JPS59139938A - Preparation of fluidized bed catalyst for phosphorus- containing metal oxide - Google Patents

Abstract

PURPOSE:To economically prepare a metal oxide fluidized bed catalyst having good catalytic activity and selectivity, by a method wherein a particulat catalyst precursor and a phosphorus-containing solid are dry blended under heating and a phosphorus component is volatilized to be deposited on the catalyst precursor. CONSTITUTION:A phosphorus-containing solid pref. containing P, P2O5 or the like and having a particle size of 0.1-1,000mum is dry blended with a metal oxide catalyst precursor which is baked at 300-1,000 deg.C, pref. contains one or more of Sb, Mo and V and has a particle size of 5-300mum and the resulting mixture is held at 300-850 deg.C for a sufficient time in a non-reductive gaseous atmosphere containing H2 or NH3 and O2 to deposit the phosphorus component volatilized from the above mentioned phosphorus solid on the above mentioned catalyst precursor. By this method, a phosphorus-containing metal oxide fluidized bed catalyst used in oxidation, ammoxidation or oxidative dehydrogenation reaction of an org. compound is obtained. In this case, the deteriorated catalyst of which the activity is lowered by using the same in the above mentioned reactions can be used as the bove-mentioned catalyst precursor.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a phosphorus-containing metal oxide fluidized bed catalyst.

The production of aldehydes, acids, nitriles, diolefins, alkenylbenzenes, etc. by oxidation, ammoxidation, or oxidative dehydrogenation of organic compounds is known. Many metal oxide catalysts have been proposed as catalysts for these reactions. For example, examples of catalysts mainly containing antimony include the oxide catalyst of antimony and iron, conorct or nickel described in Japanese Patent Publication No. 39-19111;
The 2% oxide catalyst of antimony and tin described in Japanese Publication No. 14075 and the oxide catalyst of antimony and uranium described in Japanese Publication No. 1982-24367 are known.

As a catalyst mainly composed of molybdenum,
Oxide catalysts of molybdenum and bismuth, etc. described in Japanese Patent Publication No. 870, oxide catalysts of molybdenum and cerium, lanthanum, thorium, bismuth, tellurium, etc. described in Japanese Patent Publication No. 39-8214, described in Japanese Patent Publication No. 41-7774 Oxide catalysts containing molybdenum, tellurium and zinc are known. Also, as a catalyst mainly composed of vanadium.

An oxide catalyst of vanadium and chromium described in Japanese Patent Publication No. 35-15689 and an oxide catalyst of vanadium and titanium etc. described in Japanese Patent Publication No. 49-34673 are known.

Furthermore, various attempts have been made to improve these catalysts.

Although these catalysts have good performance, they are not always satisfactory in terms of selectivity for the desired product.

It should be noted that many of these catalysts containing phosphorus tend to lose their activity or catalytic performance while being used in reactions, and attempts to regenerate such deactivated catalysts have been proposed. It was done. For example,
Publication No. 3-15065 discloses that organic phosphorus is added to the catalyst in order to regenerate the deactivated catalyst used in two reactions during the production of maleic anhydride by gas phase oxidation of butenes using a vanadium-phosphorus-oxygen catalyst. It is described that a compound gas is introduced. Furthermore, Japanese Patent Publication No. 16510/1983 describes vanadium-phosphorus based on a technical concept similar to the above.
In the production of maleic anhydride by gas-phase oxidation of butenes and/or butadiene using an oxygen-based catalyst and iron oxide, it is described that an organic phosphorus compound gas is fed into the reaction system.

Furthermore, a method for producing a phosphorus-containing catalyst by introducing an organic phosphorus compound gas into a base catalyst has also been proposed. For example, in JP-A-53-44518, an organic phosphorus compound gas is introduced into a vanadium-titanium-oxygen-based catalyst, and the resulting phosphorus-containing catalyst is subjected to gas phase oxidation of butenes or butadiene to produce maleic anhydride. It has been described that it is used as a catalyst for Nodame.

These methods (i.e., Japanese Patent Publication No. 43-15065, Japanese Patent Publication No. 55-16510, and Japanese Patent Application Laid-open No. 53-4
The methods described in Japanese Patent No. 4518) are all related to fixed bed reactions, and more importantly, the organic phosphorus compound is introduced as a gas. Since organic phosphorus compounds are generally expensive and often toxic, these methods are economically disadvantageous and have safety problems.

