WO2015119165A1

WO2015119165A1 - Method for manufacturing extrusion molding

Info

Publication number: WO2015119165A1
Application number: PCT/JP2015/053134
Authority: WO
Inventors: 拓朗渡邉; 美栄治杉山
Original assignee: 三菱レイヨン株式会社
Priority date: 2014-02-05
Filing date: 2015-02-04
Publication date: 2015-08-13
Also published as: CN105934315B; JPWO2015119165A1; SA516371200B1; KR101843666B1; KR20160045117A; SG11201603963UA; JP6468183B2; CN105934315A

Abstract

Provided is a method for manufacturing an extrusion molding, the method being capable of manufacturing an extrusion molding with minimal unevenness of quality using simple maneuvers. This method for manufacturing extrusion moldings comprises: (1) a step for manufacturing a kneaded product by kneading a starting material powder, a liquid and a binder; (2) a step for manufacturing a crushed product by crushing the kneaded product; and (3) a step for molding the crushed product using an extruder. The crushed product in step (2) is crushed to a particle size such that 80 mass% or more passes through a sieve of nominal dimension (D/2) mm when the internal cylinder diameter of the extruder in step (3) is D mm or is crushed using a crusher in step (2).

Description

Method for producing extrusion molded body

The present invention relates to a method for producing an extrusion-molded body.

In general, a catalyst, a catalyst carrier, an adsorbent, a drying material, a humidity control material, etc. are formed into a cylindrical or cylindrical shaped body having a diameter of about 2 to 10 mm and a length of about 2 to 20 mm. Filled and used in chemical processes using unit operations such as various absorption operations and chemical reactions. In order to produce such compacts such as fillers and catalysts, an extrusion molding method has been conventionally employed.

Patent Document 1 includes a primary molding process in which a kneaded product is primary molded and a secondary molding process in which the primary molded product is molded into a final shape with a piston molding machine. The secondary molding pressure P2 is primary. There has been proposed a method for producing a catalyst for producing methacrylic acid, which is in the range of (P1-0.2) MPaG to (P1-8) MPaG with respect to the molding pressure P1.

JP 2011-224482 A

Currently, there is a demand for a method for producing an extruded product that can reduce the quality unevenness of the molded product in an industrially simpler operation than the conventional method.

For example, when packing a column with a fixed volume or size, or when packing a catalyst into a reaction tube with a fixed volume or size, it is necessary to pack a predetermined amount of the packing or catalyst. . In particular, in the case of a multi-tube heat exchanger type reactor, it is necessary to fill a plurality of reaction tubes with the same amount of catalyst, and from this point of view, the stability of the packing density of the filler and catalyst is an important factor.

An object of the present invention is to provide a method for producing an extruded product that can produce an extruded product with few quality spots by a simple operation.

The method for producing an extruded product according to one aspect of the present invention includes:
(1) kneading raw material powder, liquid and binder to produce a kneaded product,
(2) crushing the kneaded product to produce a crushed product;
(3) forming the crushed material using an extruder;
Including, and
When the cylinder inner diameter of the extruder in the step (3) is Dmm, the crushed material in the step (2) is crushed to a particle size that passes 80% by mass or more through a sieve having a nominal size (D / 2) mm. Features.

The method for producing an extruded product according to another aspect of the present invention is as follows.
(1) kneading raw material powder, liquid and binder to produce a kneaded product,
(2) crushing the kneaded product to produce a crushed product;
(3) forming the crushed material using an extruder;
And crushing using a crusher in the step (2).

According to the present invention, there is provided an extrusion molded body production method capable of producing an extrusion molded body with few quality spots by a simple operation.

Examples of the raw material powder used in the production method of the present invention include a catalyst powder and precursor powder for producing methacrylic acid by vapor-phase catalytic oxidation of methacrolein [Patent Document 1 (Japanese Patent Laid-Open No. 2011-224482)] And the like.

According to the present invention, the extrusion-molded body comprises (1) a step of producing a kneaded product by kneading raw material powder, a liquid and a binder, and (2) a step of producing a crushed product by crushing the kneaded product. And (3) a step of forming the crushed material using an extruder, and usually a step of (4) further drying the formed body obtained in step (3).

(Process (1))
In the step (1), the raw material powder, the liquid and the binder are kneaded. The apparatus used for kneading is not particularly limited, and for example, a batch-type kneader equipped with a double-armed stirring blade, a continuous kneader such as a shaft rotation reciprocating type or a self-cleaning type can be used. . However, a batch type kneader is preferred in that kneading can be performed while checking the state of the kneaded product. Moreover, the end point of kneading | mixing can be judged by visual observation or a touch normally.

