WO2004099123A1

WO2004099123A1 - Process for producing (meth) acrylonitrile

Info

Publication number: WO2004099123A1
Application number: PCT/JP1996/000096
Authority: WO
Inventors: Akira Kurusu; Nobuji Kishimoto; Isao Nakamura; Etsushige Matsunami
Original assignee: Akira Kurusu; Nobuji Kishimoto; Isao Nakamura; Etsushige Matsunami
Priority date: 1993-12-03
Filing date: 1996-01-22
Publication date: 2004-11-18
Also published as: JP2798878B2; JPH07157461A

Abstract

An industrially advantageous process for producing (meth) acrylonitrile in high yields by means of ammoxidation comprising catalytically oxidizing at least one saturated hydrocarbon selected between propane and isobutane with a gaseous mixture containing molecular oxygen and ammonia, which process is characterized by using a catalyst comprising a composite oxide represented by the following general formula (I): CrαSbβWϜOx wherein α, β and Ϝ represent respectively the number of Cr, Sb and W atoms, provided when α is 1, then β is 0.5 to 5 and Ϝ is 0.2 to 2; and x is a number that is determined according to the valencies of the elements present.

Description

Specification

Method for producing (meth) acrylonitrile

Technical field

The present invention relates to a method for producing (meth) acrylonitrile by an ammoxidation method in which at least one kind of saturated hydrocarbon selected from the group consisting of propane and isobutane is brought into gaseous phase contact with molecular oxygen and ammonia.

Background art

(Meth) acrylonitrile has been produced in large quantities as an intermediate raw material for various industrial products, mainly synthetic fibers and synthetic resins. Conventionally, its production method uses olefinic raw materials, such as propylene and isobutene, in the presence of a catalyst. An ammoxidation method in which a gas phase is contacted with molecular oxygen and ammonia is generally known.

On the other hand, with the rise in price of olefins in recent years, attention has been focused on the development of methods for manufacturing various derivatives that have been conventionally manufactured using olefins as raw materials using less expensive paraffins as raw materials. Have been. The catalyst system used for producing (meth) atalylonitrile from propane or isobutane by the so-called ammoxidation method includes Sb-U-based oxide catalysts (JP-B-47-14371) and Sb-Sn-based oxidation catalysts. Catalysts (JP-B 50-28940), V-Sb based oxide catalysts (JP-A-47-33783, JP-A-11-268668, JP-A-2-95439 and JP-A-2-261544) , Bi-Mo-based oxide catalysts (JP-A-48-16887, JP-B-55-42071 and JP-A-3-157356), VP-based oxide catalysts (JP-B-58-5188), B i—V-based oxide Media (JP-A-63-295545), and more recently, V-SnSb-Cu-based oxide catalyst (JP-A-4-1275266), Mo-V-Te-Nb-based oxide Catalyst (JP-A-2-257), Ag-Bi-V-Mo-based oxide catalyst (JP-A-3-58961), Ga-Bi-Mo or Ta-Bi-Mo-based oxide catalyst (JP-A-3-58962), Mo-Ta or Mo-Nb-based oxide catalysts (JP-A-5-213849), and the like have been applied for patents. Also, a mixed catalyst system of some of the above catalyst systems and a catalyst having an ammoxidation ability of an orefin has been proposed (JP-A-63-295546, JP-A-64-38051, JP-A-2-38051). 17159, JP-A-2-43949, JP-A-2-75347, JP-A-2-111444 and JP-A-2-258065).

However, of these methods, the method of adding a small amount of a halide as a promoter to the reaction system gives the target product nitriles in a relatively high yield. Due to the problem of corrosion, there is a restriction on the material of the equipment, which makes industrial implementation difficult. In the method without the addition of a promoter, the yield of nitriles is low, and has not reached a level that can be industrially implemented.

Disclosure of the invention

Accordingly, an object of the present invention is to provide a method capable of industrially and advantageously producing (meth) acrylonitrile in a high yield by eliminating such disadvantages in the conventional method.

The present inventors have followed an ammoxidation method in which at least one saturated hydrocarbon selected from the group consisting of propane and isobutane is brought into gaseous phase contact with a mixed gas containing molecular oxygen and ammonium in the presence of a catalyst ( Meta) As a result of intensive research on the method of producing atarilonitrile, a catalyst consisting of a composite oxide containing an oxide containing three essential elements, chromium, antimony and tungsten, was used as a catalyst. It has been found that a higher yield of nitriles can be obtained by using an inorganic carrier supported on an inorganic carrier, and the process of the present invention has been achieved.

