JP3313864B2 - Preparation of supported catalysts for the synthesis of unsaturated aldehydes and unsaturated carboxylic acids - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to propylene, isobutylene, tertiary butyl alcohol (hereinafter abbreviated as TBA) or methyl tertiary butyl ether (hereinafter MTB).
Abbreviated as E. ) Is carried out in the gas phase catalytic oxidation to produce a corresponding supported catalyst for use in synthesizing the corresponding unsaturated aldehyde and unsaturated carboxylic acid.

[0002]

2. Description of the Related Art Conventionally, a catalyst used for producing acrolein and acrylic acid by gas-phase catalytic oxidation of propylene, and a catalyst used for producing methacrolein and methacrylic acid by gas-phase catalytic oxidation of isobutylene, TBA or MTBE. Numerous proposals have been made for catalysts to be used.
Also, many methods for producing such catalysts have been proposed. Among such proposals, there is known a method of adding various organic compounds such as aniline, methylamine, and pentaerythritol at the time of catalyst preparation for the purpose of controlling catalyst pores in order to improve catalyst performance. . For example, it is disclosed in JP-A-58-98143 and JP-A-3-109946. Indeed, since the added organic compound is removed by heat-treating the catalyst, there is an advantage that the pore size of the catalyst can be freely controlled by changing the size of the organic compound used.

However, in these heat treatment stages, sintering of the catalyst by combustion of the organic compound, reduction of the catalyst by the organic compound, and the like occur, so that the heat treatment as the catalyst activation treatment is complicated, and the production of the catalyst is reproduced. It has problems such as lack of properties. Also, a method of adding starch has been reported. For example, there are reports in JP-A-63-315147 and JP-A-4-4048. As shown in these examples, it is presently desired to develop a catalyst manufacturing method that can freely control the catalyst pore distribution, that is, easily improve catalyst performance and have excellent reproducibility.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel process for producing a supported catalyst which advantageously produces the corresponding unsaturated aldehyde and unsaturated carboxylic acid from propylene, isobutylene, TBA or MTBE, respectively. I have.

[0005]

SUMMARY OF THE INVENTION The present invention provides propylene,
In a catalyst containing at least molybdenum, bismuth and iron used in synthesizing isobutylene, TBA or MTBE in the gas phase using molecular oxygen to synthesize the corresponding unsaturated aldehyde and unsaturated carboxylic acid, the catalyst The mixed solution or the aqueous slurry containing the components is dried and fired, and the obtained fired product and rice powder having a particle size distribution of 1 to 1000 μm, and having an average particle size of 5 to 100 μm,
A method for producing a supported catalyst for synthesizing unsaturated aldehydes and unsaturated carboxylic acids, comprising mixing at least one selected from wheat powder or corn powder, supporting the mixture on a carrier, and heat treating the mixture.

Hereinafter, the present invention will be described in detail. In the present invention, the particle size distribution of the added rice powder, wheat powder or corn powder (generally referred to as cereal powder for the three) is preferably from 1 to 1000 μm, and the average particle size is preferably from 5 to 100 μm. In particular, those having a particle size distribution of 5 to 500 μm and an average particle size of 10 to 80 μm are preferable. If the grain powder to be added contains grain powder having a particle size of less than 1 μm or has an average particle size of less than 5 μm, the cost of producing such a grain powder is too high, but the time required for catalyst shaping is high. The handling of cereal powder is complicated and the effect of adding cereal is small. In addition, the particle size distribution of the grain powder to be added is 1000 μm
Contains grain powder exceeding 100μm and average particle size of 100μ
If it exceeds m, the grain size of the cereal powder to be added is too large, and the supporting strength as an industrial catalyst is undesirably reduced.

The amount of the cereal powder to be added is suitably in the range of 0.1 to 30% by weight, and particularly preferably in the range of 1 to 20% by weight, based on the weight of the fired catalyst. Grains that can be used in the present invention include rice, wheat, and dried corn. These grains are finely pulverized by a general pulverizer such as a sample mill.

