JP3376105B2 - Method for regenerating iron / antimony / phosphorus-containing metal oxide catalyst - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for regenerating a metal oxide catalyst containing iron, antimony and phosphorus as essential components, more specifically iron used for oxidation, ammoxidation or oxidative dehydrogenation of organic compounds. The present invention relates to a method of recovering the performance of a metal oxide catalyst containing antimony phosphorus as an essential component, the activity or the catalyst strength of which has deteriorated.

An oxide catalyst containing iron, antimony and phosphorus is
Useful for production of aldehydes by oxidation of organic compounds, production of dienes, alkenylbenzenes, unsaturated aldehydes or unsaturated acids by oxidative dehydrogenation of organic compounds, and production of nitriles by ammoxidation of organic compounds Is known. For example, Japanese Patent Publication Sho 54
-39839, JP 1-171640, JP 1-257125
JP-A No. 1-143643 and JP-A No. 3-26342 disclose an ammoxidation of methanol, an ammoxidation of methanol, an ammoxidation of propylene, an ammoxidation of isobutene, and an oxidative dehydration of ethylbenzene. Plain examples are given.

The above-mentioned catalyst is good in both activity and sustainability of activity, and particularly exhibits excellent catalytic performance in the production of hydrogen cyanide by the ammoxidation reaction of methanol. However, the activity may gradually decrease with long-term reaction use. In addition, the decrease in activity may be accelerated due to inappropriate reaction conditions. Most of them are reductions in the target product yield due to a decrease in the selectivity of the target product. When the activity decreases to a certain extent or more, it becomes impossible to use the deteriorated catalyst as it is from the economical point of view. In particular, in the case of a large industrial production scale (for example, acrylonitrile production), the deterioration of the catalyst performance has a great influence on the economical efficiency.
At some point, if not replaced with fresh catalyst, significant economic losses will occur. However, since this kind of catalyst is expensive, replacing a deteriorated catalyst with a new catalyst also causes a large economic burden. Also, such a catalyst,
The iron / antimony / phosphorus-containing metal oxide catalyst may gradually decrease in catalyst strength after long-term use. Decrease in catalyst strength is one of the factors that increase catalyst scattering, and in the worst case, stable operation becomes difficult due to blockage of the flow path.
In such a case, it will be very economically advantageous if a suitable catalyst regeneration method is found.

[0004]

2. Description of the Related Art Various methods for regenerating deteriorated antimony-containing catalysts have been proposed. For example, there is JP-A-47-8615 for an antimony-uranium oxide catalyst and JP-B-57-44375 for an iron-antimony-tellurium-containing catalyst. The method of JP-A-47-8615 discloses a method in which a regenerating gas mixture containing uncombined oxygen or oxygen optionally combined with active nitrogen is added to an antimony-uranium oxide catalyst complex at 427-10.
It is characterized by contacting at a temperature of 38 ° C. for a residence time until the complex is regenerated. The method disclosed in Japanese Examined Patent Publication No. 57-44375 is used in the production of unsaturated aldehydes, unsaturated nitriles or diolefins by olefin oxidation reaction, ammoxidation reaction or oxidative dehydrogenation, and has decreased activity (1) Fe; (2) Sb; (3) V, M
at least one element selected from the group consisting of o and W;
(4) When regenerating the catalytic activity by firing a metal oxide catalyst containing the elements (1) to (4) of Te as an essential component,
The catalyst retains the crystal structure of an iron / antimony oxide compound and substantially no free antimony trioxide is produced, and the catalyst is used in the temperature range of 600 ° C. to 950 ° C., and at the time of producing the catalyst. This is a method for regenerating an iron / antimony-containing oxide catalyst, which comprises calcination in a non-reducing atmosphere at or near the final calcination temperature.

