JP2020151612A - Catalyst and method for producing unsaturated aldehyde and unsaturated carboxylic acid using the same - Google Patents

Abstract

To propose a catalyst which has high catalytic activity and which brings about high yield of a target product, with regard to a catalyst used in methods for producing, using propylene, isobutylene, t-butyl alcohol etc. as a raw material, corresponding unsaturated aldehydes and unsaturated carboxylic acids, and to safely, stably, and at a low cost make a vapor-phase catalytic oxidation method operable for a long time by using the catalyst of this invention.SOLUTION: A catalyst contains molybdenum, bismuth, and cobalt as essential components, and a ratio (J) of the maximum peak intensity in a range of X-ray diffraction angle of 2θ=28.4±0.15° to that in a range of 2θ=26.5±0.3° in an X-ray diffraction pattern after calcination of the catalyst at 550°C is 36.0 to 57.5.SELECTED DRAWING: None

Description

The present invention relates to a novel catalyst having high activity and obtaining a target product in high yield, and particularly in the case of oxidatively producing unsaturated aldehydes and unsaturated carboxylic acids, high activity and high yield can be obtained. It will be realized. It should be noted that this catalyst has a particularly large contribution to the realization of high activity, and can obtain practical activity even when the reaction bath temperature is lowered.

Methods for producing the corresponding unsaturated aldehydes and unsaturated carboxylic acids using propylene, isobutylene, t-butyl alcohol and the like as raw materials are widely practiced industrially.
In particular, many reports have been made on methods for producing corresponding unsaturated aldehydes and unsaturated carboxylic acids using propylene, isobutylene, t-butyl alcohol, etc. as raw materials as means for improving the yield and catalytic activity. (For example, Patent Document 1 etc.).
To the intensity Ph of the diffraction peak of the Patent Document 2 appearing at 2θ = 26.5 ± 0.3 ° in X-ray diffraction pattern using Cu-K [alpha line of catalytically active components in CoMoO ₄ (h) Among them, 2 [Theta] = Control the ratio Ri = Pi / Ph of the intensity Pi of the diffraction peak (i) of β-Bi ₂ Mo ₂ O ₉ appearing at 27.76 ± 0.3 ° to the range of 0.4 or more and 2.0 or less. It is stated that a high-yield and highly selective catalyst can be obtained. In Patent Document 3, the crystallinity T in the range of 2θ = 5 ° or more and 90 ° or less measured by X-ray diffraction analysis using Cu-Kα ray as a catalytically active component is controlled in the range of 4% or more and 18% or less. It is described that the catalytic performance such as catalytic activity and crystallinity can be improved by doing so.

Even if improvements are made by means as described above, in the production of unsaturated aldehydes and / or unsaturated carboxylic acids corresponding to partial oxidation reactions of propylene, isobutylene, t-butyl alcohol and the like, further improvement in yield and catalytic activity can be achieved. Improvement is required. For example, the yield of the target product affects the amount of propylene, isobutylene, t-butyl alcohol, etc. required for production and has a great influence on the production cost. In addition, the catalytic activity affects the reaction bath temperature when producing the target product, and when a catalyst having low activity is used, the reaction bath temperature must be raised in order to maintain the yield of the target product. Then, the catalyst is subjected to thermal stress, which causes a decrease in selectivity and yield, which also leads to a decrease in catalyst life.
In addition, Patent Documents 1 to 3 do not describe that the X-ray diffraction pattern has been examined focusing on the peak intensity of 2θ = 28.4 ± 0.15 °.

International Publication 2016/136882 Japanese Unexamined Patent Publication No. 2017-024009 International Release 2010/0386777

The present invention is a catalyst used in a method for producing a corresponding unsaturated aldehyde or unsaturated carboxylic acid using propylene, isobutylene, t-butyl alcohol or the like as a raw material, and has a catalytic activity and a yield of a target product. It proposes a high catalyst. Then, by using the catalyst of the present invention, long-term operation of the vapor-phase catalytic oxidation method is possible safely, stably, and at low cost.

According to the research by the present inventors, 2θ = with respect to the maximum peak intensity within the range of the X-ray diffraction angle 2θ = 26.5 ± 0.3 ° in the X-ray diffraction pattern when the catalyst is fired at 550 ° C. It was found that the ratio (J) of the maximum peak intensity within the range of 28.4 ± 0.15 ° shows that the catalyst contained in a specific range has particularly excellent catalytic activity and also realizes a high yield. , I went to complete the present invention.

