JPH0256143B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a boron-containing metal oxide catalyst. Oxidation of organic compounds, ammoxidation, aldehydes, acids, nitriles, diolefins, by oxidative dehydrogenation,
It is known to produce alkenylbenzenes, etc. 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, cobalt or nickel described in Japanese Patent Publication No. 39-19111, the oxide catalyst of antimony and tin described in Japanese Patent Publication No. 37-14075, and the An oxide catalyst of antimony and uranium described in Publication No. 40-24367 is known. Catalysts mainly containing molybdenum include oxide catalysts of molybdenum and bismuth etc. described in Japanese Patent Publication No. 36-5870, Japanese Patent Publication No. 39-8214
Molybdenum, cerium, and lanthanum described in the publication,
Oxide catalysts containing thorium, bismuth, tellurium, etc. Oxide catalysts containing molybdenum, tellurium, and zinc described in Japanese Patent Publication No. 7774/1984 are known. In addition, as catalysts mainly containing vanadium, there are known oxide catalysts of vanadium and chromium described in Japanese Patent Publication No. 35-15689, and oxide catalysts of vanadium and titanium etc. described in Japanese Patent Publication No. 49-34673. There is. 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. The present invention aims to improve these points. The present invention provides a method for preparing a boron-containing metal oxide catalyst by contacting a previously prepared metal oxide catalyst precursor with boron or a boron compound in a gas atmosphere and depositing a boron component on the metal oxide catalyst precursor. It is a manufacturing method that is easy to operate.
Moreover, it has great industrial value in that it can produce high-performance catalysts by a method with good reproducibility. The present invention will be explained in detail below. Metal oxide catalyst precursor The metal oxide catalyst precursor used in the present invention is preferably an oxide containing at least antimony, molybdenum, or vanadium. These oxides can be used as they are, silica, alumina, silica/alumina, silica, etc.
It may be supported on various carriers such as titania, titania, and zirconia. This metal oxide catalyst precursor can be produced, for example, by any known method as shown 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 mechanical strength. The preferred temperature range varies depending on the component composition, but in many cases it is 0.5 in this temperature range, more preferably in the temperature range of 400°C to 900°C.
You can bake it for up to 50 hours. In addition to the catalyst precursors prepared as described above, catalyst precursors containing at least one element selected from the group consisting of antimony, molybdenum, and vanadium that have been used in the reaction or have been degraded after being used in the reaction can be used as catalyst precursors. It is considered a type of body. These are generally fired at temperatures between 300℃ and 1000℃,
It has sufficient mechanical strength to apply the present invention. Typical compositions of the catalyst precursor include the following. MeaQbRcTdBeOf 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 at least one element R 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, Pt, Ag,
Cd, Al, Ga, In, Tl, Ge, Pb, P, As,
At least one element selected from the group consisting of S and Se T = Te and/or Bi B represents boron Subscripts a, b, c, d, e, and f indicate atomic ratios, each within the following range be. a = 5-100 b = 5-15 c = 0-15 d = 0-10 e = 0-10 f = number corresponding to the oxide formed by the combination of the above components No boron component is included However, it may be contained in some amount. If a carrier is used, 5 to 90% by weight of the catalyst
It is recommended that the range be within the range of . The invention is applicable both for the production of solid bed catalysts and also for the production of fluidized bed catalysts. It is preferable to use a catalyst precursor molded as a fixed bed catalyst for manufacturing a fixed bed catalyst, and it is preferable to use a catalyst precursor molded as a fluidized bed catalyst for manufacturing a fluidized bed catalyst. Although it is conceivable that the treated catalyst precursor of the present invention, ie, the catalyst of the present invention, is further shaped and then subjected to the reaction, it is generally not necessary to do so. It is convenient and preferable to apply the method of the present invention by shaping the catalyst precursor into a form that will ultimately be subjected to the reaction. For fixed bed catalysts, it is preferable to use catalyst precursors shaped into cylinders, balls, etc. with a diameter of about 1 mm to 10 mm. For fluidized bed catalyst applications, catalyst precursors shaped to particle sizes ranging from 5 to 300 microns may be used. It is usually preferable to mold these by a spray drying method. Metal Oxide Catalyst The catalyst produced in the present invention contains at least one element selected from the group consisting of antimony, molybdenum, and vanadium and boron.