Thus, according to the present invention, there is provided a method for producing (meth) acrylonitrile by catalytic oxidation of propane and / or isobutane in the gas phase with molecular oxygen and ammonia in the presence of a catalyst, comprising the steps of: And the following general formula (I):

C r aSb / 3W70x (I)

Wherein, α,; 8 and a represent the number of atoms of Cr, Sb, and W, respectively, when α is 1, ^ is 0.5-5, and α is 0.2-2, X is a value determined by the valence of the existing element.)

The use of a catalyst comprising a composite oxide represented by the formula:

Among the composite oxides represented by the general formula (I), those having a composition in which 1 is 1, ^ is 1 to 3, and α is 0.5 to 1.5 are particularly suitable for the target nitrile. In high yield.

Further, in the present invention, at least one element selected from Nb, Mo, Mn, Fe, Co and Ni together with the component elements of the composite oxide represented by the general formula (I) (hereinafter referred to as A It is preferable to use a catalyst comprising a complex oxide containing the compound in an amount such that the atomic ratio of the group A element to Cr is more than 0 and not more than 0.1. These catalysts of the present invention, which additionally contain a group A element, have an improved activity or selectivity. Works on top. As the group A element, Nb is particularly preferred from the viewpoint of improving the yield of the target product. The atomic ratio of the group A element to Cr is particularly preferably in the range of 0.05 to 0.1.

Further, in the present invention, at least one element selected from V, Nb, Mo, Mn, Fe, Co and Ni together with the component elements of the complex oxide pent represented by the general formula (I) ) Is an amount such that the atomic ratio of the A 'group element to Cr is more than 0 and not more than 0.1 and the atom of the A' group element to Sb is It is also preferable to use a catalyst comprising the composite oxide contained in an amount such that the ratio is more than 0 and not more than 0.04. As the A 'group element, V or Nb is particularly preferred from the viewpoint of improving the yield of the target product. It is particularly preferable that the atomic ratio of the A 'group element to Cr is in the range of 0.05 to 0.1 in terms of improving the yield of the desired product.

It is particularly preferable that the catalyst used in the present invention described above is supported on a refractory inorganic carrier from the viewpoint of improving the activity and physical durability of the catalyst. '

As the refractory inorganic carrier, at least one oxide selected from silica, alumina, titania, zirconium, silicone-alumina, silicone-titania and silicone-zirconia is preferred, and silica-alumina 20 is particularly preferred. It is particularly preferable from the viewpoint of improving the yield of the product.

The catalyst used in the present invention can be prepared by a known method commonly used in the art. For example, dissolve chromium nitrate in warm water, add an aqueous solution of ammonium metatungstate (commercially available), add antimony trioxide in powder form, and add V, Nb, Mo, M as needed. Add an aqueous solution of at least one elemental compound selected from the group consisting of n, Fe, Co, and Ni, and if necessary, add a carrier such as silica or alumina, and mix for a certain period of time. It is prepared by stirring, heating and concentrating, drying the obtained slurry, and baking it at 400 to 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, metal ammonium salts and the like.

As a raw material for the carrier, there can be variously used oxides, hydroxide powders, gels, sols, and the like, depending on the form of use of the catalyst, in addition to alumina, silica, silica-alumina, etc. .

As a raw material gas for the ammoxidation reaction according to the present invention, besides propane and / 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 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. As the diluent gas, an inert gas such as nitrogen, helium, carbon dioxide, and the like, and steam are preferably used.

