JP2003071283A - Method for manufacturing oxidation or ammoxydation catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an oxidation or ammoxydation catalyst enhanced in the selectivity of a target substance for manufacturing an unsaturated acid or unsaturated nitrile by the vapor phase catalytic oxidation or vapor phase catalytic ammoxydation of propane or isobutane. SOLUTION: In a process for preparing a raw material so as to become a component composition represented by the formula (1): Mo1 Va Nbb Sbc On (wherein, (a), (b), (c) and (n) are atomic ratios per one molybdenum atom, (a) is 0.01<=a<=1, (b) is 0.01<=b<=1, (c) is 0.01<=c<=1, a ratio of (a) and (c) is 0.01<=a/c<1 and (n) is a number determined on the basis of the valencies or atomic ratios of constitutional metals), a mixed solution obtained from an Nb compound, an Sb compound, a dicarboxylic acid compound and hydrogen peroxide is used as at least a part of a raw material liquid of Nb and Sb to manufacture the oxidation catalyst.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an oxide catalyst used in a gas phase catalytic oxidation reaction or a gas phase catalytic ammoxidation reaction of propane or isobutane, an oxide catalyst, and an unsaturated acid using the oxide catalyst. Or, it relates to a method for producing an unsaturated nitrile.

[0002]

2. Description of the Related Art Conventionally, a method for producing a corresponding unsaturated carboxylic acid or unsaturated nitrile by subjecting propylene or isobutylene to vapor phase catalytic oxidation or vapor phase ammoxidation is well known. Attention has been focused on a method for producing a corresponding unsaturated carboxylic acid or unsaturated nitrile by subjecting propane or isobutane to vapor-phase catalytic oxidation or ammoxidation in place of isobutylene, and various catalyst production methods and reaction methods. Is proposed.

For example, a method for producing an oxide catalyst containing Mo-V-Nb-Sb is disclosed in JP-A-9-157241.
JP-A-10-330343 and JP-A-10-288
62, JP-A-11-42434, JP-A-1
1-43314, JP-A-11-226408, JP-A-10-57479, and JP-A-2000-7.
0714, JP-A-2000-143244,
JP 2001-58827A, JP 11-253A
No. 801 and Japanese Patent Laid-Open No. 2000-37623.

A method for producing an acrylic acid catalyst containing Mo-V-Sb-Nb is disclosed in JP-A-2000-354765, JP-A-2000-317309, and JP-A-200.
No. 0-254449, JP-A 2000-256257.
JP-A-2000-246108, JP-A-20
No. 00-51693, JP-A No. 11-285636, JP-A No. 11-285637, and JP-A No. 10-
It is disclosed in Japanese Patent No. 230164, Japanese Patent Laid-Open No. 2001-70788, and the like.

That is, a catalyst containing niobium and antimony is effective in producing a corresponding unsaturated carboxylic acid or unsaturated nitrile by subjecting propane or isobutane to vapor-phase catalytic oxidation or vapor-phase catalytic ammoxidation.
Much research has been done from the past.

[0006]

When the catalyst obtained by the oxide preparation method disclosed in the above publications is used for the gas phase catalytic oxidation of propane or isobutane or the gas phase catalytic ammoxidation reaction, the desired product is still obtained. The selection rate of was insufficient. In particular, the supported catalyst suitable for the fluidized bed reaction tends to have a low selectivity of the target substance. The reason for the insufficient reaction performance is that it is difficult to handle the niobium compound and the antimony compound in the raw material mixing step.

The methods disclosed in JP-A-11-253801 and JP-A-2000-37623 use a niobium-containing solution containing oxalic acid and a niobium compound and having an oxalic acid / niobium molar ratio adjusted to 2 to 4. However, no special measures have been taken for the antimony raw material liquid, and in other publications, the method for preparing the antimony raw material liquid is described. There is no particular disclosure.

From the above points, it has been earnestly desired to establish a method for producing a niobium-antimony-containing oxide catalyst for vapor-phase catalytic oxidation or vapor-phase catalytic ammoxidation, which has a high selectivity of a target substance.