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. MeaQbRcTdBeOf 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 at least one element R 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, Pt, Ag,
Cd, Al, Ga, In, Tl, Ge, Pb, P, As,
At least one element selected from the group consisting of S and Se T = Te and or Bi B represents boron Subscripts a, b, c, d, e and f indicate atomic ratios, each within the following range . a = 5-100 b = 5-15 c = 0-15 d = 0-10 e = 0.05-10 f = number corresponding to the oxide formed by the combination of the above components When using a carrier, the catalyst It is preferable to set it in the range of 5 to 90%. This catalyst can be used for oxidation of organic compounds, ammoxidation,
It can be widely used for oxidative dehydrogenation, etc. Specifically, production of formaldehyde by oxidation of methanol, production of hydrogen cyanide by ammoxidation of methanol, production of acrolein and acrylic acid by oxidation of propylene, production of acrylonitrile by ammoxidation of propylene,
Production of methacrolein and methacrylic acid by oxidation of isobutene and tertiary-butanol, production of methacrylonitrile by ammoxidation of isobutene and tertiary-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, ammoxidation of alkylpyridines. and the production of cyanopyridines. It is known that the addition of boron is effective in improving the performance of these catalysts in some cases, but in all cases, the method of mixing the boron raw material and other catalyst raw materials when preparing the catalyst, molding, and firing is known. It is being However, it is difficult to manufacture catalysts because there are relatively few compounds that have high solubility in water and are easy to use.
There were problems such as difficulty in achieving reproducibility. According to the method of the present invention, a high-performance boron-containing catalyst can be produced with good reproducibility using a simple method. However, the boron-containing catalyst obtained by the method of the present invention can be obtained by a conventional method, that is, a method in which the entire amount of the boron raw material and other catalyst raw material components are mixed, molded, and calcined at the time of preparing the catalyst. It has the advantage of giving a higher yield of the desired product than a boron-containing catalyst of the same composition. Boron and Boron Compounds Elemental boron is used as boron in an easily usable form. Many boron compounds can be used. In other words, boron oxides such as boron monoxide and boron trioxide, boric acid, borates such as ammonium borate, boron phosphate, various alcohols, boric acid esters prepared from phenols and boric acid, and carboxylic acid. Acyloxyboranes prepared from acid salts and boric anhydride, boron trichloride,
Examples include boron halides such as boron triiodide, boron hydrides, trihydrocarboxylboranes, and other organic boron compounds. In the case of a compound with a high vapor pressure, it is introduced from outside the system by entraining it with a gas. If it is solid at room temperature or above, particularly below 100°C, particularly preferably below 300°C, it may be used as a solid with an appropriate particle size. When solid boron or a boron compound is used and applied to the production of a fluidized bed medium, it is preferred that the boron or boron compound is also used in a fluidized state.
Therefore, if the particle size is too small, it will escape from the system during operation, and if the particle size is too large, it will not mix well with the catalyst precursor, and the boron component will be deposited non-uniformly, resulting in insufficient effectiveness. Not demonstrated. Preferably, the particle size of the solid boron component ranges from 0.1 to 1000 microns. When these boron components are used in solid form, boron or boron compounds may be used as they are, as described above, but they may be supported on a carrier or
It may also be used as an enriched support on a catalyst. In addition to the boron component, components such as phosphorus, tellurium, and molybdenum can also be used simultaneously. Catalyst Production Method The catalyst production method according to the present invention involves bringing a metal oxide catalyst precursor into contact with boron or a boron compound in a gaseous atmosphere at an elevated temperature. Although the method of the present invention can be applied to fixed bed catalysts and moving bed catalysts, it is particularly effective when applied to fluidized bed catalysts and carried out under the motion of the fluidized bed catalyst. That is, preferred methods include various types of rotary kilns and fluidized kilns.
In particular, it is preferable to use a fluidized calcination furnace. One of the reasons for the good results is thought to be that the boron 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 boron component to the catalyst precursor and its deposition. If the amount of boron 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. The amount of boron added to the catalyst precursor varies depending on various conditions, but the boron content in the complete catalyst is preferably within the catalyst composition range described below. It is also recommended that the boron component to be added be added little by little continuously or intermittently, rather than all at once. When the boron component is used in solid form, it may be dry mixed with the catalyst precursor before treatment, or may be added and mixed during the treatment operation. When intended for the production of fluidized bed catalysts, addition of boron components during processing operations is easy to implement. Many examples can be given of the gas atmosphere. Oxidizing or non-reducing gases such as air, oxygen, nitrogen, helium, argon, carbon dioxide, nitrous oxide, nitric oxide, nitrogen dioxide, water vapor,
Alternatively, a gas containing oxygen and at least one reducing gas selected from hydrogen, ammonia, carbon monoxide, 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, the time, etc., so it is better to avoid this except in special cases. Preferred treatment temperatures and times vary depending on the state of the boron component. If the vapor pressure of the boron component is high or if the boron 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 boron component is low, the temperature may be It is better to set the temperature higher and take a longer time.
