has risen in recent years, attention has been paid to the development of a method for producing various derivatives conventionally produced from olefins as raw materials using less expensive paraffins as raw materials. Was. The catalyst system used for producing (meth) acrylonitrile by the so-called ammoxidation method using propane or isobutane as a raw material is an Sb-U-based oxide catalyst (Japanese Patent Publication No. Sho.
No. 7-14371), Sb-Sn-based oxide catalyst (JP-B-50-28940), V-Sb-based oxide catalyst (JP-A-47-35883, JP-A-1-268668, JP-A-2-95439) No. JP-A-2-261544), B
i-Mo-based oxide catalysts (JP-A-48-16887, JP-B-55-42071, JP-A-3-157356)
No.), VP-based oxide catalyst (JP-B-58-5188)
No.), Bi-V-based oxide catalyst (JP-A-63-29554).
No. 5), and more recently V-Sn-Sb-Cu
Oxide catalyst (JP-A-4-275266), Mo-V
-Te-Nb based oxide catalyst (JP-A-2-257), A
g-Bi-V-Mo based oxide catalyst (JP-A-3-5896)
No. 1) Ga-Bi-Mo or Ta-Bi-Mo-based oxide catalyst (JP-A-3-58962), Mo-Ta or Mo-Nb-based oxide catalyst (JP-A-5-213849)
No.) has been filed for a patent. Also, a mixed catalyst system of some of the above catalyst systems and a catalyst having an olefin ammoxidation ability has been proposed (JP-A-63-295546).
JP-A-64-38051, JP-A-2-17159
JP-A-2-43949, JP-A-2-75347
JP-A-2-111444, JP-A-2-25806
No. 5).

[0004]

However, among these methods, in a system in which a small amount of a halide is added as a promoter to a reaction system, a relatively high yield of nitriles as a target product can be achieved. However, in this case, there is a fatal problem that the reactor is corroded, and the material on the device is limited, which has a great industrial problem. In addition, in the system to which the promoter is not added, the yield of nitriles is low and has not reached a level that can be carried out industrially.

The present invention has been made in order to solve such a drawback. At least one kind of saturated hydrocarbon selected from the group consisting of propane and isobutane is converted into molecular oxygen and In the ammoxidation method in which catalytic oxidation is carried out with a mixed gas containing ammonia, chromium disclosed in the present invention, by using a catalyst essentially containing antimony and tungsten, the yield of nitriles as a target product is high It is an object of the present invention to provide an industrially advantageous method for producing (meth) acrylonitrile.

[0006]

Means for Solving the Problems The present inventors vaporize at least one or more saturated hydrocarbons selected from the group consisting of propane and isobutane with a mixed gas containing molecular oxygen and ammonia in the presence of a catalyst. As a result of intensive studies on a method for producing (meth) acrylonitrile by the ammoxidation method in which the phases are brought into contact with each other, a catalyst containing a composite oxide containing an oxide containing three elements of chromium, antimony and tungsten as essential components, or the composite oxidation It has been found that a higher yield of nitriles can be obtained by using a catalyst in which the product is supported on a refractory inorganic carrier than in the conventional method, and the process of the present invention has been achieved.

That is, the present invention provides a method for producing (meth) acrylonitrile by subjecting propane and / or isobutane to a catalytic oxidation reaction of molecular oxygen and ammonia in the gas phase in the presence of a catalyst. Formula: CrαSbβWγOx (I) (wherein, Cr represents chromium, Sb represents antimony, W represents tungsten, O represents oxygen, and α, β, γ, and x represent the number of atoms of Cr, Sb, W, and O, respectively. , Α = 1, β = 0.5-5, γ = 0.2-2, and x is a value determined by the valence of the element present.) An object of the present invention is to provide a method for producing (meth) acrylonitrile, wherein the method is brought into contact.

In particular, the preferred range of the composition of the composite oxide represented by the general formula (I) is as follows when α = 1.
β = 1 to 3 and γ = 0.5 to 1.5. If the composition is out of the above range, the yield of the target nitrile becomes low.