However, when these methods are directly applied to an iron / antimony / phosphorus-containing catalyst whose catalyst composition does not contain uranium or tellurium, not only the regeneration effect is not sufficiently observed but, on the contrary, the catalyst performance is deteriorated. There were things. For example, when an iron / antimony / phosphorus-containing oxide catalyst containing a large amount of phosphorus component is fired according to the method described in JP-B-57-44375 or JP-A-47-8615, the catalyst is solidified. It was easy to understand, and it was found that the phenomenon was remarkable especially when baked in a stationary state. Further, the catalyst particles adhere to each other, which makes it difficult to remove the catalyst from the firing furnace, and the work such as loosening the catalyst is required. Furthermore, when the catalyst is regenerated in an atmosphere of an inert gas such as nitrogen, not only the regeneration effect is not shown but the catalyst performance is rather deteriorated. As described above, it was found that there is a peculiar problem in the regeneration of the iron / antimony / phosphorus-containing oxide catalyst, particularly the catalyst containing a large amount of phosphorus component.

[0006]

The present invention has been made to solve the above problems in the conventional method, and its purpose is to contain iron, antimony and phosphorus as essential components which can be industrially advantageously implemented. The purpose of the present invention is to provide a method for regenerating a metal oxide catalyst contained as a catalyst. Specifically, even in the case of regenerating an iron-antimony-phosphorus-containing oxide catalyst containing a large amount of phosphorus component, the solidification of the catalyst and the adhesion of the catalyst particles adhere to each other. An object of the present invention is to provide a method for regenerating an iron-antimony-phosphorus-containing metal oxide catalyst that can effectively recover the activity and the catalyst strength of the catalyst without causing the above.

[0007]

[Means for Solving the Problems] That is, the first aspect of the present invention is to use a metal containing iron, antimony, or phosphorus as an essential component, which is used in an oxidation, ammoxidation, or oxidative dehydrogenation reaction of an organic compound and has deteriorated catalytic performance. A method for regenerating an iron / antimony / phosphorus-containing metal oxide catalyst, which comprises subjecting an oxide catalyst to impregnation or spraying with a phosphorus component, and then performing heat treatment in the temperature range of 600 to 900 ° C. while fluidizing in the presence of oxygen. Regarding In the second aspect of the present invention, a catalyst having a composition represented by the following empirical formula, which is used in an oxidation, ammoxidation, or oxidative dehydrogenation reaction of an organic compound and has a deteriorated catalytic performance, is used to obtain a superficial linear velocity of an oxygen-containing gas. The present invention relates to a method for regenerating an iron-antimony-phosphorus-containing metal oxide catalyst, which comprises performing heat treatment in a temperature range of 600 to 900 ° C while fluidizing at 7 cm / sec or more. Empirical formula FeaSbbPcXdQeRfOg (SiO2) h where X is at least one element selected from the group consisting of V, Mo and W, and Q is Li, Na, K, C.
s, Be, Mg, Ca, Sr, Ba, Sc, Y, La,
Ce, Pr, Nd, Sm, Th, Ti, Zr, Hf, T
a, Cr, Mn, Re, Co, Ni, Ru, Rh, P
d, Os, Ir, Pt, Cu, Ag, Au, Zn, C
at least one element selected from the group consisting of d, Hg, Al, Ga, In, Tl, Ge, Sn and Pb, R
Is a minority selected from the group consisting of B, As, Bi and Se.
At least a kind of element is shown, and subscripts a, b, c, d, e,
f, g and h represent atomic ratios and are in the following ranges respectively. When a = 10, b = 5 to 60, c = 3 to 40, d
= 0 to 10, e = 0 to 15, f = 0 to 10, g = number corresponding to an oxide formed by combining the above components, h = 10
~ 200.