The first object of the present invention is to prepare an unsaturated acid or an unsaturated nitrile which has a high selectivity of the desired product,
It is to provide a novel method for preparing an oxide catalyst, which is a novel raw material preparation method for dissolving antimony using niobium.

A second object of the present invention is to subject propane or isobutane to a gas phase catalytic oxidation or a gas phase catalytic ammoxidation reaction using the oxide catalyst obtained by the above-mentioned production method to obtain a corresponding unsaturated acid or unsaturated acid. It is to provide a method for producing a saturated nitrile.

[0011]

Means for Solving the Problems The inventors of the present invention have earnestly studied a method for producing a catalyst used in a gas phase catalytic oxidation or a gas phase catalytic ammoxidation reaction of propane or isobutane. Compound, Sb
The present invention has been found to solve the above problems by using a catalyst prepared by using a mixed liquid obtained from a compound, a dicarboxylic acid compound and hydrogen peroxide as at least a part of a raw material liquid of Nb and Sb, and the present invention Came to make.

That is, the present invention comprises the following aspects. [1] A method for producing an oxide catalyst for use in a vapor-phase catalytic oxidation reaction or a vapor-phase catalytic ammoxidation reaction of propane or isobutane, which comprises a raw material having a component composition represented by the following general composition formula (1): The method for producing an oxide catalyst, wherein a mixed liquid obtained from an Nb compound, an Sb compound, a dicarboxylic acid compound and hydrogen peroxide is used as at least a part of a raw material liquid of Nb and Sb in the step of preparing. Mo ₁ V _a Nb _b Sb _c O _n (1) (In the formula (1), a, b, c and n represent atomic ratios per molybdenum atom, and a is 0.01 ≦ a ≦ 1 and b is 0.0
1 ≦ b ≦ 1, c is 0.01 ≦ c ≦ 1, and the ratio of a to c is 0.
01 ≦ a / c <1 and n is a number determined by the valence and atomic ratio of the constituent metals. )

[2] Oxidation according to the above [1], wherein the molar ratio of Nb, Sb, dicarboxylic acid and hydrogen peroxide used in the mixed solution is represented by the following general composition formula (2). Method for producing catalyst. Nb _d Sb _e X _f (H ₂ O ₂ ) _g (2) (In the formula (2), X represents a dicarboxylic acid. _D , e, f,
g represents a molar ratio per mol of molybdenum, and d is 0 <
d ≦ b, e is 0 <e <c, and the ratio of d and e is 0 <e / d ≦
5, the ratio of d to f is 1 ≦ f / d ≦ 10, and the ratio of d to g is 0.
It is a number determined by 5 ≦ g / d ≦ 20. )

[3] The method for producing an oxide catalyst according to the above [1] or [2], wherein the Sb compound is an Sb oxide.

[4] The method for producing an oxide catalyst according to any one of the above [1] to [3], wherein the dicarboxylic acid is oxalic acid.

[5] The oxide catalyst comprises a catalyst constituent element oxide represented by the general composition formula (1) and silica supporting the oxide, and the content ratio of the silica is Based on the total weight of the catalyst constituent element oxide and silica,
The above [1], which is ₂₀ to 60 wt% in terms of SiO2,
The method for producing an oxide catalyst according to [4].

[6] Oxide produced by the method for producing an oxide catalyst according to any one of the above [1] to [5], which is used for a gas phase catalytic oxidation reaction or a gas phase catalytic ammoxidation reaction of propane or isobutane. catalyst.

[7] In the method for producing a corresponding unsaturated acid or unsaturated nitrile by subjecting propane or isobutane to a gas phase catalytic oxidation reaction or a gas phase catalytic ammoxidation reaction, the oxide catalyst according to the above [6] A method for producing an unsaturated acid or an unsaturated nitrile using.

