JP4666336B2 - Method for producing antimony-containing composite metal oxide - Google Patents

Description

  The present invention relates to a method for producing an antimony-containing composite metal oxide. Using the mixed metal oxide catalyst obtained by the method of the present invention, a hydrocarbon is subjected to a gas phase catalytic oxidation reaction or a gas phase catalytic ammoxidation reaction to give a corresponding alkene, unsaturated aldehyde, unsaturated carboxylic acid, The present invention relates to a method for producing a saturated nitrile.

A composite metal oxide catalyst containing antimony as an essential component has been widely used as a catalyst for hydrocarbon gas phase catalytic oxidation reaction or a gas phase catalytic ammoxidation reaction.
For example, in a technique for producing a corresponding unsaturated aldehyde, unsaturated carboxylic acid, unsaturated nitrile, alkene by using gas phase catalytic oxidation reaction or gas phase catalytic ammoxidation reaction using propylene, isobutene, propane, isobutane as raw materials, Fe-Sb-based catalysts (for example, see Patent Document 1), Sb-U-Ni-V-based catalysts (for example, see Patent Document 2 and Patent Document 3), Sb-U-W-based catalysts (for example, Patent Document 4) Sb—U-based catalyst (see, for example, Patent Document 5), Sb—In-based catalyst (for example, see Patent Document 6), Ga—Sb-based catalyst (for example, see Patent Document 7 and Patent Document 8), Sb -Sn-based catalyst, Sb-U-based catalyst (see, for example, Patent Document 9), V-Sb-based catalyst (for example, see Patent Document 10), V-Sb-Ti-based catalyst (for example, Patent Document 11) ), V-Sb-W catalyst (for example, see Patent Document 12, Patent Document 13, and Patent Document 14), V-Sb-Sn catalyst (see, for example, Patent Document 15), V-Sb-Bi catalyst (See, for example, Patent Document 16), V—Sb—Fe-based catalyst (see, for example, Patent Document 17), V—Sn—Sb—Cu-based catalyst (for example, see Patent Document 18), Cr—Sb—W-based catalyst. (See, for example, Patent Document 19), Mo—Sb—W-based catalyst (see, for example, Patent Document 20), Mo—V—Sb—Nb-based catalyst (see, for example, Patent Document 21 and Patent Document 22), Sb—Re Catalyst (see, for example, Patent Document 23), Mo—Bi—Fe—Sb catalyst (see, for example, Patent Document 24), Mo—V—Sb—Ti catalyst (see, for example, Patent Document 25), Mo—V -Sb-Fe catalyst (for example, Patent Document 2) Reference) and the like have been disclosed.

In these publications, examples of Sb raw materials include metal antimony, antimony trioxide, niantimony tetroxide, antimony pentoxide, hydrous antimony oxide, metaantimonic acid, orthoantimonic acid, pyroantimonic acid, antimony oxide sol, Antimony halides (eg, antimony trichloride, antimony trifluoride, antimony tribromide, antimony triiodide, antimony pentachloride, antimony pentafluoride, antimony pentaiodide), antimony hydride, antimony sulfate, antimony oxysulfate, Antimony oxychloride, antimony ethoxide, antimony butoxide, antimony acetate, antimony oxalate, antimony tartrate, antimonylammonium tartrate and the like are taught.
When producing a composite metal oxide catalyst containing Sb using these Sb raw materials, there is a problem that the selectivity of the target unsaturated aldehyde, unsaturated carboxylic acid, unsaturated nitrile and alkene is low.

  When metal antimony is used by dissolving in mineral acid such as nitric acid, there is corrosion of the catalyst production facility and a specific odor, so there are restrictions on the material of the production equipment, and exhaust equipment is required. When antimony is used by boiling antimony metal or antimony oxide with a catalyst constituent element other than antimony, such as a vanadium raw material solution, under reflux, in the catalyst production process, a refluxing process occurs. There are problems that heating equipment and a reflux condenser are required, manufacturing equipment and processes become complicated, and management methods such as heating time, heating temperature, and heating atmosphere become complicated. When hydrolyzed by adding water or ammonia water to antimony halide, there is a problem that harmful halogen gas is generated during the production of the catalyst, and an exhaust facility is required. When using antimonyl ammonium tartrate, it is necessary to use ammonia water or gas that is harmful and irritating when preparing liquid, and there is a problem that ammonia gas is generated in the firing process, etc. is required.