Moreover, these methods require the precise delivery of a predetermined amount of gas and must therefore be equipped with a specially designed organophosphorus compound delivery device, which is economically disadvantageous and unsatisfactory. Moreover, the driving operation is also complicated.

Yet again. It has also been proposed to physically mix a phosphorus-containing catalyst and a phosphorus compound-containing solid to carry out gas-phase oxidation or gas-phase oxidative dehydrogenation of organic compounds in the presence of the mixture. For example, JP-A-57-72937 discloses that such phosphorus compound-containing solids are used in the production of methacrylic acid by gas phase oxidation of methacrolein using phosphomolybdic acid, phosphomolybdovanadate, or their salts as catalysts. JP-A No. 57-147441 describes such a process for producing methacrylic acid by gas-phase oxidative dehydrogenation of inbutyric acid using an iron/phosphate catalyst. Physical mixing of solids containing phosphorus compounds is described. However, these methods are all related to fixed-bed reactions, and in addition, catalyst precursor particles and phosphorus-containing solid particles are mixed into these particles.
No technical idea has been found to form a phosphorus-containing catalyst by physically mixing the phosphorus components under the movement conditions of the particles and depositing the phosphorus component volatilized from the latter onto the former.

The present invention provides a new method for preparing phosphorus-containing metal oxide catalysts that is particularly satisfactorily implemented for fluidized bed catalysts. Moreover, the present invention is from another point of view.

This method can also be applied to a method for regenerating a catalyst that has deteriorated after being used in a reaction. The present invention has significant industrial value in that it can produce a high-performance catalyst or regenerate it into a high-performance catalyst with good reproducibility through simple operations.

According to the present invention, oxidation of organic compounds, ammoxidation, -!
: For metal oxide catalyst precursors in particle form suitable for use in fluidized beds calcined at temperatures of 300°C to 1000°C in the production of metal oxide fluidized bed catalysts used in oxidative dehydrogenation reactions. , dry mixing the phosphorus-containing solids in a gaseous atmosphere at a temperature of 300 to 850 degrees Celsius under conditions of movement of the particles, and the resulting mixture is such that the phosphorus component volatilized from the phosphorus-containing solids is deposited on the catalyst precursor. Provided is a method for producing a phosphorus-containing metal oxide fluidized bed catalyst, the method comprising: maintaining the above mixing conditions for a sufficient time to form a phosphorus-containing catalyst.

Two aspects of the present invention will be specifically described below.

Metal oxide catalyst precursor The metal oxide catalyst precursor used in the present invention includes:

Preferably, it is an oxide containing at least antimony, molybdenum, or vanadium.

These oxides can be used as they are, or as silica,
It may be supported on various carriers such as alumina, silica/alumina, silica/titania, titania, and zirconia.

This metal oxide catalyst precursor can be produced by any known method as shown, for example, in the above-mentioned patents.

This catalyst precursor is calcined at 300°C to 1000°C and is said to have a certain level of strength. Although the preferable temperature range varies depending on the component composition, in most cases, firing may be performed within this temperature range, more preferably within a temperature range of 400° C. to 900° C., for 0.5 to 50 hours.

In addition to the catalyst precursors prepared as described above, they were used in two reactions. It also deteriorated after being used in the reaction. A catalyst containing at least one element selected from the group consisting of antimony, molybdenum, and vanadium is also considered a type of catalyst precursor.

These are generally fired at a temperature of 300°C to 1000°C and have sufficient mechanical strength to be used in the present invention.

Typical compositions of the catalyst precursor include the following.

Mea Qb Re Td Pe Of (SiOz
)g In the above formula, Me = at least one element selected from the group consisting of Sb, Mo and V Q = Fe, Co, Ni, Mn, Ce, U
, sn, Ti, Cu and Zn at least one element R = Li, Na, K, Rb, Cs, Be
, Mg, Ca, Sr.

Ba, Y, La, Th, Zr, Hf, Nb
, Ta, Cr.

W, fLe, Ru, Os, Rh, Ir, P
d, Pt, Ag.

Cd, B, AI, Ga, In, TI, Oe,
Pb, As.

At least one element T selected from the group consisting of S and Se = B; at least one element P selected from the group consisting of Te and Bi represents phosphorus.

The subscripts aI bl" l dl e and f indicate the atomic ratio.