Usually 0.5 to 50 at a temperature of about 300 to 850℃
All you have to do is process the time. If the temperature is below 300°C, the effect will be small, and if the temperature is above 850°C, the activity of the catalyst will decrease. The metal oxide catalyst precursor oxidizes organic compounds,
When a degraded catalyst is used for ammoxidation or oxidative dehydrogenation and the selectivity of the target product has decreased, the reaction gas itself falls under the gas atmosphere of the present invention, and the reaction temperature is generally 300°C. or 500℃
Therefore, the method of the present invention can be applied by adding a boron component during the reaction.
In this case, it is particularly preferable to apply the method of the invention under conditions of catalyst motion. Therefore, it is generally applied in the case of fluidized bed reactions. This method can be viewed as a type of catalyst regeneration. In most cases, catalyst regeneration is carried out by extracting the catalyst from the reactor.
When the present invention is applied, this is not necessary and the reaction can be carried out while the reaction is being carried out, that is, while the production of the desired product is being continued, which is economically advantageous. In this way, the selectivity of the target product can be improved by depositing the boron component on the catalyst surface, but after this treatment, the boron component is further heated at a temperature of about 400°C to about 900°C in a non-reducing atmosphere. By calcination, it may be possible to improve the selectivity of the target product and the duration of the activity. It is thought that the deposited boron component reacts with the metal oxide catalyst precursor to develop and stabilize preferred active sites. EXAMPLES The effects of the present invention will be shown below through Examples and Comparative Examples. Note that the yield and selectivity of the target product in this specification are based on the following definitions. Yield [%] =
Weight of carbon in the desired product produced [g] / Weight of carbon in the supplied raw material organic compound [g] × 100 Selectivity [%] = Weight of carbon in the desired product produced [g] / Reacted raw material organic Weight of carbon in compound [g] ×100 Activity test conditions are as follows. (1) Ammoxidation of propylene A fluidized bed reactor with a catalyst fluidization section having an inner diameter of 2.5 cm and a height of 40 cm was filled with a catalyst, and a gas having the following composition was introduced. The reaction pressure is normal pressure. O ₂ (supplied as air)/propylene
= 2・2 (mol/mol) NH ₃ /propylene = 1・1 (mol/mol) (2) Ammoxidation of isobutene Using the same reactor as in the ammoxidation reaction of propylene in the previous section, feed a gas with the following composition. did. The reaction pressure is normal pressure. O ₂ (supplied as air)/isobutene
= 2.5 (mol/mol) NH ₃ /isobutene = 1.2 (mol/mol) H ₂ O / isobutene = 1.0 (mol/mol) (3) Ammoxidation of toluene Use the same reactor as in the previous section. , a gas of the following composition was injected. The reaction pressure is normal pressure. O ₂ (supplied as air)/toluene
= 2.5 (mol/mol) NH ₃ /toluene = 1.5 (mol/mol) H ₂ O / toluene = 2.5 (mol/mol) (4) Oxidative dehydrogenation of butene Use the same reactor as in the previous section. A gas with the following composition was introduced. The reaction pressure is normal pressure. Oxygen (supplied as air)/Butene-1
=3.0 (mol/mol) Example 1 A catalyst having the empirical formula Sb ₂₅ Fe ₁₀ V _0.1 P _0.5 B _1.0 O _6.0 (SiO ₂ ) ₃₀ was prepared as follows. Take 559 g of antimony trioxide powder. () Take 85.6g of electrolytic iron powder. Nitric acid (specific gravity 1.38) 0.66
Mix and heat 0.83 of water. Add electrolytic powder little by little to this and dissolve. () Take 1381 g of silica sol (SiO ₂ 20% by weight).
() Take 1.79 g of ammonium metavanadate and dissolve it in 0.2 g of pure water. () Take 8.84 g of phosphoric acid (content 85% by weight). () While stirring () well, (), (),
Add (), () in that order. Add 15% ammonia water little by little to adjust the pH to 2.