  Moreover, since the stability as the aqueous solution is extremely low and precipitates are likely to be generated at room temperature, the storage tank to be stored requires incidental equipment and heating equipment for temperature control. In addition, when using antimony ethoxide, antimony butoxide, and antimony acetate, it is necessary to handle it such as storing it away from moisture and storing it in nitrogen, and also requires exhaust equipment because of its unique odor. When antimony oxalate and antimony tartrate are used, there is a problem that the selectivity of the target unsaturated aldehyde, unsaturated carboxylic acid, unsaturated nitrile and alkene is low.

Japanese Patent Publication No.46-2804 Japanese Patent Publication No. 47-14371 US Pat. No. 3,816,506 US Pat. No. 3,670,006 US Patent No. 4,000,178 US Pat. No. 3,678,090 Soviet Patent No. 547444 Soviet Patent No. 698646 Specification Japanese Patent Publication No. 50-28940 JP 47-33783 A JP 54-95439 A JP-A-1-268668 JP-A-2-95439 JP-A-2-261544 US Pat. No. 5,008,427 Japanese Patent Laid-Open No. 6-80620 JP-A-6-135922 JP-A-4-275266 JP-A-7-157461 JP-A-7-157462 JP-A-5-213848 Japanese Patent Laid-Open No. 9-157241 JP 2001-79397 A JP-A-2002-306968 Japanese Patent Laid-Open No. 2002-361085 JP 2002-88013 A

  In the composite metal oxide catalyst containing antimony, the present invention produces a catalyst having a high selectivity for the target unsaturated aldehyde, unsaturated carboxylic acid, unsaturated nitrile, and alkene, and is complicated in production. It aims at providing the manufacturing method of the catalyst which does not require an installation and a process.

  In order to solve the above-mentioned problems, the present inventors diligently studied a method for producing a composite metal oxide containing antimony used in a gas phase catalytic oxidation reaction or a gas phase catalytic ammoxidation reaction of hydrocarbon, and as a result, prepared raw materials. A complex obtained from a halogen-free Sb compound and / or Sb metal, an oxyacid having two or more carboxyl groups, and a hydrogen peroxide solution as at least a part of the Sb material. Has found that the desired product, especially alkene, unsaturated aldehyde, unsaturated carboxylic acid, unsaturated nitrile, has a high selectivity and can be used to produce a catalyst that does not require complicated equipment and processes. The present invention has been made.

That is, the present invention
(1) In the method for producing a composite metal oxide catalyst containing antimony used for hydrocarbon gas phase catalytic oxidation reaction or gas phase catalytic ammoxidation reaction, antimony oxide, tartaric acid or citric acid, and hydrogen peroxide A method for producing a composite metal oxide catalyst , comprising: mixing an aqueous solution of hydrogen oxide ; preparing an Sb raw material liquid containing the obtained complex ; and mixing the Sb raw material liquid with a constituent element other than antimony ;
(2) The method for producing a mixed metal oxide catalyst according to (1) , wherein the mixed solution of antimony oxide, tartaric acid or citric acid and the hydrogen peroxide solution is heated .
(3) The mixed metal according to (2) , wherein the mixed solution of the antimony oxide, the tartaric acid and the hydrogen peroxide solution is heated and then allowed to cool before being mixed with a constituent element other than the antimony. Production method of oxide catalyst,

(4) The composite metal oxide catalyst containing antimony contains lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, titanium, zirconium, vanadium, niobium, tantalum, chromium as constituent elements other than antimony. At least one element selected from molybdenum, tungsten, manganese, rhenium, iron, cobalt, nickel, zinc, boron, aluminum, gallium, indium, germanium, tin, lead, phosphorus, bismuth, tellurium, lanthanum, cerium The method for producing a composite metal oxide catalyst according to any one of (1) to (3), comprising:
(5) the hydrocarbons by gas phase catalytic ammoxidation, in producing the unsaturated nitriles the corresponding, (1) to (4) composite metal oxide catalyst obtained by the production method according to any one of method for producing an unsaturated nitrile you characterized by using a
It is about.

