JP4647858B2 - Oxidation or ammoxidation oxide catalyst and method for producing the same - Google Patents

Description

【００５３】
【発明の効果】
本発明の酸化物触媒を用いることによって、高い選択率で不飽和カルボン酸又は不飽和ニトリルを製造することが出来る。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an oxide catalyst used for gas phase catalytic oxidation or gas phase catalytic ammoxidation reaction of propane or isobutane, and a method for producing an unsaturated acid or an unsaturated nitrile using the oxide catalyst.
[0002]
[Prior art]
Conventionally, a process for producing a corresponding unsaturated carboxylic acid or unsaturated nitrile by subjecting propylene or isobutylene to a gas phase catalytic oxidation reaction or a gas phase catalytic ammoxidation is well known. On the other hand, in recent years, attention has been focused on a method for producing a corresponding unsaturated carboxylic acid or unsaturated nitrile by subjecting propane or isobutane to gas phase catalytic oxidation or gas phase catalytic ammoxidation instead of propylene or isobutylene. Catalyst production methods and reaction methods have been proposed.
[0003]
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, JP-A-10-28862, and JP-A-11-42434. JP-A-11-43314, JP-A-11-226408, JP-A-10-57479, JP-A-2000-70714, JP-A-2000-143244, JP-A-2001-58827, etc. It is disclosed.
[0004]
Moreover, the manufacturing method of the acrylic acid catalyst containing Mo-V-Sb is disclosed in JP 2000-354765, JP 2000-317309, JP 2000-254496, JP 2000-256257, It is disclosed in Japanese Unexamined Patent Publication No. 2000-246108, Japanese Unexamined Patent Publication No. 2000-51693, Japanese Unexamined Patent Publication No. 11-285636, Japanese Unexamined Patent Publication No. 11-285637, Japanese Unexamined Patent Publication No. 10-230164, Japanese Unexamined Patent Publication No. 2001-70788, and the like. ing.
[0005]
[Problems to be solved by the invention]
However, when the catalyst obtained by the oxide preparation method disclosed in the above publication is used in the gas phase catalytic oxidation or gas phase catalytic ammoxidation reaction of propane or isobutane, the selectivity of the target product is still insufficient. It was. In particular, the supported catalyst suitable for the fluidized bed reaction tends to decrease the selectivity of the target product.
[0006]
In producing the oxide catalyst, JP-A 2000-70714, JP-A 2000-354765, JP-A 2000-317309, JP-A 2000-254496, JP-A 2000-256257, In JP 2000-246108 A, JP 2000-51693 A, JP 11-285636 A, JP 11-285637 A, JP 10-230164 A, and JP 2001-70788 A, molybdenum is used. In addition, it is described that a mixed solution containing vanadium and antimony is oxidized with hydrogen peroxide.
[0007]
Japanese Patent Application Laid-Open No. 11-226408 describes a method of making a mixed solution containing a molybdenum compound and metal antimony with hydrogen peroxide. Generally, however, metal antimony is expensive and has a large industrial volume. Not suitable for manufacturing. Other publications do not mention in detail the method for producing a catalyst for preparing an Sb-containing solution using an oxidizing agent and the method for making the solution, and no specific examples are described.
[0008]
In view of the above, it has been desired to establish a method for producing an oxide catalyst for gas phase catalytic oxidation or gas phase catalytic ammoxidation having a high selectivity of the target product.
The first object of the present invention is to provide a novel oxide catalyst used in the production of an unsaturated acid or an unsaturated nitrile having a high selectivity of the target product and a method for producing the same.
A second object of the present invention is to produce a corresponding unsaturated acid or unsaturated nitrile by subjecting propane or isobutane to gas phase catalytic oxidation or gas phase catalytic ammoxidation using the oxide catalyst obtained by the above production method. Is to provide a way to do.
[0009]
[Means for Solving the Problems]
As a result of intensive studies on oxide catalysts used for gas phase catalytic oxidation reaction or gas phase catalytic ammoxidation reaction of propane or isobutane, the present inventors have found that the catalyst component satisfies a molar ratio of vanadium to antimony satisfying V / Sb <1. In the raw material preparation step, the above problem is solved by using a catalyst obtained by making a raw material mixed solution containing a molybdenum compound and / or a vanadium compound and diantimony trioxide into a solution using hydrogen peroxide in the raw material preparation step. And the present invention has been made.
