JPH1133400A - Use of Molybdenum-Containing Oxide Fluidized Bed Catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of using a fluidized bed catalyst which prevents a decrease in yield over time due to deterioration of an ammoxidation catalyst and enables stable operation for a long period of time. SOLUTION: In an ammoxidation reaction using a molybdenum-containing oxide fluidized bed catalyst, a molybdenum-containing oxide catalyst is impregnated with a solution or suspension containing a molybdenum component, and then impregnated at a temperature of 200 to 650 ° C. under motion. 5 to 1
A method of using a catalyst in which a molybdenum-enriched catalyst obtained by calcining for 0 hour is used by mixing it in a range of 0.05 to 30% based on the total amount of the catalyst used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for using a molybdenum-containing oxide fluidized bed catalyst used for an ammoxidation reaction of an organic compound. More specifically, the present invention relates to a method for ammoxidation of organic compounds in a fluidized bed using a molybdenum-enriched catalyst produced by a specific method.

[0002]

2. Description of the Related Art Molybdenum-containing oxide fluidized bed catalysts are widely used as catalysts for oxidation, ammoxidation or oxidative dehydrogenation of organic compounds. For example, oxidation of olefins yields unsaturated aldehydes or acids, ammoxidation yields unsaturated nitriles, oxidation of alcohols yields aldehydes or acids, and ammoxidation yields nitriles or hydrocyanic acid. Of these reactions, the ammoxidation reaction generally has a higher reaction temperature than the oxidation reaction. Taking propylene as an example, the oxidation reaction is usually 300 to 4
Although it is carried out at 00 ° C., the ammoxidation reaction is usually carried out at a high temperature of about 400 to 500 ° C., about 100 ° C. For this reason, in the ammoxidation reaction, the phenomenon that the molybdenum component in the catalyst escapes from the catalyst and the performance of the catalyst deteriorates with time tends to surface.

[0003] Examples of molybdenum-containing oxide fluidized bed catalysts used in the ammoxidation reaction include JP-B-36-587.
No. 0, a molybdenum-bismuth-containing catalyst described in JP-B-38-17967.
Iron-containing catalyst, catalyst containing molybdenum / bismuth / iron / cobalt / nickel described in JP-B-51-33888, and JP-A-6-95 in which other components are further diversified
No. 30, JP-A-7-289901, JP-A-4
A catalyst described in JP-A-118051 is known,
The fluidized bed catalyst production method is also disclosed in JP-B-37-8568, JP-B-57-49253, and JP-B-54-1.
No. 2913, for example. However, these catalysts have not been able to completely overcome the deterioration over time due to the escape of the molybdenum component.

As a countermeasure against this, Japanese Patent Publication No. 58-57422
JP-A-4-2270 discloses a method of supporting molybdenum oxide on an inert carrier and mixing and reacting the same with a catalyst.
No. 72, a method of adding a reactivating agent containing molybdenum and phosphorus, chromium, bismuth, or the like to a catalyst;
There is known a method of preparing and using a catalyst having an excess molybdenum component described in JP-A-7048 and JP-A-5-301051. However, all of these methods have practical problems. That is, after the molybdenum component escapes, only the carrier or a powder containing a different element remains in the catalyst layer.If an excess molybdenum component is added at the time of preparing the catalyst, the target product yield decreases. In addition, there has been a problem that the strength of the catalyst is reduced or the strength is reduced as the molybdenum component escapes due to the use of the reaction.

[0005]

It is possible to prevent a decrease in yield over time due to escape of a molybdenum component without producing problems such as the accumulation of foreign substances in the reaction system and a decrease in the strength of the catalyst as described above. An object of the present invention is to provide a method for producing a molybdenum-enriched catalyst which is industrially easy to implement in terms of the above or use, and a method for using the same.

[0006]

Means for Solving the Problems The present inventors have conducted various studies in order to solve the above-mentioned problems. As a result, the catalyst was impregnated with a molybdenum component at a high concentration under specific conditions, and the catalyst was reduced in activity. That the molybdenum-enriched catalyst functions as a normal catalyst after the molybdenum component escapes, so that problems such as accumulation of foreign substances in the reaction system do not occur. The inventors have found that since the molybdenum component works effectively, there is no trouble in operation such as scaling of the molybdenum component and the like, and arrived at the invention of an industrially advantageous method of using a molybdenum-containing oxide fluidized bed catalyst.