  The present invention relates to a step of preparing a raw material in a method for producing a composite metal oxide catalyst containing antimony used in a gas phase catalytic oxidation reaction or a gas phase catalytic ammoxidation reaction of hydrocarbon. By using a compound and / or a Sb metal, a complex obtained from an oxyacid having two or more carboxyl groups and a hydrogen peroxide solution as at least a part of the Sb raw material, a desired product, particularly an alkene, This is based on the finding that an unsaturated aldehyde, an unsaturated carboxylic acid, and an unsaturated nitrile have a high selectivity, and that no complicated equipment or process is required for production.

Hereinafter, the present invention will be specifically described.
The catalyst production method of the present invention is obtained by mixing antimony oxide, tartaric acid or citric acid and hydrogen peroxide water as the Sb raw material in the raw material preparation step of the production method comprising a raw material preparation step, a drying step, and a firing step. The complex is characterized in that it is used as at least part of the Sb raw material.
The complex obtained from antimony oxide, tartaric acid or citric acid and hydrogen peroxide water in the present invention is a complex formed when antimony oxide, tartaric acid or citric acid and hydrogen peroxide water are added to water and mixed and dissolved. It is.

The complex is preferably mixed with a raw material or raw material liquid of other catalyst constituent elements as an Sb raw material liquid in which antimony oxide, tartaric acid or citric acid and hydrogen peroxide water are mixed and dissolved in water. In the present invention, oxy acids having two or more carboxyl groups, tartaric acid, may be used citric acid, preferably tartaric acid. The tartaric acid mentioned here may be any of L (+)-tartaric acid, D-tartaric acid, DL-tartaric acid, mesotartaric acid and the like. When tartaric acid is used, the amount of tartaric acid to be used is not limited, but the molar ratio of tartaric acid / antimony is preferably 0.2 to 3, and particularly preferably the molar ratio of tartaric acid / antimony is 0.8 to 2.
In the present invention, as antimony oxide, niantimony trioxide, niantimony tetroxide, niantimony pentoxide, hydrous antimony oxide, and the like can be used, and antimony trioxide is preferable.

In the present invention, the amount of hydrogen peroxide used is not limited, but the amount of hydrogen peroxide contained in the hydrogen peroxide is preferably a hydrogen peroxide / antimony molar ratio of 0.1 to 5, particularly preferably. Has a hydrogen peroxide / antimony molar ratio of 0.5-2.
In the composite metal oxide catalyst containing antimony of the present invention, as constituent elements other than antimony, lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, titanium, zirconium, vanadium, niobium, tantalum, chromium At least one element selected from molybdenum, tungsten, manganese, rhenium, iron, cobalt, nickel, zinc, boron, aluminum, gallium, indium, germanium, tin, lead, phosphorus, bismuth, tellurium, lanthanum, cerium Preferably titanium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, iron, aluminum, gallium, tin, bismuth, tellurium, particularly preferably vanadium, niobium, chromium, molyb Emissions, tungsten, iron, more particularly preferably vanadium.

  In the composite metal oxide catalyst containing antimony of the present invention, when the constituent elements other than antimony are vanadium, niobium, chromium, molybdenum, tungsten, iron (hereinafter referred to as X element), the molar ratio of X element / antimony is The molar ratio of X element / antimony is preferably 0.7 to 1.5, and more preferably the molar ratio of X element / antimony is 0.9 to 1.1. In particular, in the case of vanadium among the X elements, the selectivity of the target alkene, unsaturated aldehyde, unsaturated carboxylic acid, and unsaturated nitrile is high in the conventional production method in a composition having a molar ratio of vanadium / antimony close to 1. Although low, a catalyst having a new composition can be provided by the production method of the present invention.

