JPH07157461A - Production of (meth)acrylonitrile - Google Patents

Abstract

PURPOSE:To provide a method for industrially advantageously producing nitriles as aimed products in high yield. CONSTITUTION:The characteristic of this method for producing (meth) acrylonitrile comprises using a catalyst containing a compound oxide expressed by the following general formula as a catalyst in a method for ammoxidation in which at least one or more saturated hydrocarbons selected between propane and isobutane are catalystically oxidized with a mixed gas containing molecular oxygen and ammonia in the presence of the catalyst: the general formula Cralpha Sbbeta Wgamma Ox [alpha, beta and gamma each denotes the number of atoms of Cr, Sb and W, respectively; when alpha is 1, beta is 0.5-5; gamma is 0.2-2; (x) is a value determined by the valences of the existing elements].

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing (meth) acrylonitrile by gas phase catalytic ammoxidation of at least one saturated hydrocarbon selected from the group consisting of propane and isobutane with molecular oxygen and ammonia. It is a thing.

[0002]

2. Description of the Related Art (Meth) acrylonitrile is a synthetic fiber,
It is produced in large quantities as an intermediate raw material for various industrial products centering on synthetic resins, but the conventional production method is olefin raw material, that is, propylene, isobutene, etc. in the presence of a catalyst with molecular oxygen and ammonia in the gas phase. Methods for carrying out catalytic ammoxidation are generally known.

On the other hand, with the recent increase in the price of olefins, attention has been paid to the development of a method for producing various derived products which have been conventionally produced from olefins as raw materials, using cheaper paraffins as raw materials. It was As a catalyst system used for producing (meth) acrylonitrile by a so-called ammoxidation method using propane or isobutane as a raw material, an Sb-U-based oxide catalyst (Japanese Patent Publication No.
7-14371), Sb-Sn-based oxide catalysts (Japanese Patent Publication No. 50-28940), V-Sb-based oxide catalysts (JP-A-47-35783, JP-A-1-268668, JP-A-2-95439). No. 2, JP-A-2-261544), B
i-Mo-based oxide catalyst (JP-A-48-16887, JP-B-55-42071, JP-A-3-157356)
No.), VP-based oxide catalyst (Japanese Patent Publication No. 58-5188).
No.), Bi-V based oxide catalyst (JP-A-63-29554).
No. 5) is known, and more recently V-Sn-Sb-Cu
-Based 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.) etc. have been applied for patents. A mixed catalyst system of some of the above catalyst systems and a catalyst having an ammoxidation ability for olefins has also been proposed (Japanese Patent Laid-Open No. 63-295546).
JP-A-64-38051, JP-A-2-17159
JP-A-2-43949 and JP-A-2-75347.
No. 2, JP-A-2-11144 and JP-A-2-25806.
No. 5).

[0004]

However, among these methods, a system in which a small amount of a halide is added to the reaction system as a promoter achieves a relatively high yield of nitriles which are the target products. However, in this case, there is a fatal problem of corrosion of the reaction device, the material on the device is limited, and there is a great industrial problem. In addition, in a system in which a promoter is not added, the yield of nitriles is low and does not reach a level that can be industrially implemented.

The present invention has been made in order to eliminate such drawbacks, and at least one or more saturated hydrocarbons selected from the group consisting of propane and isobutane are mixed with molecular oxygen and In the ammoxidation method of catalytically oxidizing with a mixed gas containing ammonia, by using the catalyst essentially containing chromium, antimony and tungsten disclosed in the present invention, the yield of the target product nitriles is high. An object is to provide an industrially advantageous method for producing (meth) acrylonitrile.

[0006]

The present inventors have proposed that at least one saturated hydrocarbon selected from the group consisting of propane and isobutane is vaporized in the presence of a catalyst by a mixed gas containing molecular oxygen and ammonia. As a result of extensive research on a method for producing (meth) acrylonitrile by an ammoxidation method of contacting 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 a substance is supported on a refractory inorganic carrier, and has reached the method of the present invention.