That is, the present invention relates to the following 1) to 10).
1)
The maximum peak intensity within the range of the X-ray diffraction angle 2θ = 26.5 ± 0.3 ° in the X-ray diffraction pattern when molybdenum, bismuth, and cobalt are contained as essential components and the catalyst is fired at 550 ° C. A catalyst having a maximum peak intensity ratio (J) in the range of 2θ = 28.4 ± 0.15 ° to 36.0 or more and 57.5 or less.
2)
The catalyst according to 1) above, wherein the catalyst composition is represented by the following formula (1).
Mo _a1 Bi _b1 Ni _c1 Co _d1 Fe _e1 X _f1 Y _g1 Z _h1 O _i1 ... (1)
(In the formula, Mo, Bi, Ni, Co and Fe represent molybdenum, bismuth, nickel, cobalt and iron, respectively, and X represents tungsten, antimony, tin, zinc, chromium, manganese, magnesium, silica, aluminum, cerium and titanium. At least one element selected from, Y is at least one element selected from sodium, potassium, cesmuth, rubidium, and tarium, Z belongs to groups 1 to 16 of the periodic table, and Mo, Bi, Ni, It means at least one element selected from elements other than Co, Fe, X, and Y, and a1, b1, c1, d1, e1, f1, g1, h1, and i1 are molybdenum, bismuth, and nickel, respectively. , Cobalt, iron, X, Y, Z and oxygen, and when a1 = 12, 0 <b1 ≦ 7, 0 ≦ c1 ≦ 10, 0 <d1 ≦ 10, 0 <c1 + d1 ≦ 20, 0 ≦ e1 ≦ 5, 0 ≦ f1 ≦ 2, 0 ≦ g1 ≦ 3, 0 ≦ h1 ≦ 5, and i1 = values determined by the oxidation state of each element)
3)
The catalyst according to the above 2), which contains nickel as an essential component, and b1, c1, and d1 in the above formula (1) are related to the following formula (2).

0.325 ≤ c1 / (b1 + d1) ≤ 0.405 ... (2)

4)
The X-ray diffraction angle in the X-ray diffraction pattern when firing at 540 ° C. is within the range of 2θ = 28.4 ± 0.15 ° with respect to the maximum peak intensity within the range of 2θ = 26.5 ± 0.3 °. The catalyst according to any one of the above 1) to 3), wherein the ratio (L) of the maximum peak intensity and the above (J) have a relationship of the following formula (3).

-0.133 ≤ (J-L) / 10 ≤ 0.869 ... (3)

5)
The catalyst according to any one of 1) to 4) above, which is supported on an inert carrier.
6)
The catalyst according to 5) above, wherein the inert carrier is silica and / or alumina.
7)
The catalyst according to any one of 1) to 6) above, wherein the catalyst is for producing an unsaturated aldehyde compound and / or an unsaturated carboxylic acid compound.
8)
A method for producing an unsaturated aldehyde compound and / or an unsaturated carboxylic acid compound using the catalyst according to any one of 1) to 7) above.
9)
The production method in which the unsaturated aldehyde compound is acrolein and the unsaturated carboxylic acid compound is acrylic acid in 8) above.
10)
An unsaturated aldehyde compound and / or an unsaturated carboxylic acid compound produced by using the catalyst according to any one of 1) to 7) above.

The catalyst of the present invention is very effective in improving the catalytic activity and yield in the gas-phase catalytic oxidation reaction, and the corresponding unsaturated aldehyde and unsaturated carboxylic acid are made from propylene, isobutylene, t-butyl alcohol and the like as raw materials. It is useful when producing acids.
In addition, the catalyst of the present invention also has an effect of improving the process stability of a partial oxidation reaction accompanied by heat generation such as reduction of hot spot temperature.

[Ratio of maximum peak intensities within the range of 2θ = 28.4 ± 0.15 ° in the X-ray diffraction pattern]
The catalyst of the present invention is characterized with respect to the maximum peak intensity within the range of 2θ = 28.4 ± 0.15 ° in the X-ray diffraction pattern. This X-ray diffraction pattern uses Cu-Kα, and the maximum peak intensity within the range of 2θ = 28.4 ± 0.15 ° is another immovable peak, 2θ = 26.5 ° ± 0. It means the value relative to the maximum peak within the range of 3 °. Specifically, it means a value obtained by dividing by the intensity of 2θ = 26.5 ° ± 0.3 ° and multiplying by 100. In the present specification, the above value when the X-ray diffraction measurement is performed after firing at 550 ° C. is defined as J, and the X-ray diffraction measurement is performed after firing at 540 ° C. The above value in the case may be defined as L and used.
As a method for measuring the X-ray diffraction angle (2θ), for example, Ultima IV manufactured by Rigaku Co., Ltd. is used, and X-ray CuKα ray (λ = 0.154 nm), output 40 kV, 30 mA, measurement range 10 to 60 °, measurement speed. The X-ray diffraction angle (2θ) may be measured under the condition of 10 ° / min, but the present invention is not limited to this as long as the measurement principle is not deviated.
Further, the catalyst of the present invention has a ratio (J) of the maximum peak intensities of 36.0 or more and 57.5 or less when calcined at 550 ° C.
A catalyst having the above value J of 36.0 or more and 57.5 or less is excellent in catalytic activity, and can maintain a high conversion rate of the raw material to the target compound even when the reaction bath temperature is lowered. The lower limit of J is more preferably 40.0, further preferably 42.0, particularly preferably 42.5, and most preferably 45.0. Further, the upper limit of J is more preferably 55.0, further preferably 50.0, and particularly preferably 46.0. A particularly preferable range of J is 45.0 ≦ J ≦ 46.0.