That is, according to the present invention, in an ammoxidation reaction of an organic compound using a molybdenum-containing oxide fluidized bed catalyst, a molybdenum-containing oxide catalyst is impregnated with a solution or a suspension containing a molybdenum component, and then the impregnated particles are removed. The molybdenum-enriched catalyst obtained by calcining at a temperature of 200 to 650 ° C. for 0.5 to 10 hours under exercise is added with 0.05 to 30% by weight based on the filled molybdenum-containing oxide catalyst.
And a fluidized bed catalyst containing a molybdenum-containing oxide.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The molybdenum-containing oxide catalyst to which the present invention can be applied has the following composition. Mo ₁₀ BiaFebSbcDdEeFfGgHhOi
(SiO ₂ ) j (wherein, Mo, Bi, Fe and Sb represent molybdenum, bismuth, iron and antimony, respectively, and D is composed of magnesium, calcium, strontium, barium, chromium, manganese, cobalt, nickel and zinc. At least one element selected from the group, E is at least one element selected from the group consisting of copper, silver, cadmium, aluminum, gallium, indium, germanium, tin, lead, titanium, zirconium and hafnium;
Is selected from the group consisting of vanadium, niobium, tantalum, tungsten, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, thorium, uranium, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum and gold. G is at least one element selected from the group consisting of phosphorus, boron and tellurium, H is at least one element selected from the group consisting of lithium, sodium, potassium, rubidium and cesium, and O is Oxygen and Si represent silicon, with subscripts a, b, c, d
, E, f, g, h, i and j represent the atomic ratio, and
When = 10, a = 0.1 to 5, b = 0.1 to 15, c = 0
-20, d = 0-10, e = 0-10, f = 0-10,
g = 0 to 5, h = 0 to 3, i = the number of oxygens corresponding to oxides generated by combining the above components, and j = 20 to 150. )

The molybdenum-enriched catalyst of the present invention comprises
It is produced by impregnating and enriching the molybdenum component with the base catalyst having the above composition. Impregnating the base catalyst with an aqueous solution of a molybdenum component corresponding to about 60 to 100%, preferably about 90 to 98% of the pore volume of the base catalyst;
Then, it is dried and fired. Examples of the aqueous solution of the molybdenum component used in this case include an aqueous solution of molybdenum trioxide in ammonium water, ammonium paramolybdate and ammonium metamolybdate, and ammonium peroxomolybdate and phosphomolybdenum obtained by dissolving these in aqueous hydrogen peroxide. An aqueous solution of an acid or the like is preferable, and particularly, an aqueous solution of ammonium peroxomolybdate, phosphomolybdic acid, or the like, which is easily impregnated at a high concentration, is preferably used.
The concentration of the molybdenum component-containing aqueous solution is 10 to 70% by weight,
Preferably it is in the range of 20 to 60% by weight.

[0010] The pore volume of the molybdenum-containing oxide catalyst of the present invention is usually 0.1 to 0.8 ml / g. If the molybdenum component concentration is the same, the larger the pore volume and the higher the concentration, the greater the amount of molybdenum enriched by one impregnation operation.

As the component to be enriched and impregnated, various elements other than molybdenum can be contained depending on the purpose.
A small amount of phosphorus, boron, potassium, tellurium, bismuth, sulfur or the like may be added in order to adjust the effect onset speed or effect persistence of the molybdenum component.

The molybdenum component-enriched impregnated catalyst is dried and calcined to obtain a molybdenum-enriched catalyst, and it is important that the catalyst be intermittently or continuously operated. If the catalyst impregnated with the high-concentration molybdenum component is dried and calcined while standing, it solidifies, and the subsequent operation becomes complicated, which is an industrial problem. Examples of the apparatus for drying and firing under the movement of catalyst particles include a rotary firing furnace, a fluidized-bed firing furnace, and a moving-bed firing furnace.