Further, as the catalyst used in the present invention, the composite oxide represented by the general formula (I) is further added with Nb, M
at least one or more elements selected from o, Mn, Fe, Co, and Ni (hereinafter sometimes referred to as group A elements; N
b is niobium, Mo is molybdenum, Mn is manganese, Fe
Represents iron, Co represents cobalt, and Ni represents nickel. )
It is preferable to use a catalyst containing a composite oxide in which the atomic ratio of the group A element to Cr, which is a constituent element of the catalyst, is more than 0 and 0.1 or less. A above
The addition of the group element is effective in improving the activity or selectivity of the catalyst, and it is particularly preferable that the group A element contains Nb from the viewpoint of improving the yield of the target product. The atomic ratio of the group A element to Cr is 0.05-0.
A range of 1 is particularly preferred. If the composition is out of the above range, the yield of the desired nitrile is undesirably low.

Further, as the catalyst used in the present invention, the composite oxide represented by the above general formula (I) is further added with V, N
b, Mo, Mn, at least one element selected from the group consisting of Fe, Co and Ni (hereinafter may be referred to as an A 'group element; V is vanadium, Nb is niobium, Mo is molybdenum, Mn is manganese, Fe Is iron, Co is cobalt, Ni
Represents nickel. ), The atomic ratio of the A ′ group element to Cr of the constituent element of the catalyst is in the range of more than 0 to 0.1 or less, and the atomic ratio of the A ′ group element to Sb of the constituent element of the catalyst is more than 0 to 0.1. It is preferable to use a catalyst containing the composite oxide added in the range of 04 or less.
As the A 'group element, in improving the yield of the target product,
V or Nb is particularly preferable, and the atomic ratio of the A 'group element to Cr, which is a constituent element of the catalyst, is 0.05 to 0.1.
Is particularly preferable from the viewpoint of improving the yield of the target product.

It is particularly preferable to use the above-described catalyst used in the present invention by supporting it on a refractory inorganic carrier, from the viewpoint of improving the activity and physical durability of the catalyst.

As the refractory inorganic carrier, an oxide containing at least one oxide selected from silica, alumina, titania, zirconia, silica-alumina, silica-titania and silica-zirconia is preferable.
Among them, silica-alumina is preferred in terms of improving the yield of the target product.
Particularly preferred.

The catalyst used in the present invention can be prepared by a known method generally used in the art, for example, the following method. Chromium nitrate is dissolved in warm water, an aqueous solution of ammonium metatungstate (commercial product) is added, and antimony trioxide is added as powder, and V, Nb, Mo, Mn, Fe, Co and An aqueous solution of a compound of at least one element selected from the group consisting of Ni is added, and in some cases, a carrier such as silica or alumina is added thereto, and the mixture is stirred for a certain period of time, and the slurry obtained by heating and concentrating is dried. And calcined at 400-800 ° C. The calcination is performed in the air, but may be performed under a high oxygen concentration or a low oxygen concentration. In the final calcination step, it is preferable to perform the treatment in an atmosphere having a low oxygen concentration (oxygen concentration: 1% to 15%) in order to obtain high catalytic performance.

The raw materials used for preparing the catalyst used in the present invention are not particularly limited. For example, nitrates, oxides, hydroxides, chlorides, carbonates, acetates, metal acids, and metal acid ammonium salts.

As raw materials for the carrier, alumina, silica,
In addition to molded bodies such as silica-alumina, they can be used in various ways depending on the form of use of the catalyst, such as powders of oxides and hydroxides, gels and sols.

As the raw material gas for the ammoxidation reaction according to the present invention, besides propane or isobutane, molecular oxygen and ammonia, a diluent gas can be used if necessary. Air or pure oxygen is used as the molecular oxygen source. The molar ratio of molecular oxygen to be supplied to the reaction is preferably 0.2 to 5 times the amount of propane, and the molar ratio of ammonia is preferably 0.2 to 3 times the amount of propane. Insoluble gases such as helium and carbon dioxide, and steam are preferably used.

The gas-phase catalytic ammoxidation reaction according to the present invention comprises:
A space velocity of 300 to 50 is applied to the catalyst on the catalyst.
It can be suitably carried out by contacting at 00 hr ^{-1 at} a temperature in the range of 300 ° C. to 600 ° C. The above-mentioned gas-phase catalytic ammoxidation reaction is usually carried out under normal pressure, but can also be carried out under reduced pressure or increased pressure. The reaction system is not particularly limited, and any of a fixed bed system, a moving bed system, and a fluidized bed system can be used. In addition, a single system or a recycling system may be used.

[0018]

The present invention will be described more specifically with reference to the following examples.