The present invention will be specifically described below. Catalyst The catalyst to be regenerated in the present invention is used for the production of unsaturated aldehyde, unsaturated nitrile or hydrogen cyanide, or diolefin by oxidation, ammoxidation or oxidative dehydrogenation of hydrocarbons or other organic compounds, and the reaction is used. This is an iron / antimony / phosphorus-based metal oxide catalyst in which the yield of the target product has decreased during or for some reason. Specifically, a metal oxide catalyst containing iron, antimony, and phosphorus as essential components, and the catalyst composition thereof is preferably within the range shown by the following empirical formula. Fea Sbb Pc Xd Qe Rf Og (SiO ₂ ) h where X is at least one element selected from the group consisting of V, Mo and W, and Q is Li, Na, K, C
s, Be, Mg, Ca, Sr, Ba, Sc, Y, La,
Ce, Pr, Nd, Sm, Th, Ti, Zr, Hf, N
d, Ta, Cr, Mn, Re, Co, Ni, Ru, R
h, Pd, Os, Ir, Pt, Cu, Ag, Au, Z
n, Cd, Hg, Al, Ga, In, Tl, Ge, Sn
And at least one element selected from the group consisting of Pb (preferably Li, Na, K, Cs, Mg, Ca, B
a, Ce, Ti, Zr, Cr, Mn, Co, Ni, C
u, Zn, Al, Sn and at least one element selected from the group consisting of Pb), R is at least one element selected from the group consisting of B, As, Bi and Se (preferably from B and Bi) At least one element selected from the group consisting of the subscripts a, b, c, d, e,
f, g and h represent atomic ratios and are in the following ranges respectively. When a = 10, b = 5 to 60 (preferably 15 to
40), c = 3-40 (preferably 5-20), d = 0
-10 (preferably 0.1-5), e = 0-15 (preferably 0.1-5), f = 0-10 (preferably 0)
3), i = the number corresponding to the oxide formed by combining the above components, h = 10 to 200 (preferably 30 to 10)
0).

The shape of the catalyst is arbitrary, but in the present invention, since the catalyst is regenerated in a fluidized state, its particle size is 1 to 50.
It should be in the range of 0 micron, preferably 5-200 microns. The weight average median diameter is preferably in the range of 20 to 120 microns.

The catalyst can be produced by any known method using a spray drying method or the like. For example,
42-22476, JP 47-18722, JP 47-187
23, JP-A 1-143643, JP-A 1-171640, JP-A 1-257125, JP-A 3-26342, and the like.

Regeneration Treatment In the present invention, the specific deteriorated catalyst as described above is heat-treated and regenerated, but the treatment conditions at that time are in the temperature range of 600 to 900 ° C., and the presence of oxygen. It is necessary to heat-treat while fluidizing the catalyst below. It is difficult to find the change of the deteriorated catalyst by the usual means, and it is not clear how it is changed, but it is considered that the deteriorated catalyst probably causes a structural change at the active site of the catalyst surface. The temperature during playback is 600
When the temperature is lower than ℃, sufficient activity or recovery of catalyst strength cannot be obtained. If the temperature is higher than 900 ° C., the selectivity may decrease, the catalyst strength may decrease, or the adhesion between the catalyst particles may increase to deteriorate the workability.

The heat treatment of the catalyst is preferably performed while fluidizing the catalyst from the viewpoint of uniform heating of the catalyst and prevention of solidification of the catalyst. Examples of the apparatus used include a rotary furnace and a fluidized furnace. When the catalyst is a fluidized bed catalyst, it is convenient and preferable to apply a fluidized bed calciner. At that time, the superficial linear velocity of the feed gas for fluidizing the catalyst was 7
The range of -60 cm / sec is preferred.

The atmosphere at the time of heating the catalyst needs to be an atmosphere in which oxygen is present. If oxygen is not present even in a non-reducing atmosphere, the performance of the catalyst is likely to be further deteriorated and the complete oxidation activity is increased. The amount of oxygen present is preferably in the range of 5 to 50 vol.%. In practice, it is convenient to carry out under air flow, but pure oxygen or air is vaporized,
It can also be carried out in the presence of a substance diluted with an inert gas such as carbon dioxide or nitrogen. Processing time is 0.5 to 2
It is selected in the range of 0 hours. If it is less than 0.5 hours, sufficient activity cannot be recovered, and if it is more than 20 hours, it is not practical.