In the gas phase catalytic ammoxidation reaction according to the present invention, the raw material gas is mixed with the catalyst at a space velocity of 300 to 500 hr- ¹ and a temperature of 300 to 600 ° C. It can be suitably carried out by contacting with. Also above The gas-phase catalytic ammoxidation reaction is usually performed under normal pressure, but can be performed 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-flow system or a recycling system may be used. Effect of the Invention In the ammoxidation method of the present invention, at least one kind of saturated hydrocarbon selected from the group consisting of propane and isobutane is converted into molecular oxygen in the presence of the above-mentioned catalyst comprising chromium, antimony and tungsten as essential components. (Meth) acrylonitrile can be industrially advantageously produced at a high yield by performing catalytic oxidation with a mixed gas containing hydrogen and ammonia. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described more specifically with reference to examples. The conversion, single-stream yield and selectivity, including by-products, are defined by the following formulas. When the raw material is propane: Number of monoles of reacted propane

Conversion (mol%) = X 100

Number of monoles of propane supplied

Number of moles of each compound generated Carbon number of each compound

Selectivity (mol%) = X X 100 Number of moles of propane reacted 3

Number of moles of each compound generated Number of carbon atoms of each compound Single stream yield (mol%) = X X 100 Number of moles of propane supplied 3

If the raw material is isobutane:

Number of moles of reacted isobutane

Conversion (mol%) = X 100

Number of moles of isobutane supplied Number of moles of each compound generated Carbon number of each compound

Selectivity (mol%) = 100 Number of moles of reacted isobutane 4 Number of moles of each compound formed Carbon number of each compound Single stream yield (mol%) = XX 100 Number of moles of supplied isobutane 4 Example 1

To 500 meters l-bi one car, alumina sol A- 200 (manufactured by Nissan Chemical Industries, Ltd., A 1 ₂ 0 ₃ concentration:. 10. 5 wt%) 30. 2 g, Shirikazorusuno ferrous box N (manufactured by Nissan Chemical Industries, Ltd., (Sio ₂ concentration: 20.5 wt.%) 15.5 g and 50 ml of water were charged, heated and stirred, and kept at about 80 ° C. Then chromium nitrate _{_{(C r (NO 3) 3}} 9H 2 0, manufactured by Wako Pure Chemical Industries, Ltd., purity 99. 9%) 24. 03 g was added to those dissolved in water 50 m 1, followed by meta tungstate acid Anmoniumu _{_{_{((NH 4) 6 H 2}}} W 12 0 48) solution MW - 2 was added remained (Nippon Inorganic Color & chemical Co., W0 ₃ as 5 OWT% containing.) 13. 9 1 g of the stock solution. Thereafter, S b ₂ 0 ₃ (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.9%) 13. Also dispersed in water of 100 m 1 to 14 g a homogenizer of the addition, 2 hours liquid amount remained about 80 ° C And kept stirring. Thereafter, the heating temperature was increased to 90 ° C, stirring was continued, and the mixture was concentrated for about 3 hours while evaporating water. The obtained paste was dried at 120 ° C for 14 hours, fired at 450 ° C for 3 hours in the air, and then fired at 560 ° C for 3 hours in an atmosphere having an oxygen concentration of 10% (remaining nitrogen). The composition of the obtained catalyst was S Ow t. ^ C r ^ SbuWo.sOxZl Owt. Al aOs— l Ow t.% S i 0 ₂ (In the following description of the composition of the catalyst, the left side of / Represents the composition of the oxide, and the right side of Z represents the composition of the carrier). 5 ml of this catalyst arranged in a mesh of 9 to 20 mesh was filled in a usual flow-type reaction apparatus and reacted. The composition of the reaction gas _{CsHsZNHs / 0 2 / H e /} H 2 0 = 1/2/4/7. 5/3 ( molar ratio), the space velocity SV is 900 hr the reaction temperature was 520 ° C. Table 1 Example 2

Chromium nitrate, metatungstate Anmoniumu aqueous-MW-2 and S b ₂ 0 ₃ of the feed amount, respectively 16. 50 g, except for changing the 19. LLG and 12. 0 3 g, the prepared as in Example 1 done to give _{8 Owt.% C riSb 2 WiOx} / 10wt.% a l 2 O 3 -10wt.% S i 0 ₂ composition catalyst. The reaction was performed 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, metatungstate Anmoniumu aqueous-MW-2 and S b ₂ 0 ₃ of the feed amount, respectively 11, 46 g, except for changing the 19. 92 g and 12. 4 7 g, prepared as in Example 1 was carried out, to obtain a 80wt.% C riSbsWLsOx l Owt. ^ a l aOs-l Owt. ^ S i 0 2 set configuration of the catalyst. The reaction was carried out in the same manner as in Example 1 except that the reaction temperature was 540 ° C. Table 1 shows the obtained results.