In the present invention, the type of the carrier is not particularly limited, and ordinary carriers such as silica, alumina, silica-alumina, magnesia and titania are used. Also, the shape is not particularly limited, and examples thereof include a sphere, a column, a cylinder, and a plate.

As a method of supporting the calcined catalyst product on a carrier, a method is preferable in which a calcined catalyst product, grain powder, a slurry of a liquid material such as inorganic fiber is adhered to the carrier, and the liquid material is simultaneously vaporized and evaporated. The liquid used here is not particularly limited, and may be water, alcohols, ketones, esters, etc., as long as they are easily vaporized and evaporated by heating and are harmless to the catalyst. Water is preferred industrially.

The method of vaporizing and evaporating the liquid at the same time as attaching the slurry to the carrier is not particularly limited. For example, the slurry is attached to the carrier in a flowing state in a rotating drum by spraying or spraying the slurry. At the same time, a method of vaporizing and evaporating the liquid material by heating the drum from the outside or directly irradiating the carrier with hot air or infrared rays is preferable because it can be easily implemented.

In the present invention, the catalyst activity and selectivity are improved by mixing the calcined product of the catalyst with a grain powder having a specific size and then adding and supporting water. Regarding the cause, unlike cereal powders, which are different from ordinary commercial starches, both components soluble in water and the like and components insoluble in water are present. A series of operations such as mixing, kneading, and heat treatment provide a fine combination of water-soluble and insoluble components and catalyst powder. It is presumed that the catalyst performance is improved due to the formation of the catalyst.

Further, the present invention provides a method for mixing a grain powder with a calcined catalyst, which has an average diameter of 0.1 to 50 μm and an average length of 10 to 10 μm.
Addition of the inorganic fiber in the range of 1000 μm improves the reaction results of the supported catalyst after heat treatment and the strength of the supported catalyst. The amount of the inorganic fiber to be added is preferably in the range of 0.1 to 30% by weight relative to the calcined catalyst, and particularly preferably in the range of 1 to 15%.
% By weight is preferred. The material of the inorganic fiber that can be used is not particularly limited, but any material may be used as long as it does not substantially affect the reaction. Specific examples include glass fiber, asbestos, ceramic fiber, carbon fiber, and the like.

When mixing the calcined catalyst and the grain powder,
Further, conventionally known additives such as polyvinyl alcohol and carboxymethyl cellulose may be added.

In the present invention, the amount of the catalyst calcined product carried on the carrier is not particularly limited. However, considering both the mechanical strength of the supported catalyst and the yield of the target product, it is particularly preferable to support the calcined product in the range of 20 to 400 parts by weight with respect to 100 parts by weight of the support.

The supported catalyst thus obtained is then heat-treated. The heat treatment conditions are not particularly limited, and known treatment conditions can be applied. Usually, a temperature of 300 to 600 ° C. is used as the heat treatment condition.

[0016] The present invention relates to compounds of the general formula _{Mo a Bi b Fe c A d} X e Y f Z g Si h O i ( respectively in Mo, Bi, Fe, Si and O wherein molybdenum, bismuth, iron, silicon and oxygen A is at least one element selected from the group consisting of cobalt and nickel, and X is selected from the group consisting of chromium, lead, manganese, calcium, magnesium, niobium, silver, barium, tin, tantalum and zinc. At least one element
Y is phosphorus, boron, sulfur, selenium, tellurium, cerium,
Z represents at least one element selected from the group consisting of tungsten, antimony and titanium, and Z represents at least one element selected from the group consisting of lithium, sodium, potassium, rubidium, cesium and thallium. a, b, c, d, e, f, g, h and i represent the atomic ratio of each element, and when a = 12, b = 0.
= 0.01-5, d = 1-12, e = 0-8, f = 0
5, g = 0.001 to 2, h = 0 to 20, and i is the number of oxygen atoms necessary to satisfy the valence of each component. )).