The conversion, single-stream yield and selectivity, including by-products, are defined by the following formulas.

[0020]

(Equation 1)

Example 1 Alumina Sol A-200 (Nissan Chemical Industries, Ltd.) was placed in a 500 ml beaker.
Manufactured by Gaku Kogyo, Al_Two O_Three Concentration: 10.5 wt%) 30.
2 g and silica sol snowtex N (Nissan Chemical Industries, Ltd.)
Made, SiO_TwoConcentration: 20.5 wt%) 15.5 g and
Add 50 ml of water, heat and keep at about 80 ° C.
Was. Next, chromium nitrate (Cr (NO_Three )_Three 9H_Two O, Wako
24.03 g of 50 ml of Junyaku Co., purity 99.9%)
Add the substance dissolved in water and add metatungstic acid
Ammonium ((NH_Four )₆ H_Two W ₁₂O₄₈) Aqueous solution MW
-2 (WO, manufactured by Nippon Inorganic Chemical Industry Co., Ltd.)_Three 50wt% as
13.91 g) was added as a stock solution. Then Sb_Two 
O_Three (Wako Pure Chemical Industries, purity 99.9%) 13.14 g
Disperse in 100 ml of water with a homogenizer and add
Well, keep stirring at 80 ℃ for 2 hours and stir.
Was. Then raise the heating temperature to 90 ° C and continue stirring.
The mixture was concentrated for about 3 hours by evaporation of water. Obtained
After drying the paste at 120 ° C for 14 hours,
Atmosphere with oxygen concentration of 10% (remaining nitrogen) at 50 ° C for 3 hours
Baking at 560 ° C. for 3 hours under. The composition of the resulting catalyst is
80wt% Cr₁ Sb_1.5W_0.5 Ox / 10wt% Al_Two
 O_Three -10 wt% SiO_Two (Hereinafter referred to as a group of catalysts)
In the description of the composition, “/” indicates a carrier component in the catalyst.
).

5 ml of this catalyst prepared in a mesh of 9 to 20 mesh was charged into a usual flow-type reaction apparatus and reacted. The reaction gas composition was C ₃ H ₈ / NH ₃ / O ₂ / He
/ H ₂ O = 1/2/4 / 7.5 / 3 (molar ratio) The space velocity was SV = 900 hr ⁻¹ and the reaction temperature was 520 ° C.
Table 1 shows the obtained results.

Example 2 Chromium nitrate, aqueous solution of ammonium metatungstate M
The charged amounts of W-2 and Sb ₂ O ₃ were each 16.50.
g, 19.11 g, and 12.03 g, except that the preparation was performed in the same manner as in Example 1, and 80 wt% Cr ₁ Sb ₂ W
A catalyst having a composition of ₁ Ox / 10 wt% Al ₂ O ₃ -10 wt% SiO ₂ was obtained. The reaction was carried out in the same manner as in Example 1 except that the reaction temperature was changed to 540 ° C. Table 1 shows the obtained results.

Example 3 Chromium nitrate, aqueous solution of ammonium metatungstate M
The charged amounts of W-2 and Sb ₂ O ₃ were 11, 46, respectively.
g, 19.92 g, and 12.47 g, except that the preparation was performed in the same manner as in Example 1, and 80 wt% Cr ₁ Sb ₃ W
_{1.5 Ox / 10wt% Al 2 O} 3 -10wt% SiO 2
Was obtained. The reaction was carried out in the same manner as in Example 1 except that the reaction temperature was changed to 540 ° C. Table 1 shows the obtained results.

Example 4 After adding the aqueous solution of ammonium metatungstate, before adding the Sb ₂ O ₃ dispersion, 0.351 g of ammonium metavanadate (NH ₄ VO ₃ , a special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) was further added. Preparation was carried out in the same manner as in Example 1 except that the substance dissolved by heating with 50 ml of water was added, and 80 wt.
_{% / Cr 1 Sb 1.5 W 0.5} V 0.05 Ox / 10wt% Al 2
A catalyst having a composition of O ₃ -10 wt% SiO ₂ was obtained. The reaction was performed in the same manner as in Example 1. Table 1 shows the obtained results.