Example 4

After adding metatungstate Anmoniumu solution, S b ₂ 0 ₃ minutes dispersion liquid before the addition of further metavanadate Anmoniumu (NH ₄ V0 _3, produced by Wako Pure Chemical Industries, Ltd. special grade reagent) 0. 351 g of 5 Om 1 Preparation was performed in the same manner as in Example 1 except that a solution heated and dissolved in water was added. It was obtained 10 wt% catalyst composition of _{S i O 2 -!. S} b .5W0 .5V 0 .05 O x XlOw t% A l 2 0 3.. The reaction was performed in the same manner as in Example 1. Table 9 shows the results obtained.

Example 5

After adding metatungstate Anmoniumu solution, before the addition of Sb ₂ 0 ₃ minutes dispersion liquid, except for adding what was further metavanadate Anmoniumu 0. 337 g is heated and dissolved in a 5 Om 1 water, carried Prepared as in Example 2 and

To obtain a 12 O 3- 1 Ow t.% S i 0 ₂ composition catalyst. The reaction was performed in the same manner as in Example 2. Table 1 shows the obtained results.

Example 6

Instead of metavanadate Anmoniumu, oxalate niobium (CBMM Co., 20. 5 wt.% Containing at Nb ₂ 0 ₅ equivalent) 1. except plus those dissolved with heating 816 g of water 100 m 1 is performed the preparation was conducted in the same manner as example 5, to obtain a 80 wt.% C ri S b 2 WiN b 0. 07 O xZ 10 wt.% a 1 2 0 3 -1 Owt.% S i 0 ₂ composition catalyst . The reaction was carried out as in Example 2. Table 1 shows the obtained results.

Example 7

After adding metatungstate Anmoniumu solution, S b ₂ 0 ₃ minutes dispersion liquid before the addition of further Paramoributen acid Anmoniumu _{_{_{((NH 4) 6 Μο 7}}} 0 24 · 4H 2 0, special grade manufactured by Wako Pure Chemical Industries, Ltd. Reagents) 1. Prepared in the same manner as in Example 1, except that 200 g was dissolved by heating in 50 ml of water.

Owt. A

O 3 -. 1 Owt% to obtain a catalyst of the S i 0 ₂ composition. Reaction is the same as in Example 1. I went to. Table 1 shows the obtained results.

Example 8

Instead of para molybdate Anmoniumu, except that addition of those dissolved by heating manganese nitrate _{_{(Mn (N 0 3) 2}} · 6H 2 0, produced by Wako Pure Chemical Industries, Ltd. special grade reagent) to 0. 861 g of water 50 m l Was prepared in the same manner as in Example 7 to obtain a catalyst having a composition of S Owt ^ CriSbi.sWo.aMno.osOx / l Owt ^ A1sOs-10 wt.% Sio ₂ . The reaction was carried out as in Example 1. Table 1 shows the obtained results.

Example 9

Instead of para molybdate Anmoniumu, iron nitrate _{_{(F e (N0 3) 3}} . 9H 2 0, produced by Wako Pure Chemical Industries, Ltd. special grade reagent) 1. except the addition of what the 212 g was dissolved by heating of water 50 m 1 performs prepared as in example _{7, 80w t% C riSbi 5} Wo.5F e o.o50 x / 10wt% a l 2 0 3 -.... 10w t% S i 0 ₂ composition catalyst Got. The reaction was performed in the same manner as in Example 1. Table 1 shows the obtained results.

Example 10

Silica sol Snowtex N, except that chromium nitrate, the charge amount of metatungstate en Moniumu aqueous-MW-2 and S b ₂ 0 _3, were changed to respectively 46. 4 g 14. 13 g 16. 38 g and 7. 73 g performs prepared as in example 1, S Owt ^ C riS bi.sWiOxZl Owt% a 1 2 0 3 - was obtained 30 wt% catalyst composition of S i O _2.... The reaction was performed in the same manner as in Example 1. Table 1 shows the obtained results.

Example 11

Without adding silica sol, chromium nitrate, ammonium metatungstate The charged amount of an anhydrous solution-MW-2 and Sb ₂ 0 _3, except for changing the respective 22. 86 g, 1 3. 24 g and 16. 67 g, performed prepared as in Example 1, 9 Owt. % was obtained C 1 S b 2Wo.5O xZl Ow t .% a 1 2 0 ₃ composition catalyst. The reaction was performed in the same manner as in Example 2. Table 2 shows the obtained results.