[0010]
That is, the aspects of the present invention are the following [1] to [9].
[1] An oxide catalyst having a component composition represented by the following general composition formula (1) for use in a gas phase catalytic oxidation reaction or gas phase catalytic ammoxidation reaction of propane or isobutane, wherein the raw material is mixed An oxide catalyst obtained by a production method comprising a step of dissolving a raw material mixture comprising a molybdenum compound and / or a vanadium compound, diantimony trioxide and an aqueous solvent using hydrogen peroxide;
_{Mo 1 V a Nb b Sb c} O n (1)
(A, b, c and n represent the atomic ratio per molybdenum atom, a is 0.01 ≦ a ≦ 1, b is 0.01 ≦ b ≦ 1, c is 0.01 ≦ c ≦ 1, a And the ratio of c is 0.01 ≦ a / c <1, and n is a number determined by the valence and composition ratio of the constituent metals.)
[0011]
[2] The oxide catalyst according to [1], wherein the molar ratio of hydrogen peroxide to antimony used in the raw material mixture is 0 <H ₂ O ₂ / Sb ≦ 20.
[0012]
[3] The molar ratio of hydrogen peroxide to antimony used in the raw material mixture is 2 <H ₂ O ₂ / Sb ≦ 10, according to any one of the above [1] or [2] Oxide catalyst.
[0013]
[4] The method according to any one of [1] to [3], wherein the step of forming a solution is a step of adding hydrogen peroxide to the raw material mixture having a liquid temperature of 70 ° C. or higher. Oxide catalyst.
[0014]
[5] The oxide catalyst according to any one of [1] to [4], wherein the molybdenum compound is ammonium heptamolybdate and the vanadium compound is ammonium metavanadate.
[0015]
[6] The niobium raw material constituting the oxide catalyst is a niobium-containing liquid containing a dicarboxylic acid / niobium compound and having a dicarboxylic acid / niobium molar ratio of 1 to 4. The oxide catalyst according to any one of [1] to [5].
[0016]
[7] The above oxide catalyst, wherein the oxide catalyst is a silica-supported catalyst supported on silica in an amount of 20 to 60% by weight in terms of SiO ₂ with respect to the total weight of the oxide of the catalyst constituent elements and silica. The oxide catalyst according to any one of [1] to [6].
[0017]
[8] In 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, according to any one of the above [1] to [7] A method for producing an unsaturated acid or an unsaturated nitrile, comprising using an oxide catalyst.
[9] The method for producing an oxide catalyst according to any one of [1] to [7] above, wherein a molybdenum compound and / or a vanadium compound, antimony trioxide and an aqueous solvent are prepared during the step of preparing the raw material. A method for producing an oxide catalyst, characterized in that a raw material mixture comprising the above is made into a solution using hydrogen peroxide.
[0018]
Hereinafter, the present invention will be described in detail.
The catalyst of the present invention is an oxide catalyst represented by the following general composition formula (1).
_{Mo 1 V a Nb b Sb c} O n (1)
(A, b, c and n represent the atomic ratio per molybdenum atom, a is 0.01 ≦ a ≦ 1, b is 0.01 ≦ b ≦ 1, c is 0.01 ≦ c ≦ 1, a And the ratio of c is 0.01 ≦ a / c <1, and n is a number determined by the valence and atomic ratio of the constituent metals.)
The atomic ratios a to c per one atom of molybdenum are preferably 0.1 to 0.4, 0.01 to 0.2, and 0.1 to 0.5, respectively.
[0019]
The oxide catalyst for oxidation or ammoxidation of the present invention is preferably a silica-supported catalyst. When the oxide catalyst is a silica-supported catalyst, it has a high mechanical strength, and therefore 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 support is preferably 20 to 60% by weight in terms of SiO ₂ , and more preferably 25 to 25% by weight based on the total weight of the silica-supported oxide catalyst comprising the oxide of the catalyst constituent element and the silica support. 55% by weight.
[0020]
The oxide catalyst for oxidation or ammoxidation of the present invention can be prepared by a general production method. For example, (I) a step of preparing a raw material, (II) a raw material preparation obtained in step (I) The liquid can be dried to produce a catalyst precursor, and (III) the catalyst precursor obtained in step (II) can be baked through three steps.