The method for producing the calcined catalyst product used in the present invention is not limited to a special method. Unless the component is significantly unevenly distributed, a conventionally well-known evaporation-drying method, precipitation method, And various methods such as an oxide mixing method.

As the raw material of the catalyst component, oxides, sulfates, nitrates, carbonates, hydroxides, ammonium salts, halides and the like of each element can be used in combination. For example, as a molybdenum raw material, ammonium paramolybdate, molybdenum trioxide and the like can be used.

In the production of unsaturated aldehydes and unsaturated carboxylic acids using the supported catalyst obtained in the present invention, the starting materials propylene, isobutylene, TBA or MT
Gas phase catalytic oxidation is performed in the presence of a catalyst by adding molecular oxygen to BE. Propylene, isobutylene, TBA or MTB
The molar ratio of E to oxygen is preferably from 1: 0.5 to 3. The source gas is preferably diluted with an inert gas for use. Although it is economical to use air as the oxygen source, air enriched with pure oxygen can be used if necessary. The reaction pressure is preferably from normal pressure to several atmospheres. The reaction temperature can be selected in the range of 200 to 450 ° C, but is particularly preferably in the range of 250 to 400 ° C.

[0020]

EXAMPLES Hereinafter, a method for producing a catalyst according to the present invention and a reaction example using the same will be specifically described. Reaction rate of the starting olefin, TBA or MTBE in Examples and Comparative Examples,
The selectivity of the resulting unsaturated aldehyde and unsaturated carboxylic acid and the loading of the catalyst component are defined as follows.
In the description, “parts” means parts by weight. The analysis was based on gas chromatography.

[0021]

(Equation 1)

[0022]

(Equation 2)

[0023]

(Equation 3)

[0024]

(Equation 4)

The powdered ratio of the loaded catalyst is defined as follows. The supported catalyst a part was dropped and filled from the upper part of the reactor installed vertically with respect to the horizontal direction, and after filling, the catalyst recovered from the lower part of the reactor was the part b which did not pass through the 14-mesh sieve. Then, the filling powder ratio is expressed as follows.

[0026]

(Equation 5)

EXAMPLE 1 500 parts of ammonium paramolybdate were added to 1000 parts of water.
And 30.8 parts of ammonium paratungstate and 1.4 parts of potassium nitrate, and the mixture was heated and stirred (Solution A-1). Separately, 41.9 parts of 60% nitric acid was added to 600 parts of water to make the mixture uniform, and then 114.5 parts of bismuth nitrate was added and dissolved. To this, 104.9 parts of ferric nitrate, 309.0 parts of cobalt nitrate and 7.0 parts of zinc nitrate were sequentially added, and 400 parts of water was further added and dissolved (solution B-1). After the solution B-1 was added to the solution A-1 to form an aqueous slurry, 27.5 parts of antimony trioxide was added, and the mixture was heated and stirred to evaporate most of the water.

After the obtained cake-like substance was dried at 130 ° C., it was baked at 300 ° C. for 1 hour in an air atmosphere and pulverized. 100 parts of the fired and crushed product obtained in 150 parts of water and 2 to 2 parts
It has a particle size distribution of 200 μm and an average particle size of 20 μm
7 parts of the milled rice powder was mixed to form a uniform slurry.

While 200 parts of a spherical alumina carrier having a diameter of 4 mmφ are made to flow in a rotating drum, the slurry obtained above is gradually sprayed on the carrier by using a spray.
At the same time, heating was performed by a gas burner from the outside of the drum to vaporize and evaporate water. After spraying of the entire slurry was completed, the obtained support was dried at 130 ° C. for 1 hour. Subsequently, heat treatment was performed at 500 ° C. for 6 hours to obtain a supported catalyst.