[0013] Even if this is done during exercise,
If the temperature exceeds 50 ° C., consolidation occurs. Therefore, the drying and baking are performed at 200 to 650 ° C, preferably 300 to 600 ° C, and particularly preferably 400 to 550 ° C under exercise.
At a temperature in the range of 0.1 to 10 hours, preferably 0.5
It is good to perform for 5 to 5 hours. The firing temperature and time may be varied in order to adjust the speed at which the molybdenum component exerts its effect. The longer the sintering temperature and the higher the sintering temperature, the lower the effect manifestation speed of the molybdenum component. Drying and firing are conveniently performed in air, but nitrogen, carbon dioxide, oxygen, or the like may be used. If necessary, the molybdenum component may be impregnated, dried or dried and fired, and then the molybdenum component may be impregnated, dried and fired a plurality of times to increase the molybdenum-enriched amount.

The molybdenum-enriched amount of the molybdenum-enriched catalyst thus prepared is 5 to 5% as molybdenum trioxide.
It is 50% by weight, preferably 8 to 30% by weight. If the molybdenum-enriched amount is less than 5%, the required mixing amount of the molybdenum-enriched catalyst with respect to the charged catalyst before adding the molybdenum-enriched catalyst (hereinafter, referred to as the filled catalyst) increases, which causes inconvenience in the reaction. In addition, the molybdenum enrichment amount is 50
If the content is more than 10% by weight, the physical properties such as the fluidity of the catalyst decrease, and the selectivity of the target product decreases due to the increase in ammonia combustion. As a molybdenum-enriched catalyst having physical properties that can be used as a fluidized bed catalyst and having a large yield improving effect, one having the following composition is particularly preferred. Mo ₁₀ Bia'Feb'Sbc'Dd'Ee'Ff'Gg'Hh'Oi '
(SiO ₂ ) j ′ (wherein, Mo, Bi, Fe and Sb represent molybdenum, bismuth, iron and antimony, respectively, and D represents magnesium, calcium, strontium, barium, chromium, manganese, cobalt, nickel and zinc. E is at least one element selected from the group consisting of copper, silver, cadmium, aluminum, gallium, indium, germanium, tin, lead, titanium, zirconium and hafnium; and F is at least one element selected from the group consisting of
Is selected from the group consisting of vanadium, niobium, tantalum, tungsten, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, thorium, uranium, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum and gold. G is at least one element selected from the group consisting of phosphorus, boron and tellurium, H is at least one element selected from the group consisting of lithium, sodium, potassium, rubidium and cesium, and O is Oxygen and Si represent silicon with subscripts a ', b', c ',
d ', e', f ', g', h ', i' and j 'indicate atomic ratios, and
= 10, a '= 0.02 to 4, b' = 0.02 to 12, c '
= 0 to 15, d '= 0 to 8, e' = 0 to 8, f '= 0 to 8, g'
= 0 to 4, h '= 0 to 2, i' = the number of oxygens corresponding to the oxides formed by combining the above components, and j '= 4 to 120. )

The molybdenum-enriched catalyst of the present invention is mixed in an amount of 0.05 to 30% by weight, preferably 0.1 to 20% by weight, based on the charged catalyst. The method of replenishing the reactor with the molybdenum-enriched catalyst can be any known method. During or after the reaction, the molybdenum-enriched catalyst may be fed alone or together with the catalyst. The molybdenum content increase of the catalyst in the reactor after mixing the molybdenum-enriched catalyst is in the range of 0.01 to 1% by weight, preferably 0.03 to 0.7% by weight. If the time required for the effect to appear is relatively fast, care should be taken because adding too much will deteriorate the reaction results.

Although the activity can be restored by adding the molybdenum-enriched catalyst of the present invention to a catalyst whose activity has been reduced, the molybdenum-enriched catalyst can be added continuously during the reaction to obtain a long-term catalyst. High activity and selectivity of the desired product can also be maintained.