The liquid used in the step (1) is not particularly limited as long as it has a function of wetting the raw material powder. For example, water, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol or the like has 1 to 4 carbon atoms. Examples include alcohol. These may use only 1 type and may use 2 or more types together. Among these, water and ethyl alcohol are preferable from the viewpoint of handleability. In the present invention, the liquid means a liquid compound under the conditions of normal temperature and normal pressure (25 ° C., 0.101 MPa).

The amount of liquid used in step (1) is appropriately selected depending on the type and size of the raw material powder, the type of liquid, etc., but is 10 to 80 parts by mass with respect to 100 parts by mass of the raw material powder to be kneaded. It is preferable.

When the amount of liquid used is 10 parts by mass or more, extrusion can be performed more smoothly, so that the shape of the molded body is stabilized. On the other hand, when the amount of the liquid used is 80 parts by mass or less, the adhesion during molding is reduced and the handleability is improved. The amount of the liquid used is more preferably 5 to 50 parts by weight, more preferably 10 to 45 parts by weight, and particularly preferably 15 to 40 parts by weight with respect to 100 parts by weight of the raw material powder to be kneaded. preferable.

The binder used in the step (1) is not particularly limited as long as it has a function of adhering the raw material powder. Examples of the organic binder include polymer compounds such as polyvinyl alcohol, α-glucan derivatives, and β-glucan derivatives. Etc. These may use only 1 type and may use 2 or more types together.

In the present invention, an α-glucan derivative refers to a polysaccharide composed of glucose in which glucose is bound in an α-type structure, such as α1-4 glucan, α1-6 glucan, α1-4 / 1-6 glucan, etc. The derivative | guide_body can be illustrated. Examples of such α-glucan derivatives include amylose, glycogen, amylopectin, pullulan, dextrin, cyclodextrin and the like. These may use only 1 type and may use 2 or more types together.

In the present invention, a β-glucan derivative refers to a polysaccharide composed of glucose in which glucose is bound in a β-type structure. Β1-4 glucan, β1-3 glucan, β1-6 glucan, β1-3 / Examples thereof include derivatives such as 1-6 glucan. Examples of such β-glucan derivatives include celluloses such as methylcellulose, ethylcellulose, carboxymethylcellulose, sodium carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, hydroxyethylmethylcellulose, hydroxybutylmethylcellulose, ethylhydroxyethylcellulose, and hydroxypropylcellulose. Derivatives, curdlan, laminaran, paramylon, callose, pakiman, β1-3 glucan such as scleroglucan and the like can be mentioned. These may use only 1 type and may use 2 or more types together.

The organic binder may be used unpurified or may be used after purification, but in order to prevent the catalyst performance from being deteriorated due to the metal as an impurity or the residue on ignition, It is preferable that the content of the ignition residue is smaller.

Examples of inorganic binders include conventionally known silica, alumina, silica-alumina, silicon carbide, titania, magnesia, inorganic compounds such as graphite and diatomaceous earth, ceramic balls and stainless steel, glass fibers, ceramic fibers and carbon fibers. An inert carrier such as inorganic fiber can be used. These may use only 1 type and may use 2 or more types together. Of course, it is also possible to use a mixture of an organic binder and an inorganic binder.

The mixing method of the raw material powder, liquid and binder is not particularly limited. Specifically, a method of mixing a raw material powder and a binder that are dry-mixed and a liquid, a method of mixing or dissolving a binder in a liquid and a raw material powder, and the like can be exemplified. In particular, a method of mixing a raw material powder and a binder that are dry-mixed with a liquid is preferable. In the case of a binder that can be obtained in a state of being dissolved or dispersed in a liquid, the amount of liquid newly added to be mixed with the raw material powder may be adjusted according to the amount of liquid contained in the binder.

The amount of the binder used in step (1) is appropriately selected depending on the type and size of the raw material powder, the type of liquid, etc., but is usually 0.05 to 15 parts by mass with respect to 100 parts by mass of the raw material powder. Yes, preferably 0.1 to 10 parts by mass.