Each falls within the following range.

a = 5 ~ 100 b -5 ~ 15 c = Q ~ 15 d = Q ~ 10 e = 0 ~ 10 f - number corresponding to the oxide produced by the combination of the above components g = o ~ 200 The phosphorus component is Although it does not need to be contained, it may be contained in some amount.

The carrier components include the aforementioned silica and alumina.

Silica alumina, silica titania, titania.

Although zirconia and the like can be used, silica is particularly preferred.

The invention applies in particular to the production of fluidized bed catalysts.

As a catalyst precursor for this purpose, it is preferable to use one molded by the same method as in the case of producing a fluidized bed catalyst. That is, it is convenient and preferable to apply the method of the present invention after shaping the product into a form that can be subjected to the final reaction.

The particle size of the catalyst precursor is preferably in the range of 5 to 300 microns.

These are usually molded by spray drying.

Metal Oxide Catalyst The catalyst produced in the present invention contains phosphorus and at least one element selected from the group consisting of antimony, molybdenum, and vanadium. The composition is preferably as shown by the following empirical formula. These compositions may be used as they are or supported on various carriers such as silica, alumina, silica/alumina, silica/titania, titania, and zirconia. Perilla is particularly preferred as the carrier component.

Aa Eb Cc Dd Pe Of (Si02)
g In the above formula, A = at least one element selected from the group consisting of Sb, Mo and V B = Fe, Co, Ni, Mn, Ce, U
, Sn, Ti, Cu, and at least one element C selected from the group consisting of Zn = Li, Na, K, Rb, Cs, Be,
Mg, Ca, Sr, Ba.

Y, La, Th, Zr, Hf, Nb, Ta
, Cr, W, Re.

Ru, Os, Rh, Ir, Pd, Pi, Ag, Cd, B
, A.I.

Ga, In, TI, Ge, Pb, As, S
and at least one element D selected from the group consisting of Se represents B, and at least one element P selected from the group consisting of Te and Bi represents phosphorus.

Subscripts a, b, c, d, e, f and g indicate atomic ratios, each within the following range.

a = 5-100 b=5~15 c=Q~15 d=0~10 e=0.05~10 f - Number corresponding to the oxide formed by combining each of the above components g=Q~200 This catalyst is used for the oxidation of organic compounds and ammoxidation.

It can be widely used for oxidative dehydrogenation, etc.

Specifically, the production of formaldehyde by oxidation of methanol, the production of hydrogen cyanide by ammoxidation of methanol, the production of acrolein and acrylic acid by oxidation of propylene, and the production of acrylonitrile by ammoxidation of propylene.

Production of methacrolein and methacrylic acid by oxidation of isobutyne and tert-butanol, production of methacrylonitrile by ammoxidation of isobutyne and tert-butanol, production of maleic anhydride by oxidation of n-butenes, oxidation of n-butenes Production of butadiene by dehydrogenation, production of benzaldehyde by oxidation of toluene, production of benzonitrile by ammoxidation of toluene.

Production of phthalonitrile, isophthalonitrile, terephthalonitrile, etc. by ammoxidation of xylene.

This includes the production of cyanopyridines by ammoxidation of alkylpyridines.

The fact that the addition of phosphorus is effective in improving the performance of these catalysts is that
Some examples are known, but in all of them, the phosphorus raw material and other catalyst raw materials are mixed, molded, and fired when preparing the catalyst. but.

Addition of a phosphorus component generally increases the calcination temperature dependence of the catalyst and has problems such as poor reproducibility.

According to the method of the present invention, a high-performance phosphorus-containing catalyst can be produced in a simple manner and with good reproducibility. However, the phosphorus-containing catalyst obtained by the method of the present invention is different from the phosphorus of the same composition obtained by the conventional method, that is, the method of mixing the entire amount of phosphorus raw material and other catalyst raw material components at the time of preparation of the catalyst, molding, and firing. It has the advantage of giving higher yields of the desired product than containing catalysts.

Many phosphorus-containing solids can be used.

Elemental phosphorus, phosphorus pentoxide, condensed phosphoric acid, ammonium phosphate, or ammonium salts of condensed phosphoric acid as
Alternatively, examples include those in which at least one of these or phosphoric acid is supported on an inert carrier, a metal oxide catalyst precursor, a metal oxide catalyst, or the like.