There is no particular limitation as a raw material for constituent elements other than antimony, and compounds such as oxalates, hydroxides, oxides, nitrates, acetates, ammonium salts, carbonates, alkoxides of metals used, and metals or metal compounds used Can be used solubilized with an appropriate reagent.
The composite metal oxide catalyst obtained by the production method of the present invention can be used alone as a catalyst, but the composite metal oxide catalyst obtained by the production method of the present invention and one or more carriers such as silica and alumina You may use it in the state which contained the component in the same particle. Further, the composite metal oxide may be used for the reaction in a state where the particles and particles made of one or more oxides such as silica and alumina are mixed.

As described above, the method for producing a catalyst of the present invention includes three steps: a raw material preparation step, a drying step, and a firing step. These steps will be described below.
<Raw material preparation process>
The Sb raw material liquid can be produced, for example, by dissolving niantimony trioxide in an aqueous solution containing tartaric acid and hydrogen peroxide. Although it can melt | dissolve by mixing, you may heat and melt | dissolve at 60-80 degreeC. The mixing time is preferably 5 minutes to 10 hours, particularly preferably 10 minutes to 2 hours. When tartaric acid is used, the amount of tartaric acid to be used is not limited, but the molar ratio of tartaric acid / antimony is preferably 0.2 to 3, and particularly preferably the molar ratio of tartaric acid / antimony is 0.8 to 2. The amount of hydrogen peroxide used is not limited, but the amount of hydrogen peroxide contained in the hydrogen peroxide solution is preferably a hydrogen peroxide / antimony molar ratio of 0.1 to 5, particularly The hydrogen peroxide / antimony molar ratio is preferably 0.5-2.

When the constituent element other than antimony is vanadium, it is preferable to use an aqueous solution of vanadium pentoxide, ammonium metavanadate, vanadyl oxalate, or a V raw material solution in which vanadium pentoxide, ammonium metavanadate is dissolved in hydrogen peroxide. it can.
Constituent elements other than antimony are lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, titanium, zirconium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium, iron, cobalt, nickel, zinc, When using boron, aluminum, gallium, indium, germanium, tin, lead, phosphorus, bismuth, tellurium, lanthanum, cerium, oxalate, hydroxide, oxide, nitrate, acetate, ammonium of the metal used A compound obtained by solubilizing a compound such as a salt, carbonate, alkoxide or the like or a metal to be used or a metal compound with an appropriate reagent can be used.

  A catalyst raw material liquid can be produced by mixing the raw material liquids in an appropriate order. The catalyst raw material liquid can be mixed by stirring at about room temperature, for example, 20 to 30 ° C. The mixing time is preferably 5 minutes to 10 hours, particularly preferably 10 minutes to 2 hours.

<Drying process>
The catalyst raw material liquid obtained in the raw material preparation step can be dried by spray drying or evaporation to dryness to obtain a dry powder. The atomization in the spray drying method can employ a centrifugal method, a two-fluid nozzle method, or a high-pressure nozzle method. As the drying heat source, air heated by steam, an electric heater or the like can be used. At this time, the dryer inlet temperature of hot air is preferably 150 to 300 ° C. Spray drying can also be performed simply by spraying the catalyst raw material liquid onto an iron plate heated to 100 ° C to 300 ° C.