The processing capacity of the apparatus for kneading in step (1), that is, the kneading machine is not particularly limited, but the total maximum processing capacity of the apparatus for kneading is the maximum processing capacity of the extruder used in step (3). Is preferably larger. When the sum of the maximum processability of the kneader is larger than the maximum processability of the extruder, it is possible to easily prevent the waiting time for raw material supply from occurring in the extruder used in the step (3). Therefore, it is possible to easily prevent the occurrence of spots between the raw material remaining in the extruder and the newly supplied raw material when the waiting time occurs. To that end, it is preferable to supply the raw material continuously if it is a continuous extruder, and it is preferable to supply the raw material so as not to generate a waiting time for raw material input if it is a batch type extruder. The maximum processing capability of the device used in (1) is preferably larger than the maximum processing capability of the device used in step (3).

Here, the maximum processing capability of a certain device is the amount of processing [kg] per unit time [h] when the object is processed by the device and the obtained product satisfies the quality specifications in the process. It is the maximum value.

(Process (2))
In the step (2), the kneaded material obtained in the step (1) is crushed.

In the present invention, pulverization means to break up a lump into a particle size smaller than that state.

The method of crushing is not particularly limited, and examples thereof include a method of crushing by hand and a method of crushing using a crusher, a loosening machine, or the like. Among these, the method of pulverization using a pulverizer is preferable because it can be pulverized to a target particle size in a short time.

As the crusher, various types such as a shearing type, an impact type and a cutting type can be adopted. For example, a rotary mill type, a screw type, an auger type, etc. are preferable. Further, as specific examples, a scraping-type bale crusher manufactured by Ohara Iron Works Co., Ltd., a twin-screw rotary crusher, a single-screw crusher or a screw auger crusher, and a screw auger crusher manufactured by Kobelco Construction Machinery Co., Ltd. Aisin Sangyo Co., Ltd. 1-shaft type crusher, Tokuju Kogakusho Co., Ltd. Landel mill crusher, etc. can be used.

In the present invention, when the cylinder inner diameter of the extruder of the step (3) is Dmm, the crushed material of the step (2) passes through a sieve having a nominal size (D / 2) mm of 80% by mass or more. Can be crushed. When the ratio of the crushed material passing through a sieve with a nominal size (D / 2) mm is 80% by mass or more, air extrusion into the molded product is suppressed during extrusion molding, and the quality unevenness of the extruded product is large. It is easy to suppress. The proportion of the crushed material passing through a sieve having a nominal size (D / 2) mm is preferably 85% by mass or more, and more preferably 90% by mass or more. In the present invention, the nominal dimension refers to the length of one side of the mesh of the sieve (also referred to as an opening).

When the crusher is used in step (2), the processing capacity is not particularly limited, but it is preferable that the total maximum processing capability of the crusher to be used is larger than the maximum processing capability of the extruder used in step (3). If the total maximum processing capability of the crusher to be used is larger than the maximum processing capability of the extruder used in the step (3), it is easy for the extruder used in the step (3) to wait for the raw material supply. Can be prevented. Therefore, it is possible to easily prevent the occurrence of spots between the raw material remaining in the extruder and the newly supplied raw material when the waiting time occurs. Therefore, it is preferable that the sum of the maximum processability of the crusher used in the step (2) is larger than the maximum processability of the extruder used in the step (3). Further, it is preferable to supply the raw material continuously so as not to generate a standby time for waiting for the raw material to be charged if it is a continuous extruder and a batch type extruder.

When using a crusher in the step (2), the power of the disintegrator is not particularly limited, the power to volume pulverizer is preferably ^{^{10kW / m 3 ~ 500kW / m}} 3, is ^{50kW / m 3 ~ 400kW / m} 3 More preferred. When the power with respect to the volume of the crusher is 10 kW / m ³ or more, it is easy to satisfactorily crush the kneaded material obtained in the step (1). In the present invention, the volume of the crusher does not include the volume of the piping for supplying and discharging the raw material, but is the volume of the crusher body that is crushing the raw material, and the power of the crusher is This is the power of the motor used for crushing.

(Process (3))
In step (3), the crushed product obtained in step (2) is extruded to produce an extruded product. For example, an auger type extruder or a plunger type extruder can be used for the extrusion molding. However, it is easy to add suitable kneading to the kneaded material, and the performance change of the molded catalyst is small. It is preferable to use a jar type extruder. There is no limitation in particular as a shape of an extrusion molded object, For example, it can be set as arbitrary shapes, such as a ring shape, a column shape, and a star shape. The cylinder inner diameter D of the extruder is preferably 10 mm or more and 600 mm or less, preferably 20 mm or more and 400 mm or less, and more preferably 30 mm or more and 300 mm or less. Further, L / D when the cylinder length is Lmm is preferably 1 or more and 20 or less, and more preferably 1.1 or more and 10 or less.