The slurry thus obtained was heated at 100° C. for 5 hours while stirring well. This slurry was then spray-dried at room temperature using a rotating disk type spray dryer. The fine spherical particles obtained in this way were
It was baked at 500°C for 4 hours. This was placed in a small rotary kiln and fired at 850°C for 1 hour, after which 9.48 g of orthoboric acid was added and fired for an additional 3 hours under the same conditions. The catalyst thus prepared was tested under activity test conditions.
It was used in the reaction according to (1). Example 2 A catalyst having the empirical formula Sb ₂₅ Fe ₁₀ Co ₅ W _0.5 B _0.5 O _72.25 (SiO ₂ ) ₃₀ was prepared in the same manner as in Example 1. That is, 998 g of a catalyst precursor (calcined at 500°C for 4 hours) of Sb ₂₅ Fe ₁₀ Co ₅ W _0.5 O _71.5 (SiO ₂ ) ₃₀ was placed in a fluidized fluidized furnace and fired at 850°C for 1 hour. was dry mixed with 4.45 g of orthoboric acid, charged again into the fluidized fluidized firing furnace, and further fired at 850°C for 3 hours. The catalyst thus prepared was tested under activity test conditions.
It was used in the reaction according to (1). Example 3 A catalyst having the empirical formula Sb ₂₅ Sn ₁₀ B _1.2 O _71.8 (SiO ₂ ) ₃₀ was prepared as follows. Metallic antimony powder (less than 100 mesh) 423g
and 165g of metal tin powder (less than 100 mesh),
Add little by little to 1840ml of heated nitric acid (specific gravity 1.38). After the generation of brown gas has stopped, leave it at room temperature for 16 hours. Afterwards, excess nitric acid is removed and the precipitate is washed three times with 100 ml of water. Add this to 1253g of silica sol (SiO ₂ 20% by weight)
Mix well and spray dry using conventional methods. After baking at 200℃ for 2 hours and then at 400℃ for 2 hours,
It was baked at 880°C for 4 hours. 10.3 g of orthoboric acid was added thereto, and the mixture was placed in a small rotary kiln and fired at 500°C for 5 hours, then at 450°C for 1 hour under flowing gas consisting of 71.1% nitrogen, 18.9% oxygen, and 10% ammonia. The catalyst thus prepared was tested under activity test conditions.
It was used in the reaction according to (1). Example 4 A catalyst having the empirical formula Sb ₃₀ U ₁₀ B _1.5 O _88.92 (SiO ₂ ) ₆₀ was prepared as follows. Metallic antimony powder (less than 100 mesh) 328g
Add little by little to 1210ml of heated nitric acid (specific gravity 1.38). After all the antimony has been added and the evolution of brown gas has stopped, leave it at room temperature for 16 hours. Afterwards, excess nitric acid is removed and the precipitate is washed three times with 800 ml of water. () Uranyl nitrate UO ₂ (NO ₃ ) ₂・6H ₂ O451g in pure water
Dissolve in 300ml. () Take 1620 g of silica sol (SiO ₂ 20% by weight).
() (), (), and () are mixed well and spray-dried using 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. 7.33 g of ammonium borate was added to this, charged into 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 empirical formula is Mo ₁₂ Bi ₆ Sb ₁₀ Ni ₆ P _1.0 K _1.5 B _0.5 O _74.5
A catalyst (SiO ₂ ) ₇₀ was prepared as follows. Take 2219g of silica sol (SiO ₂ 20% by weight),
To this was added 12.2 g of phosphoric acid (content 85% by weight).
() 224g of ammonium paramolybdate and 550g of pure water
ml and added to (). () 184g of nickel nitrate and 16.0g of potassium nitrate were added to (). () 307g of bismuth nitrate, 330g of nitric acid (30% by weight)
and added to (). () Take 154g of antimony trioxide and add it to (),
Stir well. This slurry was spray-dried using a conventional method, and
C. for 2 hours, 400.degree. C. for 2 hours, and 600.degree. C. for 3 hours. Add 3.26g of orthoboric acid,
It was baked at 500°C for 1 hour. The catalyst thus prepared was tested under activity test conditions.