The present invention will be described in detail below. The catalyst obtained by the production method of the present invention has the following general composition formula (1):
Is an oxide catalyst represented by. _{Mo 1 V a Nb b Sb c} O n (1) (a, b, c, n represents the atomic ratio per molybdenum 1 atom, a is 0.01 ≦ a ≦ 1, b is 0.01 ≦ b ≦ 1,
c is 0.01 ≦ c ≦ 1, the ratio of a and c is 0.01 ≦ a / c
<1 and n are numbers determined by the valence and atomic ratio of the constituent metals. ) Also, the atomic ratio a, b, c per atom of molybdenum is
0.1 to 0.4, 0.01 to 0.2, 0.1 respectively
~ 0.5 is preferred.

Nb compound and S used in the production method of the present invention
The mixed solution obtained by using the compound b, the dicarboxylic acid compound and hydrogen peroxide is preferably represented by the following general composition formula (2). Nb _d Sb _e X _f (H ₂ O ₂ ) _g (2) (In the formula (2), X represents a dicarboxylic acid. _D , e, f,
g represents a molar ratio per mol of molybdenum, and d is 0 <
d ≦ b, e is 0 <e <c, and the ratio of d and e is 0 <e / d ≦
5, the ratio of d to f is 1 ≦ f / d ≦ 10, and the ratio of d to g is 0.
It is a number determined by 5 ≦ g / d ≦ 20. ) Also, the molar ratio d, e / d, f per mol of molybdenum
/ D and g / d are 0.005-1 and 0.01, respectively.
~ 2, 1-4, 1-10 are preferred.

The oxide catalyst obtained by the production method of the present invention is preferably a silica-supported catalyst. When the oxide catalyst is a silica-supported catalyst, it has high mechanical strength and is suitable for a gas phase catalytic oxidation reaction or a gas phase catalytic ammoxidation reaction using a fluidized bed reactor. The content of the silica carrier is _{2 in} terms of SiO _{2 with} respect to the total weight of the silica-supported oxide catalyst including the oxide of the catalyst constituent elements and the silica carrier.
It is preferably 0 to 60 wt%, and more preferably 25 to 55 wt%.

The method for producing an oxide catalyst of the present invention can be prepared by a general method, for example, (I) a step of preparing raw materials, (II) a raw material preparation liquid obtained in step (I). To obtain a catalyst precursor, (III) step (II)
It can be manufactured through the three steps of calcining the catalyst precursor obtained in (1).

"Preparation" in the present specification means to dissolve or disperse the raw materials of the catalyst constituent elements in an aqueous solvent. The "raw material" in this specification is used in the step (I). The metal raw material used in the preparation method of the present invention is not particularly limited, but the following compounds can be used, for example.

The raw materials for Mo and V are ammonium heptamolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ , respectively.
・ 4H ₂ O] and ammonium metavanadate [NH ₄ VO
₃ ] can be preferably used.

As the raw material of Nb, niobic acid, an inorganic acid salt of niobium and an organic acid salt of niobium can be used, and niobic acid is particularly preferable. Niobate is Nb ₂ O ₅ · n
It is represented by H ₂ O and is also called niobium hydroxide or niobium oxide hydrate. Furthermore, it is preferable to use as a Nb raw material liquid having a dicarboxylic acid / niobium molar ratio of 1 to 4. Oxalic acid is preferably used as the dicarboxylic acid.

As the raw material of Sb, it is preferable to use Sb oxide, and especially diantimony trioxide [Sb ₂ O ₃ ]
Is preferred. It is preferable to use silica sol as a raw material of silica.

The preferred catalyst preparation example of the present invention comprising the steps (I) to (III) will be described below. <Step (I): Step of Mixing Raw Materials> Using the raw materials described above, a raw material preparation liquid is obtained. An example is shown below. Ammonium heptamolybdate and diantimony trioxide are added to water, and heated and stirred at 80 ° C. or higher to obtain a mixed solution. Next, hydrogen peroxide is added little by little to the mixed solution with stirring, and after adding a predetermined amount of hydrogen peroxide, a transparent solution is obtained within about 30 minutes. At this time, H ₂ O ₂ / Sb (molar ratio) is 0 to
20, especially 1-10 is preferable. Further, ammonium metavanadate was added to the obtained solution to give Mo-VS
A b-containing mixed solution (A) is obtained.