Example 12

Preparation was carried out in the same manner as in Example 2 except that alumina sol was not used and the charge amount of silica sol snotex N was changed to 30.9 g.80 wt.% Cr ₁ Sb ₂ W ₁₀ x / 20 wt. % to obtain a catalyst of the S i 0 ₂ composition. The reaction was performed in the same manner as in Example 2. Table 2 shows the obtained results.

Example 13

Mixing alumina sol and silica force sol, heated stirring, at maintained at about 80 ° C, further anatase T i 0 ₂ (manufactured by Wako Pure Chemical Industries, Ltd. 1 grade reagent) 3. 17 g was added as a powder it and chromium nitrate, the charge amount of Metatandasute phosphate Anmoniumu aqueous-MW-2 and S b ₂ 0 _3, respectively 1 6. 49 g, except for changing the 19. LLG and 9. 02 g, example 1 performed similarly prepared, T Owt C riSbuWiOxZl Owt% a 1 2 0 3 - was obtained 10 wt% S i O2- 10 wt % T i 0 ₂ composition catalyst..... The reaction was performed in the same manner as in Example 1. Table 2 shows the obtained results. Example 14

To 300 meters l beaker one, 16. 50 g of what was dissolved chromium nitrate in water of 5 Om 1 and successively charged metatungstate Anmoniumu water solution-MW-2 of 19. LLG, then S b ₂ 0 ₃ l 2. Add 03 g dispersed in 10 Om 1 of water with a homogenizer, heat and stir. Maintained at 80 ° C. This Z r 0 ₂ (Mitsuwa Chemicals Co., Ltd., purity 99.9%) was added 6. 35 g remained powder was subjected to stirring maintained for 2 hours liquid amount remained about 80 ° C. Thereafter, the heating temperature was raised to 90 ° C, stirring was continued, and the mixture was concentrated for about 2 hours while evaporating water. Subsequent drying and firing were performed in the same manner as in Example 1 to obtain 80 wt.% Cr! To obtain a S b sWiO xZ20 wt.% Z r 0 ₂ composition catalyst. The reaction was performed in the same manner as in Example 2. Table 2 shows the obtained results.

Example 15

Without using the Z r 0 _2, the charge of metatungstate Anmoniumu aqueous-MW-2 and S b ₂ 0 _3, except for using each of 9.56 g and 6.02 g performs prepared as in Example 14, l O OWT. to obtain a C i Sbj Wo. ₅ catalyst having the composition of Ox. The reaction was performed in the same manner as in Example 1. Table 2 shows the obtained results.

Example 16

Without using the Z r0 _2, changing the charged amount of metatungstate Anmoniumu aqueous-MW-2 to 9. 56 g, the final calcination temperature outside than that was changed to 600 ° C is performed prepared as in Example 14 to obtain a _{_{100wt.% C riSb 2 W 0}} . 5 0 catalyst X composition.

The reaction was performed in the same manner as in Example 2. Table 2 shows the obtained results.

Comparative Example 1

Without the use of metatungstate Anmoniumu, the charged amount of chromium nitrate and S b 2 0 _3, instead was except Each 26. 47 g and 19. 30 g, performed prepared as in Example 1, 80 wt .% was obtained _{C riSb 2 Ox 1 0wt.%} a 1 2 0 3 -10 wt.% catalyst having the composition of S i O 2. The reaction is Performed in the same manner as in Example 2. Table 3 shows the obtained results.

Comparative Example 2

Without the use of S b ₂ 0 _3, chromium nitrate and charge of metatungstate en ΐ Niu anhydrous solution-MW-2, except for changing each 32.98 g and 38.20 g, The preparation was conducted in the same manner as in Example 1 to obtain a 80 wt.% C r Ox / 10wt.% a l 2 O 3 -10wt.% S i 0 ₂ composition catalyst. The reaction was performed in the same manner as in Example 2. Table 3 shows the obtained results.

Comparative Example 3

Without the use of chromium nitrate, metatungstate Anmoniumu aqueous MW - 2 and the charge of S b ₂ 0 _3, except for changing the respective 30. 48 g and 9. 59 g, the prepared as in Example 1 performed, S Owt S biWi 0 xZ 10 wt% a 12 O 3 - was obtained 10 wt% S i 0 ₂ composition catalyst.... The reaction was performed in the same manner as in Example 2. Table 3 shows the obtained results.