Baking at 550 ° C means that the temperature of the section where the catalyst inside the firing furnace is fired is 550 ° C, and firing at 540 ° C means that the section where the catalyst inside the firing furnace is fired. It means that the temperature is 540 ° C. However, when firing at 550 ° C, the temperature of the above section may be kept at a temperature higher than 545 ° C and lower than 555 ° C, and when firing at 540 ° C, the temperature is higher than 535 ° C and lower than 545 ° C. It suffices if it is kept.
Further, the firing at 550 ° C. or 540 ° C. has a function as a pretreatment for measuring the X-ray diffraction angle (2θ), and in the catalyst manufacturing process, any firing step can be used. There is no problem even if there is no firing step. However, when the firing step is performed at 550 ° C or 540 ° C, there is no problem even if the X-ray diffraction angle (2θ) is measured as it is as the pretreatment.
The firing time is not particularly limited, but is preferably 1 hour or more and 40 hours or less, more preferably 2 hours or more and 10 hours or less, and particularly preferably 3 hours or more and 5 hours or less. In conducting this test, the X-ray diffraction angle (2θ) may be measured by limiting the firing time to 4 hours. However, this firing time means the holding time at the maximum temperature, and does not include the temperature raising time and the temperature lowering time. That is, even when the firing time is 4 hours, it is 4 hours after the maximum temperature is reached, and the temperature raising time and the temperature lowering time are not included in the firing time.
The atmosphere in the firing furnace is not particularly limited, but the oxygen concentration is preferably 10% or more and 30% or less, and more preferably 15% or more and 25% or less.

[Catalyst composition]
The catalyst of the present invention preferably has a composition represented by the following formula (1).
Mo _a1 Bi _b1 Ni _c1 Co _d1 Fe _e1 X _f1 Y _g1 Z _h1 O _i1 ... (1)
(In the formula, Mo, Bi, Ni, Co and Fe represent molybdenum, bismuth, nickel, cobalt and iron, respectively, and X represents tungsten, antimony, tin, zinc, chromium, manganese, magnesium, silica, aluminum, cerium and titanium. At least one element selected from, Y is at least one element selected from sodium, potassium, cesmuth, rubidium, and tarium, Z belongs to groups 1 to 16 of the periodic table, and Mo, Bi, Ni, It means at least one element selected from elements other than Co, Fe, X, and Y, and a1, b1, c1, d1, e1, f1, g1, h1 and i1 are molybdenum, bismuth, nickel, respectively. Represents the number of atoms of cobalt, iron, X, Y, Z and oxygen, and when a1 = 12, 0 <b1 ≦ 7, 0 ≦ c1 ≦ 10, 0 <d1 ≦ 10, 0 <c1 + d1 ≦ 20, 0 ≦ e1 ≦ 5, 0 ≦ g1 ≦ 2, 0 ≦ f1 ≦ 3, 0 ≦ h1 ≦ 5, and i1 = values determined by the oxidation state of each element)

In the above formula (1), the preferable ranges of b1 to i1 are as follows.
0.2 <b1 ≦ 2, 1 ≦ c1 ≦ 5, 3 ≦ d1 ≦ 8, 5 ≦ c1 + d1 ≦ 15, 0.5 ≦ e1 ≦ 4, 0.01 ≦ g1 ≦ 1, 0 ≦ f1 ≦ 1.5, 0 ≦ h1 ≦ 2.
Further preferable ranges are as follows.
0.5 <b1 ≦ 1, 2 ≦ c1 ≦ 4, 5 ≦ d1 ≦ 7, 7 ≦ c1 + d1 ≦ 12, 1 ≦ e1 ≦ 3, 0.02 ≦ g1 ≦ 0.2, 0 ≦ f1 ≦ 1, 0 ≦ h1 ≦ 1.
It is preferable that two or less types of Y are contained, and one type is particularly preferable. Further, it is a particularly preferable embodiment that f1 and h1 are 0.

[About support]
The catalyst in which the pre-baked powder obtained by pre-firing after preparing the catalyst is supported on an inert carrier is particularly effective as the catalyst of the present invention.
As the material of the inert carrier, known materials such as alumina, silica, titania, zirconia, niobia, silica alumina, silicon carbide, carbides, and mixtures thereof can be used, and further, the particle size, water absorption rate, mechanical strength, and the like. The degree of crystallization and mixing ratio of the crystal phase are not particularly limited, and an appropriate range should be selected in consideration of the final catalyst performance, moldability, production efficiency, and the like. The mixing ratio of the carrier and the pre-baked powder is calculated as the loading ratio from the following formula based on the charged mass of each raw material.
Support rate (% by mass) = (mass of pre-baked powder used for molding) / {(mass of pre-baked powder used for molding) + (mass of carrier used for molding)} × 100
The preferred upper limit of the loading ratio is 80%, more preferably 60%.
The lower limit is preferably 20%, more preferably 30%.
As the inert carrier, silica and / or alumina are preferable, and a mixture of silica and alumina is particularly preferable.
It is preferable to use a binder for supporting. Specific examples of binders that can be used include water, ethanol, methanol, propanol, polyhydric alcohol, polyvinyl alcohol of polymer binder, silica sol aqueous solution of inorganic binder and the like, but ethanol, methanol, propanol and polyhydric. Alcohol is preferable, diol such as ethylene glycol and triol such as glycerin are preferable, and an aqueous solution having a concentration of glycerin of 5% by mass or more is preferable. By using an appropriate amount of the glycerin aqueous solution, the moldability is improved, and a high-performance catalyst having high mechanical strength can be obtained. The amount of these binders used is usually 2 to 60 parts by mass with respect to 100 parts by mass of the pre-baked powder, but 10 to 30 parts by mass is preferable in the case of an aqueous glycerin solution. Upon carrying, the binder and the pre-baked powder may be supplied to the molding machine alternately or at the same time.