The present invention can be applied to the above-mentioned ammoxidation reaction of various organic compounds, but can be particularly effectively applied to the ammoxidation reaction of propylene. The ammoxidation reaction of propylene was carried out in a fluidized bed reactor using the above molybdenum-containing oxide fluidized bed catalyst at a reaction temperature of 400 to 500 ° C.
The present invention is effectively applied to the case where the activity is reduced when the reaction is carried out, particularly when the activity is reduced due to the loss during the reaction of the molybdenum component.

As described above, by using the method for producing a molybdenum-enriched catalyst suitable for being mixed with a molybdenum-containing oxide fluidized bed catalyst of the present invention and its effective use method, the molybdenum-containing oxide fluidized bed catalyst can be obtained. In the ammoxidation reaction used, it was possible to maintain the activity of the catalyst for a long period of time, thereby enabling stable continuous operation for a long period of time.

[0019]

EXAMPLES Next, the embodiments and effects of the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

The reaction was carried out in a fluidized bed reactor having a tower diameter of 2 inches, the reaction pressure was 0.5-1 kg / cm ² G, the reaction temperature was 430-450 ° C., and the supply gas composition was air / propylene (molar ratio). The reaction was performed in the range of 9 to 10.5 and ammonia / propylene (molar ratio) of 1.0 to 1.2.

Example 1 The catalyst composition was Mo ₁₀ Bi ₁ Fe ₅ Sb ₅ Ni _6.5 P _0.5 K _0.5 O _57.2
A catalyst of (SiO ₂ ) ₄₀ was used for the ammoxidation of propylene. The acrylonitrile yield was 81.6% before the deterioration, but decreased to 79.2% after a long reaction. Analysis of the catalyst showed that molybdenum had been reduced by 0.4% by weight. On the other hand, the molybdenum-enriched catalyst was added to
When the reaction was continued with the addition of 5% by weight, the acrylonitrile yield was 82.0% after 5 hours. This result was maintained after 50 hours. The molybdenum-enriched catalyst used here was prepared as follows. Take 10 kg of unused catalyst. The pore volume was 0.25 ml / g (water titration method).
0.18 kg of 35% hydrogen peroxide solution is added to 1.30 kg of pure water, the liquid temperature is adjusted to 50 ° C., and 2.25 kg of ammonium paramolybdate is added thereto to completely dissolve. The liquid volume was adjusted to 2.38 l (corresponding to 95% of the pore volume), and this was mixed well with the above catalyst. Next, the impregnated catalyst was fed into the rotary firing furnace little by little, and dried and fired. The firing was performed at 450 ° C. for 2 hours. The molybdenum-enriched catalyst thus prepared was free of caking and had good fluidity. The amount of molybdenum enriched was 15.5% by weight as molybdenum trioxide, and the composition was Mo ₁₀ Bi _0.56 Fe _2.8 Sb _2.8 Ni _3.6 P _0.28 K _0.28
O _45.1 (SiO ₂ ) _22.29 .

Example 2 The catalyst composition was Mo ₁₀ Bi _0.6 Fe ₁₂ Sb _12.5 Mg _0.5 Mn _0.5 Ni ₆
A catalyst of V _0.1 K _0.6 Cs _0.1 O _82.1 (SiO ₂ ) ₄₀ was used for the ammoxidation of propylene. The acrylonitrile yield was 80.5% before deterioration, but decreased to 78.2% after a long reaction. Analysis of the catalyst showed that molybdenum had been reduced by 0.4% by weight. On the other hand, when the molybdenum-enriched catalyst was added at 3% by weight to the charged catalyst and the reaction was continued, the acrylonitrile yield was 80.4% after 3 hours. The molybdenum-enriched catalyst used here was prepared as follows. Take 10 kg of unused catalyst. The pore volume was 0.22 ml / g. 1.16Kg of pure water and 0.16K of 35% hydrogen peroxide solution
g, and the solution temperature is adjusted to 50 ° C., and 2.017 kg of ammonium paramolybdate is added thereto to completely dissolve.
The liquid volume was adjusted to 2.13 l (corresponding to 97% of the pore volume) and this was mixed well with the above catalyst. Next, after drying this impregnated catalyst, it was calcined in a fluidized calcining furnace at 550 ° C. for 2 hours under fluidized condition. The molybdenum-enriched catalyst thus prepared was free of caking and had good fluidity. The amount of molybdenum enriched was 14.1% by weight as molybdenum trioxide.
And the composition is Mo ₁₀ Bi _0.32 Fe _6.5 Sb _6.8 Mg _0.27 Mn _0.27 Ni
_3.25 V _0.05 K _0.32 Cs _0.05 O _58.1 (SiO ₂ ) _21.6