That is, the present invention provides a method for producing (meth) acrylonitrile by subjecting propane and / or isobutane to catalytic oxidation reaction of molecular oxygen and ammonia in the gas phase in the presence of a catalyst. Formula: CrαSbβWγOx (I) (wherein Cr is chromium, Sb is antimony, W is tungsten, O is oxygen, and α, β, γ and x are the numbers of atoms of Cr, Sb, W and O, respectively. , Α = 1, β = 0.5 to 5, γ = 0.2 to 2, and x is a value determined by the valence of the existing element). The present invention provides a method for producing (meth) acrylonitrile, which is characterized by bringing them into contact with each other.

Particularly, as a preferable composition range of the composite oxide represented by the general formula (I), 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 desired nitrile will be low.

As the catalyst used in the present invention, the composite oxide represented by the general formula (I) is further supplemented with Nb and M.
At least one element selected from o, Mn, Fe, Co and Ni (hereinafter sometimes referred to as A group element).
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 complex oxide in which the atomic ratio of the group A element to Cr, which is a constituent element of the catalyst, exceeds 0 and is 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 in order to improve the yield of the target substance. The atomic ratio of the group A element to Cr is 0.05 to 0.
A range of 1 is especially preferred. If the composition is out of this range, the yield of the desired nitriles will be low, which is not preferable.

Further, as a catalyst used in the present invention, V, N is further added to the composite oxide represented by the general formula (I).
At least one element selected from b, Mo, Mn, Fe, Co, and Ni (hereinafter sometimes referred to as A'group element. V is vanadium, Nb is niobium, Mo is molybdenum, Mn is manganese, and Fe. Is iron, Co is cobalt, Ni
Represents nickel. ) In the range where the atomic ratio of the A'group element to Cr of the constituent elements of the catalyst exceeds 0 and is 0.1 or less and the atomic ratio of the A'group element to Sb of the constituent elements of the catalyst exceeds 0 to 0. It is preferable to use the catalyst containing the complex oxide added in the range of 04 or less.
As the A ′ group element, in terms of improving the yield of the target substance,
It is particularly preferable to contain V or Nb, and the atomic ratio of the A ′ group element to Cr of the constituent elements of the catalyst is 0.05 to 0.1.
The range is particularly preferable because it improves the yield of the desired product.

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

The refractory inorganic carrier is preferably an oxide containing at least one oxide selected from silica, alumina, titania, zirconia, silica-alumina, silica-titania and silica-zirconia,
Among them, silica-alumina is preferable 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 usually used in this field, for example, the following method. Chromium nitrate was dissolved in warm water, an aqueous solution of ammonium metatungstate (commercial product) was added, and antimony trioxide was added as powder, and V, Nb, Mo, Mn, Fe, Co and An aqueous solution of a compound of one or more elements selected from the group consisting of Ni is added, and in some cases, a carrier such as silica or alumina is added, and the mixture is stirred for a certain period of time and heated and concentrated. It is prepared by firing at 400 to 800 ° C. The calcination is performed in the air, but it can be performed under a high oxygen concentration or a low oxygen concentration. In the final calcination step, it is preferable to treat in an atmosphere of low oxygen concentration (oxygen concentration: 1% to 15%) in order to obtain high catalyst performance.

There are no particular restrictions on the raw materials used to prepare the catalyst used in the present invention. Examples thereof include nitrates, oxides, hydroxides, chlorides, carbonates, acetates, metal acids and ammonium metal salts.

Raw materials for the carrier include alumina, silica,
In addition to molded bodies such as silica-alumina, oxides, hydroxide powders or gels, sols, and the like can be used in various ways according to the usage form of the catalyst.

As a raw material gas for the ammoxidation reaction according to the present invention, propane or isobutane, molecular oxygen and ammonia, and if necessary, a diluting gas may be used. Air or pure oxygen is used as the molecular oxygen source. The molar ratio of molecular oxygen donated to the reaction is preferably 0.2 to 5 times that of propane, the molar ratio of ammonia is preferably 0.2 to 3 times that of propane, and the diluent gas is nitrogen. 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:
The space velocity of the raw material gas on the catalyst is 300 to 50.
It can be suitably carried out by bringing them into contact with each other at a temperature of 00 hr ⁻¹ and 300 ° C. to 600 ° C. The vapor-phase catalytic ammoxidation reaction is usually carried out under normal pressure, but it can also be carried out under reduced pressure or increased pressure. The reaction system is also not particularly limited, and any of a fixed bed type, a moving bed type and a fluidized bed type is possible. Further, either a single method or a recycling method may be used.