Comparative Example 4

Chromium nitrate, a charge of metatungstate Anmoniumu aqueous-MW-2 and S b ₂ 0 _3, respectively 7. 35 g, except for changing the 8. 51 g and 18. 74 g, prepared as in Example 1 was carried out, .8 Owt% C r iS b 7 WiOx / l Owt% a 1 2 0 3 - was obtained 10 wt% S i 0 ₂ composition catalyst.... The reaction was performed in the same manner as in Example 2. Table 3 shows the obtained results. Comparative Example 5

Chromium nitrate, a charge of metatungstate Anmoniumu aqueous-MW-2 and S b ₂ 0 _3, except for changing the respective 6. 94 g. 32. 16 g and 7. 59 g, prepared as in Example 1 % C rb3W ₄ Ox / 10wt.% Al ₂ O 3-10wt.% Sio ₂ Got. The reaction was performed in the same manner as in Example 2. Table 3 shows the obtained results. Comparative Example 6

Preparation was performed in the same manner as in Example 4 except that the amount of ammonium metavanadate was changed to 1.05 g.

to obtain a _{x / 10wt.% A l 2} O 3 -10wt.% S i 0 ₂ composition catalyst. The reaction was performed in the same manner as in Example 1. Table 3 shows the obtained results.

Example 17

The reaction was carried out using the same catalyst used in Example 4. . The composition of the reaction gas _{_{_{i -C 4 H 10 / NH 3}}} / / 0 2 / H e / H 2 0 = 1/2/4/7 5/3 ( molar ratio), the space velocity SV is 900 hr - The reaction temperature was 470 ° C. The results showed that the conversion of isobutane was 72.2%, the selectivity of methacrylonitrile was 30.4%, and the single-stream yield of methacrylonitrile was 21.9%.

Example Carrier ¹ ) Reaction Propane Selectivity (%) Single-stream yield (%) No. 0 0

00 Catalyst component Temperature conversion

0 (° C) (%) AN ² ) C ₃ ' ³⁾ HCN ⁴⁾ AN ² ) AN + C3' ⁵ )

1 8 Owt% CriSb1.5Wo .5Ox A 520 82.3 42.5 3.7 7.9 35.0 38.0

2 8 Owt.% CriSbzWiOx A 540 83.4 46.4 4.1 8.1 38.7 42.1

_{3 8 Owt.% CrjSbsWi. 5} 0 x A 540 79.7 37.8 4.9 7.0 30.1 34.0

4 8 Owt.% Cr1Sbi.5Wo .5 o .05Ox A 520 84.0 48.8 3.2 8.7 41.0 43.7

5 8 Owt.% Cr ₁ Sb ₂ W ₁ Vo.on i ₇ Ox A 540 86.2 46.5 3.1 9.1 40.1 42.8

a

6 8 Owt.% Cr ₁ Sb ₂ Wi bo. ₀ 70x A 540 84.5 46.4 4.0 8.2 39.2 42.6

7 8 Owt.% Cr1Sb1.5Wo.5Moo.05O 0x A 86.0 42.4

0 520 3.7 8.6 36.5 39.6

8 A 520 84.5 42.3 3.8 8.0 35.7 39.0

9 A 520 86.1 41.8 2.5 8.2 36.0 38.1

10 6 Owt.% CriSbi. ₅ WiO _x B 520 83.8 40.8 4.0 8.7 34.2 37.5

1) Support component in the catalyst: A = l 0 wt.% Al ₂ O ₃ -l 0 wt.% SiO ₂

B = l 0wt.% Al ₂ O ₃ -30wt.% SiO ₂

2) AN: acrylonitrile 3) C ₃ ,: propylene 4) HCN: hydrogen cyanide

5) AN + Cs': sum of acrylonitrile and propylene

Example Carrier ¹ ) Reaction Propane Selectivity (%) Single Stream Yield (%) No. Catalyst Component ίΠΠ, βϊ. Conversion

(° C) (%) AN ² ) (V ³⁾ Recommended ⁴⁾ AN ² ) AN + C ₃ ' ⁵ )