[0021]
“Preparation” in the present specification is to dissolve or disperse a raw material of a catalyst constituent element in an aqueous solvent. In addition, the “raw material” in this specification is used in step (I). Although the raw material used when preparing the catalyst of this invention is not specifically limited, For example, the following compound can be used.
[0022]
As a raw material of molybdenum, ammonium heptamolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O] can be suitably used.
As the vanadium raw material, ammonium metavanadate [NH ₄ VO ₃ ] can be preferably used.
[0023]
As the niobium raw material, niobic acid, an inorganic acid salt of niobium, and an organic acid salt of niobium can be used, and niobic acid is particularly preferable. Niobic acid is represented by Nb ₂ O ₅ .nH ₂ O and is also referred to as niobium hydroxide or niobium oxide hydrate. Further, it is preferably used as a niobium raw material liquid having a dicarboxylic acid / niobium molar ratio of 1 to 4. Oxalic acid is preferably used as the dicarboxylic acid. Silica sol is preferably used as the silica raw material.
[0024]
Below, the preferable preparation example of the catalyst of this invention which consists of said process (I)-(III) is demonstrated.
[0025]
<Step I: Step of preparing raw materials>
A raw material preparation liquid is obtained using the raw materials described above. An example is shown below.
Ammonium heptamolybdate and antimony 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 this mixed solution with stirring, and a transparent solution is obtained within about 30 minutes after adding a predetermined amount of hydrogen peroxide. At this time, the H ₂ O ₂ / Sb (molar ratio) is preferably 0 to 20, and particularly preferably 2 to 10. Furthermore, ammonium metavanadate is added to the obtained solution to obtain a Mo—V—Sb-containing mixed solution (A).
[0026]
On the other hand, 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-11-253801 can be used. In some cases, further, the mixture (B _0), adding hydrogen peroxide to prepare a mixed solution (B). At this time, H ₂ O ₂ / Nb (molar ratio) of 0.5 to 10 are preferred, 1-5 being preferred.
[0027]
According to the target composition, the mixed solution (A), the mixed solution (B), and the mixed solution (B ₀ ) are suitably mixed to obtain a raw material preparation solution. When the oxide 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 as appropriate.
[0028]
When preparing the mixed solution (A), ammonium metavanadate and antimony trioxide can also be used as starting materials. In that case, ammonium heptamolybdate is added after the reaction with hydrogen peroxide to obtain a mixed solution (A). Moreover, it is also possible to use ammonium heptamolybdate, ammonium metavanadate, and antimony trioxide at the same time, and let the transparent solution after hydrogen peroxide addition be a liquid mixture (A).
[0029]
(Process II: Drying process)
The raw material preparation liquid obtained in the above step (I) is dried by a spray drying method to obtain a dry powder. As a spraying means in the spray drying method, a centrifugal method, a two-fluid nozzle method or a high pressure nozzle method can be adopted. As the drying heat source, air heated by steam, an electric heater or the like can be used. The dryer inlet temperature of hot air is preferably 150 to 300 ° C.
[0030]
(Process III: Firing process)
By calcining the dry powder obtained in the drying step of the above step (II), the oxide catalyst for oxidation or ammoxidation of the present invention is obtained. Firing is performed in an inert gas atmosphere substantially free of oxygen such as nitrogen gas, argon gas, helium gas, preferably at 500 to 800 ° C., preferably 600 to 700 ° C. while circulating the inert gas. . The firing time is 0.5 to 20 hours, preferably 1 to 8 hours. Firing can be performed using a rotary furnace, tunnel furnace, tubular furnace, fluidized firing furnace or the like, and firing can be performed repeatedly. Moreover, it is also preferable to pre-fire the dry powder at 200 to 400 ° C. for 1 to 5 hours in an air atmosphere or air circulation before the firing step.
[0031]
Propane or isobutane is subjected to gas phase catalytic oxidation or gas phase catalytic ammoxidation in the presence of the oxide catalyst thus prepared to produce the corresponding unsaturated acid or unsaturated nitrile. In the production of unsaturated acids or unsaturated nitriles, the propane or isobutane and ammonia feedstock need not necessarily be of high purity, and industrial grade gases can be used.