The reason why the catalyst of the present invention shows the effect of the above invention is unknown, but in general, a diffraction peak of cobalt molybdate appears in the vicinity of 2θ = 26.5 ° in the measurement in X-ray diffraction analysis, and 2θ = 28. A diffraction peak of bismuth cobaltate appears around 4 °. In addition, cobalt molybdate has a role of taking oxygen into the catalyst, and bismuth molybdate has a role of converting a raw material compound into a target product as an active site of a catalytic reaction.
When the value of J of the present invention is less than 36.0, the number of bismuth moribdate crystals in the catalyst is small, and the activity is reduced due to the slow conversion of the raw material compound to the target product. When J is larger than 57.5, it is considered that the activity is lowered due to the fact that the number of cobalt molybdate crystals in the catalyst is small and the number of oxygen atoms incorporated in the catalyst is small.

As a means for adjusting the value of J described above, control can be performed by changing each condition in each manufacturing step described later. For example, (I) a method for changing the catalyst composition and (II) a solution in the compounding step. The method of changing the temperature, (III) the method of changing the time taken in the compounding process, (IV) the method of changing the drying temperature in the drying process, (V) the method of changing the temperature and time in the baking process, and ( A method of combining (I) to (V) can be mentioned. When the adjustment is carried out by the method (I), it is preferable that the catalyst composition in the catalytically active component is the following formula (2) in the above formula (1) with c1 / (b1 + d1).

0.325 ≤ c1 / (b1 + d1) ≤ 0.405 ... (2)

The upper limit of c1 / (b1 + d1) is more preferably 0.390, further preferably 0.350, and particularly preferably 0.340. The lower limit of c1 / (b1 + d1) is more preferably 0.330. That is, the case of 0.330 or more and 0.340 is one of the particularly preferable aspects.

[About equation (3)]
The catalyst of the present invention has 2θ = 28.4 ± 0. For the maximum peak intensity within the range of the X-ray diffraction angle 2θ = 26.5 ± 0.3 ° in the X-ray diffraction pattern when calcined at 540 ° C. The ratio of the maximum peak intensity within the range of 15 ° (L) and the maximum peak intensity within the range of the X-ray diffraction angle 2θ = 26.5 ± 0.3 ° in the X-ray diffraction pattern when firing is performed at 550 ° C. It is preferable that the ratio (J) of the maximum peak intensity within the range of 2θ = 28.4 ± 0.15 ° to 2θ = 28.4 ± 0.15 ° has the relationship of the following equation (3).

-0.133 ≤ (J-L) / 10 ≤ 0.869 ... (3)

The above (JL) is the maximum within the range of the X-ray diffraction angle 2θ = 26.5 ± 0.3 ° when the firing temperature is changed from 540 ° C. to 550 ° C., that is, when the firing temperature is changed by 10 ° C. It is the amount of change in the ratio of the maximum peak intensity within the range of 2θ = 28.4 ± 0.15 ° with respect to the peak intensity, and the value obtained by dividing this by 10 is the value of dependence on the firing temperature. The catalyst of the present invention can further enhance the effect of improving the yield at the time of high activity by keeping the calcination temperature dependence of the ratio of the above-mentioned cobalt molybdate and bismuth molybdate within a certain range.
The upper limit of (JL) / 10 is more preferably 0.600, further preferably 0.400, and particularly preferably 0.200. The lower limit is more preferably −0.100, further preferably 0, and particularly preferably 0.100. Therefore, the case where 0.100 ≦ (JL) / 10 ≦ 0.200 is one of the most preferable embodiments.

[Catalyst manufacturing method, etc.]
The starting material for the pre-baked powder of the present invention and each element constituting the catalyst is not particularly limited, but for example, the raw material for the molybdenum component includes molybdate oxide such as molybdenum trioxide, molybdic acid, and paramolybdenum. Molybdic acid such as ammonium acid and ammonium metamolybdate or a salt thereof, a heteropolyacid containing molybdenum such as phosphomolybdic acid and silicate molybdate or a salt thereof can be used.

As the raw material of the bismuth component, bismuth nitrate, bismuth carbonate, bismuth sulfate, bismuth salt such as bismuth acetate, bismuth trioxide, metal bismuth and the like can be used. These raw materials can be used as a solid or as a slurry of an aqueous solution, a nitric acid solution, or a bismuth compound produced from the aqueous solution, but it is preferable to use nitrate, a solution thereof, or a slurry produced from the solution.