[0018]

EXAMPLES The present invention will be described in more detail with reference to the following examples.

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

[0020]

[Equation 1]

Example 1 Alumina sol A-200 (manufactured by Nissan
Gaku Kogyo Co., Al₂ O₃ (Concentration: 10.5 wt%) 30.
2g and Silica Sol Snowtex N (Nissan Chemical Industry Co., Ltd.
Made of SiO₂Concentration: 20.5 wt%) 15.5 g and
Add 50 ml of water, stir by heating, and keep at about 80 ° C.
It was Next, chromium nitrate (Cr (NO₃ )₃ 9H₂ O, Wako
Manufactured by Junyaku Co., Ltd., purity 99.9%)
Add the one dissolved in water and continue to metatungstic acid
Ammonium ((NH_Four )₆ H₂ W ₁₂O₄₈) Aqueous solution MW
-2 (WO made by Japan Inorganic Chemical Industry Co., Ltd.₃ As 50 wt%
13.91 g (containing) was added as a stock solution. Then Sb₂ 
O₃ 13.14 g (manufactured by Wako Pure Chemical Industries, purity 99.9%)
Add the product dispersed in 100 ml of water with a homogenizer.
Eh, stirring at a liquid volume of about 80 ° C for 2 hours
It was After this, raise the heating temperature to 90 ° C and continue stirring.
After that, concentration was performed by evaporation of water for about 3 hours. Obtained
Dried paste at 120 ° C for 14 hours and then in air 4
At 50 ° C for 3 hours, atmosphere with oxygen concentration of 10% (remaining nitrogen)
Baking at 560 ° C for 3 hours under. The composition of the obtained catalyst is
80 wt% Cr₁ Sb_1.5W_0.5 Ox / 10wt% Al₂
 O₃ -10wt% SiO₂ It was
In the description of the composition, "/" or less represents the carrier component in the catalyst.
).

5 ml of 9 to 20 mesh of this catalyst was charged into a normal flow reactor to carry out the reaction. The reaction gas composition is C ₃ H ₈ / NH ₃ / O ₂ / He
/ H ₂ O = 1/2/4 / 7.5 / 3 (molar ratio), space velocity was SV = 900 hr ⁻¹ , and reaction temperature was 520 ° C.
The results obtained are shown in Table 1.

Example 2 Chromium nitrate, ammonium metatungstate aqueous solution M
The charge amounts of W-2 and Sb ₂ O ₃ were 16.50 each.
g, 19.11 g, and 12.03 g except that the preparation was performed in the same manner as in Example 1 to obtain 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 performed in the same manner as in Example 1 except that the reaction temperature was 540 ° C. The results obtained are shown in Table 1.

Example 3 Chromium nitrate, ammonium metatungstate aqueous solution M
The amount of W-2 and Sb ₂ O ₃ charged was 11, 46, respectively.
g, 19.92 g, 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 / 10 wt% Al ₂ O ₃ -10 wt% SiO ₂
A catalyst having the following composition was obtained. The reaction was performed in the same manner as in Example 1 except that the reaction temperature was 540 ° C. The results obtained are shown in Table 1.

Example 4 After adding the ammonium metatungstate aqueous solution and before adding the Sb ₂ O ₃ dispersion, 0.351 g of ammonium metavanadate (NH ₄ VO ₃ , special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) was further added. 80 wt% was prepared in the same manner as in Example 1 except that the one heated and dissolved in 50 ml of water was added.
% / 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 carried out in the same manner as in Example 1. The results obtained are shown in Table 1.