<Baking process>
A composite metal oxide catalyst can be obtained by calcining the dry powder obtained in the drying step. Firing can be performed at 500 to 800 ° C., preferably 550 to 700 ° C., using a rotary furnace, tunnel furnace, tubular furnace, fluidized firing furnace or the like. The firing time is 0.5 to 5 hours, preferably 1 to 3 hours.
In the presence of the catalyst thus produced, the hydrocarbon is subjected to gas phase catalytic oxidation reaction or gas phase catalytic ammoxidation reaction to produce the corresponding alkene, unsaturated aldehyde, unsaturated carboxylic acid, and unsaturated nitrile. For example, a method of producing acrylonitrile or methacrylonitrile by vapor-phase catalytic ammoxidation of propane or isobutane, a method of producing acrylic acid or methacrylic acid by vapor-phase catalytic oxidation of propane or isobutane, propylene or isobutene Is a method of producing acrylonitrile or methacrylonitrile by vapor phase catalytic ammoxidation, a method of producing propylene or isobutene by vapor phase catalytic oxidation to produce acrolein or methacrolein, and ethane is vapor phase catalytically oxidized to produce ethylene. There are methods for manufacturing.

The feedstock for hydrocarbons and ammonia is not necessarily highly pure, and industrial grade gases can be used.
As the oxygen source supplied to the reaction system, air, air enriched with oxygen, or pure oxygen can be used. Further, helium, argon, carbon dioxide gas, water vapor, nitrogen or the like may be supplied as a dilution gas.
In the case of gas phase catalytic ammoxidation, the molar ratio of ammonia to the hydrocarbon supplied to the reaction system is 0.1 to 1.5, preferably 0.2 to 1.2. When performing vapor phase catalytic ammoxidation in a recycle mode, the gas composition at the reactor inlet is preferably such that the molar ratio of ammonia to hydrocarbon is 0.2 to 1.0, 0.5 to 0.8 More preferably.

  Further, the molar ratio of molecular oxygen to hydrocarbons supplied to the reaction system is preferably 0.2 to 6, and more preferably 0.4 to 4. When performing vapor phase catalytic ammoxidation in a recycle mode, the gas composition at the inlet of the reactor is preferably such that the molar ratio of molecular oxygen to hydrocarbon is 0.8 to 2.2, and 1.5 to 1 .9 is more preferable. On the other hand, when performing vapor phase catalytic oxidation, the molar ratio of molecular oxygen to hydrocarbon is 0.1 to 10, preferably 0.1 to 5. Moreover, it is preferable to add water vapor | steam to a reaction system, In that case, the molar ratio with respect to the hydrocarbon of the water vapor | steam supplied to a reaction system is 0.1-70, Preferably it is 3-40.

For both gas phase catalytic oxidation and gas phase catalytic ammoxidation, the reaction pressure is 0.01 to 1 MPa in absolute pressure, preferably 0.1 to 0.3 MPa in absolute pressure. The reaction temperature of the gas phase ammoxidation is 300 to 600 ° C, preferably 380 to 480 ° C. The reaction temperature of the gas phase catalytic oxidation is 300 to 600 ° C, preferably 350 to 440 ° C. For both gas phase catalytic oxidation and gas phase catalytic ammoxidation, the contact time is 0.05 to 30 (g · sec / ml), preferably 0.1 to 10 (g · sec / ml). The contact time is defined by the following formula.
Contact time (g · sec / ml) = W / F × 60 × 273 / (273 + T) × ((P + 0.101) /0.101)
[W is the weight (g) of the composite metal oxide catalyst, F is the flow rate of the raw material mixed gas (ml / min), T is the reaction temperature (° C.), and P is the reaction pressure (gauge pressure) (MPa). . For both gas phase catalytic oxidation and gas phase catalytic ammoxidation, conventional methods such as a fixed bed, a fluidized bed and a moving bed can be used for the reaction, but a fluidized bed is preferred. The reaction may be a single flow method or a recycle method.