It was used in the reaction according to (2). Example 6 A catalyst having the empirical formula V ₁₂ P _1.0 B _1.0 O _34.0 (SiO ₂ ) ₅₀ was prepared as follows. Take 3575g of silica sol (SiO ₂ 20% by weight),
Add 27.4 g of 85% phosphoric acid to this and stir well.
() 334g of ammonium metapanadate with 33g of pure water
Add to. () Add () to () while stirring well, and heat to 50°C while stirring and hold for 1 hour. This slurry was spray dried in a conventional manner. This was baked at 150°C for 16 hours and then at 500°C for 2 hours. To 992 g of the catalyst precursor thus prepared, 8.28 g of boron oxide was added, and the mixture was heated at 400°C for 2 hours.
After being fluidized in air and treated, it was used in the reaction according to activity test conditions (3). Example 7-1 The experimental formula is Sb ₂₅ Fe ₁₀ Cu ₃ Mo _0.5 W _0.3 Te _1.0 O _72.0
When a (SiO ₂ ) ₆₀ fluidized bed catalyst was used for a long period of time in the ammoxidation reaction of propylene, its activity decreased. Boron oxide was added to this catalyst and used for reaction according to activity test conditions (1). By adding the boron component, the empirical formula of the catalyst became the following composition. Sb ₂₅ Fe ₁₀ Cu ₃ Mo _0.5 W _0.3 Te _1.0 B _0.5 O _73.15 (SiO ₂ ) _60Example 7-2 Boron was added to the same deterioration medium used in Example 7-1, and the activity test conditions (1) was used in the reaction. By adding the boron component, the empirical formula of the catalyst became the following composition. Sb ₂₅ Fe ₁₀ Cu ₃ Mo _0.5 W _0.3 Te _1.0 B _0.5 O _73.15 (SiO ₂ ) _60Example 8 The empirical formula is Sb ₂₅ Fe ₁₀ Cu ₃ Mo _0.5 W _0.3 Te _1.0 B _0.5
A fluidized bed catalyst of O _73.15 (SiO ₂ ) ₆₀ was prepared as follows. A catalyst precursor containing components below boron was prepared by a spray drying method in the same manner as in Example 1. Cu component raw material is copper nitrate, Mo component raw material is ammonium paramolybdate, W component raw material is ammonium paratungstate Fe.
Telluric acid was used as a component raw material. After spray drying, it was calcined at 200°C for 4 hours, at 400°C for 4 hours, and finally at 780°C for 5 hours. To 998 g of the catalyst precursor prepared in this way,
5.4 g of boron was added, and the mixture was treated at 500° C. for 3 hours while passing a mixed gas of ammonia and air (10% ammonia). The catalyst thus prepared is a boron-containing fluidized bed catalyst having the composition indicated. Using this catalyst, a reaction was carried out according to activity test conditions (1). Example 9 The experimental formula is Sb ₂₀ Fe ₁₀ Cu ₃ Mo _0.5 Te _0.5 B _3.0 O _65.0
A (SiO ₂ ) ₆₀ fluidized bed catalyst was prepared as follows. A catalyst precursor containing components other than boron was prepared by spray drying in the same manner as in Example 1. The Co component raw material is cobalt nitrate, the Mo component raw materials are ammonium paramolybdate, Te
Telluric acid was used as a component raw material. After spray drying, it was fired at 200°C for 4 hours, at 400°C for 4 hours, and finally at 810°C for 5 hours. 20.5 g of ammonium borate was added to 987 g of the catalyst precursor thus prepared, fluidized in air, and treated at 750° C. for 3 hours. The catalyst thus prepared is a boron-containing fluidized bed catalyst having the composition indicated. Using this catalyst, a reaction was carried out according to the activity test conditions (4). Comparative Example 1 A catalyst (same composition as the catalyst in Example 1) whose empirical formula is Sb ₂₅ Fe ₁₀ V _0.1 P _0.5 B _1.0 O _68.0 (SiO ₂ ) ₃₀ was prepared in the same manner as in Example 1. The boron component was prepared by dissolving a predetermined amount of orthoboric acid in the slurry before spray drying. 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 A catalyst with the empirical formula Sb ₂₅ Sn ₁₀ B _1.2 O _71.8 (SiO ₂ ) ₃₀ (same composition as the catalyst in Example 3) was prepared in the same manner as in Example 3, except that orthoboronate was used as the boron component. A predetermined amount of acid was prepared by mixing into the slurry before spray drying. The final firing was at 880°C for 4 hours. A reaction was carried out under the activity test conditions (1) using this catalyst. Comparative Example 3 A fluidized bed catalyst (same composition as the catalyst of Example 6) whose empirical formula is V ₁₂ P _1.0 B _1.0 O _34.0 (SiO ₂ ) ₅₀ was prepared in the same manner as in Example 6, except that the boron component was A predetermined amount of boron oxide powder was mixed into the slurry before spray drying. The final firing was at 500°C for 2 hours. Using this catalyst, a reaction was carried out according to activity test conditions (3). Comparative Example 4 A catalyst having the empirical formula Sb ₂₅ Fe ₁₀ V _0.5 P _0.5 O _66.5 (SiO ₂ ) ₃₀ (same as the catalyst precursor in Example 1) was prepared in the same manner as in Example 1. The final firing was at 850°C for 4 hours. A reaction was carried out using this catalyst under activity test conditions (1). The above Examples and Comparative Examples and their activity test results are summarized in the following table.