Further, for the purpose of further improving the physical properties and activity of the catalyst, the deteriorated catalyst may be impregnated with or sprayed with a specific component such as molybdenum or phosphorus, followed by firing. Particularly, impregnation or spraying with phosphorus is effective, and the catalyst strength is improved at the same time as the recovery of the catalyst activity. In that case, the amount of phosphorus used for impregnation or spraying is preferably in the range of 0.2 or less in atomic ratio with respect to antimony in the catalyst.
If the amount is larger than this, the catalyst particles are likely to adhere to each other, which may cause problems such as not being able to perform uniform calcination and making it difficult to extract the catalyst. It is convenient to use phosphoric acid (commercial orthophosphoric acid, etc.) as the phosphorus component raw material used for impregnation or spraying, but various other phosphorus-containing compound solutions can also be used. Also, if necessary, a component other than the phosphorus component may be impregnated or sprayed at the same time to perform a regeneration treatment.

[0015]

FUNCTION AND EFFECT The catalyst regenerated by the method of the present invention recovers the yield and the reaction rate to the same extent as the unused catalyst in terms of activity, and also improves the catalyst physical properties. Therefore, the optimum reaction conditions hardly change, so that the catalyst can be treated in the same manner as the unused catalyst, or can be used as a mixture with it. The catalyst regeneration method of the present invention can be repeated many times. As described above, the method for regenerating an iron / antimony / phosphorus-containing metal oxide catalyst according to the present invention has a great industrial significance, and the resulting economic effect is very large.

[0016]

EXAMPLES The effects of the present invention will be specifically described below with reference to examples.

The catalyst A has an empirical formula of Fe ₁₀ Sb ₂₅ P ₁₂ V _0.5 Mo _0.1 Al ₃ K _0.3 Bi _0.8 O _102.4 (SiO 2
₂ ) A fluidized bed catalyst of ₅₀ was prepared by the following method. (I) Take 326.7 g of antimony trioxide powder. (II) 390 ml of nitric acid (specific gravity 1.38) and 480 ml of pure water are mixed and heated, and 50.1 g of electrolytic iron powder is gradually added and dissolved therein. (III) 1347 g of silica sol (20% by weight of SiO ₂ ) is taken. (IV) 2.64 g of ammonium paramolybdate is dissolved in 7 ml of pure water. 530 g of (V) ammonium metavanadate (5.24 g)
Dissolve in g. (VI) 112.1 g of aluminum nitrate is dissolved in 560 g of pure water. (VII) 3.02 g of potassium nitrate is dissolved in 15 g of pure water. (VIII) 2.8 ml of nitric acid (specific gravity 1.38) and 36 ml of pure water are mixed, and 36.2 g of bismuth nitrate is added and dissolved therein. (II) to (III), (I), (IV) to (VIII)
In that order, add well while stirring well, and adjust to pH 2 with 15% ammonia water. While stirring this slurry,
Heat treatment was performed at 8 ° C. for 3 hours. (IV) Take 120.6 g of phosphoric acid (content 85% by weight). (IV) is added to the slurry prepared as above, and the mixture is stirred well. The thus-obtained aqueous slurry was spray-dried using a rotary disk type spray dryer. The obtained fine spherical particles were fired at 200 ° C. for 2 hours, 400 ° C. for 3 hours, and further fired at 800 ° C. for 3 hours.

Catalyst B A fluidized bed catalyst having an empirical formula of Fe ₁₀ Sb ₁₉ P ₈ V ₁ Mg ₂ O _77.5 (SiO ₂ ) ₈₀ was prepared in the same manner as Catalyst A. However, magnesium nitrate was dissolved in pure water as a Mg raw material and added after antimony trioxide. The final firing was 820 ° C. for 3 hours.

Catalyst C A fluidized bed catalyst having an empirical formula of Fe ₁₀ Sb ₂₃ P ₁₄ Mo _0.5 W _0.2 Mn ₂ Co ₁ O _101.1 (SiO ₂ ) ₅₅ was prepared in the same manner as Catalyst A. However, as the W raw material, ammonium paratungstate, M
Manganese nitrate as an n raw material and cobalt nitrate as a Co raw material were dissolved in pure water and added next to antimony trioxide. The final firing was 850 ° C. for 3 hours.