Niobic acid and oxalic acid are heated and stirred in water to prepare a mixed solution (B ₀ ). As the mixed liquid (B ₀ ), a niobium-containing liquid obtained by the method taught in JP-A No. 11-253801 can be used. Further, hydrogen peroxide and diantimony trioxide are added to at least a part of the mixed solution (B ₀ ) to prepare a mixed solution (B). This time,
H ₂ O ₂ / Nb (molar ratio) is 0.5 to 20, particularly 1 to 1.
0 is preferable, Sb / Nb (molar ratio) is 0 to 5, and 0.01 to 2 is particularly preferable. Oxalic acid may be added to the mixed solution (B).

The liquid mixture (A), the liquid mixture (B) and the liquid mixture (B ₀ ) are suitably mixed according to the desired composition to obtain a raw material preparation liquid. When the ammoxidation catalyst of the present invention is a silica-supported catalyst, the raw material preparation liquid is prepared so as to contain silica sol. Silica sol can be added in an appropriate amount.

<Step (II) Drying Step> The raw material preparation liquid obtained in step (I) is dried by a spray drying method to obtain a dry powder. As the spraying means in the spray drying method, a centrifugal system, a two-fluid nozzle system or a high pressure nozzle system can be adopted. As the dry heat source, air heated by steam, an electric heater or the like can be used. The hot air dryer inlet temperature is preferably 150 to 300 ° C.

<Step III: Calcination Step> The dry powder obtained in the drying step is calcined to obtain an oxide catalyst.
Firing is carried out under an atmosphere of an inert gas substantially free of oxygen such as nitrogen gas, argon gas, helium gas, preferably while flowing an inert gas at 500 to 800 ° C.
It is preferably carried out at 600 to 700 ° C. The firing time is 0.5 to 20 hours, preferably 1 to 8 hours. The firing can be performed using a rotary furnace, a tunnel furnace, a tubular furnace, a fluidized firing furnace, or the like, and the firing can be repeated.
It is also preferable that the dry powder is pre-baked at 200 to 400 ° C. for 1 to 5 hours in an air atmosphere or in the air flow before the baking step.

Propane or isobutane is subjected to a gas phase catalytic oxidation or a gas phase catalytic ammoxidation reaction in the presence of the oxide catalyst thus produced to produce a corresponding unsaturated acid or unsaturated nitrile. The propane, isobutane and ammonia feedstocks do not necessarily have to be of high purity and industrial grade gases can be used.

As the supply oxygen source, air, air enriched with oxygen, or pure oxygen can be used. Further, as the diluting gas, helium, argon, carbon dioxide gas, steam, nitrogen or the like may be supplied.

The preferred reaction conditions for the gas phase catalytic oxidation reaction and the gas phase ammoxidation reaction of propane or isobutane are shown below. (Conditions for Gas Phase Catalytic Oxidation Reaction of Propane or Isobutane) The molar ratio of oxygen supplied to the reactor to propane or isobutane is 0.1 to 6, preferably 0.5 to 4. The reaction temperature is 300 ° C to 500 ° C, preferably 35 ° C.
It is 0 ° C to 450 ° C. Reaction pressure is 5 × 10 ^{4 to} 5 × 1
It is 0 ⁵ Pa, preferably 1 × 10 ^{5 to} 3 × 10 ⁵ Pa. The contact time is 0.1 to 10 (sec · g / cc), preferably 0.5 to 5 (sec · g / cc). In the present invention, the contact time is determined by the following equation. Contact time (sec · g / cc) = (W / F) × 273 /
(273 + T) Here, W = filled catalyst amount (g) F = raw material mixed gas flow rate (Ncc / sec) in standard state (0 ° C., 1.013 × 10 ⁵ Pa) T = reaction temperature (° C.)