As starting materials for other constituent elements, ammonium salts, nitrates, nitrites, carbonates, hypocarbonates, acetates, chlorides, inorganic acids, and salts of inorganic acids, which are metal elements generally used in this type of catalyst. , Heteropolyacids, heteropolyacid salts, sulfates, hydroxides, organic acid salts, oxides or mixtures thereof may be used in combination, but ammonium salts and nitrates are preferably used.

The compound containing these active ingredients may be used alone or in combination of two or more. The slurry liquid can be obtained by uniformly mixing each active ingredient-containing compound and water. The amount of water used in the slurry liquid is not particularly limited as long as the total amount of the compound used can be completely dissolved or uniformly mixed. The amount of water used may be appropriately determined in consideration of the drying method and drying conditions. Usually, it is 100 parts by mass or more and 2000 parts by mass or less with respect to 100 parts by mass of the total mass of the compound for slurry preparation. The amount of water may be large, but if it is too large, the energy cost of the drying process becomes high, and there are many disadvantages such as the case where the water cannot be completely dried.

The slurry liquid of the source compound of each component element is a method of (a) mixing the above source compounds collectively, (b) a method of collectively mixing and then aging treatment, and (c) stepwise. It is preferable to prepare by a method of mixing, (d) a method of repeating the mixing and aging treatment stepwise, and a method of combining (a) to (d). Here, the above-mentioned aging means "processing an industrial raw material or a semi-finished product under specific conditions such as a constant time and a constant temperature to acquire, increase, or proceed with a predetermined reaction having required physical properties and chemical properties. It means "operation to measure such things". In the present invention, the above-mentioned constant time means a range of 5 minutes or more and 24 hours or less, and the above-mentioned constant temperature means a range of an aqueous solution or an aqueous dispersion above room temperature and below the boiling point. Of these, the method of (c) stepwise mixing is preferable in terms of the activity and yield of the catalyst finally obtained, and more preferably, each raw material to be mixed stepwise with the mother liquor is a completely dissolved solution. The most preferable method is to mix various mixed solutions of alkali metal solution and nitrate with a mother liquor containing a molybdenum raw material as a mixed solution or a slurry. However, it is not always necessary to mix all the catalyst constituent elements in this step, and some elements or some amounts thereof may be added in the subsequent steps.

In the present invention, the shape of the stirring blade of the stirrer used when mixing the essential active ingredients is not particularly limited, and the propeller blade, the turbine blade, the paddle blade, the inclined paddle blade, the screw blade, the anchor blade, the ribbon blade, and the large lattice are not particularly limited. Any stirring blade such as a blade can be used in one stage, or the same blade or different types of blades can be used in two or more stages in the vertical direction. In addition, a baffle (obstruction plate) may be installed in the reaction tank as needed.

Then, the slurry liquid thus obtained is dried. The drying method is not particularly limited as long as the slurry liquid can be completely dried, and examples thereof include drum drying, freeze drying, spray drying, and evaporation drying. Of these, in the present invention, spray drying, which can dry the slurry liquid into powder or granules in a short time, is particularly preferable. The drying temperature of spray drying varies depending on the concentration of the slurry liquid, the liquid feeding speed, and the like, but the temperature at the outlet of the dryer is generally 70 ° C. or higher and 150 ° C. or lower.

The catalyst precursor obtained as described above can be pre-fired, molded, and then main-fired to control and retain the molded shape, resulting in a catalyst having particularly excellent mechanical strength for industrial use. It can be obtained and stable catalytic performance can be exhibited.

As the molding, either a supported molding method of supporting on a carrier such as silica or a non-supported molding method using no carrier can be adopted. Specific molding methods include, for example, tableting molding, press molding, extrusion molding, granulation molding and the like. As the shape of the molded product, for example, a columnar shape, a ring shape, a spherical shape, or the like can be appropriately selected in consideration of operating conditions, and the catalytically active component is supported on a spherical carrier, particularly an inert carrier such as silica or alumina. A supported catalyst having an average particle size of 3.0 mm or more and 10.0 mm or less, preferably an average particle size of 3.0 mm or more and 8.0 mm or less is preferable. As a supporting method, a rolling granulation method, a method using a centrifugal flow coating device, a wash coating method and the like are widely known, and the method is not particularly limited as long as the pre-baked powder can be uniformly supported on the carrier, but the catalyst. The rolling granulation method is preferable in consideration of the production efficiency of the above. Specifically, in a device having a flat or uneven disk at the bottom of a fixed cylindrical container, the carrier charged in the container is rotated and revolved by rotating the disk at high speed. This is a method in which the powder component is supported on a carrier by vigorously stirring by repeating the exercise and adding a pre-baked powder to the stirring. It is preferable to use a binder for supporting. Specific examples of binders that can be used include water, ethanol, methanol, propanol, polyhydric alcohol, polyvinyl alcohol of polymer binder, silica sol aqueous solution of inorganic binder and the like, but ethanol, methanol, propanol and polyhydric. Alcohol is preferable, diol such as ethylene glycol and triol such as glycerin are more preferable, and an aqueous solution having a concentration of glycerin of 5% by mass or more is further preferable. By using an appropriate amount of the glycerin aqueous solution, the moldability is improved, and a high-performance catalyst having high mechanical strength can be obtained. The amount of these binders used is usually 2 to 60 parts by mass with respect to 100 parts by mass of the pre-baked powder, but 15 to 50 parts by mass is preferable in the case of an aqueous glycerin solution. Upon carrying, the binder and the pre-baked powder may be supplied to the molding machine alternately or at the same time. Further, at the time of molding, a small amount of known additives such as graphite and talc may be added. The molding aid, pore-forming agent, and carrier added in molding are all constituent elements of the active ingredient in the present invention, regardless of whether or not they are active in the sense of converting the raw material into some other product. It shall not be considered.