11 9 Owt.% CrjSbaWo.sOx C 540 82.1 42.0 2.9 7.8 34.5 36.9

12 8 Owt.% CriSb ₂ WiO _x D 540 73.3 39.8 3.9 8.1 29.2 32.0

13 7 Owt.% CrtSbi.sWiOx E 520 83.1 38.0 4.2 7.7 31.6 35.1

14 8 Owt.% CriSbzWiOx F 540 67.2 43.2 4.0 9.1 29.0 31.7

15 10 Owt.% CrxSbiffo.sOx ― 520 59.6 49.8 4.4 8.9.29.7 32.3

. 16 10 Owt% CriSba o - 5 0 x - 540 51.4 52.1 3.0 9.3 26.8 28.3

1) Carrier component in the catalyst: C = 10wt.% Al ₂ O ₃

D = ₂ Owt% Si0 2

E = l 0% Al ₂ O ₃ -l 0wt.% SiO ₂ -l 0wt.% TiO ₂

F = 20wt.% ZrO ₂

2) AN: acrylonitrile 3) C ₃ ,: propylene 4) HCN: hydrogen cyanide

5) AN + C ₃ ,: Sum of acrylonitrile and propylene

Table 3

2) AN: acrylonitrile 3) C ₃ ,: propylene 4) HCN: hydrogen cyanide 5) AN + C ₃ ,: sum of acrylonitrile and propylene

Claims

The scope of the claims

1. According to the ammoxidation method, at least one saturated hydrocarbon selected from the group consisting of propane and disobutane is catalytically oxidized with a mixed gas containing molecular oxygen and ammonia in the presence of a catalyst. In the method for producing tolyl,

The following general formula (I):

C r aS b ^ WrOx (I)

(Where α, 3 and a represent the number of atoms of Cr, Sb and W, respectively, and when is 1, / 3 is 0.5-5 and α is 0.2-2, X Is the value determined by the valence of the element present.)

A method comprising using a catalyst comprising a composite oxide represented by the following formula:

2. As the catalyst, at least one element selected from Nb, Mo, Mn, Fe, Co, and Ni, together with the component elements of the composite oxide represented by the general formula (I), 2. The method according to claim 1, wherein a catalyst comprising the composite oxide is used in an amount such that the atomic ratio of the element to the compound is more than 0 and not more than 0.1.

3. As the catalyst, at least one element selected from V, Nb, Mo, Mn, Fe, Co and Ni, together with the component elements of the composite oxide represented by the general formula (I). A quantity such that the atomic ratio of the element to Cr is greater than 0 and less than or equal to 0.1 and the atomic ratio of the element to Sb is greater than 0 and less than or equal to 0.04; 2. The method according to claim 1, wherein a catalyst comprising a composite oxide is used.

4The catalyst according to any one of claims 1 to 3 is used as a refractory inorganic carrier substance. A method characterized by being used by being carried on a substrate.

5. for ammoxidizing at least one saturated hydrocarbon selected from the group consisting of propane and isobutane to produce (meth) acrylonitrile,

The following general formula (I):

C r aS biSWrO (I)

(Where,, 3 and y represent the number of atoms of Cr, Sb and W, respectively. When «is 1, 3 is 0.5-5, y is 0.2-2, and x is It is a value determined by the valence of the existing element.)

A catalyst comprising a composite oxide represented by the following formula:

6. At least one element selected from Nb, Mo, Mn, Fe, Co and Ni, together with the constituent elements of the composite oxide represented by the general formula (I) described in claim 5. 6. The catalyst according to claim 5, comprising a complex oxide containing the element in an amount such that the atomic ratio of the element to Cr is more than 0 and not more than 0.1.

7. At least one element selected from V, Nb, Mo, Mn, Fe, Co and Ni, together with the constituent elements of the composite oxide represented by the general formula (I) according to claim 5. With an amount such that the atomic ratio of the element to Cr is greater than 0 and less than or equal to 0.1 and the atomic ratio of the element to Sb is greater than 0 and less than or equal to 0.04; 6. The catalyst according to claim 5, comprising a composite oxide.

8. Ammoxidizing at least one type of saturated hydrocarbon selected from the group consisting of propane and isobutane, wherein the complex oxide according to any one of claims 5 to 7 is supported on a refractory inorganic carrier substance. (Meta) Acry Roni Catalyst for producing toril.