(Conditions for Propane or Isobutane Gas-Phase Catalytic Ammoxidation Reaction) The molar ratio of oxygen supplied to the reactor to propane or isobutane is 0.1 to 6, preferably 0.5 to 4. The molar ratio of ammonia supplied to the reactor to propane or isobutane is 0.3 to
It is 1.5, preferably 0.8 to 1.0. The reaction temperature is 350 ° C to 500 ° C, preferably 380 ° C to 470 ° C. The reaction pressure is 5 × 10 ^{4 to} 5 × 10 ⁵ Pa, preferably 1 × 10 ^{5 to} 3 × 10 ⁵ Pa. Contact time is 0.1
-10 (sec · g / cc), preferably 0.5-5
(Sec · g / cc).

As a reaction system, a conventional system such as a fixed bed, a fluidized bed or a moving bed can be adopted, but a fluidized bed reactor which can easily remove reaction heat is preferable. Further, the reaction of the present invention may be a single flow type or a recycle type.

[0037]

BEST MODE FOR CARRYING OUT THE INVENTION The oxide catalyst obtained by the production method of the present invention will be described below with reference to a catalyst preparation example and an acrylonitrile production example by a gas phase catalytic ammoxidation reaction of propane. The present invention is not limited to these examples as long as the gist thereof is not exceeded.

The results of the ammoxidation reaction of propane were evaluated based on the results of analysis of the reaction gas, using the propane conversion rate and acrylonitrile selectivity defined by the following formulas as indexes. Propane conversion rate (%) = {(number of moles of propane reacted)
/ (Mol number of propane supplied)} × 100 acrylonitrile selectivity (%) = {(mol number of acrylonitrile produced) / (mol number of reacted propane)} × 100

(Preparation of Niobium Mixture) JP-A-11-25
A niobium mixed solution was prepared according to the method described in Japanese Patent No. 3801 by the following method. 8 as Nb ₂ O _{5 in} 8562 g of water
1188 g of niobic acid containing 0.2 wt% was mixed with 4492 g of oxalic acid dihydrate [H ₂ C ₂ O ₄ .2H ₂ O]. The charged oxalic acid / niobium molar ratio was 5.05, and the charged niobium concentration was 0.503 (mol-Nb / Kg-
Liquid). The solution was heated and stirred at 95 ° C. for 1 hour to obtain an aqueous solution in which niobium was dissolved. The aqueous solution was allowed to stand and cooled with ice, and then the solid was filtered off by suction filtration to obtain a uniform niobium mixed solution. Oxalic acid of this niobium mixture /
The molar ratio of niobium was 2.36 according to the following analysis.

10 g of this niobium mixed solution was precisely weighed in a crucible, dried overnight at 95 ° C., and then heat-treated at 600 ° C. for 1 hour,
0.8546 g of Nb ₂ O ₅ was obtained. From this result, the niobium concentration was 0.643 (mol-Nb / Kg-solution).

3 g of this niobium mixed solution was precisely weighed in a 300 ml glass beaker, 200 ml of hot water at about 80 ° C. was added, and subsequently 10 ml of 1: 1 sulfuric acid was added. The obtained solution was titrated with 1 / 4N KMnO ₄ under stirring while maintaining the liquid temperature at 70 ° C. on a hot stirrer. KMnO ₄
The end point was a faint light pink color for about 30 seconds or longer. The oxalic acid concentration was 1.517 (mol-oxalic acid / Kg) as a result of calculation from the titration amount according to the following formula. 2KMnO ₄ + 3H ₂ SO ₄ + 5H ₂ C ₂ O ₄ → K ₂ SO ₄ +2
MnSO ₄ + 10CO ₂ + 8H ₂ O The obtained niobium mixed solution was used as a niobium mixed solution (B ₀ ) for catalyst preparation described below.