Next, the present invention will be described with reference to examples of vapor-phase catalytic ammoxidation of propane. In each example, propane conversion and acrylonitrile selectivity are in accordance with the following definitions.
Propane conversion (%) = {(moles of reacted propane (μmol)) / (moles of propane fed (μmol))} × 100
Acrylonitrile selectivity (%) = {(number of moles of acrylonitrile produced (μmol)) / (number of moles of reacted propane (μmol))} × 100

[Example 1]
<Catalyst preparation>
V _{1.0 Sb 1.0} O _n ingredients formula _(n is a number determined by the valency and atomic ratio of the constituent metals.) Was prepared composite metal oxide catalyst represented by the following manner.
4. To 58 g of water, 9.0 g of L (+)-tartaric acid and 6.8 g of 30% by weight hydrogen peroxide water were added and dissolved by stirring at room temperature for 30 minutes, and then niantimony trioxide (Sb ₂ O ₃ ). 83 g was added and dissolved by heating at 70 ° C. for 30 minutes, and then allowed to cool at 30 ° C. to obtain an Sb raw material liquid. To 300 g of water, 4.68 g of ammonium metavanadate (NH ₄ VO ₃ ) was added, dissolved by heating at 70 ° C. for 15 minutes, and then allowed to cool at 30 ° C. to obtain a V raw material liquid. The Sb raw material liquid was added to the V raw material liquid and stirred at room temperature for 1 hour to obtain a catalyst raw material liquid. The obtained catalyst raw material liquid was sprayed onto a Teflon (registered trademark) coated iron plate heated to 140 ° C. to obtain a dry powder. From the obtained dry powder, 2.0 g was filled in a quartz tube having an inner diameter of 20 mm, and calcined at 600 ° C. for 2 hours under an air flow of 350 Nml / min to obtain a composite metal oxide catalyst.

<Propane Ammoxidation Test>
A 0.20 g mixed metal oxide catalyst was charged into a fixed bed type reaction tube having an inner diameter of 4 mm, reaction temperature T = 460 ° C. (external temperature), propane: ammonia: oxygen: helium = 1: 0.7: 1.7: A raw material mixed gas having a molar ratio of 5.3 was supplied at a flow rate F = 12 Nml / min. At this time, the pressure P was 0 MPa as a gauge pressure. The contact time is 0.38 g · s / ml (the contact time is W / F × 60 × 273 / (273 + T) × ((P + 0.101) / 0, where the weight of the composite metal oxide catalyst is W (g)) .101))). Analysis of the reaction gas was performed by on-line gas chromatography. The obtained results are shown in Table 1.

[Comparative Example 1]
<Catalyst preparation>
V _{1.0 Sb 1.0} O _n ingredients formula _(n is a number determined by the valency and atomic ratio of the constituent metals.) Was prepared composite metal oxide catalyst represented by the following manner.
The catalyst preparation of Example 1 was repeated except that L (+)-tartaric acid and 30 wt% aqueous hydrogen peroxide were not used in the Sb raw material liquid.
<Propane Ammoxidation Test>
The resulting mixed metal oxide catalyst was subjected to propane ammoxidation reaction, the raw material mixed gas at a flow rate F = 12 Nml / min to 18 Nml / min, and the contact time from 0.38 g · s / ml to 0.25 g · s / ml. The procedure was the same as in Example 1 except that the change was made. The obtained results are shown in Table 1.

[Comparative Example 2]
<Catalyst preparation>
V _{1.0 Sb 1.0} O _n ingredients formula _(n is a number determined by the valency and atomic ratio of the constituent metals.) Was prepared composite metal oxide catalyst represented by the following manner.
The catalyst preparation of Example 1 was repeated except that 30% by weight of hydrogen peroxide solution was not used in the Sb raw material liquid.
<Propane Ammoxidation Test>
The obtained mixed metal oxide catalyst was subjected to an ammoxidation reaction of propane, a raw material mixed gas at a flow rate F = 12 Nml / min to 48 Nml / min, and a contact time of 0.38 g · s / ml to 0.09 g · s / ml. The procedure was the same as in Example 1 except that the change was made. The obtained results are shown in Table 1.