Example 3 The catalyst composition was Mo ₁₀ Bi _0.4 Fe _4.5 Sb ₄ Ni ₆ Ce _0.1 P _0.2 T
A catalyst of e _0.25 K _0.6 Cs _0.1 O _52.8 (SiO ₂ ) ₄₀ was used for the ammoxidation of propylene. The acrylonitrile yield was 82.0% before deterioration, but decreased to 78.8% after a long reaction. Analysis of the catalyst showed that molybdenum had been reduced by 0.3% by weight. On the other hand, when the molybdenum-enriched catalyst was added at 6% by weight to the charged catalyst and reacted, the acrylonitrile yield was 82.3% after 3 hours. The molybdenum-enriched catalyst used here was prepared as follows. The weight of the catalyst used in the reaction and reduced in activity is 10 kg. The pore volume was 0.25 ml / g. 35% in 1.30kg of pure water
0.18 kg of hydrogen peroxide solution was added, and the liquid temperature was adjusted to 50 ° C.
To this is added 1.9 kg of ammonium paramolybdate and completely dissolved. The liquid volume is 2.38 l (96 of the pore volume).
%) And mixed well with the catalyst.
Next, the impregnated catalyst was fed into the rotary firing furnace little by little, and dried and fired. The firing was performed at 450 ° C. for 2 hours. The molybdenum-enriched catalyst thus prepared is
There was no caking and the fluidity was good. The amount of molybdenum enriched was 15.5% by weight as molybdenum trioxide, and the composition was Mo ₁₀ Bi _0.24 Fe _2.65 Sb _2.36 Ni _3.54 Ce _0.06 P
_0.12 Te _0.15 K _0.35 Cs _0.03 O _43.5 (SiO ₂ ) _23.6 .

Example 4 The same catalyst as in Example 1 was used for the ammoxidation of propylene. The same molybdenum-enriched catalyst as used in Example 1 was added twice a month to the charged catalyst to continue the reaction with 1.5% added.
The initial acrylonitrile yield was 81.5%. The reaction was continued for 5 months in this way, but the acrylonitrile yield was almost unchanged, showing 81.8%.

Example 5 The same catalyst as in Example 2 was used for the ammoxidation of propylene. Before the deterioration, the acrylonitrile yield was 80.7%, but after long-term reaction, it decreased to 79.8%. Analysis of the catalyst showed that molybdenum had been reduced by 0.2% by weight. On the other hand, when the molybdenum-enriched catalyst was added in an amount of 0.5% by weight with respect to the charged catalyst and the reaction was continued, the acrylonitrile yield was 80.5% after 3 hours. The molybdenum-enriched catalyst used here was prepared as follows.
This operation was repeated in the same manner as in Example 2, except that after impregnation, drying and firing, the operation was repeated. The molybdenum-enriched catalyst thus prepared was free of caking and had good fluidity. The amount of molybdenum enriched was 24.4% by weight as molybdenum trioxide, and the composition was Mo ₁₀ Bi _0.24 Fe _4.85 Sb _5.02 Mg _0.2 Mn _0.2 Ni.
_2.43 V _0.04 K _0.24 Cs _0.04 O _51.0 (SiO ₂ ) _16.2 .