[0032]
Air, oxygen-enriched air, or pure oxygen can be used as the supply oxygen source. Further, helium, argon, carbon dioxide gas, water vapor, nitrogen or the like may be supplied as a dilution gas.
[0033]
In the following, preferred reaction conditions in the gas phase catalytic oxidation reaction and gas phase ammoxidation reaction of propane or isobutane are shown.
[0034]
(Conditions for gas phase catalytic oxidation of propane or isobutane)
The molar ratio of oxygen supplied to the reaction to propane or isobutane is 0.1 to 6, preferably 0.5 to 4.
The reaction temperature is 300 ° C to 500 ° C, preferably 350 ° C to 450 ° C.
The reaction pressure is 5 × 10 ^{4 to} 5 × 10 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)
Where 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.)
It is.
[0035]
(Conditions for vapor-phase catalytic ammoxidation reaction of propane or isobutane)
The molar ratio of oxygen supplied to the reaction to propane or isobutane is 0.1 to 6, preferably 0.5 to 4.
The molar ratio of ammonia to propane or isobutane supplied to the reaction is 0.3 to 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. The contact time is 0.1 to 10 (sec · g / cc), preferably 0.5 to 5 (sec · g / cc). As the reaction method, a conventional method such as a fixed bed, a fluidized bed, or a moving bed can be adopted, but a fluidized bed reactor in which reaction heat can be easily removed is preferable. The reaction of the present invention may be a single flow type or a recycle type.
[0036]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the oxide catalyst of the present invention will be described with reference to catalyst preparation examples and examples of acrylonitrile production by propane gas-phase catalytic ammoxidation reaction, but the present invention is not limited to these examples. .
[0037]
In the following Examples and Comparative Examples, the results of the propane ammoxidation reaction were evaluated based on the results of analyzing the reaction gas, using the propane conversion rate and the acrylonitrile selectivity defined by the following equations as indices.
Propane conversion rate (%)
= {(Mole number of reacted propane) / (Mole number of supplied propane)} × 100
Acrylonitrile selectivity (%)
= {(Mole number of acrylonitrile produced) / (Mole number of reacted propane) × 100
[0038]
(Preparation of niobium raw material liquid)
Following the method described in JP-A-11-253801, a niobium raw material liquid was prepared by the following method. To 4785 g of water, 662.6 g of niobic acid containing 80.2 wt% as Nb ₂ O ₅ and 2569 g of oxalic acid dihydrate [H ₂ C ₂ O ₄ .2H ₂ O] were mixed. The molar ratio of the charged oxalic acid / niobium is 5.2 and the charged niobium concentration is 0.502 (mol-Nb / Kg-solution). This mixed 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 ice-cooled, and then the solid was separated by suction filtration to obtain a uniform niobium-containing liquid. The molar ratio of oxalic acid / niobium in this niobium-containing liquid was 2.39 according to the following analysis.
[0039]
First, precisely weighed niobium-containing solution 10g in a crucible, dried overnight at 95 ° C., and heat-treated for 1 hour at 600 ° C., to obtain a Nb ₂ O ₅ 0.864g. From this result, the niobium concentration was 0.65 (mol-Nb / Kg-solution).
[0040]
Meanwhile, 3 g of this niobium-containing liquid was precisely weighed into a 300 ml glass beaker, 200 ml of hot water at about 80 ° C. was added, and then 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. The end point was a point where a faint pale pink color by KMnO ₄ lasted for about 30 seconds or more. The concentration of oxalic acid was 1.488 (mol-oxalic acid / Kg) as a result of calculation according to the following formula from titration.
2KMnO ₄ + 3H ₂ SO ₄ + 5H ₂ C ₂ O ₄ → K ₂ SO ₄ + 2MnSO ₄ + 10CO ₂ + 8H ₂ O
[0041]
The niobium-containing liquid obtained as described above was used as a niobium raw material liquid (mixed liquid B ₀ ) for catalyst preparation described below without adjusting the molar ratio of oxalic acid / niobium.
[0042]
[Example 1]
(Preparation of catalyst)
An oxide catalyst having a charging composition formula of Mo ₁ V _0.21 Nb _0.11 Sb _0.28 O _n /45.0 wt% -SiO ₂ was produced as follows.