The composition of elements other than oxygen in the obtained catalyst (the same applies hereinafter) is Mo ₁₂ W _0.5 Bi ₁ Fe _1.1 Sb _0.8 Co
_4.5 Zn _0.1 K _0.06 . The loading of the catalyst component was 33%. This catalyst was filled in a stainless steel reaction tube, and a raw material mixed gas of 5% of propylene, 12% of oxygen, 10% of steam and 73% of nitrogen (by volume) was contacted for 3.6 hours.
After passing through the catalyst layer in seconds, the reaction was carried out at 310 ° C. As a result, the conversion of propylene was 99.3%, the selectivity of acrolein was 88.9%, and the selectivity of acrylic acid was 6.8%. In addition, the filling powdering ratio was 1.4%.

Example 2 A heat treatment and a reaction were carried out in the same manner as in Example 1 except that crushed wheat powder having a particle size distribution of 2 to 300 μm and an average particle size of 25 μm was used instead of milled rice powder. Was done. As a result, the loading of the catalyst component was 33%, the conversion of propylene was 99.3%, and the selectivity of acrolein was 88.9.
%, And the selectivity for acrylic acid was 6.9%. The filling powdering ratio was 1.5%.

Example 3 5 parts of dried corn powder having a particle size distribution of 6 parts to 400 μm, having an average particle diameter of 50 μm, and 200 parts of water and 102 parts of the calcined and pulverized product obtained in Example 1 were prepared. 7 parts of glass fiber having a diameter of 10 μm and an average length of 200 μm are mixed to form a uniform slurry, and the carrier has a diameter of 5 μm.
Example 1 except that spherical silica-alumina of mmφ was used.
The heat treatment and the reaction were performed in the same manner as described above. As a result, the loading of the catalyst component was 33%, and the conversion of propylene was 99.3.
%, Acrolein selectivity was 88.9%, and acrylic acid selectivity was 6.8%. The filling powdering ratio was 0.8%.

Example 4 10 parts of polished rice powder having a particle size distribution of 280 parts of water, 2 to 200 μm and an average particle diameter of 20 μm were added to 140 parts of the calcined and pulverized product obtained in Example 1, and Diameter 5
Ceramic fiber 10 with an average length of 200 μm
Example 1 except that the parts were mixed to form a uniform slurry.
The heat treatment and the reaction were performed in the same manner as described above. As a result, the catalyst component loading was 40%, and the propylene conversion was 99.4.
%, Acrolein selectivity was 89.0%, and acrylic acid selectivity was 6.9%. In addition, the filling powdering ratio was 0.4%.

Example 5 215 parts of water, 15 parts of crushed wheat powder having a particle size distribution of 2 to 300 μm, an average particle diameter of 25 μm, and 215 parts of the calcined and pulverized product obtained in Example 1, 10
A heat treatment and a reaction were carried out in the same manner as in Example 1 except that 15 parts of a glass fiber having a thickness of 200 μm and an average length of 200 μm were mixed to form a uniform slurry. As a result, the loading of the catalyst component was 50%, the conversion of propylene was 99.5%,
The selectivity for acrolein was 89.1% and the selectivity for acrylic acid was 6.9%. The filling powdering ratio was 0.3%.

Comparative Example 1 A heat treatment and a reaction were performed in the same manner as in Example 1 except that the milled rice powder was not used. As a result, the loading of the catalyst component was 33%, and the conversion of propylene was 99.
0%, acrolein selectivity was 87.6%, and acrylic acid selectivity was 6.3%. The filling powdering rate is 2.1%
Met.

Comparative Example 2 A heat treatment was performed in the same manner as in Example 1 except that a commercial product starch having a particle size distribution of 1 to 150 μm and an average particle size of 27 μm was used instead of milled rice powder. And the reaction was performed. As a result, the loading ratio of the catalyst component was 33%.
The conversion of propylene was 99.1%, the selectivity of acrolein was 88.2%, and the selectivity of acrylic acid was 6.5%. The filling powdering ratio was 1.9%.

Comparative Example 3 A heat treatment and a reaction were carried out in the same manner as in Example 1 except that the milled rice powder had a particle size distribution of 2 to 200 μm and had an average particle size of 120 μm. . As a result, the loading of the catalyst component was 33%, the conversion of propylene was 99.2%, the selectivity of acrolein was 88.1%, and the selectivity of acrylic acid was 6.6%. In addition, the filling powder ratio was 2.5%.