Example 6 The catalyst composition was Mo ₁₀ Bi _0.3 Fe _0.6 Ni ₆ P _0.2 Te _0.25 K _0.7 O
_A catalyst of _38.7 (SiO ₂ ) ₄₀ was used for the ammoxidation of propylene. The acrylonitrile yield was 80.1% before the deterioration, but decreased to 77.2% after a long reaction. Analysis of the catalyst showed that molybdenum had been reduced by 0.5% by weight. On the other hand, the molybdenum-enriched catalyst was added to
When 2% by weight was added and the reaction was continued, the acrylonitrile yield was 80.5% after 10 hours. The molybdenum-enriched catalyst used here was prepared as follows. Take 10 kg of unused catalyst. The pore volume is 0.30 ml /
g. After dissolving 1.54 kg of phosphomolybdic acid in 2.5 kg of pure water, the liquid volume was adjusted to 2.88 l (corresponding to 96% of the pore volume), and this was mixed well with the above catalyst. Next, this was dried and then fired in a rotary firing furnace at 450 ° C. for 2 hours under particle motion. The molybdenum-enriched catalyst thus prepared was free of caking and had good fluidity. The amount of enriched molybdenum is 10.0 as molybdenum trioxide.
% By weight, and the composition is Mo ₁₀ Bi _0.22 Fe _0.45
Ni _4.45 P _0.14 Te _0.19 K _0.52 O _36.5 (SiO ₂ ) _29.7
It is.

Comparative Example 1 A molybdenum-enriched catalyst was prepared in the same manner as in Example 1.
However, the impregnated catalyst was filled in a ceramic container, placed in a tunnel furnace, and heated at 250 ° C. for 2 hours. When it was taken out after firing, it was solidified with considerable strength and it was difficult to loosen.

Comparative Example 2 A molybdenum-enriched catalyst was prepared in the same manner as in Example 2.
However, the firing temperature was set at 660 ° C. However, a fluidized bed could not be formed within a short time, and it became difficult to control the temperature. When the firing furnace was opened after cooling, the catalyst was found to adhere to the furnace walls in a layer.

Comparative Example 3 A molybdenum-enriched catalyst was prepared in the same manner as in Example 2.
However, firing was carried out by using a box-type electric furnace, placed in a ceramic container, and left standing. Calcination is 450 as in Example 2.
C. for 2 hours. The catalyst after calcination was solidified and could not be used as a fluidized bed catalyst unless it was loosened carefully.

Comparative Example 4 The same catalyst as in Example 1 was used for the ammoxidation of propylene. Before the deterioration, the acrylonitrile yield was 81.8%, but it decreased to 79.5% after prolonged reaction. On the other hand, when the same molybdenum-enriched catalyst as in Example 1 was added to 35% by weight of the charged catalyst and reacted, the combustion of ammonia was intense, and the acrylonitrile yield further decreased to 77.6%.

[0031]

According to the present invention, a method for producing a molybdenum-enriched catalyst suitable for use in combination with the molybdenum-containing oxide fluidized bed catalyst of the present invention and its effective use method enable an ammonia using the molybdenum-containing oxide fluidized bed catalyst to be used. In the oxidation reaction, it has become possible to maintain the activity of the catalyst for a long time. The method of the present invention has the following effects. (1) The catalyst performance of the molybdenum-containing oxide fluidized bed catalyst whose activity has been reduced can be easily recovered. (2) Since there is no accumulation of foreign matter in the reaction system, continuous operation can be continued for a long period of time, and the catalyst can be easily recovered and reused. (3) Operational troubles such as scaling of the molybdenum component do not occur. (4) There is no reduction in catalyst strength.

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI B01J 27/199 B01J 27/199 Z C07C 253/26 C07C 253/26 255/08 255/08 // C07B 61/00 300 C07B 61/00 300 (72) Inventor Kunio Mori 10-1 Ogurocho, Tsurumi-ku, Yokohama, Kanagawa Prefecture Nitto Chemical Industry Co., Ltd.

Claims (8)