[0042]

Example 1 (Preparation of catalyst) The composition formula was Mo ₁ V
Was prepared oxide catalyst represented by the _{0.21 Nb 0.11 Sb 0.28 O n /45.0wt%-SiO} 2 as follows. Water 33
40 g of ammonium heptamolybdate [(NH ₄ ) ₆
Mo ₇ O ₂₄ · 4H ₂ O] was 666.7G, added 110.1g diantimony trioxide [Sb ₂ O _3], with stirring 9
It heated at 0 degreeC and set it as the liquid mixture. H ₂ was added to the obtained mixed liquid.
Hydrogen peroxide solution containing 30 wt% as O ₂ 171.
2 g was added little by little with stirring and after about 30 minutes a clear solution was obtained. Further, 92.8 g of ammonium metavanadate [NH ₄ VO ₃ ] was added to the solution to prepare a mixed solution A.
-1 was obtained.

A mixed solution B-1 represented by the composition formula of Nb _0.11 Sb _0.08 X _0.26 (H ₂ O ₂ ) _0.38 (wherein X represents a dicarboxylic acid) was produced as follows. To 646.0 g of the niobium mixed solution (B ₀ ), 162.7 g of hydrogen peroxide containing 30 wt% as H ₂ O ₂ was added, and 44.0 g of diantimony trioxide [Sb ₂ O ₃ ] was added little by little. In addition, the mixture was stirred and mixed at room temperature for 10 minutes to dissolve diantimony trioxide, thereby preparing a mixed solution B-1 .

After cooling the obtained mixed liquid A-1 to 70 ° C., 2206 g of silica sol containing 30.6 wt% as SiO ₂ was added, and then mixed liquid B-1 was added to prepare a raw material preparation liquid. Obtained. The obtained raw material preparation liquid was supplied to a centrifugal spray dryer and dried to obtain a fine spherical dry powder.
Dryer inlet temperature is 210 ° C and outlet temperature is 120
It was ℃.

480 g of the obtained dry powder was filled in a SUS calcining tube having a diameter of 3 inches, and calcined at 640 ° C. for 2 hours while rotating the tube under a nitrogen gas flow of 5.0 NL / min to obtain a catalyst. Obtained.

(Propane ammoxidation reaction) Inner diameter 25 m
m of Vycor glass fluidized bed type reaction tube was filled with 45 g of the above catalyst, and the reaction temperature was 440 ° C. and the reaction pressure was normal pressure. Propane: ammonia: oxygen: helium =
A mixed gas having a molar ratio of 1: 0.6: 1.5: 5.6 was supplied at a contact time of 3.0 (sec · g / cc). The results obtained are shown in Table 1.

[0047]

[Comparative Example 1] (Preparation of catalyst) The composition formula was Mo ₁ V.
Was prepared oxide catalyst represented by the _{0.21 Nb 0.11 Sb 0.28 O n /45.0wt%-SiO} 2 as follows. Water 33
40 g of ammonium heptamolybdate [(NH ₄ ) ₆
Mo ₇ O ₂₄ · 4H ₂ O] was 666.7G, added 154.1g diantimony trioxide [Sb ₂ O _3], with stirring 9
It heated at 0 degreeC and set it as the liquid mixture. H ₂ was added to the obtained mixed liquid.
Hydrogen peroxide water containing 30 wt% as O ₂ 239.
7 g was added little by little with stirring and after about 30 minutes a clear solution was obtained. Further, 92.8 g of ammonium metavanadate [NH ₄ VO ₃ ] was added to the solution to prepare a mixed solution A.
-2 was obtained.

To 646.0 g of the niobium mixed solution (B ₀ ) was added H ₂
Hydrogen peroxide solution containing 30 wt% as O ₂ was added to 94.
Add 2 g, stir and mix at room temperature for 10 minutes, and mix solution B-
2 was prepared. After cooling the obtained mixed liquid A-2 to 70 ° C., 2206 g of silica sol containing 30.6 wt% as SiO ₂ was added, and then the mixed liquid B-2 was added to obtain a raw material preparation liquid. A catalyst was obtained in the same manner as in Example 1 except that the raw material preparation liquid was prepared.

(Propane ammoxidation reaction) Using the obtained catalyst, a propane ammoxidation reaction was carried out under the same conditions as in Example 1. The results are shown in Table 1.