Comparative Example 4 A heat treatment and a reaction were performed in the same manner as in Example 1 except that the milled rice powder had a particle size distribution of 0.1 to 200 μm and an average particle size of 20 μm. went.
As a result, the loading of the catalyst component was 33%, the conversion of propylene was 99.2%, the selectivity of acrolein was 87.8%,
The selectivity for acrylic acid was 6.6%. The filling powdering rate was 1.7%.

Comparative Example 5 A heat treatment and a reaction were performed in the same manner as in Example 1 except that the milled rice powder had a particle size distribution of 2 to 1200 μm and an average particle size of 50 μm. Was.
As a result, the loading of the catalyst component was 33%, the conversion of propylene was 99.3%, the selectivity of acrolein was 88.0%,
The selectivity for acrylic acid was 6.6%. The filling powdering ratio was 2.8%.

Comparative Example 6 In Example 1, the milled rice powder was used in an amount of 0.1 to 1200 μm.
The heat treatment and the reaction were carried out in the same manner as in Example 1 except that the particles had a particle size distribution of 120 μm and an average particle size of 120 μm. As a result, the loading of the catalyst component was 33%, the conversion of propylene was 99.3%, and the selectivity of acrolein was 88.
The selectivity for acrylic acid was 6.6%. The filling powdering ratio was 3.8%.

Example 6 42 parts of 60% nitric acid was added to 400 parts of water to make a uniform solution, and 68.7 parts of bismuth nitrate was added and dissolved. To this were added 274.5 parts of nickel nitrate and 24.1 parts of antimony trioxide.
Parts were added sequentially and dissolved and dispersed. 165 parts of 28% aqueous ammonia was added to this mixture to obtain a white precipitate and a blue solution. This was heated and stirred, and most of the water was evaporated. After drying the obtained slurry-like substance at 120 ° C. for 16 hours,
Heat treated at 750 ° C. for 2 hours and pulverized. 500 parts of ammonium paramolybdate, 18.5 parts of ammonium paratungstate and cesium nitrate 2 in 1000 parts of water
0.7 parts was added, and the mixture was heated and stirred (Solution A-6).

Separately, ferric nitrate 200.2 was added to 700 parts of water.
Parts, 171.7 parts of cobalt nitrate and 9 magnesium nitrate
0.8 parts were sequentially added and dissolved (solution B-6). After B-6 solution was added to A-6 solution to form a slurry, 354.5 parts of a 20% silica sol and fine powder of the bismuth-nickel-antimony compound were added and heated and stirred to evaporate most of water. After the obtained cake-like substance was dried at 130 ° C., it was baked at 300 ° C. for 1 hour in an air atmosphere and pulverized. 100 parts of the fired and crushed product obtained in 150 parts of water and 2 to 200 parts
7 parts of milled rice powder having a particle size distribution of μm and an average particle size of 20 μm were mixed to form a uniform slurry. 4m diameter
While flowing 200 parts of a spherical alumina carrier having a diameter of mφ in a rotating drum, a slurry was gradually sprayed on the carrier using a spray, and at the same time, water was vaporized and evaporated from the outside of the drum by a gas burner. After spraying of the entire slurry was completed, the obtained support was dried at 130 ° C. for 1 hour. Subsequently, heat treatment was performed at 500 ° C. for 6 hours.

The composition of the element of the catalyst obtained was Mo ₁₂ W
_0.3 Bi _0.6 Fe _2.1 Sb _0.7 Ni ₄ Co _2.5 Cs _0.45
Mg _1.5 Si ₅ . This catalyst was charged into a stainless steel reaction tube, and isobutylene 5%, oxygen 12%, steam 1
A mixed gas of 0% and nitrogen 73% (vol%) was passed through the catalyst layer at a contact time of 3.6 seconds, and reacted at 350 ° C. As a result, the conversion of isobutylene was 97.3%, the selectivity of methacrolein was 89.6%, and the selectivity of methacrylic acid was 3.4%. The filling powdering ratio was 1.5%.