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

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

Example 7 After addition of the ammonium metatungstate aqueous solution and before addition of the Sb ₂ O ₃ dispersion, further ammonium paramolybdate ((NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂
O, special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) was prepared in the same manner as in Example 1 except that 1.200 g of which was heated and dissolved in 50 ml of water was added, and 80 wt% Cr ₁ Sb _1.5 W _0.5 Mo
_0.05 Ox / 10 wt% Al ₂ O ₃ -10 wt% SiO ₂
A catalyst having the following composition was obtained. The reaction was carried out in the same manner as in Example 1.
The results obtained are shown in Table 1.

[0029] Instead of manganese nitrate in Example 8 Ammonium paramolybdate _{(Mn (NO 3) 2 ·} 6H 2 O, Wako Pure Chemical Co., Ltd. special grade reagent)
80 wt% C was prepared in the same manner as in Example 7, except that 0.861 g of the mixture was heated and dissolved in 50 ml of water.
r ₁ Sb _1.5 W _0.5 Mn _0.05 Ox / 10 wt% Al ₂ O ₃
A catalyst having a composition of −10 wt% SiO ₂ was obtained. The reaction was carried out in the same manner as in Example 1. The results obtained are shown in Table 1.

Example 9 Instead of ammonium paramolybdate, iron nitrate (Fe
_{(NO 3) 3 · 9H 2} O, Wako Pure Chemical Co., Ltd. special grade reagent) 1.
80 wt% Cr ₁ was prepared in the same manner as in Example 7 except that 212 g of 50 ml of water heated and dissolved was added.
Sb _1.5 W _0.5 Fe _0.05 Ox / 10 wt% Al ₂ O ₃ −
A catalyst having a composition of 10 wt% SiO ₂ was obtained. The reaction was carried out in the same manner as in Example 1. The results obtained are shown in Table 1.

Example 10 Silica Sol Snowtex N, chromium nitrate, ammonium metatungstate aqueous solution MW-2 and Sb ₂ O ₃ were charged in amounts of 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, except that 60 wt% Cr ₁ Sb _1.5 W ₁ Ox / 10w was used.
A catalyst having a composition of t% Al ₂ O ₃ -30 wt% SiO ₂ was obtained. The reaction was carried out in the same manner as in Example 1. The obtained results are shown in Table 2.

Example 11 Except that silica sol was not added and the amounts of chromium nitrate, ammonium metatungstate aqueous solution MW-2 and Sb ₂ O ₃ were changed to 22.86 g, 13.24 g and 16.67 g, respectively. Preparation 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 carried out in the same manner as in Example 2. The obtained results are shown in Table 2.

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 of 30.9 g was changed to 80 wt% Cr ₁ Sb ₂ W ₁ Ox / 20w.
A catalyst having a composition of t% SiO ₂ was obtained. The reaction was carried out in the same manner as in Example 2. The obtained results are shown in Table 2.

Example 13 Alumina sol and silica sol were mixed and stirred by heating to about 8
When kept at 0 ° C, further anatase type TiO ₂
(Wako Pure Chemical Industries, Ltd. first-grade reagent) 3.17 g was added as a powder, and the amounts of chromium nitrate, ammonium metatungstate aqueous solution MW-2, and Sb ₂ O ₃ charged were 1 respectively.
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 used.
_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 carried out in the same manner as in Example 1. The obtained results are shown in Table 2.

Example 14 In a 300 ml beaker, 50.50 g of chromium nitrate was added.
What was dissolved in ml of water, ammonium metatungstate aqueous solution MW- ₂ , 19.11 g were sequentially added, and then 12.03 g of Sb ₂ O _{3 was} added to 100 ml with a homogenizer.
Add what is dispersed in water and stir for about 8 hours.
It was kept at 0 ° C. ZrO ₂ (manufactured by Mitsuwa Chemicals,
6.35 g of powder (purity 99.9%) was added as a powder to about 80
Stirring was performed while maintaining the liquid volume for 2 hours at 0 ° C. Then, the heating temperature was raised to 90 ° C., stirring was continued, and the water was evaporated to perform concentration for about 2 hours. The subsequent drying and firing are performed in the same manner as in Example 1, and 80 wt% Cr ₁ Sb ₂ W ₁ O
A catalyst having a composition of x / 20 wt% ZrO ₂ was obtained. The reaction was carried out in the same manner as in Example 2. The obtained results are shown in Table 2.