[0050]

[Comparative Example 2] (Preparation of catalyst) The composition formula was Mo ₁ V.
Was prepared oxide catalyst represented by the _{0.21 Nb 0.11 Sb 0.28 O n /45.0wt%-SiO} 2 as follows. Instead of the mixed solution B-1 in Example 1, a niobium mixed solution (B
₀ ) To 646.0 g, diantimony trioxide [S
b ₂ O ₃ ] was added and the mixture was stirred and mixed at room temperature for 2 hours, and a mixed solution prepared was used to obtain a catalyst in the same manner as in Example 1.

(Propane ammoxidation reaction) Using the obtained catalyst, a propane ammoxidation reaction was carried out under the same conditions as in Example 1. The results are shown in Table 1.

[0052]

[Comparative Example 3] (Preparation of catalyst) The composition formula was Mo ₁ V.
Was prepared oxide catalyst represented by the _{0.21 Nb 0.11 Sb 0.28 O n /45.0wt%-SiO} 2 as follows. Instead of the mixed solution B-1 in Example 1, 1 as Nb ₂ O ₅ was used.
To 552.1 g of niobium pentoxide sol containing 0 wt%,
16% hydrogen peroxide solution containing 30 wt% as H ₂ O ₂
2.7 g was added, 44.0 g of diantimony trioxide [Sb ₂ O ₃ ] was added little by little, and the same procedure as in Example 1 was repeated except that a mixed solution prepared by stirring and mixing at room temperature for 2 hours was used to carry out the catalyst. Obtained.

(Propane ammoxidation reaction) Using the obtained catalyst, a propane ammoxidation reaction was carried out under the same conditions as in Example 1. The results are shown in Table 1.

[0054]

[Example 2] (Preparation of catalyst) The composition formula was Mo ₁ V.
Was prepared oxide catalyst represented by the _{0.21 Nb 0.11 Sb 0.28 O n /45.0wt%-SiO} 2 as follows. Water 33
40 g of ammonium heptamolybdate [(NH ₄ ) ₆
The Mo ₇ O ₂₄ · 4H ₂ O] 666.7G, ammonium metavanadate [NH ₄ VO _3] 92.8 g, was added 110.1g of diantimony trioxide [Sb ₂ O _3], with stirring 90 ° C. The mixture was heated for 2 hours and 30 minutes to obtain a mixed solution A-5 .

After cooling the obtained mixed liquid A-5 to 70 ° C., 2206 g of silica sol containing 30.6 wt% as SiO ₂ was added. Furthermore, 30 wt% as H ₂ O ₂
% Hydrogen peroxide containing 171.2 g was added,
Stirring was continued for 1 hour at ° C. A catalyst was obtained in the same manner as in Example 1 except that the above mixed solution A-5 containing silica sol was used in place of the mixed solution A-1 containing silica sol in Example 1.

(Propane ammoxidation reaction) Using the obtained catalyst, a propane ammoxidation reaction was carried out under the same conditions as in Example 1. The results are shown in Table 1.

[0057]

[Comparative Example 4] (Preparation of catalyst) The composition formula was Mo ₁ V.
Was prepared oxide catalyst represented by the _{0.21 Nb 0.11 Sb 0.28 O n /45.0wt%-SiO} 2 as follows. Water 33
40 g of ammonium heptamolybdate [(NH ₄ ) ₆
The Mo ₇ O ₂₄ · 4H ₂ O] 666.7G, ammonium metavanadate [NH ₄ VO _3] 92.8 g, was added 154.1g of diantimony trioxide [Sb ₂ O _3], with stirring 90 ° C. The mixture was heated for 2 hours and 30 minutes to obtain a mixed solution A-6 .