[Comparative Example 3]
<Catalyst preparation>
V _{1.0 Sb 1.0} O _n ingredients formula _(n is a number determined by the valency and atomic ratio of the constituent metals.) Was prepared composite metal oxide catalyst represented by the following manner.
In the Sb raw material liquid, 7.56 g of oxalic acid dihydrate (H ₂ C ₂ O ₄ .2H ₂ O) was used instead of L (+)-tartaric acid, and 30% by weight of hydrogen peroxide was not used. The catalyst preparation of Example 1 was repeated except for the above.
<Propane Ammoxidation Test>
The resulting mixed metal oxide catalyst was subjected to propane ammoxidation reaction, the raw material mixed gas at a flow rate F = 12 Nml / min to 18 Nml / min, and the contact time from 0.38 g · s / ml to 0.25 g · s / ml. The procedure was the same as in Example 1 except that the change was made. The obtained results are shown in Table 1.

[Comparative Example 4]
<Catalyst preparation>
V _{1.0 Sb 1.0} O _n ingredients formula _(n is a number determined by the valency and atomic ratio of the constituent metals.) Was prepared composite metal oxide catalyst represented by the following manner.
The catalyst preparation of Example 1 was repeated except that L (+)-tartaric acid was not used in the Sb raw material liquid.
<Propane Ammoxidation Test>
The resulting mixed metal oxide catalyst was subjected to propane ammoxidation reaction, the raw material mixed gas at a flow rate F = 12 Nml / min to 18 Nml / min, and the contact time from 0.38 g · s / ml to 0.25 g · s / ml. The procedure was the same as in Example 1 except that the change was made. The obtained results are shown in Table 1.

[Example 2]
<Sb raw material stability test>
The manufacturing method of the Sb raw material liquid in Example 1 was repeated to obtain an Sb raw material liquid. The obtained Sb raw material liquid was allowed to stand at room temperature for 1 year, but no precipitate was observed, and it was found to be a stable Sb raw material liquid.

[Example 3]
<Catalyst preparation>
V _{1.0 Sb 1.0} O _n ingredients formula _(n is a number determined by the valency and atomic ratio of the constituent metals.) Was prepared composite metal oxide catalyst represented by the following manner.
The catalyst preparation of Example 1 was repeated except that the Sb raw material liquid left for one year in Example 2 was used as the Sb raw material liquid.
<Propane Ammoxidation Test>
The obtained composite metal oxide catalyst was subjected to propane ammoxidation reaction under the same conditions as in Example 1. The obtained results are shown in Table 1.

  INDUSTRIAL APPLICABILITY The present invention can be suitably used as a method for producing a composite metal oxide containing antimony as an essential component, particularly in the catalyst field, particularly as a method for producing a hydrocarbon gas phase catalytic oxidation and a gas phase catalytic ammoxidation catalyst.

Claims (5)

Antimony oxide, tartaric acid or citric acid and hydrogen peroxide solution in the step of preparing the raw material in the method for producing a composite metal oxide catalyst containing antimony used for gas phase catalytic oxidation reaction or gas phase catalytic ammoxidation reaction of hydrocarbon And preparing a Sb raw material solution containing the resulting complex , and mixing the Sb raw material solution with a constituent element other than antimony . The method for producing a mixed metal oxide catalyst according to claim 1 , wherein a mixed liquid of the antimony oxide, the tartaric acid or the citric acid and the hydrogen peroxide solution is heated . 3. The composite according to claim 2 , wherein the mixed solution of the antimony oxide, the tartaric acid or the citric acid, and the hydrogen peroxide solution is heated and then allowed to cool before being mixed with a constituent element other than the antimony. A method for producing a metal oxide catalyst. Composite metal oxide catalyst containing antimony as an element other than the antimony, lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, titanium, zirconium, vanadium, niobium, tantalum, chromium, molybdenum Including at least one element selected from tungsten, manganese, rhenium, iron, cobalt, nickel, zinc, boron, aluminum, gallium, indium, germanium, tin, lead, phosphorus, bismuth, tellurium, lanthanum, cerium The manufacturing method of the composite metal oxide catalyst in any one of Claims 1-3 characterized by the above-mentioned. Hydrocarbons by gas phase catalytic ammoxidation, in producing the unsaturated nitriles the corresponding, characterized by using a composite metal oxide catalyst obtained by the process according to any one of claims 1 to 4 method for producing an unsaturated nitrile shall be the.