The pre-firing method, pre-firing conditions, main firing method, and main firing conditions are not particularly limited, and known treatment methods and conditions can be applied. The pre-calcination and the main calcination are usually performed at 200 ° C. or higher and 600 ° C. or lower, preferably 300 ° C. or higher and 550 ° C. or lower, for 0.5 hours or longer, preferably under the flow of an oxygen-containing gas such as air or an inert gas. Perform in 1 hour or more and 40 hours or less. Here, the inert gas refers to a gas that does not reduce the reaction activity of the catalyst, and specific examples thereof include nitrogen, carbon dioxide, helium, and argon. The optimum conditions for the main firing differ depending on the reaction conditions when the unsaturated aldehyde and / or the unsaturated carboxylic acid is produced using the catalyst, and the process parameters of the main firing step, that is, the atmosphere. Since it is known to those skilled in the art to change the oxygen content, the maximum temperature reached, the firing time, etc., it falls within the scope of the present invention. Further, the main firing step shall be performed after the above-mentioned pre-baking step, and the maximum reached temperature (main firing temperature) in the main firing step is higher than the maximum reached temperature (pre-baking temperature) in the above-mentioned pre-baking step. It shall be expensive. The firing method is not particularly limited to fluidized beds, rotary kilns, muffle furnaces, tunnel firing furnaces, etc., and an appropriate range should be selected in consideration of the final catalyst performance, mechanical strength, moldability, production efficiency, etc. Is.

The catalyst of the present invention is preferably used as a catalyst for producing an unsaturated aldehyde compound or an unsaturated carboxylic acid compound, and is preferably used as a catalyst for producing an unsaturated aldehyde compound in the first stage. More preferably, it is particularly preferably used as a catalyst for producing achlorine from propylene.

[About the second stage catalyst]
When the catalyst of the present invention is used as a catalyst for producing an unsaturated aldehyde compound, an unsaturated carboxylic acid compound can be obtained by performing a second-stage oxidation reaction.
In this case, the catalyst of the present invention can be used as the catalyst of the second stage, but it is preferably the catalyst represented by the following formula (4).
Mo ₁₂ V _a2 W _b2 Cu _c2 Sb _d2 X2 _e2 Y2 _f2 Z2 _{g2 Oh2} (4)
(In the formula, Mo, V, W, Cu, Sb and O represent molybdenum, vanadium, tungsten, copper, antimony and oxygen, respectively, and X2 is at least one element selected from the group consisting of alkali metals and tallium. Y2 is at least one element selected from the group consisting of magnesium, calcium, strontium, barium and zinc, and Z is from niobium, cerium, tin, chromium, manganese, iron, cobalt, sumalium, germanium, titanium and arsenic. Represents at least one element selected from the group. A2, b2, c2, d2, e2, f2, g2 and h2 represent the atomic ratio of each element, and a2 is 0 <for molybdenum atom 12. a2 ≦ 10, b2 is 0 ≦ b2 ≦ 10, c2 is 0 <c2 ≦ 6, d2 is 0 <d2 ≦ 10, e2 is 0 ≦ e2 ≦ 0.5, f2 is 0 ≦ f2 ≦ 1, g2 is 0 ≦ It represents g2 <6, and h2 is the number of oxygen atoms required to satisfy the atomic value of each component.)

In the production of the catalyst represented by the above formula (4), a method generally known as a method for preparing a catalyst of this type, for example, an oxide catalyst, a heteropolyacid or a catalyst having a salt structure thereof can be adopted. The raw materials that can be used in producing the catalyst are not particularly limited, and various materials can be used. For example, molybdenum oxides such as molybdenum trioxide, molybdates, molybdates such as ammonium molybdate or salts thereof, heteropolyacids containing molybdenum such as phosphomolybdic acid and silicate molybdate or salts thereof may be used. The raw material for the antimony component that can be produced is not particularly limited, but antimony trioxide or antimonate acetate is preferable. As raw materials for other elements such as vanadium, tungsten and copper, each nitrate, sulfate, carbonate, phosphate, organic acid salt, halide, hydroxide, oxide, metal and the like can be used.

The compound containing these active ingredients may be used alone or in combination of two or more.

Next, the slurry liquid obtained above is dried to obtain a solid catalytically active component. The drying method is not particularly limited as long as the slurry liquid can be completely dried, and examples thereof include drum drying, freeze drying, spray drying, and evaporative drying, and the slurry liquid can be made into powder or granules in a short time. Spray drying, which can be dried, is preferred. The drying temperature of spray drying varies depending on the concentration of the slurry liquid, the liquid feeding speed, and the like, but the temperature at the outlet of the dryer is generally 70 to 150 ° C. Further, it is preferable to dry the dried slurry liquid obtained at this time so that the average particle size is 10 to 700 μm.