The crushing machine and the extrusion molding machine used for the step (2) and the process (3), respectively, may be connected to perform the crushing operation to the molding operation continuously.

(Process (4))
In the step (4), the extruded product obtained in the step (3) is dried. The drying method is not particularly limited, and for example, generally known methods such as hot air drying, humidity drying, far infrared drying, and microwave drying can be arbitrarily used. The drying conditions can be appropriately selected as long as the desired moisture content can be achieved.

(About catalyst)
The raw material powder is a catalyst powder for producing an unsaturated carboxylic acid containing at least molybdenum and phosphorus as catalyst components, which is used when producing an unsaturated carboxylic acid by vapor-phase catalytic oxidation of an unsaturated aldehyde with molecular oxygen. It may be a precursor powder.

In this case, for example, an extruded product of the catalyst can be produced by the method of the present invention, and the extruded product can be heat-treated to produce an unsaturated carboxylic acid production catalyst. In particular, when the unsaturated carboxylic acid is (meth) acrylic acid, it is possible to produce a catalyst for producing (meth) acrylic acid, and using this catalyst, (meth) acrolein is vapor-phase contacted with molecular oxygen. It can be oxidized to produce (meth) acrylic acid.

Further, the raw material powder is obtained by subjecting propylene, isobutylene, primary butyl alcohol, tertiary butyl alcohol or methyl tertiary butyl ether to gas phase catalytic oxidation with molecular oxygen, and corresponding unsaturated aldehydes and unsaturated compounds. It may be an unsaturated aldehyde and unsaturated carboxylic acid production catalyst powder or precursor powder thereof containing at least molybdenum and bismuth as catalyst components used in the production of carboxylic acid.

In this case, for example, an extrudate of the catalyst can be produced by the method of the present invention, and the extrudate can be heat-treated to produce an unsaturated aldehyde and unsaturated carboxylic acid production catalyst. In particular, when the unsaturated aldehyde is (meth) acrolein and the unsaturated carboxylic acid is (meth) acrylic acid, a catalyst for producing (meth) acrolein and (meth) acrylic acid can be produced. To produce (meth) acrolein and (meth) acrylic acid by vapor phase catalytic oxidation of propylene, isobutylene, primary butyl alcohol, tertiary butyl alcohol or methyl tertiary butyl ether with molecular oxygen can do.

In the case of producing a catalyst, it is preferable to calcine the extruded product. However, if it is calcined before extrusion molding, the calcining may be omitted. When calcination is omitted, a dried product of the catalyst molded body is a catalyst, and when heat treatment is performed, the heat-treated product is a catalyst. The firing method is not particularly limited, and the firing method and conditions can be appropriately selected. The firing conditions vary depending on the raw material compound used, the composition of the catalyst components, the preparation method, and the like, but are preferably 200 to 600 ° C. and 0.5 hours or longer under the flow of an oxygen-containing gas such as air or an inert gas. Here, the inert gas indicates a gas that does not decrease the reaction activity of the catalyst, and specifically includes nitrogen, carbon dioxide, helium, argon, and the like. Calcination may be performed using a heating device, but may also be performed in a catalyst molded product charged into a reactor.

In the context of the present invention, “heat treatment” may include one or both of heat treatment for drying and heat treatment for firing. The extruded product can be dried (not fired) by heat treatment to obtain a catalyst, or the extruded product can be dried and calcined by heat treatment to obtain a catalyst.

Hereinafter, the present invention will be specifically described using examples and comparative examples, but the present invention is not limited to these examples.

In the manual crushing in the examples and comparative examples, the kneaded material was collected in a plastic bag, and the portion that had been hardened in a clay shape was loosened by hand.

The sieving of the kneaded materials in the examples and comparative examples was carried out by vibrating a sieve having a nominal size (D / 2) mm by hand to the left and right, and throwing the kneaded materials at a speed that does not overlap the sieves.

The quality unevenness of the extruded molded body was determined 10 times from the standard deviation of the filling density of each molded body after being molded 10 times under the same molding conditions. The packing density was calculated from the mass X of the compact body filled with a compact body having an inner diameter of 27 mm up to a scale of 100 ml as follows.

Packing density (g / L) = X × 10
Further, “part” described in Examples and Comparative Examples means “part by mass”.

In the reaction evaluation described later, analysis of the raw material gas and the product was performed using gas chromatography. The methacrolein reaction rate, methacrylic acid selectivity, and methacrylic acid yield are defined as follows.

Methacrolein reaction rate (%) = (B / A) × 100
Methacrylic acid selectivity (%) = (C / B) × 100
Methacrylic acid yield (%) = (C / A) × 100
Here, A is the number of moles of methacrolein supplied, B is the number of moles of reacted methacrolein, and C is the number of moles of methacrylic acid produced.

[Examples 1 to 4, Comparative Example 1]
In each of Examples 1 to 4 and Comparative Example 1, the following operation was performed.

In 4000 parts of pure water, 1000 parts of molybdenum trioxide, 34 parts of ammonium metavanadate, 80 parts of 85 mass% phosphoric acid aqueous solution and 7 parts of copper nitrate are dissolved, and the temperature is raised to 95 ° C. while stirring, and the liquid temperature is 95. The mixture was stirred for 3 hours while maintaining the temperature. After cooling to 90 ° C., a solution obtained by dissolving 124 parts of cesium bicarbonate in 200 parts of pure water was added and stirred for 15 minutes while stirring using a rotary blade stirrer. Next, a solution obtained by dissolving 92 parts of ammonium carbonate in 200 parts of pure water was added, and the mixture was further stirred for 20 minutes. The mixed slurry containing the raw material compound of the catalyst component obtained as described above was dried under the conditions of a dryer inlet temperature of 300 ° C. and a slurry spraying rotary disk of 18,000 rpm using a co-current spray dryer.

100 parts of the raw material powder thus obtained is mixed with 3 parts of hydroxypropyl cellulose and 18 parts of ethyl alcohol until it is made into a clay with a batch kneader equipped with a double-armed sigma blade. Kneaded.

50 parts of the obtained kneaded material was crushed by a single-shaft crusher or manually, and sieved using a sieve having a nominal size (D / 2) mm. Table 1 shows the crushing method, the crushing time, the nominal size of the sieve used (D / 2), and the ratio of passing through the sieve of the nominal size D / 2 of the crushed material.

Next, the crushed product obtained by combining the crushed product that passed through the sieve and the crushed product that did not pass through the sieve was extruded using a plunger-type extruder, dried at 90 ° C. for 12 hours with a hot air dryer, and the outer diameter. A cylindrical catalyst molded body having a length of 5.5 mm and a length of 5.5 mm was obtained. In order to eliminate the influence of the size of the compact on the packing density, the outer shape and the length were all adjusted to 5.5 mm. The same crushed material was extruded 10 times, and the standard deviation of the packing density of the molded body was measured. Table 1 shows the cylinder inner diameter of the plunger extruder, the ratio L / D of the cylinder length L to the cylinder inner diameter D, and the standard deviation of the packing density of the molded product.

The maximum processing capability of the used kneader was 5.7 when the maximum processing capability of the used extruder was 1. Moreover, the maximum processability of the used crusher was 8.3 when the maximum processability of the used extruder was set to 1.

The ratio of power to the volume of the crusher used was 92 kW / m ³ .

All the molded products obtained were mixed and the reaction was evaluated under the following conditions.

This catalyst (extruded product) was filled in a stainless steel reaction tube having an outer diameter of 27.5 mm and a height of 6 m having an external heat medium bath so that the catalyst filling length was 5 m. Next, the temperature of the heat medium bath provided outside the reaction tube was set to 370 ° C., and heat treatment was performed for 10 hours while circulating air. Subsequently, the temperature of the heat medium bath is set to 290 ° C., and a reaction gas comprising 6% by volume of methacrolein, 12% by volume of oxygen, 10% by volume of water vapor and 72% by volume of nitrogen is passed through the catalyst layer at a gas space velocity of 1200 hr ⁻¹ . Under conditions, methacrolein was subjected to a gas phase catalytic oxidation reaction. The product 24 hours after the start of the reaction was collected and analyzed by gas chromatography to determine the reaction rate of methacrolein, the selectivity of methacrylic acid, and the yield of methacrylic acid. The results are shown in Table 2.

[Comparative Examples 2 and 3]
Catalyst molded bodies were produced and molded in the same manner as described in Examples 1 to 4 and Comparative Example 1 except that the kneaded material was not crushed and the kneaded material was supplied to the plunger type extruder as it was. The standard deviation of the packing density of the product was measured, and the gas phase catalytic oxidation reaction of methacrolein was performed. Conditions and results are shown in Tables 1 and 2.

Claims

(1) kneading raw material powder, liquid and binder to produce a kneaded product,
(2) crushing the kneaded product to produce a crushed product;
(3) forming the crushed material using an extruder;
Including, and
When the cylinder inner diameter of the extruder in the step (3) is Dmm, the crushed material in the step (2) is crushed to a particle size that passes 80% by mass or more through a sieve having a nominal size (D / 2) mm. A method for producing an extruded product.
(1) kneading raw material powder, liquid and binder to produce a kneaded product,
(2) crushing the kneaded product to produce a crushed product;
(3) forming the crushed material using an extruder;
Including, and
A method for producing an extrusion-molded product, comprising crushing using a crusher in the step (2).
The total maximum processing capability of the apparatus for kneading in the step (1) is larger than the maximum processing capability of the extruder used in the step (3), and the total of the crushers used in the step (2) The method for producing an extruded product according to claim 2, wherein the maximum processable capacity is larger than the maximum processable capacity of the extruder used in the step (3).
The method for producing an extruded product according to claim 2 or 3, wherein in the step (2), the ratio of power to the volume of the crusher is 10 kW / m 3 to 500 kW / m 3 .
In the step (2), crushing is performed using any one of a scraping-type bale crusher, a twin-screw rotary crusher, a single-screw crusher, a screw auger crusher, and a rotary mill crusher. The method for producing an extruded product according to any one of claims 2 to 4.
The method for producing an extruded product according to any one of claims 1 to 5, wherein in the step (3), the product is molded using a plunger-type extruder.
The method for producing an extruded product according to any one of claims 1 to 6, wherein a cylinder inner diameter D of the extruder in the step (3) is 10 mm to 600 mm.
The method for producing an extruded product according to claim 6 or 7, wherein the ratio L / D of the cylinder length L to the cylinder inner diameter D of the extruder in the step (3) is 1 to 20.
The raw material powder is a catalyst powder for producing an unsaturated carboxylic acid containing at least molybdenum and phosphorus as catalyst components, which is used when producing an unsaturated carboxylic acid by vapor-phase catalytic oxidation of an unsaturated aldehyde with molecular oxygen. The manufacturing method of the extrusion molding of any one of Claim 1 to 8 which is a precursor powder.
A method for producing a catalyst for producing an unsaturated carboxylic acid, comprising a step of producing an extruded product by the method according to claim 9 and subjecting the extruded product to heat treatment.
The method for producing a catalyst for producing an unsaturated carboxylic acid according to claim 10, wherein the unsaturated carboxylic acid is (meth) acrylic acid.
The raw material powder is obtained by subjecting propylene, isobutylene, primary butyl alcohol, tertiary butyl alcohol or methyl tertiary butyl ether to gas phase catalytic oxidation with molecular oxygen, and corresponding unsaturated aldehyde and unsaturated carboxylic acid respectively. The catalyst powder for producing an unsaturated aldehyde and unsaturated carboxylic acid containing at least molybdenum and bismuth as catalyst components, or a precursor powder thereof, which is used in the production of A method for producing an extruded product.
A method for producing a catalyst for producing unsaturated aldehydes and unsaturated carboxylic acids, comprising a step of producing an extruded product by the method according to claim 12 and subjecting the extruded product to heat treatment.
The method for producing a catalyst for producing an unsaturated aldehyde and an unsaturated carboxylic acid according to claim 13, wherein the unsaturated aldehyde is (meth) acrolein and the unsaturated carboxylic acid is (meth) acrylic acid.
A (meth) acrylic acid production catalyst is produced by the method according to claim 11, and (meth) acrylic acid is produced by vapor-phase catalytic oxidation of (meth) acrolein with molecular oxygen using this catalyst ( Method for producing (meth) acrylic acid.
A catalyst for producing (meth) acrolein and (meth) acrylic acid is produced by the method according to claim 14, and using this catalyst, propylene, isobutylene, primary butyl alcohol, tertiary butyl alcohol or methyl tertiary A method for producing (meth) acrolein and (meth) acrylic acid, wherein (meth) acrolein and (meth) acrylic acid are produced by vapor-phase catalytic oxidation of molecular butyl ether with molecular oxygen.