To 4454 g of water, 889.0 g of ammonium heptamolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O] and 205.5 g of antimony trioxide [Sb ₂ O ₃ ] are added and heated to 90 ° C. with stirring. To obtain a mixed solution. To the obtained mixed solution, 319.7 g of hydrogen peroxide containing 30 wt% as H ₂ O ₂ was added little by little with stirring, and a transparent solution was obtained after about 30 minutes. Further, 123.7 g of ammonium metavanadate [NH ₄ VO ₃ ] was added to the solution to obtain a mixed solution A-1. After cooling the obtained mixed liquid A-1 to 70 ° C., silica sol 2941.2 containing 30.6 wt% as SiO ₂ was added, and then 852.1 g of the mixed liquid B ₀ (the above niobium raw material liquid) was added. The raw material preparation liquid was obtained by adding.
[0043]
The raw material mixture obtained as described above was supplied to a centrifugal spray dryer and dried to obtain a fine spherical dry powder. The dryer inlet temperature was 210 ° C and the outlet temperature was 120 ° C. Next, 480 g of the obtained dry powder was filled in a SUS firing tube having a diameter of 3 inches and fired at 640 ° C. for 2 hours while rotating the tube under a nitrogen gas flow of 5.0 NL / min. An oxide catalyst for ammoxidation was obtained.
[0044]
(Propane ammoxidation reaction)
45 g of the catalyst prepared as described above was charged into a 25 mm inner diameter Vycor glass fluidized bed reaction tube, and propane: ammonia: oxygen: helium = 1: 0. Under a reaction temperature of 440 ° C. and a normal pressure of the reaction. A mixed gas having a molar ratio of 6: 1.5: 5.6 was supplied at a contact time of 3.0 (sec · g / cc). The results of the reaction results obtained are shown in Table 1 below.
[0045]
[Comparative Example 1]
(Preparation of catalyst)
Was prepared oxide catalyst prepared composition formula represented by _{Mo 1 V 0.21 Nb 0.11 Sb 0.18} O n /45.0wt%-SiO 2 as follows. In this comparative example, a catalyst was produced in the same manner as in Example 1 except that the weight of diantimony trioxide added in Example 1 was 132.1 g and the weight of the hydrogen peroxide solution was 205.5 g.
(Propane ammoxidation)
Using the obtained catalyst, an ammoxidation reaction of propane was performed under the same conditions as in Example 1. The results of the reaction results obtained are shown in Table 1.
[0046]
[Comparative Example 2]
(Preparation of catalyst)
An oxide catalyst having a charging composition formula of Mo ₁ V _0.21 Nb _0.11 Sb _0.28 O _n /45.0 wt% -SiO ₂ was produced as follows. In this comparative example, a catalyst was produced in the same manner as in Example 1 except that no hydrogen peroxide solution was added.
(Propane ammoxidation)
Using the obtained catalyst, an ammoxidation reaction of propane was performed under the same conditions as in Example 1. The results of the reaction results obtained are shown in Table 1.
[0047]
[Example 2]
(Preparation of catalyst)
In this embodiment, were prepared oxide catalyst prepared composition formula represented by _{Mo 1 V 0.21 Nb 0.11 Sb 0.28} O n /45.0wt%-SiO 2 as follows. In Example 1, instead of the mixed solution B _0, the mixture B ₀ 852.1g, was added 125.6g of hydrogen peroxide water containing 30 wt% as H ₂ O _2, stirred and mixed for 10 minutes at room temperature A catalyst was produced in the same manner as in Example 1 except that the mixed solution B obtained in this way was used.
(Propane ammoxidation)
Using the obtained catalyst, an ammoxidation reaction of propane was performed under the same conditions as in Example 1. The results of the reaction results obtained are shown in Table 1.
[0048]
[Example 3]
(Preparation of catalyst)
In this embodiment, were prepared oxide catalyst prepared composition formula represented by _{Mo 1 V 0.21 Nb 0.11 Sb 0.28} O n /45.0wt%-SiO 2 as follows. To 4454 g of water, 889.0 g of ammonium heptamolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O], 123.7 g of ammonium metavanadate [NH ₄ VO ₃ ], antimony trioxide [Sb ₂ O ₃ ] Was added to the mixture and heated to 90 ° C. with stirring to obtain a mixed solution. To the obtained mixed solution, 319.7 g of hydrogen peroxide containing 30 wt% as H ₂ O ₂ was added little by little with stirring, and after about 30 minutes, a transparent mixed solution A-3 was obtained.