The catalyst D has an empirical formula of Fe ₁₀ Sb ₃₁ P _7.5 V _0.4 Mo _0.1 Zn _2.5 Li _0.1 Na _0.1 B _0.4 O
A fluidized bed catalyst of _100.25 (SiO ₂ ) ₅₀ was prepared in the same manner as Catalyst A. However, Zn nitrate is zinc nitrate, B raw material is anhydrous boric acid, Na raw material is sodium nitrate,
Lithium nitrate as a Li raw material was dissolved in pure water and added after antimony trioxide. The final firing is 800
The temperature was 3 hours.

The catalyst E has an empirical formula of Fe ₁₀ Sb ₂₈ P ₉ V _0.2 Mo _0.4 W _0.1 Cu ₂ Bi ₁ B _0.5 O _99.75 (Si
A fluidized bed catalyst of O ₂ ) ₆₀ was prepared by the following method. (I) Take 331.3 g of antimony trioxide powder. (II) 350 ml of nitric acid (specific gravity 1.38) and 440 g of pure water are mixed and heated, and 45.3 g of electrolytic iron powder is gradually added and dissolved therein. Then, add 39.2 copper nitrate to this solution.
Add g and dissolve. (III) Silica sol (silica concentration 20% by weight) 1463
84.2g of phosphoric acid (content 85% by weight)
Add and stir well. (IV) 5.7 g of ammonium paramolybdate was added to pure water 1
Dissolve in 4 ml. (V) Ammonium metavanadate 1.9 g of pure water 19
Dissolve in 0 ml. (VI) 2.1 g of ammonium paratungstate is dissolved in 11 ml of pure water. (VII) 2.9 ml of nitric acid (specific gravity 1.38) and 36 ml of pure water are mixed, and 39.4 g of bismuth nitrate is added and dissolved therein. (VIII) 2.5 g of orthoboric acid is dissolved in 13 ml of pure water. With good stirring, (III) is added to (II), and then (I) and (IV) to (VIII) are added. The slurry thus obtained was heated at 100 ° C. for 8 hours with good stirring. The slurry thus obtained was spray-dried using a rotary disk type spray dryer. The obtained fine spherical particles were fired at 250 ° C. for 8 hours, then 400 ° C. for 5 hours, and finally in a fluidized firing furnace at 710 ° C. for 3 hours.

Activity test of catalyst The activity test was conducted by passing methanol, air and ammonia to a catalyst bed packed in a fluidized bed reactor having an inner diameter of the catalyst flow section of 2.5 cm and a height of 40 cm. The reaction pressure is normal pressure. However, the conversion rate of methanol, the yield of the target product, and the selectivity in Examples and Comparative Examples are defined as follows.

The reaction conditions are as follows. (1) O ₂ (supplied as air) /methanol=4.3
(Mol / mol) NH ₃ /methanol=1.1 (mol / mol) (2) O ₂ (supplied as air) /methanol=1.6
(Mol / mol) NH ₃ /methanol=1.1 (mol / mol)

Catalyst Strength Test "Test Methods for Synthetic Cracking" America known as a test method for fluid catalytic cracking catalyst (FCC catalyst)
It was carried out according to the method described in ann Cyanamid Co. 6 / 31-4m-1 / 57. The test was provided with catalyst particles in the size range 63 to 105 μ. The wear loss R (%) is obtained by the following equation. R = (B / C−A) × 100 where A; weight of catalyst worn in 0 to 5 hours (g) B; weight of catalyst worn in 5 to 15 hours (g) C; catalyst used in test Weight of (g)

Example 1 Catalyst A was charged into a reactor having an inner diameter of the catalyst flow section of 4.3 cm and a height of 70 cm, and O ₂ (supplied as air) /methanol=0.8 (mol / mol), NH ₃ / methanol = 1.0
When the reaction was conducted under the conditions of (mol / mol), contact time of 6 sec and temperature of 420 ° C., it was observed that the yield of hydrogen cyanide decreased with time. The reaction was continued for 4 hours under these conditions. The extracted catalyst (used as a deteriorated catalyst) is charged into a fluidized-bed calcining furnace with an inner diameter of 28 m / mφ, and the catalyst is fluidized with air to 70
It was calcined at 0 ° C. for 3 hours (used as a regenerated catalyst). The superficial linear velocity of air was 10 cm / sec. Table 1 shows the activity test results of the new catalyst, the deteriorated catalyst and the regenerated catalyst. The activity of the regenerated catalyst was comparable to the fresh catalyst.