Example 5 Except that after adding an aqueous solution of ammonium metatungstate, before adding the Sb ₂ O ₃ dispersion, a solution obtained by heating and dissolving 0.337 g of ammonium metavanadate with 50 ml of water was added. Preparation was carried out in the same manner as in Example 2, and 80 wt% Cr ₁ Sb ₂ W ₁ V _0.07 Ox / 10 w
A catalyst having a composition of t% Al ₂ O ₃ -10 wt% SiO ₂ was obtained. The reaction was performed in the same manner as in Example 2. Table 1 shows the obtained results.

Example 6 Instead of ammonium metavanadate, 1.816 g of niobium oxalate (manufactured by CBMM Inc., containing 20.5 wt% in terms of Nb ₂ O ₅ ) was dissolved by heating in 100 ml of water. Was prepared in the same manner as in Example 5, and 80 w
t% Cr ₁ Sb ₂ W ₁ Nb _0.07 Ox / 10wt% Al ₂
A catalyst having a composition of O ₃ -10 wt% SiO ₂ was obtained. The reaction was performed in the same manner as in Example 2. Table 1 shows the obtained results.

[0028] After addition of Example 7 aqueous solution of ammonium metatungstate, further Paramoributen ammonium before adding Sb ₂ O ₃ dispersion _{((NH 4) 6 Mo 7} O 24 · 4H 2
O, a special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) Prepared in the same manner as in Example 1 except that 1.200 g dissolved by heating in 50 ml of water was added, and 80 wt% Cr ₁ Sb _1.5 W _0.5 Mo was prepared.
_{0.05 Ox / 10wt% Al 2 O} 3 -10wt% SiO 2
Was obtained. The reaction was performed in the same manner as in Example 1.
Table 1 shows the obtained results.

Example 8 Manganese nitrate (Mn (NO ₃ ) ₂ .6H ₂ O, special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) in place of ammonium paramolybdate
Preparation was performed in the same manner as in Example 7 except that 0.861 g obtained by heating and dissolving 0.861 g with 50 ml of water was added.
r ₁ Sb _1.5 W _0.5 Mn _0.05 Ox / 10 wt% Al ₂ O ₃
To obtain a catalyst having the composition of -10 wt% SiO _2. The reaction was performed in the same manner as in Example 1. Table 1 shows the obtained results.

Example 9 Instead of ammonium paramolybdate, iron nitrate (Fe
_{(NO 3) 3 · 9H 2} O, Wako Pure Chemical Co., Ltd. special grade reagent) 1.
Except that the addition of those heated and dissolved in water 50 ml 212g performs prepared as in Example 7, 80wt% Cr _{1
Sb 1.5 W 0.5 Fe 0.05 Ox /} 10wt% Al 2 O 3 -
A catalyst having a composition of 10 wt% SiO ₂ was obtained. The reaction was performed in the same manner as in Example 1. Table 1 shows the obtained results.

Example 10 The amounts of silica sol snowtex N, chromium nitrate, aqueous solution of ammonium metatungstate MW-2 and Sb ₂ O ₃ were 46.4 g, 14.13 g and 16.38, respectively.
g, 7.73 g except that the preparation was carried out in the same manner as in Example 1, and 60 wt% Cr ₁ Sb _1.5 W ₁ Ox / 10 w
A catalyst having a composition of t% Al ₂ O ₃ -30 wt% SiO ₂ was obtained. The reaction was performed in the same manner as in Example 1. Table 2 shows the obtained results.

Example 11 The procedure was carried out except that the charged amounts of chromium nitrate, aqueous solution of ammonium metatungstate MW-2 and Sb ₂ O ₃ were changed to 22.86 g, 13.24 g and 16.67 g, respectively, without adding silica sol. Prepared as in Example 1, 90 wt%
A catalyst having a composition of Cr ₁ Sb ₂ W _0.5 Ox / 10 wt% Al ₂ O ₃ was obtained. The reaction was performed in the same manner as in Example 2. Table 2 shows the obtained results.

Example 12 Silica Sol Snowtex N without using alumina sol
Was prepared in the same manner as in Example 2 except that the charged amount was changed to 30.9 g, and 80 wt% of Cr ₁ Sb ₂ W ₁ Ox / 20 w
A catalyst having a composition of t% SiO ₂ was obtained. The reaction was performed in the same manner as in Example 2. Table 2 shows the obtained results.