Example 15 ZrO ₂ was not used, and the amounts of ammonium metatungstate aqueous solution MW-2 and Sb ₂ O ₃ charged were 9.
A catalyst having a composition of 100 wt% Cr ₁ Sb ₁ W _0.5 Ox was obtained in the same manner as in Example 14 except that the amounts were changed to 56 g and 6.02 g. The reaction was carried out in the same manner as in Example 1. The obtained results are shown in Table 2.

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

Comparative Example 1 Without using ammonium metatungstate, the amounts of chromium nitrate and Sb ₂ O ₃ charged were 26.47 g and 1 respectively.
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 was used.
₃ to obtain a catalyst of -10 wt% SiO ₂ composition. The reaction was carried out in the same manner as in Example 2. The results obtained are shown in Table 3.

Comparative Example 2 Chromium nitrate and ammonium metatungstate aqueous solution MW-2 were charged in amounts of 3 without using Sb ₂ O ₃ , respectively.
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
A catalyst having a composition of% Al ₂ O ₃ -10 wt% SiO ₂ was obtained. The reaction was carried out in the same manner as in Example 2. The results obtained are shown in Table 3.

Comparative Example 3 Chromium nitrate was not used, and the amounts of the ammonium metatungstate aqueous solutions MW-2 and Sb ₂ O ₃ charged were 3 respectively.
Preparation was performed 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 carried out in the same manner as in Example 2. The results obtained are shown in Table 3.

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

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

Comparative Example 6 80 wt% was prepared in the same manner as in Example 4 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 carried out in the same manner as in Example 1. The results obtained are shown in Table 3.

Example 17 Using the same catalyst 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 a reaction temperature of 470 ° C. Isobutane conversion 72.2%, methacrylonitrile selectivity 3
0.4%, single-flow yield of methacrylonitrile is 21.9%
Met.

[0045]

[Table 1]

[0046]

[Table 2]

[0047]

[Table 3]

[0048]

INDUSTRIAL APPLICABILITY The present invention provides an ammoxidation method of catalytically oxidizing at least one saturated hydrocarbon selected from the group consisting of propane and isobutane with a mixed gas containing molecular oxygen and ammonia in the presence of a catalyst, By using the catalyst essentially containing chromium, antimony and tungsten disclosed in the present invention, the yield of the target product nitriles is high and (meth) acrylonitrile can be industrially produced advantageously.

Continuation of front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI technical display location // C07B 61/00 300 (72) Inventor Matsunami Koshisei 5-8 Nishimitabicho Suita City Osaka Prefecture Co., Ltd. Central Research Institute of Nippon Shokubai

Claims (4)

[Claims] 1. In an ammoxidation method in which at least one or more saturated hydrocarbons selected from the group consisting of propane and isobutane are catalytically oxidized by a mixed gas containing molecular oxygen and ammonia in the presence of a catalyst, the following catalyst is used. 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, and when α = 1, β = 0.5 to 5, γ = 0.2 to 2, and x is a value determined by the valence of the existing element.) A method for producing (meth) acrylonitrile, which comprises bringing the catalyst into contact with the catalyst. 2. The catalyst according to claim 1, wherein the composite oxide represented by the general formula (I) further comprises Nb and M.
A composite oxide containing at least one element selected from o, Mn, Fe, Co, and Ni in a range where the atomic ratio of the element of the catalyst to Cr of the element is more than 0 and 0.1 or less. A catalyst is used, and a catalyst is used.
A method for producing the (meth) acrylonitrile described. 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 Mo, Mn, Fe, Co, and Ni is contained in 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 elements exceeds 0 and is 0.0
The method for producing (meth) acrylonitrile according to claim 1, wherein a catalyst containing a complex oxide added in a range of 4 or less is used. 4. A method for producing (meth) acrylonitrile, which comprises using the catalyst according to any one of claims 1 to 3 supported on a refractory inorganic carrier material.