The catalyst-active component solid of the second stage obtained as described above can be used as it is in the coating mixture, but it is preferable because the moldability may be improved by firing. The firing method and firing conditions are not particularly limited, and known processing methods and conditions can be applied. The optimum conditions for firing differ depending on the catalyst raw material used, the catalyst composition, the preparation method, and the like, but the firing temperature is usually 100 to 350 ° C., preferably 150 to 300 ° C., and the firing time is 1 to 20 hours. The firing is usually carried out in an air atmosphere, but may be carried out in an inert gas atmosphere such as nitrogen, carbon dioxide, helium or argon, or further after firing in an inert gas atmosphere, if necessary. The firing may be performed in an air atmosphere. The calcined solid thus obtained is preferably pulverized before molding. The crushing method is not particularly limited, but a ball mill may be used.

Further, the compound containing the active ingredient in preparing the slurry of the second stage does not necessarily have to contain all the active ingredients, and some of the ingredients may be used before the following molding step. ..

The shape of the catalyst in the second stage is not particularly limited, and it is molded into a columnar shape, a tablet, a ring shape, a spherical shape, or the like in order to reduce the pressure loss of the reaction gas in the oxidation reaction. Of these, since improvement in selectivity and removal of heat of reaction can be expected, it is particularly preferable to support the catalytically active component solid on the inert carrier and use it as a supported catalyst. The rolling granulation method described below is preferable for this support. In this method, for example, in a device having a flat or uneven disk at the bottom of a fixed container, the carrier in the container is vigorously agitated by repeating rotation and revolution by rotating the disk at high speed. This is a method of supporting a carrier with a binder, a catalyst-active ingredient solid, and, if necessary, a supporting mixture to which other additives such as a molding aid and a strength improver are added. The method of adding the binder is as follows: 1) it is mixed in advance with the supporting mixture, 2) the supporting mixture is added at the same time as being added into the fixed container, and 3) the supporting mixture is added after being added into the fixed container. 4) The supporting mixture is added before being added into the fixed container, 5) the supporting mixture and the binder are separated from each other, and 2) to 4) are appropriately combined and added in total. .. Of these, in 5), for example, the addition rate is adjusted by using an autofeeder or the like so that the supporting mixture does not adhere to the wall of the fixed container and the supporting mixture does not aggregate with each other and a predetermined amount is supported on the carrier. Is preferable. Examples of the binder include water, ethanol, polyhydric alcohol, polyvinyl alcohol as a high molecular weight binder, celluloses such as crystalline cellulose, methyl cellulose and ethyl cellulose, and an aqueous solution of silica sol as an inorganic binder, such as celluloses and ethylene glycol. Diol, triol such as glycerin, etc. are preferable, and an aqueous solution having a concentration of glycerin of 5% by mass or more is particularly preferable. No. The amount of these binders used is usually 2 to 60 parts by mass, preferably 10 to 50 parts by mass with respect to 100 parts by mass of the supporting mixture.

Specific examples of the carrier in the above-mentioned carrier include spherical carriers having a diameter of 1 to 15 mm, preferably 2.5 to 10 mm, such as silicon carbide, alumina, silica-alumina, mullite, and random. As these carriers, those having a porosity of 10 to 70% are usually used. The ratio of the carrier to the supporting mixture is usually 10 to 75% by mass, preferably 15 to 60% by mass of the supporting mixture / (supporting mixture + carrier). When the proportion of the supporting mixture is large, the reaction activity of the supporting catalyst is large, but the mechanical strength tends to be small. On the contrary, when the ratio of the supporting mixture is small, the mechanical strength tends to be large, but the reaction activity tends to be small. In the above, examples of the molding aid used as necessary include silica gel, diatomaceous earth, and alumina powder. The amount of the molding aid used is usually 1 to 60 parts by mass with respect to 100 parts by mass of the catalytically active component solid. Further, if necessary, the use of the catalytically active component solid and the inorganic fiber (for example, ceramic fiber or whiskers) inactive with respect to the reaction gas as the strength improver is useful for improving the mechanical strength of the catalyst. Glass fiber is preferred. The amount of these fibers used is usually 1 to 30 parts by mass with respect to 100 parts by mass of the catalytically active component solid. In the molding of the catalyst in the first stage, the molding aid, the pore forming agent, and the carrier added may or may not be active in the sense of converting the raw material into some other product. It shall not be considered as a constituent element of the active ingredient in the present invention.

The supported catalyst obtained as described above can be directly used as a catalyst for the vapor phase catalytic oxidation reaction, but it is preferable that the catalyst activity may be improved by firing. The firing method and firing conditions are not particularly limited, and known processing methods and conditions can be applied. The optimum firing conditions vary depending on the catalyst raw material used, the catalyst composition, the preparation method, and the like, but the firing temperature is usually 100 to 450 ° C., preferably 270 to 420 ° C., and the firing time is 1 to 20 hours. The firing is usually carried out in an air atmosphere, but may be carried out in an inert gas atmosphere such as nitrogen, carbon dioxide, helium or argon, or further after firing in an inert gas atmosphere, if necessary. The firing may be performed in an air atmosphere.