[Claims] In an ammoxidation reaction of an organic compound using a molybdenum-containing oxide fluidized bed catalyst containing molybdenum, bismuth and iron as essential components, a molybdenum-containing oxide catalyst is impregnated with a solution or suspension containing a molybdenum component. Thereafter, the molybdenum-enriched catalyst obtained by calcining the impregnated particles at a temperature of 200 to 650 ° C. for 0.5 to 10 hours under exercise is added with 0.05 to 30% by weight of the filled molybdenum-containing oxide catalyst. Use of a molybdenum-containing oxide fluidized bed catalyst characterized by being mixed and used within the range described above. 2. The method according to claim 1, wherein the molybdenum-containing oxide catalyst before molybdenum enrichment has the following composition. Mo ₁₀ BiaFebSbcDdEeFfGgHhOi
(SiO ₂ ) j (wherein, Mo, Bi, Fe and Sb represent molybdenum, bismuth, iron and antimony, respectively, and D is composed of magnesium, calcium, strontium, barium, chromium, manganese, cobalt, nickel and zinc. At least one element selected from the group, E is at least one element selected from the group consisting of copper, silver, cadmium, aluminum, gallium, indium, germanium, tin, lead, titanium, zirconium and hafnium;
Is selected from the group consisting of vanadium, niobium, tantalum, tungsten, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, thorium, uranium, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum and gold. G is at least one element selected from the group consisting of phosphorus, boron and tellurium, H is at least one element selected from the group consisting of lithium, sodium, potassium, rubidium and cesium, and O is Oxygen and Si represent silicon, with subscripts a, b, c, d
, E, f, g, h, i and j represent the atomic ratio, and
When = 10, a = 0.1 to 5, b = 0.1 to 15, c = 0
-20, d = 0-10, e = 0-10, f = 0-10,
g = 0 to 5, h = 0 to 3, i = the number of oxygens corresponding to oxides generated by combining the above components, and j = 20 to 150. ) 3. The method for using a molybdenum-containing oxide fluidized bed catalyst according to claim 1, wherein the ammoxidation reaction is a synthesis reaction of acrylonitrile by a reaction of propylene, oxygen and ammonia. 4. A calcining method under motion for producing a molybdenum-enriched catalyst includes a rotary calcining furnace, a fluid calcining furnace,
4. The method for using a molybdenum-containing fluidized bed catalyst according to claim 1, wherein at least one kind of sintering method selected from the group consisting of a moving bed sintering furnace and a moving bed sintering furnace is used. . 5. The molybdenum raw material of the impregnating liquid or suspension for producing the molybdenum-enriched catalyst is selected from the group consisting of molybdenum trioxide, ammonium molybdate, peroxomolybdic acid and / or its ammonium salt, and phosphomolybdic acid. The method for using a molybdenum-containing fluidized-bed catalyst according to any one of claims 1 to 4, wherein at least one compound is used. 6. The method according to claim 1, wherein the impregnated and enriched component contains at least one element selected from the group consisting of phosphorus, boron, and potassium, in addition to molybdenum. The use of the fluidized bed catalyst containing molybdenum described in 1 above. 7. The catalyst for a fluidized-bed molybdenum-containing oxide according to claim 1, wherein the amount of the molybdenum enriched is 5 to 50% by weight as molybdenum trioxide. Usage of. 8. The use of the fluidized-bed molybdenum-containing catalyst according to claim 1, wherein the molybdenum-enriched catalyst has the following composition. Mo ₁₀ Bia'Feb'Sbc'Dd'Ee'Ff'Gg'Hh'Oi '
(SiO ₂ ) j ′ (wherein, Mo, Bi, Fe and Sb represent molybdenum, bismuth, iron and antimony, respectively, and D represents magnesium, calcium, strontium, barium, chromium, manganese, cobalt, nickel and zinc. E is at least one element selected from the group consisting of copper, silver, cadmium, aluminum, gallium, indium, germanium, tin, lead, titanium, zirconium and hafnium; and F is at least one element selected from the group consisting of
Is selected from the group consisting of vanadium, niobium, tantalum, tungsten, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, thorium, uranium, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum and gold. G is at least one element selected from the group consisting of phosphorus, boron and tellurium, H is at least one element selected from the group consisting of lithium, sodium, potassium, rubidium and cesium, and O is Oxygen and Si represent silicon with subscripts a ', b', c ',
d ', e', f ', g', h ', i' and j 'indicate atomic ratios, and
= 10, a '= 0.02 to 4, b' = 0.02 to 12, c '
= 0 to 15, d '= 0 to 8, e' = 0 to 8, f '= 0 to 8, g'
= 0 to 4, h '= 0 to 2, i' = the number of oxygens corresponding to the oxides formed by combining the above components, and j '= 4 to 120. )