[0049]
After cooling the obtained mixed liquid A-3 to 70 ° C., silica sol 2941.2 containing 30.6 wt% as SiO ₂ was added, and then 852.1 g of mixed liquid B ₀ was added to prepare a raw material preparation liquid. Obtained. Using the raw material preparation solution thus obtained, a drying step and a firing step were performed in the same manner as in Example 1 to produce a catalyst.
[0050]
(Propane ammoxidation)
Using the obtained catalyst, an ammoxidation reaction of propane was performed under the same conditions as in Example 1. The results of the reaction results obtained are shown in Table 1.
[0051]
[Example 4]
(Preparation of catalyst)
In this embodiment, were prepared oxide catalyst prepared composition formula represented by _{Mo 1 V 0.21 Nb 0.11 Sb 0.28} O n /45.0wt%-SiO 2 as follows. In Example 3, instead of the mixed solution B _0, the mixture B ₀ 852.1g, was added 125.6g of hydrogen peroxide water containing 30 wt% as H ₂ O _2, stirred and mixed for 10 minutes at room temperature A catalyst was produced in the same manner as in Example 3 except that the mixed solution B obtained in this way was used.
(Propane ammoxidation)
Using the obtained catalyst, an ammoxidation reaction of propane was performed under the same conditions as in Example 1. The results of the reaction results obtained are shown in Table 1.
[0052]
[Table 1]

[0053]
【The invention's effect】
By using the oxide catalyst of the present invention, an unsaturated carboxylic acid or an unsaturated nitrile can be produced with high selectivity.

Claims (9)

An oxide catalyst having a component composition represented by the following general composition formula (1) for use in a gas phase catalytic oxidation reaction or gas phase catalytic ammoxidation reaction of propane or isobutane, wherein a molybdenum compound is added during the step of preparing the raw material. And / or an oxide catalyst obtained by a production method comprising a step of dissolving a raw material mixture composed of a vanadium compound, antimony trioxide and an aqueous solvent with hydrogen peroxide;
_{Mo 1 V a Nb b Sb c} O n (1)
(A, b, c and n represent the atomic ratio per molybdenum atom, a is 0.01 ≦ a ≦ 1, b is 0.01 ≦ b ≦ 1, c is 0.01 ≦ c ≦ 1, a And c are 0.01 ≦ a / c <1, and n is a number determined by the valence and composition of the constituent metals.
) _2. The oxide catalyst according to claim 1, wherein a molar ratio of hydrogen peroxide to antimony used in the raw material mixture is 0 <H ₂ O ₂ / Sb ≦ 20. 3. The oxide catalyst according to claim 1, wherein the molar ratio of hydrogen peroxide to antimony used in the raw material mixture is 2 <H ₂ O ₂ / Sb ≦ 10. The oxide catalyst according to any one of claims 1 to 3, wherein the step of forming a solution is a step of adding hydrogen peroxide to the raw material mixture liquid having a liquid temperature of 70 ° C or higher. . The oxide catalyst according to any one of claims 1 to 4, wherein the molybdenum compound is ammonium heptamolybdate and the vanadium compound is ammonium metavanadate. 6. The niobium raw material constituting the oxide catalyst is a niobium-containing liquid containing a dicarboxylic acid / niobium compound and having a dicarboxylic acid / niobium molar ratio of 1 to 4. The oxide catalyst according to any one of the above. The oxide catalyst is a silica-supported catalyst supported on silica in an amount of 20 to 60% by weight in terms of SiO ₂ with respect to the total weight of the oxide of the catalyst constituent elements and silica. The oxide catalyst according to any one of the above. In 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 any one of claims 1 to 7 is used. A method for producing an unsaturated acid or an unsaturated nitrile, characterized by being used. It is a manufacturing method of the oxide catalyst in any one of Claims 1-7, Comprising: During the process of preparing a raw material, the raw material liquid mixture which consists of a molybdenum compound and / or a vanadium compound, diantimony trioxide, and an aqueous solvent is used. The manufacturing method of the oxide catalyst characterized by making into a solution using hydrogen peroxide.