Example 2 The same deteriorated catalyst as in Example 1 was used as in Example 1.
It was baked at 0 ° C. for 3 hours. Table 1 shows the activity test results of the new catalyst, the deteriorated catalyst and the regenerated catalyst. The activity of the regenerated catalyst was comparable to the fresh catalyst.

Example 3 The same deteriorated catalyst as in Example 1 was used in the same manner as in Example 1.
It was baked at 0 ° C. for 3 hours. However, the linear velocity of the superficial air is 8
It was set to cm / sec. Table 1 shows the activity test results of the new catalyst, the deteriorated catalyst and the regenerated catalyst. The activity of the regenerated catalyst was comparable to the fresh catalyst.

Example 4 When a reaction was carried out using the catalyst B under the same conditions as in Example 1, a decrease in the hydrogen cyanide yield with time was observed. The reaction was continued for 4 hours under these conditions. The extracted catalyst (deteriorated catalyst) was calcined in the same manner as in Example 1 at 850 ° C. for 1 hour (regenerated catalyst). Table 1 shows the activity test results of the new catalyst, the deteriorated catalyst and the regenerated catalyst. The activity of the regenerated catalyst was comparable to the fresh catalyst.

Example 5 When a reaction was carried out using the catalyst C under the same conditions as in Example 1, a decrease in the hydrogen cyanide yield with time was observed. The reaction was continued for 4 hours under these conditions. The extracted catalyst (deteriorated catalyst) was calcined in the same manner as in Example 1 at 800 ° C. for 3 hours (regenerated catalyst). Table 1 shows the activity test results of the new catalyst, the deteriorated catalyst and the regenerated catalyst. The activity of the regenerated catalyst was comparable to the fresh catalyst.

Example 6 When using Catalyst D under the same conditions as in Example 1, a decrease in the hydrogen cyanide yield with time was observed. The reaction was continued for 4 hours under these conditions. The extracted catalyst (deteriorated catalyst) was calcined at 800 ° C. for 8 hours in the same manner as in Example 1 (regenerated catalyst). Table 1 shows the activity test results of the new catalyst, the deteriorated catalyst and the regenerated catalyst. The activity of the regenerated catalyst was comparable to the fresh catalyst.

Example 7 Catalyst E was charged into a reactor having an inner diameter of the catalyst flow section of 2.5 cm and a height of 40 cm, and O2 (supplied as air) /methanol=1.4 (mol / mol) NH3 / methanol = 1.0
(Mole / mole), contact time 6 sec, temperature 420 ° C. When the reaction was carried out, a decrease in hydrogen cyanide yield with time was observed. The reaction was continued for 100 hours under these conditions. The extracted catalyst (deteriorated catalyst) was calcined in the same manner as in Example 1 at 750 ° C. for 3 hours (regenerated catalyst). Further, the deteriorated catalyst was impregnated with phosphoric acid so that the atomic ratio of P / Sb was 0.04 and calcined at 750 ° C. for 3 hours (impregnated regenerated catalyst). Table 1 shows the activity test results of the new catalyst, the deteriorated catalyst, the regenerated catalyst and the impregnated regenerated catalyst. The activity of the regenerated catalyst and impregnated regenerated catalyst was equal to or higher than that of the new catalyst.

Further, the results of measuring the catalyst strength of a new catalyst, a deteriorated catalyst, a regenerated catalyst and an impregnated regenerated catalyst are shown below.
The catalyst strength of the regenerated catalyst and the impregnated regenerated catalyst was equal to or higher than that of the new catalyst.

Comparative Example 1 The same deteriorated catalyst as in Example 1 was used in the same manner as in Example 1.
It was calcined at 0 ° C. for 3 hours (regenerated catalyst). New catalyst,
Table 2 shows the activity test results of the deteriorated catalyst and the regenerated catalyst.
The activity of the regenerated catalyst is insufficient and has not reached the level of fresh catalyst.