All of these phosphorus-containing solids must be used in combination with a catalyst precursor. When applied to the production of fluidized bed catalysts, it is particularly preferred to apply the method of the invention under fluidized conditions of both the phosphorus-containing solid and the metal oxide catalyst precursor.

Therefore, if the particle size of the phosphorus-containing solid is too small, it will escape out of the system during operation.

Furthermore, if the particle size is too large, mixing with the catalyst precursor will be poor, resulting in non-uniform deposition of the phosphorus component and insufficient effectiveness. The particle size of the phosphorus-containing solid is o, 1 to 1000
It is preferable to set it in the micron range.

Catalyst Manufacturing Method The method for manufacturing a catalyst according to the present invention involves bringing a metal oxide catalyst precursor into contact with a phosphorus-containing solid in a gaseous atmosphere at an elevated temperature.

Although the method of the present invention can be applied to fixed bed catalysts and fluidized bed catalysts, it is particularly effective when carried out under the motion of fluidized bed catalysts. That is, as preferred methods, there are two types of rotary kilns and fluidized kilns. In particular, it is preferable to use a fluidized calcination furnace. It is believed that one reason for the good results is that the phosphorus component and the metal oxide catalyst precursor are brought into contact evenly in the fluidized state.

The effects of the present invention are manifested by the transfer of the phosphorus component to the catalyst precursor and its deposition. If the amount of phosphorus supplied is too small, there will be little effect, and if it is too large, the reaction rate will be lowered and the yield of the desired product will be lowered. Although the amount of the phosphorus component added to the catalyst precursor varies depending on two various conditions, it is preferable that the phosphorus content in the finished catalyst falls within the catalyst composition range described below.

It is also recommended that the phosphorus component to be added be added little by little continuously or intermittently, rather than all at once.

The phosphorus-containing solid may be dry mixed with the catalyst precursor before treatment or may be added and mixed during the treatment operation. When targeting the production of fluidized bed catalysts.

Addition of phosphorus-containing solids during processing operations is easy to implement.

Many examples can be given of the gas atmosphere.

Air, oxygen, nitrogen, helium, argon.

Carbon dioxide, nitrous oxide, -nitric oxide, nitrogen dioxide.

An oxidizing or non-reducing gas such as water vapor, or a gas containing oxygen and at least one reducing gas selected from hydrogen, ammonia, carbon oxide, methanol, hydrocarbons, and other organic compounds. Can be used.

When using only a reducing gas, it becomes very difficult to set the processing conditions, ie, the selection of the reducing gas, the temperature for 1 hour, etc., so it is better to avoid this except in special cases.

Preferred treatment temperatures and times vary depending on the state of the phosphorus component. If the vapor pressure of the phosphorus component is high, or if the phosphorus component is easily converted into something with a high vapor pressure, a relatively low temperature and short time may be required; if the vapor pressure of the phosphorus component is low, the temperature may be It is best to set the temperature higher and make it 2 hours longer. Normally.

Temperature of about 300℃ to 850℃, 0.5 to 50
All you have to do is process the time. If the temperature is below 30°C, the effect will be small, and if the temperature is above 850°C, the activity of the catalyst will decrease.

Metal oxide catalyst precursors for the oxidation of organic compounds.

If the catalyst is used for ammoxidation or oxidative dehydrogenation, the selectivity of the target product is reduced.

Since the reaction gas itself is contained in the gas atmosphere of the present invention and the reaction temperature is generally 300°C to 600°C, the method of the present invention can be applied by adding a phosphorus-containing solid during the reaction. I can do it. In this case, it is preferred to apply the method of the invention under the motion of the catalyst, so that it is generally applied in the case of fluidized bed reactions. This method can be viewed as a type of catalyst regeneration. In many cases, the catalyst is regenerated by extracting it from the entire catalyst reactor, but when the present invention is applied, this is not necessary and two reactions are being carried out.

That is, the process can be carried out while continuing to produce the desired product, which is economically advantageous. Also.

Unlike the method of feeding a gaseous phosphorus-containing compound, this method does not require the installation of a special supply device and can be carried out with existing equipment, making it easy to implement and economical.

In this way, the selectivity of the target product can be improved by depositing the phosphorus component on the catalyst surface, but after this treatment, about 400
By calcining at a temperature of .degree. C. to about 900.degree. C., it may be possible to improve the selectivity of the desired product and the sustainability of the activity.

The deposited phosphorus component reacts with the metal oxide catalyst precursor,
It is thought that the expression and stabilization of favorable active sites can be achieved.

EXAMPLES The effects of the present invention will be illustrated by the following two examples and comparative examples.

Note that 1. The yield and selectivity of the target product in this specification are 2.
According to the following definition.

The activity test conditions were the following energization.

(1) Propylene ammoxidation catalyst A fluidized bed reactor with an inner diameter of 2.5 m and a height of 140 cm was filled with a catalyst, and a gas having the following composition was introduced.

The reaction pressure is normal pressure.

02 (supplied as air) / propylene = 2.2 (1) mol NH3 / propylene - 1,1 (1) mol (2) Ammoxidation of isobutyne Use the same reactor as the ammoxidation reaction of glopylene in the previous section 2
A gas of the following composition was introduced.

The reaction pressure is normal pressure.

H20/isobutine -1,0(/ )
Ammoxidation of mol (3) toluene The same reactor as in the previous section was used, and a gas having the secondary composition was introduced.

The reaction pressure is normal pressure.

02 (supplied as air)/toluene =2.5(/
) mol NH3/) Luene -1,5(/ )
Mol H20/l Luene -2,5(/ )
Oxidative dehydrogenation of mole (4) butene The same reactor as in the previous section was used, and a gas having the secondary composition was introduced.

The reaction pressure is normal pressure.

Oxygen (supplied as air)/butene-1=3.0(/
)mol(5) Oxidation of Butene The same reactor as in the previous section was used, and a gas having the secondary composition was introduced.

The reaction pressure is normal pressure.

Oxygen (supplied as air)/Butene-1=5.2(/
)Mole Example 1 Empirical formula is r 5b25 Feto Vo-t Pl, O
A catalyst having a temperature of 067,75 (S 1o2) 3° was prepared as follows.

Take 558 g of antimony trioxide powder. (1) Take 85.6 g of electrolytic iron powder. Nitric acid (specific gravity 1.38) 0.66
t and pure water 0.831 are mixed and heated. Add electrolytic iron powder little by little to this and dissolve. (II) Silica sol (8
10220% by weight). (III) Take 1.79 g of ammonium metavanadate and add 0.0 g of pure water.
．． Dissolve in 18t. (IV) While stirring (III) well, (IV), (II)
) and (I) in this order.

15 Add ammonia water little by little to adjust the pH to 2.

While stirring the slurry thus obtained,
The mixture was heated at 00°C for 5 hours.

This slurry was then spray-dried in a conventional manner using a rotating disk type spray dryer.

The fine spherical particles thus obtained were calcined at 200°C for 4 hours and at 500°C for 4 hours.

This was placed in a small rotary firing furnace and fired at 850°C for 1 hour, then 10.9 g of phosphorus pentoxide was added and fired under the same conditions for an additional 3 hours.

The catalyst thus prepared was used in the reaction according to activity test conditions (1).

Example 2 The empirical formula is r 5b25 Fe1o COs Wo, s
A catalyst with Pa, s 072.75(5i02)30 was prepared in a similar manner to Example 1.

That is, 5bzs Fe , o Co5 w,, 07
The catalyst precursor (50
995g of product baked at 0°C for 4 hours was placed in a fluidized kiln.85
After firing at 0°C for 1 hour, a portion of it was taken out, 5.09 g of phosphorus pentoxide was added thereto, and the mixture was filled again, and fired at 850°C for 3 hours in air.

The catalyst thus prepared was used in the reaction according to activity test conditions (1).

Example 3 The empirical formula is pS')25S,nlO"0.50?0.
13 (S'02)3G was prepared as follows.

423 g of metal antimony powder (100 mesh or less) and 165 g of metal tin powder (100 mesh or less) are added little by little into 1840 ml of heated nitric acid (specific gravity 1.38). After the generation of brown gas has stopped, leave it at room temperature for 16 hours. After that, excess nitric acid was removed and the precipitate was
Wash 3 times with 000 mA water.

This is silica sol (Si0220 Xi%) 1254
Mix well with g and spray dry in a conventional manner.

After baking at 200°C for 2 hours and at 400°C for 2 hours.

It was fired at 880°C for 4 hours.

4.94 g of phosphorus pentoxide was added to this, and the mixture was placed in a small rotary firing furnace and fired at 500°C for 5 hours under the flow of a gas consisting of 71.1% nitrogen, 18.9% oxygen, and 10% ammonia.

The catalyst thus prepared was used in the reaction according to activity test conditions (1).

Example 4 The empirical formula is 5b30 UIOPo,s Oss,6t (
A catalyst, S jOz )6o, was prepared as follows.

Metallic antimony powder (less than 10'Om) 328g
Add it little by little into 1210 m of heated nitric acid (specific gravity 1.38). Add all the antemos.

After the brown gas is generated and the mixture freezes, it is left at room temperature for 16 hours. Afterwards, excess nitric acid is removed and the precipitate is washed three times with 700 Tnl of water. (I) Dissolve 20451 g of uranyl nitrate UO2 (NO26H) in 300 ml of pure water. (II) Take 1619 g of silica sol (20% by weight of Si02).

(III) (1), (n), and (III) are thoroughly mixed and spray-dried by a conventional method.

This was fired at 200°C for 2 hours, then at 400°C for 2 hours, and then at 900°C for 2 hours.

Add 8.26'g of monoammonium phosphate to this.

The mixture was placed in a small rotary kiln and fired at 500°C for 4 hours in nitrogen.

The catalyst thus prepared was used in the reaction according to activity test conditions (1).

Example 5 The experimental formula is MO12B i6 Sb1°N ie
P t,s K1. lI 075.5 (Sich)
A catalyst No. 70 was prepared as follows.

2215 g of silica sol (SiOz 20% by weight) was poured.

To this was added 15.5 g of phosphoric acid (content 85% by weight).

(1) 223 g of ammonium paramolybdate was dissolved in 550 g of pure water and added to 1). (II) Nickel nitrate 184
g, and 24.0 g of potassium nitrate were added to (II). (I
II) 307 g of bismuth nitrate, 330 g of nitric acid (30% by weight)
g and added to (■). (R') Add 154 g of antimony dioxide to and υ and (■).

Stir well.

This slurry was spray-dried by a conventional method and calcined at 200°C for 2 hours and at 400°C for 2 hours.

The composition of the catalyst precursor thus prepared is:

MOO20Bi6 Sb1g Ns6 Pl, O
K1.5 074.25 (SI02) 70
be.

Add 6.06 g of monoammonium phosphate to this.

The mixture was placed in a rotary firing furnace and fired at 600°C for 3 hours in air.

The catalyst thus prepared was used in the reaction according to activity test conditions (2).

Example 6 The experimental formula is V12 Pl, 50ssrs (S !O
z ) io catalyst was prepared in the following manner.

Take 3653g of silica sol (5i0220% by weight),
Add 27.7 g of 85-thiphosphoric acid to this and stir well. (
I) Add 337 g of ammonium metavanadate to 33 tons of pure water. (n) Add (II) to (1) while stirring well, and stir for 50 minutes.
Warm to ℃ and hold for 1 hour.

This slurry was spray dried in a conventional manner.

This was fired at 150°C for 16 hours and then at 500°C for 2 hours.

The catalyst composition of the catalyst precursor thus prepared was V12
Pl, 0032.5 (S iOz )so.

To this 971 g, 29 g of a separately prepared phosphorus component enriched catalyst (described later) was added, fluidized in air at 400° C. for 1 hour, and then used for reaction according to activity test conditions (3).

The phosphorus-enriched catalyst used here was obtained by impregnating the above catalyst precursor with phosphoric acid, drying it, and finally calcining it at 300°C for 1 hour.

The composition of this phosphorus-enriched catalyst is r V12 P 2g-42
, 093-55 (Sin2) 5o.

Example 7-1 The empirical formula is 5b25 Fe16 CLI3 MOo,
5 Wo, 3 Te1.00?2.4(Si02)60
When a fluidized bed catalyst was used for a long period of time in the ammoxidation reaction of propylene, its activity decreased.

For this catalyst, silica-supported solid phosphoric acid particles (average particles,
50 microns in diameter) and used in the reaction according to activity test conditions (1).

By adding the phosphorus component, the experimental formula of the catalyst became the following composition.

8 b25 F e 10 C03' Mo(1,5W
o, 3 T el, o P [1,5073,65(S
402) 60 Example 7-2 For the same degraded catalyst used in Example 7-1.

Ammonium phosphate was added and used for reaction according to activity test (1).

By adding the phosphorus component, the experimental formula of the catalyst became the following composition.

5b25 Fed(,Cu3Mo(,,5W,),3
're1. o po, 5 o73.65 (S 10
2) 6.1 Example 8 The empirical formula is 5b25 pelo Cu3 MOO,5
wo, 3Te4. ．． 1 F 1.2075.4 (S
A fluidized bed catalyst with i 02 ) 63.4 was prepared as follows.

The empirical formula is 5b25 Fed0 Cu3 MO(1,
5W. , 3'1"el, Oo72.4 (S 1o2)
A catalyst precursor No. 60 was prepared by spray drying in the same manner as in Example 1.

Copper nitrate was used as the Cu component raw material, ammonium paramolybdate was used as the Mo component raw material, ammonium paratungstate was used as the W component raw material, and telluric acid was used as the Te component raw material.

After spray drying, it was baked at 200°C for 4 hours and at 400°C for 4 hours.

Finally, it was fired at 780°C for 5 hours.

To the thus prepared catalyst precursor, 35 g of solid phosphoric acid supported on silica was added and treated at 400° C. for 2 hours while passing a mixed gas of ammonia and air (10% ammonia).

. The catalyst thus prepared is a phosphorus-containing metal oxide fluidized bed catalyst having the composition indicated.

Using this catalyst, a reaction was carried out according to activity test conditions (1).

Example 9 The empirical formula is 5b2oF'elOco3Moo, 5'
A fluidized bed catalyst with I''45 pO, 8o62.5 (S 102)60 was prepared as follows.

A catalyst precursor containing components other than phosphorus was prepared by spray drying in the same manner as in Example 1.

The raw material for the Co component was cobal nitrate), the raw material for the Mo component was ammonium paramolybdate, and the raw material for the Te component was telluric acid.

After spray drying, it was baked at 200°C for 4 hours and then at 400°C for 4 hours.

Finally, it was fired for 81,005 hours.

18 g of pentoxide phosphorus was added to 993 g of the catalyst precursor thus prepared, and the mixture was treated at 400° C. for 1 hour while passing a mixed gas of ammonia and air (10 cups of ammonia).

The catalyst thus prepared is a phosphorus-containing metal oxide fluidized bed catalyst having the composition shown.

Using this catalyst, a reaction was carried out according to the activity test conditions (4).

Example 10 The experimental formula is Vs P+s Fe5057.5 (Ti
02)20 (S 1Oz)t.

A catalyst was prepared in the following manner.

Dissolve 508 g of ferric nitrate in 200 ml of pure water.

To this was added 377 g of 85q6 phosphoric acid, and then 147 g of ammonium metavanadate was mixed and stirred well.

Take 56 g of silica sol (SiC) + 20 weight retaining plate.

This was prepared earlier. Add slurry containing V, Fe, and P components, and then add 402 g of titanium dioxide powder.
was added and mixed well.

This was spray dried using a conventional method.

Then, it was fired at 350°C for 2 hours and finally at 550°C for 2 hours.

The composition of the catalyst precursor prepared in this way is ■5P13
Fes 062.5 (Ti02)20 (S i
Oz)io.

To 832 g of this catalyst precursor, 168 g of a separately prepared phosphorus enriched catalyst was added and used in the reaction according to the activity test conditions (5).

Accordingly, the catalyst has the indicated composition.

The phosphorus-enriched catalyst used here was obtained by impregnating the above catalyst precursor with phosphoric acid, drying it, and finally calcining it at 300'C for 1 hour. The composition of this phosphorus-enriched catalyst is V5 P27.56 Fe50S&9 (TiOz
)20(S!Oz)to.

Comparative Example 1 Empirical formula is r 5b2S Fe1OVo, t Pl, O0
67,75(S 1o2)3° (same composition as the catalyst of Example 1) in the same manner as Example 1, but with the phosphorus component.

A predetermined amount of phosphoric acid was added to the slurry and mixed well before adjusting the pH of the slurry.

The final firing was carried out at 850°C for 4 hours.

Using this catalyst, a reaction was carried out under activity test conditions (1).

Comparative Example 2 Empirical formula is +, S b255n10 P o, s 07
0.13 (S 102 )30 (Example 3)
(same composition as the catalyst) was prepared in the same manner as in Example 3, except that a predetermined amount of phosphoric acid as the phosphorus component was added to the slurry before pH adjustment and mixed well.

The final firing was carried out at 880°C for 4 hours.

Using this catalyst, a reaction was carried out under the activity test conditions (1).

Comparative Example 3 The empirical formula is r V12 Pl, 5033.75 (SiO
z) so catalyst (same composition as the catalyst of Example 6),
A sample was prepared in the same manner as in Example 6, except that a predetermined amount of phosphoric acid as a raw material for the phosphorus component was mixed into the slurry before pH adjustment.

The final firing was carried out at 500°C for 2 hours.

Using this catalyst, a reaction was carried out under activity test conditions (3).

The catalysts used in the above Examples and Comparative Examples and their activity test results are summarized in the following table.

Claims (9)

[Claims] (1) Particle shape suitable for use in a fluidized bed calcined at a temperature of 300°C to 1000°C in the production of metal oxide fluidized bed catalysts used in oxidation, ammoxidation, or oxidative dehydrogenation reactions of organic compounds. of metal oxide catalyst precursor in a gas atmosphere under conditions of movement of the particles.
Dry mixing the phosphorus-containing solids at a temperature between 850°C and the resulting mixture for a time sufficient for the phosphorus component volatilized from the phosphorus-containing solids to deposit on the catalyst precursor to form a phosphorus-containing catalyst. A method for producing a phosphorus-containing metal oxide fluidized bed catalyst, which is maintained under the above mixing conditions. (2) The method according to claim 1, wherein the catalyst contains at least one element selected from the group consisting of antimony, molybdenum, and vanadium. (3) The particle size of the metal oxide catalyst precursor is 5 to 300
Claim 1 or 2 in the micron range
The method described in section. (4) The metal oxide catalyst precursor is a degraded catalyst whose activity has decreased when used for oxidation, ammoxidation, or oxidative dehydrogenation of organic compounds. A method according to any one of claims 1 to 3. (5) A phosphorus-containing solid is dry mixed with a catalyst precursor. Phosphorus, phosphorus pentoxide, condensed phosphoric acid, ammonium phosphate,
Ammonium salts of condensed phosphoric acids, at least one of these or phosphoric acid supported on an inert carrier, at least one of these or phosphoric acid enriched and supported on a metal oxide catalyst precursor or a metal oxide catalyst The method according to any one of claims 1 to 4, which is any of the above. (6) Any one of claims 1 to 5, wherein the gas atmosphere is a gas containing oxygen and at least one gas selected from the group consisting of hydrogen, ammonia, carbon oxide, and organic compounds. The method described in. (7) Dry mixing a metal oxide catalyst precursor with a phosphorus-containing solid and treating it in a gas atmosphere to deposit a phosphorus component onto the catalyst precursor to form a phosphorus-containing catalyst; 7. The method according to any one of claims 1 to 6, wherein the firing is performed at about 400<0>C to about 900<0>C in a non-reducing atmosphere. (8) The particle size of the metal oxide catalyst precursor is 5 to 300
micron, and the particle size of the phosphorus-containing solid is 0.1 to 1
8. A method according to any one of claims 1 to 7 in the range of 0.000 microns. (9) The method according to any one of claims 1 to 8, wherein the prepared catalyst has the following composition. Aa Bb Cc Dd Pe Of (SiOz)g
In the above formula, A = at least one element selected from the group consisting of Sb, Mo, and ■ B == Fe, Co, Ni, Mn, Ce,
At least one element C selected from the group consisting of U, Sn, Ti, Cu, and Zn = Li, Na, Rb, Cs, Be, Mg, Ca
, Sr., Ba. Y, La, Th, Zr, Hf, Nb, Ta, Cr, W,
Re. Ru, Os, Rh, Ir, Pd, Pt, Ag, Cd, B
, A.I. Ga, In, TI, Ge, Pb, As, S
and at least one element selected from the group consisting of Se, D = B, at least one element selected from the group consisting of Te and Bi. The subscripts a, b, c, d, e, f and g indicate the atomic ratio. , respectively, are in the following ranges. a = 5 ~ 100 1) = 5 ~ 15 C = O ~ 15 d = Q ~ 10 e = 0.05 ~ 10 f - number corresponding to the oxide produced by the combination of the above components g = o ~ 200 α0) The metal oxide catalyst precursor is a degraded catalyst that has been used in the oxidation, ammoxidation, or oxidative dehydrogenation reaction of an organic compound and has a reduced selectivity to the target product, and is phosphorized during the reaction. The method according to any one of claims 1 to 5 and 7 to 9, wherein the solid is mixed with the contained solid.