To 646.0 g of the niobium mixed solution (B ₀ ) was added H ₂
Hydrogen peroxide solution containing 30 wt% as O ₂ was added to 94.
Add 2 g, stir and mix at room temperature for 10 minutes, and mix solution B-
6 was prepared. After cooling the obtained mixed liquid A-6 to 70 ° C., 2206 g of silica sol containing 30.6 wt% as SiO ₂ was added. Furthermore, 30w as H ₂ O ₂
239.7 g of hydrogen peroxide solution containing t% was added, and 3
After continuing stirring at 0 ° C. for 1 hour, the mixed solution B-6 was added to obtain a raw material preparation liquid. Example 2 except for the preparation of the raw material preparation liquid
A catalyst was obtained in the same manner as above.

(Propane ammoxidation reaction) Using the obtained catalyst, a propane ammoxidation reaction was carried out under the same conditions as in Example 1. The results are shown in Table 1.

[0060]

[Table 1]

[0061]

The Sb raw material can be easily dissolved by the method for producing a catalyst of the present invention. Further, by using the catalyst obtained by the method for producing a catalyst of the present invention, unsaturated nitrile can be produced from propane or isobutane with high selectivity.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4G069 AA02 AA03 AA08 BA02A                       BA02B BB06A BB06B BC26A                       BC26B BC54A BC54B BC55A                       BC55B BC59A BC59B BD05A                       BD05B CB53 DA05 FB06                       FB09                 4H006 AA02 AA05 AC54 BA12 BA13                       BA14 BA30 BE14 BE30 QN24                 4H039 CA70 CL50

Claims (7)

[Claims] 1. A method for producing an oxide catalyst for use in a vapor-phase catalytic oxidation reaction or a vapor-phase catalytic ammoxidation reaction of propane or isobutane, which has a component composition represented by the following general composition formula (1). In the step of preparing the raw materials in the above step, a mixed solution obtained from an Nb compound, an Sb compound, a dicarboxylic acid compound and hydrogen peroxide is used as at least a part of the raw material solutions of Nb and Sb to produce an oxide catalyst. Method. Mo ₁ V _a Nb _b Sb _c O _n (1) (In the formula (1), a, b, c and n represent atomic ratios per molybdenum atom, and a is 0.01 ≦ a ≦ 1 and b is 0.0
1 ≦ b ≦ 1, c is 0.01 ≦ c ≦ 1, and the ratio of a to c is 0.
01 ≦ a / c <1 and n is a number determined by the valence and atomic ratio of the constituent metals. ) 2. The molar ratio of Nb, Sb, dicarboxylic acid and hydrogen peroxide used in the mixed solution is represented by the following general composition formula (2).
The method for producing an oxide catalyst according to claim 1, characterized by: Nb _d Sb _e X _f (H ₂ O ₂ ) _g (2) (In the formula (2), X represents a dicarboxylic acid. _D , e, f,
g represents a molar ratio per mol of molybdenum, and d is 0 <
d ≦ b, e is 0 <e <c, and the ratio of d and e is 0 <e / d ≦
5, the ratio of d to f is 1 ≦ f / d ≦ 10, and the ratio of d to g is 0.
It is a number determined by 5 ≦ g / d ≦ 20. ) 3. The method for producing an oxide catalyst according to claim 1, wherein the Sb compound is an Sb oxide. 4. The method for producing an oxide catalyst according to claim 1, wherein the dicarboxylic acid is oxalic acid. 5. The oxide catalyst comprises a catalyst constituent element oxide represented by the general composition formula (1) and silica carrying the oxide, and the content ratio of the silica is the catalyst. Based on the total weight of the constituent element oxide and silica,
It is ₂₀ to 60 wt% in terms of SiO2, The manufacturing method of the oxide catalyst of any one of Claims 1-4 characterized by the above-mentioned. 6. Use in a gas phase catalytic oxidation reaction or a gas phase catalytic ammoxidation reaction of propane or isobutane, which is produced by the method for producing an oxide catalyst according to any one of claims 1 to 5. Oxide catalyst. 7. A method for producing a corresponding unsaturated acid or unsaturated nitrile by subjecting propane or isobutane to a gas phase catalytic oxidation reaction or a gas phase catalytic ammoxidation reaction, wherein the oxide catalyst according to claim 6 is used. A method for producing an unsaturated acid or an unsaturated nitrile, which comprises: