JP2022067427A - Method for producing catalyst for synthesizing unsaturated aldehyde and unsaturated carboxylic acid - Google Patents

Abstract

To provide a catalyst which is excellent in conversion ratio of a raw material, has high selectivity of a target product, can be produced in high yield, has high mechanical strength and can perform a long-term stable gas-phase catalytic oxidation reaction even under conditions where a large load is applied to a catalyst as a catalyst used in synthesizing the corresponding unsaturated aldehyde and unsaturated carboxylic acid by subjecting an olefin to gas phase contact oxidation with an oxygen-containing gas.SOLUTION: There is provided a method for producing a catalyst for synthesizing unsaturated aldehyde and unsaturated carboxylic acid which comprises a molding step of introducing a carrier, a powder containing catalyst component elements and a binder into a granulator and carrying the powder containing catalyst component elements on the carrier to form a catalyst precursor, wherein a carrier is introduced into a granulator, then a binder in an amount of 1 mass% or more and 50 mass% or less relative to amount of the powder containing catalyst component elements is introduced and further a powder containing catalyst component elements and a binder in an amount of 5 mass% or more and 50 mass% or less relative to the amount of the carrier are introduced to form a catalyst precursor.SELECTED DRAWING: None

Description

The present invention relates to a method for producing a catalyst for synthesizing unsaturated aldehydes and unsaturated carboxylic acids. Specifically, the production of a catalyst for synthesizing unsaturated aldehydes and unsaturated carboxylic acids used in the production of unsaturated aldehydes and unsaturated carboxylic acids by catalytically oxidizing olefins such as propylene and isobutylene with an oxygen-containing gas in the gas phase. Regarding the method.

As a catalyst for producing an unsaturated aldehyde and an unsaturated carboxylic acid by catalytically oxidizing an olefin such as propylene or isobutylene with an oxygen-containing gas in a gas phase, a catalyst containing molybdenum as an essential component is generally used. Specifically, there are various improvements in the catalysts used for producing acrolein and acrylic acid made from propylene and the like, the catalysts used for producing methacrolein and methacrylic acid made from isobutylene and the like, and the methods for producing them. It is being energetically promoted from the viewpoint of.

The method for producing an unsaturated aldehyde or an unsaturated carboxylic acid comprises contact-oxidizing an olefin such as propylene or isobutylene with an oxygen-containing gas in a fixed-bed reactor filled with a catalyst.

The catalyst filled in the fixed-bed reactor has a shape such as a cylinder shape, a ring shape, a tablet shape, a spherical shape, etc., and is generally a catalyst formed by molding a powder of a catalytically active component or a shape similar to the above-mentioned shape. A catalyst in which a catalyst component element is supported on an inert carrier having a catalyst component is used.

As a catalyst for oxidizing olefins such as propylene and isobutylene, Patent Document 1 uses a catalyst containing molybdenum, bismuth, cobalt, nickel and iron, having a specific pore volume, and being pulverized under specific pulverization conditions. It is disclosed that this provides sufficient mechanical strength and catalytic performance in the production of unsaturated aldehydes and unsaturated carboxylic acids.
Further, Patent Document 2 is a supported catalyst in which a catalyst powder containing molybdenum as an essential component and may contain bismuth, vanadium, etc. is coated on an inert carrier, and it is sufficient to use a catalyst having a specific shape. It is disclosed that the catalytic performance in the production of the unsaturated aldehyde and the unsaturated carboxylic acid can be obtained.

WO2019 / 182809 Pamphlet WO2009 / 147965 Pamphlet

However, even if the previously known catalysts for synthesizing unsaturated aldehydes and unsaturated carboxylic acids are used, the mechanical strength of the produced catalysts for synthesizing unsaturated aldehydes and unsaturated carboxylic acids, the conversion rate of raw materials, which is the catalytic performance, and the like. The product selectivity was not always satisfactory.

The present invention has been made to solve the above problems. That is, a catalyst used when olefins such as propylene and isobutylene are vapor-phase contact-oxidized with an oxygen-containing gas to synthesize a corresponding unsaturated aldehyde such as achlorine and methacrolein, and an unsaturated carboxylic acid such as acrylic acid and methacrolein. As a result, even under conditions where the load applied to the catalyst is high, the conversion rate of the raw material is excellent, the selectivity of the desired unsaturated aldehyde and unsaturated carboxylic acid is high, the production can be performed in high yield, and the mechanism is mechanical. It is an object of the present invention to provide a catalyst having high strength and capable of stable gas-phase catalytic oxidation reaction for a long period of time.

As a result of diligent research to solve the above problems, the present inventors have introduced a carrier, a powder containing the catalyst component element and a binder into the granulator, and the powder containing the catalyst component element is added to the carrier. A method for producing a catalyst for synthesizing unsaturated aldehydes and unsaturated carboxylic acids, which comprises a molding step of carrying and using a catalyst precursor, wherein the carrier is introduced into the granulator and then contains the catalyst component element. By introducing a specific amount of binder with respect to the amount of powder, and further introducing a powder containing the catalyst component element and a specific amount of binder with respect to the amount of the carrier to prepare a catalyst precursor. The produced unsaturated aldehyde and unsaturated carboxylic acid synthesis catalyst has high strength, and olefins such as propylene and isobutylene are vapor-phase contacted with oxygen-containing gas using the unsaturated aldehyde and unsaturated carboxylic acid synthesis catalyst. When oxidized, the conversion rate of olefins such as propylene and isobutylene is excellent even under conditions where the load on the catalyst is high, and unsaturated aldehydes such as achlorine and metachlorine, and unsaturated aldehydes such as acrylic acid and methacrylic acid are unsaturated. We have found that the selectivity of the carboxylic acid is good, and as a result, it is possible to improve the yields of unsaturated aldehydes such as achlorine and metachlorine, and unsaturated carboxylic acids such as acrylic acid and methacrylic acid. It came.

That is, the gist of the present invention is as follows.
[1] Unsaturated aldehyde including a molding step of introducing a carrier, a powder containing a catalyst component element and a binder into a granulator, and supporting the powder containing the catalyst component element on the carrier to serve as a catalyst precursor. And a method for producing a catalyst for synthesizing an unsaturated carboxylic acid, wherein the carrier is introduced into the granulator, and then 1% by mass or more and 50% by mass or less with respect to the amount of the powder containing the catalyst component element. Introduce the binder of the above, and further introduce the powder containing the catalyst component element and the binder of 5% by mass or more and 50% by mass or less with respect to the amount of the carrier, and use the unsaturated aldehyde and unsaturated as the catalyst precursor. A method for producing a catalyst for carboxylic acid synthesis.

[2] The unsaturated aldehyde and unsaturated carboxylic acid according to [1], wherein the total amount of the binder introduced into the granulator is 10% by mass or more and 60% by mass or less with respect to the amount of the carrier introduced into the granulator. A method for producing a synthetic catalyst.
[3] The total amount of the binder introduced into the granulator is 10% by mass or more and 70% by mass or less with respect to the amount of the powder containing the catalyst component element introduced into the granulator [1] or [2]. The method for producing a catalyst for synthesizing unsaturated aldehydes and unsaturated carboxylic acids according to.
[4] The method for producing an unsaturated aldehyde and an unsaturated carboxylic acid synthesis catalyst according to any one of [1] to [3], wherein the binder contains an organic compound.

[5] The unsaturated aldehyde and unsaturated element according to any one of [1] to [4] represented by the following formula (1) as catalyst component elements of the unsaturated aldehyde and unsaturated carboxylic acid synthesis catalyst. A method for producing a catalyst for carboxylic acid synthesis.
Mo ₁₂ Bi _a Fe _b Co _c Ni _d X _e Y _f Z _{g Si h} Oi (1)
(In formula (1), X represents at least one element selected from the group consisting of Na, K, Rb, Cs and Tl, and Y is selected from the group consisting of Mg, Ca, Sr, Ba, Mn and Zn. Z indicates at least one element selected from the group consisting of F, Cl, B, P, As, W and Nb. A to i indicate the atomic ratio of each element. , 0.5 ≦ a ≦ 7, 0.05 ≦ b ≦ 5, 0 ≦ c ≦ 10, 0 ≦ d ≦ 10, 0 ≦ e ≦ 2, 0 ≦ f ≦ 5, 0 ≦ g ≦ 5, 0 ≦ h It is in the range of ≦ 500, and i is a value that satisfies the oxidation state of other elements.)

[6] Using the unsaturated aldehyde and unsaturated carboxylic acid synthesis catalyst produced by the production method according to any one of [1] to [5], propylene is vapor-phase catalytically oxidized with an oxygen-containing gas. Method for producing acrolein and acrylic acid.

The unsaturated aldehyde and unsaturated carboxylic acid synthesis catalyst produced by the production method of the present invention has high mechanical strength, and the unsaturated aldehyde and unsaturated carboxylic acid synthesis catalyst is used to prepare propylene, isobutylene, etc. When olefins are vapor-phase contact oxidized with an oxygen-containing gas, the conversion rate of olefins such as propylene and isobutylene is excellent even under conditions where the load on the catalyst is high, and unsaturated aldehydes such as achlorine and metachlorine, and unsaturated aldehydes such as metachlorine, and The selectivity of unsaturated carboxylic acids such as acrylic acid and methacrylic acid is good, and as a result, the yields of unsaturated aldehydes such as achlorine and metachlorine and unsaturated carboxylic acids such as acrylic acid and methacrylic acid are improved. In addition, the strength of the produced unsaturated aldehyde and unsaturated carboxylic acid synthesis catalyst can be improved, and a stable gas-phase catalytic oxidation reaction can be performed for a long period of time.

Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following description, and can be variously modified and implemented within the scope of the gist thereof.

A method for producing a catalyst for synthesizing unsaturated aldehydes and unsaturated carboxylic acids (hereinafter, may be simply referred to as “catalyst”) according to the present invention will be described in detail.
The catalyst according to the present invention uses an olefin such as propylene or isobutylene (hereinafter, may be simply referred to as "olefin") as a raw material, and is subjected to gas-phase catalytic oxidation with an oxygen-containing gas to be unsaturated such as achlorine and metachlorine. Produces aldehydes (hereinafter, may be simply referred to as "unsaturated aldehydes") and unsaturated carboxylic acids such as acrylic acid and methacrylic acid (hereinafter, may be simply referred to as "unsaturated carboxylic acids"). , A catalyst for the synthesis of unsaturated aldehydes and unsaturated carboxylic acids.

[Catalyst manufacturing method]
The method for producing a catalyst according to the present invention comprises a granulator, a carrier, a powder containing an element as a component of the carrier (hereinafter, may be referred to as a "catalyst component element") as each component constituting the catalyst, and a powder. It is a method including a molding step of introducing a binder to obtain a catalyst precursor.
In this molding step, the carrier is first introduced into the granulator, then a specific amount of binder is introduced with respect to the amount of the powder containing the catalyst component element, and further, the catalyst component element is contained. It is characterized in that a catalyst precursor is obtained by introducing a powder and a specific amount of a binder with respect to the amount of the carrier.

The powder containing the catalyst component element can be obtained by including the following steps. That is, a compound having a catalyst component element is used as a compound serving as a catalyst supply source (hereinafter, referred to as "source compound"), and each source compound having this catalyst component element is added to a solvent or a solution. It includes a step of integrating and heating as necessary to obtain a prepared solution (preparation step), and a step of drying the prepared solution to form a powder (drying step).
Further, the catalyst precursor obtained in the molding step can be used as a catalyst by firing the catalyst precursor (calcination step).

[Liquid preparation process]
The liquid preparation step is a step of integrating each source compound containing the catalyst component element in an aqueous system and heating to obtain a prepared liquid.
The above-mentioned integration in an aqueous system means that each source compound is added to an aqueous solvent or solution to perform integration. This aqueous solvent is an aqueous medium for dissolving or suspending each source compound, and refers to a solvent consisting of water, an organic solvent compatible with water such as methanol and ethanol, or a mixture thereof. Further, the aqueous solution means a solution in which one or more source compounds are dissolved, suspended or integrated in the aqueous solvent.

The above-mentioned integration means that an aqueous solution or an aqueous dispersion of a source compound of each catalyst component element is mixed collectively or stepwise, and heating is performed as necessary. Specifically, a method of collectively mixing the above-mentioned source compounds, a method of collectively mixing the above-mentioned source compounds and then heating, and a method of stepwise mixing of the above-mentioned source compounds. , The method of repeating the mixing and heat treatment of each of the above-mentioned source compounds step by step, and the method of combining these methods, all of which are based on the concept of integration of the source compounds of each catalyst component element. included.

The above-mentioned heating means that the mixed liquid or the mixed dispersion obtained in the above-mentioned integration step is stirred at a predetermined temperature for a predetermined time. This heating increases the viscosity of the mixed solution or the mixed dispersion, and in the case of the mixed dispersion, to alleviate the sedimentation of the solid components in the mixed dispersion, and particularly to suppress the non-uniformity of the components in the next drying step. It becomes effective, and the catalytic activity such as the raw material conversion rate and the product selectivity of the obtained final product catalyst becomes better.

The temperature in the heating is preferably 60 ° C to 100 ° C, more preferably 60 ° C to 90 ° C, still more preferably 60 ° C to 80 ° C. When the heating temperature is within the above range, the activity of the produced catalyst may be improved.

The heating time is preferably 2 hours to 12 hours, more preferably 3 hours to 8 hours. When the heating time is within the above range, the activity of the produced catalyst may be improved.
As the stirring method, any method can be adopted, and examples thereof include a method using a stirrer having a stirring blade, a method using an external circulation by a pump, and the like.

[Source compound]
This catalyst preferably contains molybdenum (Mo), bismuth (Bi), and iron (Fe) as catalyst component elements, and contains cobalt (Co) and nickel (Ni) as other catalyst component elements. Is more preferable, and further, sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), titanium (Ti), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba). , Manganese (Mn), Zinc (Zn), Fluorine (F), Chlorine (Cl), Boron (B), Phosphorus (P), Arsenic (As), Tungsten (W), Niob (Nb), Silicon (Si) Or the like may be contained in one kind or a plurality of kinds.

Examples of the molybdenum (Mo) source compound include ammonium paramolybdate, molybdenum trioxide, molybdenum acid, ammonium phosphomolybdate, and phosphomolybdic acid.

Examples of the source compound of bismuth (Bi) include bismuth chloride, bismuth nitrate, bismuth oxide, and bismuth subcarbonate. The amount of bismuth added is preferably 0.5 or more and 7 or less, more preferably 0.5 or more and 5 or less, and further preferably 0.5 or more and 7 or less when the molybdenum atom is 12 as the atomic number ratio of the catalyst component element. Addition is preferably 0.5 or more and 4 or less, and particularly preferably 0.5 or more and 3 or less. Within this range, it can be used as a catalyst capable of producing unsaturated aldehydes and unsaturated carboxylic acids with excellent raw material conversion and high selectivity.

Examples of the iron (Fe) source compound include ferric nitrate, ferric sulfate, ferric chloride, ferric acetate and the like. The amount of iron added is preferably 0.05 or more and 5 or less, more preferably 0.1 or more and 4 or less, and further preferably 0.1 or more and 4 or less when the molybdenum atom is 12 as the atomic number ratio of the catalyst component element. It is preferably added so as to be 0.2 or more and 3 or less, and particularly preferably 0.3 or more and 3 or less. Within this range, it can be used as a catalyst capable of producing unsaturated aldehydes and unsaturated carboxylic acids with excellent raw material conversion and high selectivity.

Examples of the cobalt (Co) source compound include cobalt nitrate, cobalt sulfate, cobalt chloride, cobalt carbonate, and cobalt acetate. The amount of cobalt added is preferably 0 or more and 10 or less, more preferably 0.5 or more and 9 or less, still more preferably, when the molybdenum atom is 12 as the atomic number ratio of the catalyst component element. Add so as to be 1 or more and 8 or less, particularly preferably 2 or more and 7 or less. Within this range, it can be used as a catalyst capable of producing unsaturated aldehydes and unsaturated carboxylic acids with excellent raw material conversion and high selectivity.

Examples of the nickel (Ni) source compound include nickel nitrate, nickel sulfate, nickel chloride, nickel carbonate, nickel acetate and the like. The amount of nickel added is preferably 0 or more and 10 or less, more preferably 0.5 or more and 9 or less, still more preferably, when the molybdenum atom is 12 as the atomic number ratio of the catalyst component element. Add so as to be 1 or more and 8 or less, particularly preferably 2 or more and 7 or less. Within this range, it can be used as a catalyst capable of producing unsaturated aldehydes and unsaturated carboxylic acids with excellent raw material conversion and high selectivity.

Examples of the sodium (Na) source compound include sodium chloride, sodium carbonate, sodium nitrate, sodium sulfate, sodium acetate, sodium borate and the like. Examples of the source compound of potassium (K) include potassium nitrate, potassium sulfate, potassium chloride, potassium carbonate, potassium acetate and the like. Examples of the source compound of rubidium (Rb) include rubidium nitrate, rubidium sulfate, rubidium chloride, rubidium carbonate, rubidium acetate and the like. Examples of the source compound of cesium (Cs) include cesium nitrate, cesium sulfate, cesium chloride, cesium carbonate, cesium acetate and the like. Examples of the titanium (Ti) source compound include titanium oxide and titanium chloride. The amount of at least one element selected from sodium, potassium, rubidium, cesium and titanium is preferably 0 or more and 2 or less when molybdenum is 12, and more preferably 0.01 or more and 2 or less. , More preferably 0.02 or more and 2 or less. Within this range, it can be used as a catalyst capable of producing unsaturated aldehydes and unsaturated carboxylic acids with excellent raw material conversion and high selectivity.

Examples of the source compound of magnesium (Mg) include magnesium oxide, magnesium carbonate, magnesium sulfate and the like. Examples of the calcium (Ca) source compound include calcium oxide, calcium carbonate, calcium hydroxide and the like. Examples of the source compound of strontium (Sr) include strontium oxide, strontium carbonate, strontium hydroxide, strontium nitrate and the like. Examples of the barium (Ba) source compound include barium oxide, barium carbonate, barium nitrate, barium acetate, barium sulfate and the like. Examples of the manganese (Mn) source compound include manganese dioxide, manganese carbonate and the like. Examples of the zinc (Zn) source compound include zinc oxide, zinc carbonate, zinc hydroxide, zinc nitrate and the like.
The amount of at least one element selected from the group consisting of magnesium, calcium, strontium, barium, manganese and zinc is added so that the atomic number ratio of the catalyst component element is 0 or more and 5 or less when molybdenum is 12. It is preferably added so as to be 0 or more and 4 or less, and more preferably 0 or more and 3 or less. Within this range, it can be used as a catalyst capable of producing unsaturated aldehydes and unsaturated carboxylic acids with excellent raw material conversion and high selectivity.

Examples of the fluorine (F) source compound include calcium fluoride and sodium fluoride. Examples of the chlorine (Cl) source compound include sodium chloride, ammonium chloride and the like. Examples of the source compound of boron (B) include borax, ammonium borate, boric acid and the like. Examples of the phosphorus (P) source compound include ammonium phosphate, ammonium phosphate, phosphoric acid, phosphorus pentoxide and the like. Examples of the source compound of arsenic (As) include ammonium diarseno-18 molybdate and ammonium diarseno18 ammonium tungstate.
Examples of the source compound of tungsten (W) include tungstic acid and salts thereof. Examples of the source compound of niobium (Nb) include niobium hydroxide.
The amount of at least one element selected from fluorine, chlorine, boron, phosphorus, arsenic, tungsten and niobium is preferably 0 or more and 5 or less when molybdenum is 12, more preferably 0 or more. Add 4 or less, more preferably 0 or more and 3 or less. Within this range, the catalyst can be used as a catalyst capable of producing unsaturated aldehydes and unsaturated carboxylic acids with excellent raw material conversion and high selectivity.

Examples of the silicon (Si) source compound include silica, granular silica, colloidal silica, and fumed silica. The amount of silicon added is preferably 0 or more and 500 or less, more preferably 0 or more and 400 or less, still more preferably 0 or more, when the molybdenum atom is 12 as the atomic number ratio of the catalyst component element. Add so that it is 300 or less. Within this range, it can be used as a catalyst capable of producing unsaturated aldehydes and unsaturated carboxylic acids with excellent raw material conversion and high selectivity.

[Method of adding source compound]
In the above-mentioned liquid preparation step, all of each source compound may be used as one preparation solution, and each source compound may be used alone or divided into several groups to form a plurality of preparation solutions, and the plurality of preparation solutions may be used. It may be mixed at once or in order to form one preparation, or one or more preparations may be dried and then calcined to form a solid, and the solid may be prepared with the remaining source compounds. It may be added to a new preparation solution.

[Drying process]
The obtained preparation liquid is dried in a drying step to obtain a powder containing a catalyst component element (hereinafter, may be simply referred to as "powder"). The drying treatment method in this drying step is not particularly limited, and for example, a powder may be obtained using a normal spray dryer, slurry dryer, drum dryer, or the like.

The powder obtained by the drying treatment may be further heat-treated, if necessary. This heat treatment is a treatment performed in the air in a temperature range of 300 ° C. to 600 ° C., preferably 350 ° C. to 550 ° C. for a short time. The method is not particularly limited, and for example, the powder may be heated in a fixed state using a normal box-type heating furnace, a tunnel-type heating furnace, or the like, or the powder may be heated using a rotary kiln or the like. It may be heated while flowing.
Further, the powder in the present invention is also a dried product that has been further subjected to a treatment such as pulverization.

The catalyst component element of the powder obtained by the drying step preferably contains molybdenum and bismuth, and more preferably iron in addition to the molybdenum and bismuth. It is more preferable to be done. By setting the catalyst component element of the powder within the above range, the produced catalyst has high mechanical strength, excellent raw material conversion rate even under high load conditions, and unsaturated aldehyde and unsaturated carboxylic acid. The selectivity of the acid is good, and it is possible to improve the yields of the unsaturated aldehyde and the unsaturated carboxylic acid.

Mo ₁₂ Bi _a Fe _b Co _c Ni _d X _e Y _f Z _{g Si h} Oi (1)
(In formula (1), X represents at least one element selected from the group consisting of Na, K, Rb, Cs and Tl, and Y is selected from the group consisting of Mg, Ca, Sr, Ba, Mn and Zn. Z indicates at least one element selected from the group consisting of F, Cl, B, P, As, W and Nb. A to i indicate the atomic ratio of each element. , 0.5 ≦ a ≦ 7, 0.05 ≦ b ≦ 5, 0 ≦ c ≦ 10, 0 ≦ d ≦ 10, 0 ≦ e ≦ 2, 0 ≦ f ≦ 5, 0 ≦ g ≦ 5, 0 ≦ h It is in the range of ≦ 500, and i is a value that satisfies the oxidation state of other elements.)

[Molding process]
The molding step is a step of introducing a carrier, a powder obtained in the above-mentioned drying step, and a binder into a granulator to obtain a catalyst precursor.

As a specific example of the molding process, the granulator, for example, a granulator having a flat or uneven disk at the bottom of the granulator is used, and the disk of the granulator is rotated. The carrier introduced into the granulator is stirred by repeating rotation and revolution, a powder containing a catalyst component element and a binder are introduced therein, and other additives may be added as the case may be added to obtain the powder. Examples thereof include a step using a method of obtaining a catalyst precursor by supporting it on a carrier (hereinafter, may be referred to as “rolling granulation method”).

Examples of the carrier include spherical carriers having a major axis diameter of preferably 2.5 mm to 10 mm, more preferably 2.5 mm to 6 mm, such as silica, silicon carbide, alumina, mullite, and random. Of these, the porosity of the carrier is preferably 20% to 60%, more preferably 30% to 57%, and even more preferably 40% to 55%. The water absorption rate of the carrier is preferably 10% to 60%, more preferably 12% to 50%, and even more preferably 15% to 40%. By setting the porosity and water absorption of the carrier within the above ranges, the powder containing the catalyst component element can be easily supported on the carrier. The carrier is preferably inactive in the reaction of gas-phase catalytic oxidation of the olefin with an oxygen-containing gas.

In the method for producing a catalyst of the present invention, a carrier is introduced into the granulator, and then a binder containing 1% by mass or more and 50% by mass or less with respect to the amount of powder containing the catalyst component element in the granulator ( Hereinafter, it may be referred to as "binder A"), and further, a powder containing the catalyst component element and a binder of 5% by mass or more and 50% by mass or less with respect to the amount of the carrier (hereinafter, "binder"). B ”may be referred to.) Is introduced.
The upper limit of the amount of the binder A with respect to the amount of the powder containing the catalyst component element is preferably 48% by mass, more preferably 45% by mass, still more preferably 42% by mass. The lower limit of the amount of the binder A with respect to the amount of the carrier is preferably 0.6% by mass, more preferably 0.7% by mass, still more preferably 0.8% by mass.
The upper limit of the amount of the binder B with respect to the amount of the carrier is preferably 48% by mass, more preferably 46% by mass, still more preferably 45% by mass. The lower limit of the amount of the binder B with respect to the amount of the powder containing the catalyst component element is preferably 6% by mass, more preferably 7% by mass, still more preferably 8% by mass.

When the amount of the binder A and the amount of the binder B are within the above ranges, the produced catalyst has high mechanical strength, is excellent in raw material conversion rate even under high load conditions, and is an unsaturated aldehyde and unsaturated aldehyde. The selectivity of the unsaturated carboxylic acid is good, and it is possible to improve the yields of the unsaturated aldehyde and the unsaturated carboxylic acid.
The carrier surface is covered with an appropriate binder by introducing the carrier into the granulator and then introducing a specific amount of the binder A with respect to the amount of the powder containing the catalyst component element into the granulator. Therefore, it is possible to improve the adhesiveness between the powder containing the catalyst component element and the carrier, and further, the powder containing the catalyst component element and the binder B in a specific amount with respect to the amount of the carrier are introduced. As a result, the produced catalyst has high mechanical strength, excellent raw material conversion rate even under high load conditions, and has a possibility of forming an optimum pore structure as a catalyst precursor. The selectivity of unsaturated aldehyde and unsaturated carboxylic acid is good, and it is possible to improve the yield of unsaturated aldehyde and unsaturated carboxylic acid.

Examples of the binder include organic compounds such as ethylene glycol, glycerin, propionic acid, maleic acid, benzyl alcohol, propyl alcohol, butyl alcohol, polyvinyl alcohol, stearic acid or phenol, sulfuric acid, ammonium sulfate, nitrate, ammonium nitrate, ammonium carbonate, water and the like. Inorganic compounds of the above, preferably containing organic compounds, more preferably containing organic compounds having a hydroxyl group, and even more preferably containing glycerin and / or polyvinyl alcohol. By containing the compound as a binder, the produced catalyst has high mechanical strength, excellent raw material conversion rate even under high load conditions, and good selectivity of unsaturated aldehyde and unsaturated carboxylic acid. Therefore, it is possible to improve the yields of unsaturated aldehydes and unsaturated carboxylic acids.
Among the binders, it is particularly preferable that the binder A contains an organic compound.
Further, the binder A and the binder B may be the same binder or different binders.

When the binder is introduced into a granulator, it is preferably an aqueous solution, and the concentration is preferably 2% by mass or more and 50% by mass or less. The lower limit is more preferably 3% by mass. The upper limit is more preferably 40% by mass. Within the above range, the binder can be uniformly dispersed in the carrier or powder in the granulator.

As a method for introducing the powder containing the catalyst component element and the binder B into the granulator,
(1) A method of mixing a powder or the like containing a catalyst component element with a binder B to prepare a homogeneous mixture, and introducing the homogeneous mixture into a granulator.
(2) A method of simultaneously introducing a powder containing a catalyst component element and a binder B into a granulator.
(3) A method of introducing the binder B into the granulator after introducing the powder containing the catalyst component element into the granulator.
(4) A method of adding a binder B to a powder containing a catalyst component element to form a heterogeneous mixture, and introducing the heterogeneous mixture into a granulator.
(5) Examples thereof include a method in which a powder or the like containing a catalyst component element and a binder B are separated and introduced into a granulator at the same time, alternately or in no particular order.
In the present invention, a method such as appropriately combining (1) to (5) and adding the entire amount can be arbitrarily adopted. Of these, in (5), for example, the autofeeder is such that the powder containing the catalyst component element does not adhere to the inner wall of the granulator and the powders containing the catalyst component element do not aggregate with each other, and a predetermined amount is supported on the carrier. It is preferable to adjust the addition rate by using the above.

In the method for producing a catalyst of the present invention, a method of appropriately combining the above-mentioned (1) to (5) can be adopted, but the produced catalyst has high mechanical strength and is a raw material even under high load conditions. The method (5) is based on the fact that the conversion rate is excellent, the selectivity of unsaturated aldehyde and unsaturated carboxylic acid is good, and it is easy to improve the yield of unsaturated aldehyde and unsaturated carboxylic acid. preferable.
In the method (5), if there is a binder introduced into the granulator before the powder containing the catalytically active component, the binder corresponds to the binder A.

The total amount of the binder introduced into the granulator is preferably 10% by mass or more and 60% by mass or less with respect to the amount of the carrier introduced into the granulator. The lower limit is more preferably 13% by mass, still more preferably 15% by mass. The upper limit is more preferably 58% by mass, still more preferably 55% by mass. Within the above range, the produced catalyst has high mechanical strength, excellent raw material conversion rate even under high load conditions, and good selectivity of unsaturated aldehyde and unsaturated carboxylic acid. Therefore, it is possible to improve the yields of unsaturated aldehydes and unsaturated carboxylic acids.

The total amount of the binder introduced into the granulator is preferably 10% by mass or more and 70% by mass or less with respect to the amount of the powder containing the catalyst component element introduced into the granulator. The lower limit is more preferably 13% by mass, still more preferably 15% by mass. The upper limit is more preferably 67% by mass, further preferably 64% by mass. Within the above range, the produced catalyst has high mechanical strength, excellent raw material conversion rate even under high load conditions, and good selectivity of unsaturated aldehyde and unsaturated carboxylic acid. It is possible to improve the yields of unsaturated aldehydes and unsaturated carboxylic acids.

The amount of the powder containing the catalyst component element is preferably 20% by mass or more and 300% by mass or less with respect to the amount of the carrier introduced into the granulator. The lower limit is more preferably 30% by mass, further preferably 40% by mass. The upper limit is more preferably 250% by mass, still more preferably 200% by mass. Within the above range, the produced catalyst has high mechanical strength, excellent raw material conversion rate even under high load conditions, and good selectivity of unsaturated aldehyde and unsaturated carboxylic acid. It is possible to improve the yields of unsaturated aldehydes and unsaturated carboxylic acids.

In the molding step, other molding aids may be added in addition to the above-mentioned carriers, powders and binders. Other molding aids include, for example, silica, alumina, glass, silicon carbide, silicon nitride, graphite, cellulose, methylcellulose, starch and the like.

If the strength of the catalyst is low, the catalyst may be pulverized when the catalyst is filled in a reaction tube or the like for producing unsaturated aldehyde and unsaturated carboxylic acid by gas-phase catalytic oxidation of the olefin with an oxygen-containing gas. , There is a possibility of cracking, and the differential pressure (pressure difference between the inlet and outlet of the reaction tube) may increase. When the differential pressure becomes large, a large load may be applied to a compressor or the like that blows a raw material mixed gas containing an olefin and an oxygen-containing gas into a reaction tube filled with a catalyst.
Further, if the strength of the catalyst is low, the pulverization of the catalyst may be accelerated in proportion to the progress of gas-phase catalytic oxidation, and the differential pressure may be further increased with time.
Therefore, the pulverization rate of the catalyst, which is an index of the strength of the catalyst, is preferably 5.0% or less, more preferably 3.0% or less, still more preferably 2.0% or less. The pulverization rate indicates the ratio of the fine particle weight to the catalyst sample weight when the catalyst is dropped from a height of 1 m.

[Baking process]
The catalyst precursor obtained in the molding step is calcined at a temperature condition of preferably 400 ° C. to 600 ° C., more preferably 450 ° C. to 550 ° C. for about 1 hour to 16 hours in an appropriate oxygen atmosphere. As the firing method, the method used in the heat treatment in the drying step can be adopted.
As described above, it is possible to obtain a catalyst having high mechanical strength, high activity, and excellent yields of the desired unsaturated aldehyde and unsaturated carboxylic acid.
The obtained catalyst preferably contains molybdenum and bismuth as catalyst component elements, more preferably iron, and more preferably represented by the following general formula (2). By setting the catalyst component element of the catalyst within the above range, the produced catalyst has high mechanical strength, excellent raw material conversion rate even under high load conditions, and unsaturated aldehyde and unsaturated carboxylic acid. The selectivity of the above is good, and it becomes possible to improve the yields of unsaturated aldehydes and unsaturated carboxylic acids.

Mo ₁₂ Bi _a Fe _b Co _c Ni _d X _e Y _f Z _{g Si h} Oi (1)
(In formula (1), X represents at least one element selected from the group consisting of Na, K, Rb, Cs and Tl, and Y is selected from the group consisting of Mg, Ca, Sr, Ba, Mn and Zn. Z indicates at least one element selected from the group consisting of F, Cl, B, P, As, W and Nb. A to i indicate the atomic ratio of each element. , 0.5 ≦ a ≦ 7, 0.05 ≦ b ≦ 5, 0 ≦ c ≦ 10, 0 ≦ d ≦ 10, 0 ≦ e ≦ 2, 0 ≦ f ≦ 5, 0 ≦ g ≦ 5, 0 ≦ h It is in the range of ≦ 500, and i is a value that satisfies the oxidation state of other elements.)

[Use]
By using the catalyst produced by the production method of the present invention, the mechanical strength is high, the catalytic performance such as raw material conversion rate and product selectivity can be further improved, and olefins such as propylene and isobutylene are contained in oxygen. Gas-phase catalytic oxidation can be carried out to produce the corresponding unsaturated aldehydes such as acrolein and methacrolein, and unsaturated carboxylic acids such as acrylic acid and methacrolein in high yield.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.
The propylene conversion rate, acrolein and acrylic acid selectivity, and acrolein and acrylic acid yields are defined as the following formulas (1) to (3).
(1) Propylene conversion rate (mol%) = 100 × (number of moles of reacted propylene) / (number of moles of supplied propylene)
(2) Acrolein and acrylic acid selectivity (mol%) = 100 × (number of moles of acrolein and acrylic acid produced) / (number of moles of converted propylene)
(3) Yield of acrolein and acrylic acid (mol%) = 100 × (number of moles of acrolein and acrylic acid produced) / (number of moles of supplied propylene)

<Phistric contact oxidation reaction of propylene>
A reaction tube having an inner diameter of 21.4 mm was filled with 13.3 ml of the catalyst. A raw material mixed gas having the following composition was introduced from the inlet of the reaction tube, and the reaction was evaluated at a space velocity of 3064 / hr. The heat medium temperature was 380 ° C. The reaction evaluation results are shown in Table 1.
The composition of the raw material mixed gas used is as follows.
-Propene: 10% by volume, steam: 17% by volume, oxygen: 15% by volume, (nitrogen-containing inert gas + other gas): 58% by volume

<Measurement of catalyst pulverization rate>
The catalyst was sieved by a sieve having a mesh size of 2.36 mm, and the sample on the sieve was used as a pulverization rate measurement sample. A funnel (conical upper diameter 150 mm, conical lower diameter 25 mm) was inserted into the upper part of an acrylic cylinder (φ66 mm) having a height of 1 m, and a saucer was installed in the lower part of the cylinder. Approximately 20 g of the pulverization rate measurement sample was precisely weighed, charged from the upper part of the cone of the funnel, and dropped onto the saucer via the cylinder. The dropped pulverization rate measurement sample was collected from the saucer, the weight of the fine particles sieved by a sieve having a mesh size of 2.36 mm (the pulverization weight) was measured, and the catalytic pulverization rate was calculated from the following formula.
Catalyst pulverization rate (%) = (powder weight / pulverization rate measurement sample weight) x 100

(Example 1)
1700 ml of warm water was placed in a container, and 447.2 g of ammonium molybdate was further added and dissolved. Then, 2.1 g of potassium nitrate was added and dissolved. Then, 1.1 g of ammonium chloride was further added and dissolved to obtain a solution (hereinafter referred to as "solution A").
Next, a solution prepared by adding 159.8 g of iron nitrate, 376.2 g of cobalt nitrate and 174.1 g of nickel nitrate in 376 ml of warm water was added to the solution A and mixed for 1 hour so as to be uniform (hereinafter, "" Solution B "). Next, a solution prepared by adding 22.1 g of nitric acid and 96.5 g of bismuth nitrate in 104.8 ml of pure water at room temperature was added to the solution B and mixed for 2 hours so as to be uniform to obtain a starting material mixture. rice field.
The starting material mixture was spray-dried at 150 ° C. and then heat-treated in the air at a heating temperature of 440 ° C. for 6 hours to obtain a dried product.

This dried product was pulverized to a size of 200 μm or less using a stirring blade type pulverizer to obtain a pulverized product. This pulverized product was used as a supporting powder. 4.1 g of scale glass and 4.1 g of cellulose were added to 81.8 g of this supporting powder and mixed so as to be uniform to obtain a supported mixed powder.
100 g of a spherical inert carrier having a diameter of 4.5 mm and containing alumina-silica as a main component is introduced into a bread-type granulator, and then 9.2 with respect to the amount of the supporting powder to be introduced into the granulator. Binder A of mass% was introduced. The binder A was glycerin and water, and was prepared as an aqueous solution of 10% by mass of glycerin.
Further, the supporting mixed powder and the binder B having a weight of 39.5% by mass based on the amount of the carrier introduced into the granulator are each divided and alternately introduced from the divided supporting mixed powder. As a result, a catalyst precursor which was supported and was a molded product was obtained. The binder B was glycerin and water, and was prepared as an aqueous solution of 10% by mass of glycerin.
This catalyst precursor was calcined at 510 ° C. for 2 hours in an air atmosphere to obtain a catalyst. The composition ratio (excluding oxygen) of the catalyst component elements of this catalyst was as follows.
Mo ₁₂ Bi _0.94 Fe _1.87 Co _6.30 Ni _2.84 K _0.1 Cl _0.1
Table 1 shows the evaluation results of the gas phase contact oxidation reaction of propylene using the produced catalyst.

(Example 2)
A dried product was obtained in the same manner as in Example 1.
This dried product was pulverized to a size of 200 μm or less using a stirring blade type pulverizer to obtain a pulverized product. This pulverized product was used as a supporting powder. 4.1 g of scale glass and 4.1 g of cellulose were added to 81.8 g of this supporting powder and mixed so as to be uniform to obtain a supported mixed powder.
Introduce 100 g of a spherical inert carrier having a diameter of 4.5 mm containing alumina-silica as a main component into a bread-type granulator, and then 6.1 with respect to the amount of the supporting powder to be introduced into the granulator. Binder A of mass% was introduced. The binder A was glycerin and water, and was prepared as an aqueous solution of 10% by mass of glycerin.
Further, the supporting mixed powder and the binder B having a weight of 42.0% by mass based on the amount of the carrier introduced into the granulator are each divided and alternately introduced from the divided supporting mixed powder. As a result, a catalyst precursor which was supported and was a molded product was obtained. The binder B was glycerin and water, and was prepared as an aqueous solution of 10% by mass of glycerin.
This catalyst precursor was calcined at 510 ° C. for 2 hours in an air atmosphere to obtain a catalyst. The composition ratio (excluding oxygen) of the catalyst component elements of this catalyst was as follows.
Mo ₁₂ Bi _0.94 Fe _1.87 Co _6.30 Ni _2.84 K _0.1 Cl _0.1
Table 1 shows the evaluation results of the gas phase contact oxidation reaction of propylene using the produced catalyst.

(Example 3)
A dried product was obtained in the same manner as in Example 1.
This dried product was pulverized to a size of 200 μm or less using a stirring blade type pulverizer to obtain a pulverized product. This pulverized product was used as a supporting powder. 4.1 g of scale glass and 4.1 g of cellulose were added to 81.8 g of this supporting powder and mixed so as to be uniform to obtain a supported mixed powder.
3.1 g of a spherical inert carrier having a diameter of 4.5 mm containing alumina-silica as a main component is introduced into a bread-type granulator, and then 3.1 with respect to the amount of the supporting powder to be introduced into the granulator. Binder A of mass% was introduced. The binder A was glycerin and water, and was prepared as an aqueous solution of 10% by mass of glycerin.
Further, the supporting mixed powder and the binder B having a weight of 44.5% by mass based on the amount of the carrier introduced into the granulator are each divided and alternately introduced from the divided supporting mixed powder. As a result, a catalyst precursor which was supported and was a molded product was obtained. The binder B was glycerin and water, and was prepared as an aqueous solution of 10% by mass of glycerin.
This catalyst precursor was calcined at 510 ° C. for 2 hours in an air atmosphere to obtain a catalyst. The composition ratio (excluding oxygen) of the catalyst component elements of this catalyst was as follows.
Mo ₁₂ Bi _0.94 Fe _1.87 Co _6.30 Ni _2.84 K _0.1 Cl _0.1
Table 1 shows the evaluation results of the gas phase contact oxidation reaction of propylene using the produced catalyst.

(Example 4)
A dried product was obtained in the same manner as in Example 1.
This dried product was pulverized to a size of 200 μm or less using a stirring blade type pulverizer to obtain a pulverized product. This pulverized product was used as a supporting powder. 4.1 g of scale glass and 4.1 g of cellulose were added to 81.8 g of this supporting powder and mixed so as to be uniform to obtain a supported mixed powder.
Introduce 100 g of a spherical inert carrier having a diameter of 4.5 mm containing alumina-silica as a main component into a bread-type granulator, and then 12.2 with respect to the amount of the supporting powder to be introduced into the granulator. Binder A of mass% was introduced. The binder A was glycerin and water, and was prepared as an aqueous solution of 10% by mass of glycerin.
Further, the supporting mixed powder and the binder B having a weight of 37.0% by mass based on the amount of the carrier introduced into the granulator are each divided and alternately introduced from the divided supporting mixed powder. As a result, a catalyst precursor which was supported and was a molded product was obtained. The binder B was glycerin and water, and was prepared as an aqueous solution of 10% by mass of glycerin.
This catalyst precursor was calcined at 510 ° C. for 2 hours in an air atmosphere to obtain a catalyst. The composition ratio (excluding oxygen) of the catalyst component elements of this catalyst was as follows.
Mo ₁₂ Bi _0.94 Fe _1.87 Co _6.30 Ni _2.84 K _0.1 Cl _0.1
Table 1 shows the evaluation results of the gas phase contact oxidation reaction of propylene using the produced catalyst.

(Example 5)
A dried product was obtained in the same manner as in Example 1.
This dried product was pulverized to a size of 200 μm or less using a stirring blade type pulverizer to obtain a pulverized product. This pulverized product was used as a supporting powder. 4.1 g of scale glass and 4.1 g of cellulose were added to 81.8 g of this supporting powder and mixed so as to be uniform to obtain a supported mixed powder.
Introduce 100 g of a spherical inert carrier having a diameter of 4.5 mm containing alumina-silica as a main component into a bread-type granulator, and then 15.3 with respect to the amount of the supporting powder to be introduced into the granulator. Binder A of mass% was introduced. The binder A was glycerin and water, and was prepared as an aqueous solution of 10% by mass of glycerin.
Further, the supporting mixed powder and the binder B having a weight of 34.5% by mass based on the amount of the carrier introduced into the granulator are each divided and alternately introduced from the divided supporting mixed powder. As a result, a catalyst precursor which was supported and was a molded product was obtained. The binder B was glycerin and water, and was prepared as an aqueous solution of 10% by mass of glycerin.
This catalyst precursor was calcined at 510 ° C. for 2 hours in an air atmosphere to obtain a catalyst. The composition ratio (excluding oxygen) of the catalyst component elements of this catalyst was as follows.
Mo ₁₂ Bi _0.94 Fe _1.87 Co _6.30 Ni _2.84 K _0.1 Cl _0.1
Table 1 shows the evaluation results of the gas phase contact oxidation reaction of propylene using the produced catalyst.

(Example 6)
A dried product was obtained in the same manner as in Example 1.
This dried product was pulverized to a size of 200 μm or less using a stirring blade type pulverizer to obtain a pulverized product. This pulverized product was used as a supporting powder. 4.1 g of scale glass and 4.1 g of cellulose were added to 81.8 g of this supporting powder and mixed so as to be uniform to obtain a supported mixed powder.
100 g of a spherical inert carrier having a diameter of 4.5 mm and containing alumina-silica as a main component is introduced into a bread-type granulator, and then 36.7 with respect to the amount of the supporting powder to be introduced into the granulator. Binder A of mass% was introduced. The binder A was glycerin and water, and was prepared as an aqueous solution of 10% by mass of glycerin.
Further, the supporting mixed powder and the binder B having a weight of 17.0% by mass based on the amount of the carrier introduced into the granulator are each divided and alternately introduced from the divided supporting mixed powder. As a result, a catalyst precursor which was supported and was a molded product was obtained. The binder B was glycerin and water, and was prepared as an aqueous solution of 10% by mass of glycerin.
This catalyst precursor was calcined at 510 ° C. for 2 hours in an air atmosphere to obtain a catalyst. The composition ratio (excluding oxygen) of the catalyst component elements of this catalyst was as follows.
Mo ₁₂ Bi _0.94 Fe _1.87 Co _6.30 Ni _2.84 K _0.1 Cl _0.1
Table 1 shows the evaluation results of the gas phase contact oxidation reaction of propylene using the produced catalyst.

(Comparative Example 1)
A dried product was obtained in the same manner as in Example 1.
This dried product was pulverized to a size of 200 μm or less using a stirring blade type pulverizer to obtain a pulverized product. This pulverized product was used as a supporting powder. 4.1 g of scale glass and 4.1 g of cellulose were added to 81.8 g of this supporting powder and mixed so as to be uniform to obtain a supported mixed powder.
100 g of a spherical inactive carrier having a diameter of 4.5 mm and containing alumina-silica as a main component was introduced into a pan-type granulator, and then the amount of the mixed powder for support and the carrier introduced into the granulator was adjusted. On the other hand, 47.0% by mass of the binder was divided into pieces, and the divided supporting mixed powders were alternately introduced first to support the catalyst precursor, which is a molded product.
This catalyst precursor was calcined at 510 ° C. for 2 hours in an air atmosphere to obtain a catalyst. The binder was glycerin and water, and an aqueous solution of 10% by mass of glycerin was used. The composition ratio (excluding oxygen) of the catalyst component elements of this catalyst was as follows.
Mo ₁₂ Bi _0.94 Fe _1.87 Co _6.30 Ni _2.84 K _0.1 Cl _0.1
Table 1 shows the evaluation results of the gas phase contact oxidation reaction of propylene using the produced catalyst.

(Comparative Example 2)
A dried product was obtained in the same manner as in Example 1.
This dried product was pulverized to a size of 200 μm or less using a stirring blade type pulverizer to obtain a pulverized product. This pulverized product was used as a supporting powder. 4.1 g of scale glass and 4.1 g of cellulose were added to 81.8 g of this supporting powder and mixed so as to be uniform to obtain a supported mixed powder.
100 g of a spherical inert carrier having a diameter of 4.5 mm and containing alumina-silica as a main component is introduced into a bread-type granulator, and then 54.4 with respect to the amount of the supporting powder to be introduced into the granulator. Binder A of mass% was introduced. The binder A was glycerin and water, and was prepared as an aqueous solution of 10% by mass of glycerin.
Further, the supporting mixed powder and 2.0% by mass of the binder B with respect to the amount of the carrier introduced into the granulator are each divided and alternately introduced from the divided supporting mixed powder. As a result, a catalyst precursor which was supported and was a molded product was obtained. The binder B was glycerin and water, and was prepared as an aqueous solution of 10% by mass of glycerin.
This catalyst precursor was calcined at 510 ° C. for 2 hours in an air atmosphere to obtain a catalyst. The composition ratio (excluding oxygen) of the catalyst component elements of this catalyst was as follows.
Mo ₁₂ Bi _0.94 Fe _1.87 Co _6.30 Ni _2.84 K _0.1 Cl _0.1
Table 1 shows the evaluation results of the gas phase contact oxidation reaction of propylene using the produced catalyst.

From the above, according to the production method of the present invention, it is possible to produce a catalyst having high mechanical strength, high propylene conversion rate, high acrolein and acrylic acid selectivity, and excellent yields of obtained acrolein and acrylic acid. I understand.

Claims (6)

An unsaturated aldehyde and unsaturated including a molding step of introducing a carrier, a powder containing a catalyst component element and a binder into a granulator, and supporting the powder containing the catalyst component element on the carrier to prepare a catalyst precursor. A method for producing a catalyst for carboxylic acid synthesis.
The carrier is introduced into the granulator, then a binder of 1% by mass or more and 50% by mass or less with respect to the amount of the powder containing the catalyst component element is introduced, and further, the powder containing the catalyst component element is introduced. A method for producing a catalyst for synthesizing unsaturated aldehydes and unsaturated carboxylic acids as a catalyst precursor by introducing a binder of 5% by mass or more and 50% by mass or less with respect to the amount of the carrier. The catalyst for synthesizing unsaturated aldehydes and unsaturated carboxylic acids according to claim 1, wherein the total amount of the binder introduced into the granulator is 10% by mass or more and 60% by mass or less with respect to the amount of the carrier introduced into the granulator. Manufacturing method. The unsaturated according to claim 1 or 2, wherein the total amount of the binder introduced into the granulator is 10% by mass or more and 70% by mass or less with respect to the amount of the powder containing the catalyst component element introduced into the granulator. A method for producing a catalyst for synthesizing aldehydes and unsaturated carboxylic acids. The method for producing an unsaturated aldehyde and an unsaturated carboxylic acid synthesis catalyst according to any one of claims 1 to 3, wherein the binder contains an organic compound. The catalyst for synthesizing unsaturated aldehyde and unsaturated carboxylic acid according to any one of claims 1 to 4, wherein the catalyst component element of the catalyst for synthesizing unsaturated aldehyde and unsaturated carboxylic acid is represented by the following formula (1). Manufacturing method.
Mo ₁₂ Bi _a Fe _b Co _c Ni _d X _e Y _f Z _{g Si h} Oi (1)
(In formula (1), X represents at least one element selected from the group consisting of Na, K, Rb, Cs and Tl, and Y is selected from the group consisting of Mg, Ca, Sr, Ba, Mn and Zn. Z indicates at least one element selected from the group consisting of F, Cl, B, P, As, W and Nb. A to i indicate the atomic ratio of each element. , 0.5 ≦ a ≦ 7, 0.05 ≦ b ≦ 5, 0 ≦ c ≦ 10, 0 ≦ d ≦ 10, 0 ≦ e ≦ 2, 0 ≦ f ≦ 5, 0 ≦ g ≦ 5, 0 ≦ h It is in the range of ≦ 500, and i is a value that satisfies the oxidation state of other elements.) Acrolein and acrylic acid in which propylene is vapor-phase contact-oxidized with an oxygen-containing gas using the unsaturated aldehyde and unsaturated carboxylic acid synthesis catalyst produced by the production method according to any one of claims 1 to 5. Production method.