Example 13 Alumina sol and silica sol were mixed and heated and stirred for about 8 hours.
At 0 ° C., anatase-type TiO ₂
(1st grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) 3.17 g was added as powder, and the charged amounts of chromium nitrate, aqueous solution of ammonium metatungstate MW-2 and Sb ₂ O ₃ were each 1
Preparation was performed in the same manner as in Example 1 except that the amounts were changed to 6.49 g, 19.11 g, and 9.02 g, and 70 wt% Cr ₁ Sb was prepared.
_1.5 W ₁ Ox / 10 wt% Al ₂ O ₃ -10 wt% Si
A catalyst having a composition of O ₂ -10 wt% TiO ₂ was obtained. The reaction was performed in the same manner as in Example 1. Table 2 shows the obtained results.

Example 14 50.50 g of chromium nitrate was placed in a 300 ml beaker.
19.11 g of an aqueous solution of MW- ₂ dissolved in water and ammonium metatungstate aqueous solution MW-2 were successively added, and then 12.03 g of Sb ₂ O _{3 was} added to 100 ml of the homogenizer.
Of water, add heat and stir to about 8
It was kept at 0 ° C. ZrO ₂ (Mitsuwa Chemicals,
6.99 g) was added as a powder.
Stirring was performed while maintaining the liquid volume at 2 ° C. for 2 hours. Thereafter, the heating temperature was raised to 90 ° C., stirring was continued, and concentration was performed for about 2 hours by evaporation of water. Subsequent drying and firing were performed in the same manner as in Example 1, except that 80 wt% of Cr ₁ Sb ₂ W ₁ O was used.
A catalyst having a composition of x / 20 wt% ZrO ₂ was obtained. The reaction was performed in the same manner as in Example 2. Table 2 shows the obtained results.

Example 15 The amounts of ammonium metatungstate aqueous solution MW-2 and Sb ₂ O ₃ were respectively set to 9. without using ZrO ₂ .
Preparation was carried out in the same manner as in Example 14 except that the amounts were changed to 56 g and 6.02 g, thereby obtaining a catalyst having a composition of 100 wt% Cr ₁ Sb ₁ W _0.5 Ox. The reaction was performed in the same manner as in Example 1. Table 2 shows the obtained results.

Example 16 Preparation was performed in the same manner as in Example 14 except that ZrO ₂ was not used, the amount of the aqueous solution of ammonium metatungstate MW-2 was changed to 9.56 g, and the final firing temperature was changed to 600 ° C. As a result, a catalyst having a composition of 100 wt% Cr ₁ Sb ₂ W _0.5 Ox was obtained. The reaction was performed in the same manner as in Example 2. Table 2 shows the obtained results.

Comparative Example 1 Without using ammonium metatungstate, the charged amounts of chromium nitrate and Sb ₂ O ₃ were 26.47 g and 1
Preparation was performed in the same manner as in Example 1 except that the amount was changed to 9.30 g, and 80 wt% Cr ₁ Sb ₂ Ox / 10 wt% Al ₂ O
₃ to obtain a catalyst of -10 wt% SiO ₂ composition. The reaction was performed in the same manner as in Example 2. Table 3 shows the obtained results.

Comparative Example 2 Without using Sb ₂ O ₃ , the charged amounts of chromium nitrate and ammonium metatungstate aqueous solution MW-2 were each 3
Preparation was performed in the same manner as in Example 1 except that the amounts were changed to 2.98 g and 38.20 g, and 80 wt% Cr ₁ W ₁ Ox / 10 wt.
% Al ₂ O ₃ -10 wt% SiO ₂ was obtained. The reaction was performed in the same manner as in Example 2. Table 3 shows the obtained results.

Comparative Example 3 Without using chromium nitrate, the charged amounts of the aqueous solution of ammonium metatungstate MW-2 and Sb ₂ O ₃ were each 3
Preparation was carried out in the same manner as in Example 1 except that the amounts were changed to 0.48 g and 9.59 g, and 80 wt% Sb ₁ W ₁ Ox / 10 wt%
A catalyst having a composition of Al ₂ O ₃ -10 wt% SiO ₂ was obtained.
The reaction was performed in the same manner as in Example 2. Table 3 shows the obtained results.