【table】

【table】

【table】

Claims (1)

[Claims] 1. In the production of metal oxide catalysts used in oxidation, ammoxidation, or oxidative dehydrogenation reactions of organic compounds, a metal oxide catalyst precursor calcined at a temperature of 300°C to 1000°C, In gas atmosphere, 300
Production of a boron-containing metal oxide catalyst, characterized by contacting boron or a boron compound at a temperature of 850°C to 850°C, and continuing the contact for a time sufficient to deposit a boron component on the metal oxide catalyst precursor. Law. 2. The method according to claim 1, wherein the metal oxide catalyst precursor 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 5.
A method according to claim 1 or 2 in the range of 300 microns. 4. The metal oxide catalyst precursor according to any one of claims 1 to 3, wherein the metal oxide catalyst precursor is a degraded catalyst with reduced activity used in oxidation, ammoxidation, or oxidative dehydrogenation of organic compounds. Method. 5 The form of the boron component is a gaseous compound that is a gas at 100°C or lower, and the compound is mixed with other gases or is fed to the metal oxide catalyst precursor layer in a moving state without mixing. A method according to any one of claims 1 to 4. 6 Boron oxides, boric acid, borates, boron phosphates, organic boron compounds whose boron component is solid at 100°C or below, at least one of these supported on an inert carrier, at least one of these The method according to any one of claims 1 to 4, wherein the metal oxide catalyst is enriched and supported on a metal oxide catalyst precursor or a metal oxide catalyst. 7. The method according to any one of claims 1 to 4 and 6, wherein the boron component on a solid and the metal oxide catalyst precursor are brought into contact under a state of movement of both. 8. Any one of claims 1 to 7, wherein the gas atmosphere is a gas atmosphere containing oxygen and at least one gas selected from the group consisting of hydrogen, ammonia, carbon monoxide, and organic compounds. Method described. 9 Bringing boron or a boron compound into contact with a metal oxide catalyst precursor to deposit a boron component to produce a boron-containing catalyst, and then calcining the catalyst at about 400°C to about 900°C in a non-reducing atmosphere. A method according to any one of claims 1 to 8. 10 The particle size of the metal oxide catalyst precursor is 5 or more
300 microns, and the boron component has a particle size of 0.1 to
A method according to any one of claims 1 to 4 and 6 to 9, wherein the solid is in the range of 1000 microns. 11. The method according to any one of claims 1 to 10, wherein the prepared catalyst has the following composition: Me _a Q _b R _c T _d B _{e Of} (SiO ₂ ) _{gIn 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 at least one element R 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, Tr, Pd, Pt, Ag,
Cd, Al, Ga, In, Tl, Ge, Pb, P, As,
At least one element selected from the group consisting of S and Se T = Te and/or Bi B represents boron Subscripts a, b, c, d, e, f and g indicate atomic ratios, each within the following range It is in. a=5 to 100 b=5 to 15 c=0 to 15 d=0 to 10 e=0.05 to 10 f=number corresponding to the oxide formed by combining each of the above components g=0 to 200 12 Metal oxidation The catalyst precursor is a degraded catalyst that is used in the oxidation, ammoxidation, or oxidative dehydrogenation reaction of an organic compound and has a reduced selectivity for the target product, and a boron-containing solid is added to it during the reaction. Claims 1 to 4 for addition and mixing
The method according to any one of Items 6 to 7, and 9 to 11.