Example 7 A heat treatment and a reaction were carried out in the same manner as in Example 6, except that crushed wheat powder having a particle size distribution of 2 to 300 μm and an average particle size of 25 μm was used instead of the polished rice powder. Was done. As a result, the loading of the catalyst component was 33%, the conversion of isobutylene was 97.3%, and the selectivity of methacrolein was 8%.
The selectivity of 9.7% and methacrylic acid was 3.4%. The filling powdering ratio was 1.6%.

Example 8 With respect to 102 parts of the calcined and crushed product obtained in Example 6, 200 parts of water, 5 parts of dried corn powder having a particle size distribution of 6 to 400 μm and an average particle size of 50 μm, and 5 parts of an average 7 parts of glass fiber having a diameter of 10 μm and an average length of 200 μm are mixed to form a uniform slurry, and the carrier has a diameter of 5 μm.
The heat treatment and the reaction were carried out in the same manner as in Example 6 except that spherical silica of mmφ was used. As a result, the loading of the catalyst component was 33%, the conversion of isobutylene was 97.3%, the selectivity of methacrolein was 89.6%, and the selectivity of methacrylic acid was 3.4%. The filling powdering ratio was 0.7%.

Example 9 10 parts of milled rice powder having a particle size distribution of 280 parts of water, 2 to 200 μm, an average particle diameter of 20 μm, and an average diameter of 140 parts of the calcined and crushed product obtained in Example 6 5μ
Heat treatment and reaction were carried out in the same manner as in Example 6 except that 10 parts of a ceramic fiber having an average length of 200 μm and a uniform slurry were mixed. As a result, the carrying ratio of the catalyst component was 40%, and the conversion of isobutylene was 97.4.
%, Methacrolein selectivity was 89.7%, and methacrylic acid selectivity was 3.4%. In addition, the filling powder ratio is 0.3
%Met.

Example 10 215 parts of water, 235 parts of crushed wheat powder having a particle size distribution of 2 to 300 μm, an average particle diameter of 25 μm, and 215 parts of the calcined and pulverized product obtained in Example 6, 10
A heat treatment and a reaction were carried out in the same manner as in Example 6, except that 15 parts of a glass fiber having an average length of 200 μm and a uniform length of slurry were mixed. As a result, the carrying ratio of the catalyst component was 50%, and the conversion of isobutylene was 97.6.
%, Methacrolein selectivity was 89.6%, and methacrylic acid selectivity was 3.4%. In addition, the filling powder ratio is 0.2
%Met.

Example 11 To 140 parts of the calcined and crushed product obtained in Example 6, 280 parts of water, 9 parts of glutinous rice powder having a particle size distribution of 2 to 300 μm and an average particle size of 55 μm were added. Average diameter 1
10 μm glass fiber with an average length of 200 μm
Example 6 except that the parts were mixed to form a uniform slurry.
The heat treatment and the reaction were performed in the same manner as described above. As a result, the loading of the catalyst component was 40%, and the conversion of isobutylene was 97.
The selectivity for methacrolein was 59.6% and the selectivity for methacrylic acid was 3.5%. Further, the filling powdering ratio is 0.1.
5%.

Example 12 Using the catalyst of Example 6, the reaction was carried out in the same manner as in Example 6, except that the raw material was changed to TBA. As a result, TB
A conversion 100%, methacrolein selectivity 87.7
% And methacrylic acid selectivity was 3.1%.

Comparative Example 7 A heat treatment and a reaction were performed in the same manner as in Example 6, except that the milled rice powder was not used. As a result, the loading ratio of the catalyst component was 33%, and the conversion of isobutylene was 9%.
The selectivity of 6.9%, methacrolein was 87.8%, and the selectivity of methacrylic acid was 3.0%. The filling powdering ratio was 2.2%.