Comparative Example 4 Chromium nitrate, aqueous solution of ammonium metatungstate M
The charged amounts of W-2 and Sb ₂ O ₃ were each 7.35.
g, 8.51 g and 18.74 g, except that the preparation was carried out in the same manner as in Example 1, and 80 wt% Cr ₁ Sb ₇ W ₁ O.
A catalyst having a composition of x / 10 wt% Al ₂ O ₃ -10 wt% SiO ₂ was obtained. The reaction was performed in the same manner as in Example 2. Table 3 shows the obtained results.

Comparative Example 5 Chromium nitrate, aqueous solution of ammonium metatungstate M
The charged amounts of W-2 and Sb ₂ O ₃ were 6.94, respectively.
g, 32.16 g and 7.59 g, except that the preparation was carried out in the same manner as in Example 1, and 80 wt% Cr ₁ Sb ₃ W ₄ O
A catalyst having a composition of x / 10 wt% Al ₂ O ₃ -10 wt% SiO ₂ was obtained. The reaction was performed in the same manner as in Example 2. Table 3 shows the obtained results.

Comparative Example 6 The procedure of Example 4 was repeated except that the amount of ammonium metavanadate charged was changed to 1.05 g.
_{Cr 1 Sb 1.5 W 0.5 V 0.15} Ox / 10wt% Al 2 O
₃ to obtain a catalyst of -10 wt% SiO ₂ composition. The reaction was performed in the same manner as in Example 1. Table 3 shows the obtained results.

Example 17 Using the same catalyst as used in Example 4, i-C ₄ H
_{10 / NH 3/0 2 /} He / H 2 O = 1/2/4 / 7.5
/ 3 (molar ratio) reaction gas composition, space velocity SV = 900
The reaction was carried out at hr ^-1 and at a reaction temperature of 470 ° C. Isobutane conversion 72.2%, methacrylonitrile selectivity 3
0.4%, single stream yield of methacrylonitrile is 21.9%
Met.

[0045]

[Table 1]

[0046]

[Table 2]

[0047]

[Table 3]

[0048]

According to the present invention, there is provided an ammoxidation method in which at least one kind of saturated hydrocarbon selected from the group consisting of propane and isobutane is contact-oxidized with a mixed gas containing molecular oxygen and ammonia in the presence of a catalyst. By producing using a catalyst essentially containing chromium, antimony and tungsten disclosed in the present invention, the yield of nitriles as target products is high and (meth) acrylonitrile can be produced industrially advantageously.

Continuation of the front page (51) Int.Cl. ⁶ Identification symbol FI C07B 61/00 300 C07B 61/00 300 Examiner Toshiro Fujimori (56) References JP-A-2-261544 (JP, A) (58) Investigated Field (Int.Cl. ⁶ , DB name) C07C 255/08 C07C 253/24

Claims (4)

(57) [Claims] 1. An ammoxidation method in which at least one kind of saturated hydrocarbon selected from the group consisting of propane and isobutane is catalytically oxidized with a mixed gas containing molecular oxygen and ammonia in the presence of a catalyst, General formula (I): CrαSbβWγOx (I) (wherein, Cr represents chromium, Sb represents antimony, W represents tungsten, O represents oxygen, and α, β, γ and x represent Cr, Sb, W and O, respectively. Represents the number of atoms, when α = 1, β = 0.5-5, γ = 0.2-2, and x is a value determined by the valence of the existing element.) A method for producing (meth) acrylonitrile, which is brought into contact with a contained catalyst. 2. The catalyst according to claim 1, wherein the composite oxide represented by the general formula (I) further comprises Nb, M
Contains a composite oxide in which at least one element selected from o, Mn, Fe, Co, and Ni is added in a range where the atomic ratio of the element to Cr as a catalyst constituent element is more than 0 and 0.1 or less. 2. The method according to claim 1, wherein a catalyst is used.
A method for producing the (meth) acrylonitrile described above. 3. The catalyst according to claim 1, wherein the composite oxide represented by the general formula (I) further comprises V, Nb,
At least one element selected from the group consisting of Mo, Mn, Fe, Co and Ni is added to the catalyst constituent element Cr in an atomic ratio of more than 0 to 0.1 or less and to the catalyst constituent element Sb. The atomic ratio of the element exceeds 0 to 0.0
The method for producing (meth) acrylonitrile according to claim 1, wherein a catalyst containing a composite oxide added in a range of 4 or less is used. 4. A method for producing (meth) acrylonitrile, comprising using the catalyst according to claim 1 on a refractory inorganic carrier substance.