Comparative Example 2 The same deteriorated catalyst as in Example 1 was used as in Example 1.
It was calcined at 0 ° C. for 3 hours (regenerated catalyst). New catalyst,
Table 2 shows the activity test results of the deteriorated catalyst and the regenerated catalyst.
The regenerated catalyst had particles attached to each other. Its activity is insufficient and has not reached the level of fresh catalyst.

Comparative Example 3 The same deteriorated catalyst as in Example 1 was calcined in the same manner as in Example 1, except that nitrogen was used instead of air at 820 ° C. for 3 hours (regenerated catalyst). Table 2 shows the activity test results of the new catalyst, the deteriorated catalyst and the regenerated catalyst. The activity of the regenerated catalyst was inferior to that of the deteriorated catalyst, and no regeneration effect was observed, and the hydrocyanic acid yield was rather deteriorated.

Comparative Example 4 The same deteriorated catalyst as in Example 5 was treated in the same manner as in Example 5. However, the linear velocity of the superficial air was set to 6 cm / sec. The regenerated catalyst had particles attached to each other. New catalyst,
Table 2 shows the activity test results of the deteriorated catalyst and the regenerated catalyst.
The activity of the treated catalyst is insufficient as compared with the case of Example 5.

[0037]

[Table 1]

[0038]

[Table 2]

Claims (5)

(57) [Claims] 1. A metal oxide catalyst containing, as an essential component, iron, antimony, and phosphorus whose catalytic performance has been deteriorated by being used for oxidation, ammoxidation, or oxidative dehydrogenation of an organic compound, after impregnating or spraying with a phosphorus component, A method for regenerating an iron-antimony-phosphorus-containing metal oxide catalyst, which comprises heat-treating in the temperature range of 600 to 900 ° C while fluidizing in the presence of oxygen. 2. A catalyst having a composition represented by the following empirical formula, which has been used in an oxidation, ammoxidation or oxidative dehydrogenation reaction of an organic compound and has a deteriorated catalytic performance, and a superficial linear velocity of oxygen-containing gas is 7 cm / sec or more. A method for regenerating an iron-antimony-phosphorus-containing metal oxide catalyst, which comprises heat-treating in a temperature range of 600 to 900 ° C. while fluidizing the solution. Empirical formula FeaSbbPcXdQeRfOg (SiO2) h where X is at least one element selected from the group consisting of V, Mo and W, and Q is Li, Na, K, C.
s, Be, Mg, Ca, Sr, Ba, Sc, Y, La,
Ce, Pr, Nd, Sm, Th, Ti, Zr, Hf, T
a, Cr, Mn, Re, Co, Ni, Ru, Rh, P
d, Os, Ir, Pt, Cu, Ag, Au, Zn, C
at least one element selected from the group consisting of d, Hg, Al, Ga, In, Tl, Ge, Sn and Pb, R
Is a minority selected from the group consisting of B, As, Bi and Se.
At least a kind of element is shown, and subscripts a, b, c, d, e,
f, g and h represent atomic ratios and are in the following ranges respectively. When a = 10, b = 5 to 60, c = 3 to 40, d
= 0 to 10, e = 0 to 15, f = 0 to 10, g = number corresponding to an oxide formed by combining the above components, h = 10
~ 200. 3. The method for regenerating a catalyst of iron-antimony-phosphorus-containing metal oxide according to claim 2, wherein the deteriorated catalyst is impregnated with or sprayed with a phosphorus component and then heat-treated. 4. The method for regenerating a catalyst according to claim 1, 2 or 3, wherein the amount of the phosphorus component added to the deteriorated catalyst is 0.2 or less in atomic ratio with respect to antimony in the catalyst. 5. The catalyst regeneration method according to claim 1, 2, 3 or 4, wherein the deteriorated catalyst is a catalyst whose activity is deteriorated when used in the production of hydrogen cyanide by the ammoxidation reaction of methanol.