Comparative Example 8 A heat treatment and a reaction were carried out in the same manner as in Example 6 except that a commercial product starch having a particle size distribution of 1 to 150 μm and an average particle size of 27 μm was used instead of the milled rice powder. Was done. As a result, the loading of the catalyst component was 33%, the conversion of isobutylene was 97.1%, the selectivity of methacrolein was 88.9%, and the selectivity of methacrylic acid was 3.1%. The filling powdering ratio was 1.9%.

Comparative Example 9 A heat treatment and a reaction were carried out in the same manner as in Example 6 except that the milled rice powder had a particle size distribution of 2 to 200 μm and an average particle size of 120 μm. Was.
As a result, the loading of the catalyst component was 33%, the conversion of isobutylene was 97.1%, and the selectivity of methacrolein was 88.4.
% And methacrylic acid selectivity was 3.1%. The filling powdering ratio was 2.8%.

Comparative Example 10 In Example 6, the milled rice powder had a particle size distribution of 0.1 to 200 μm and had an average particle size of 20 μm. went.
As a result, the catalyst component loading was 33%, the conversion of isobutylene was 97.1%, and the selectivity of methacrolein was 87.9.
% And a selectivity of methacrylic acid of 3.2%. The filling powdering rate was 1.7%.

Comparative Example 11 Heat treatment and reaction were carried out in the same manner as in Example 6 except that the milled rice powder had a particle size distribution of 2 to 1200 μm and an average particle size of 50 μm. Was.
As a result, the carrying ratio of the catalyst component was 33%, the conversion of isobutylene was 97.0%, and the selectivity of methacrolein was 88.5.
% And methacrylic acid selectivity was 3.1%. In addition, the powdering ratio was 2.9%.

Comparative Example 12 In Example 6, the milled rice powder was used in an amount of 0.1 to 1200 μm.
The heat treatment and the reaction were carried out in the same manner as in Example 6, except that the particle size distribution was 120 μm and the average particle size was 120 μm. As a result, the catalyst component loading was 33%, the conversion of isobutylene was 97.0%, and the selectivity of methacrolein was 8%.
8.7% and selectivity of methacrylic acid were 3.1%. In addition, the filling powdering ratio was 3.7%.

Comparative Example 13 Using the catalyst of Comparative Example 8, the reaction was carried out in the same manner as in Example 6 except that the raw material was changed to TBA. As a result, TB
A reaction rate of 100%, selectivity of methacrolein is 85.
The selectivity of methacrylic acid was 2.8%.

Comparative Example 14 Using the catalyst of Comparative Example 12, the reaction was carried out in the same manner as in Example 6 except that the raw material was changed to TBA. As a result, T
BA conversion 100%, methacrolein conversion 8
6.1% and methacrylic acid selectivity was 2.9%.

Continuation of front page (58) Field surveyed (Int. Cl. ⁷ , DB name) B01J 21/00-38/74 C07C 45/35 C07C 47/22

Claims (2)

(57) [Claims] 1. A method for producing a corresponding unsaturated aldehyde and unsaturated carboxylic acid by subjecting propylene, isobutylene, tertiary butyl alcohol or methyl tertiary butyl ether to gas-phase catalytic oxidation using molecular oxygen. In a catalyst containing at least molybdenum, bismuth and iron to be used, a mixed solution or an aqueous slurry containing a catalyst component is dried and then fired, and the fired product obtained is 1 to 1000 μm.
m having a particle size distribution, and mixing at least one selected from rice powder, barley powder or corn powder having an average particle size of 5 to 100 μm, supporting the mixture on a carrier, and then subjecting the mixture to heat treatment. A method for producing a supported catalyst for synthesizing aldehydes and unsaturated carboxylic acids. 2. The catalyst according to claim 1, which has an average diameter of 0.1-5.
The method for producing a supported catalyst according to claim 1, wherein an inorganic fiber having a length of 0 µm and an average length of 10 to 1000 µm is added.