A reaction for producing the corresponding unsaturated aldehyde and unsaturated carboxylic acid using the catalyst of the present invention as a raw material of propylene, isobutylene, t-butyl alcohol, etc., particularly propylene in gas phase contact with molecular oxygen or a gas containing molecular oxygen. When used in a reaction for producing acrolein and acrylic acid by oxidation, the catalytic activity can be improved and the yield can be improved, which greatly improves the price competitiveness of the product as compared with known methods. It is valid. In addition, the effect of improving the process stability of the partial oxidation reaction accompanied by heat generation such as reduction of the hot spot temperature can be expected. Furthermore, the catalyst of the present invention is also effective in reducing by-products that adversely affect the environment and the quality of final products, such as carbon monoxide (CO) and carbon dioxide (CO ₂ ), acetaldehyde, acetic acid and formaldehyde.

The catalyst of the present invention thus obtained can be used, for example, in producing acrolein and / or acrylic acid by vapor-phase catalytic oxidation of propylene with a molecular oxygen-containing gas. In the production method of the present invention, the distribution method of the raw material gas may be an ordinary single distribution method or a recycling method, and can be carried out under generally used conditions, and is not particularly limited. For example, propylene as a starting material is 1 to 10% by volume, preferably 4 to 9% by volume, molecular oxygen is 3 to 20% by volume, preferably 4 to 18% by volume, and water vapor is 0 to 60% by volume at room temperature. The catalyst of the present invention is filled with a mixed gas preferably containing 4 to 50% by volume and 20 to 80% by volume, preferably 30 to 60% by volume of an inert gas such as carbon dioxide or nitrogen, on the catalyst of the present invention. The reaction is carried out at 450 ° C. under a pressure of normal pressure to 10 atm and introduced at a space velocity of 300 to 5000 h- ¹ .

In the present invention, the improvement of the catalytic activity means that the raw material conversion rate is high when the catalytic reaction is carried out at the same reaction bath temperature and the comparison is made unless otherwise specified.
Unless otherwise specified, the high yield in the present invention means that when an oxidation reaction is carried out using propylene, isobutylene, t-butyl alcohol or the like as a raw material, the corresponding unsaturated aldehyde and / or unsaturated carboxylic acid is used. Indicates that the total yield of
In the present invention, the constituent elements of the catalytically active component refer to all the elements used in the catalyst manufacturing process unless otherwise specified, but the raw materials that disappear, sublimate, volatilize, and burn at the maximum temperature or lower in the main firing process. And its constituent elements shall not be included in the constituent elements of the active component of the catalyst. Further, the elements constituting the molding aid and the carrier in the molding process and other inorganic materials are not included as the constituent elements of the active component of the catalyst.
In the present invention, the hot spot temperature is the maximum temperature of the temperature distribution in the catalyst packed bed measured by installing a thermocouple in the long axis direction in the multi-tube reaction tube, and the reaction bath temperature is the heat generation of the reaction tube. It is the set temperature of the heat medium used for the purpose of cooling. The number of points for measuring the temperature distribution is not particularly limited, but for example, the catalyst filling length is evenly divided from 10 to 1000.
In the present invention, the unsaturated aldehyde and the unsaturated aldehyde compound are organic compounds having at least one double bond and at least one aldehyde in the molecule, and are, for example, acrolein and methacrolein. In the present invention, the unsaturated carboxylic acid and the unsaturated carboxylic acid compound are organic compounds having at least one double bond and at least one carboxy group in the molecule, or an ester group thereof, for example, acrylic acid, methacrylic acid, and the like. It is methyl methacrylate.

Hereinafter, the present invention will be described in more detail with reference to Examples. In the examples, the conversion rate, yield, selectivity, and loading rate were calculated according to the following formulas.
Raw material conversion rate (%) = (number of moles of reacted propylene or t-butyl alcohol or isobutylene) / (number of moles of supplied propylene or t-butyl alcohol or isobutylene) × 100
Effective yield (%) = (total number of moles of acrolein and acrylic acid or methacrolein and methacrolein produced) / (number of moles of supplied propylene or t-butyl alcohol or isobutylene) x 100
Support rate (% by mass) = (mass of pre-baked powder used for molding) / {(mass of pre-baked powder used for molding) + (mass of carrier used for molding)} × 100

The X-ray diffraction angle (2θ) is measured by using UltraIV manufactured by Rigaku Co., Ltd., X-ray CuKα ray (λ = 0.154 nm), output 40 kV, 30 mA, measurement range 10 to 60 °, measurement speed. The condition is 10 ° / min. Further, the firing time described in each of the following examples does not include the temperature raising time and the temperature lowering time, and means the time from the time when each firing temperature is reached.

[Example 1]
100 parts by mass of ammonium heptamolybdate was completely dissolved in 380 parts by mass of pure water heated to 60 ° C. (mother solution 1). Next, 0.17 parts by mass of potassium nitrate was dissolved in 1.6 parts by mass of pure water and added to the mother liquor 1. Next, 37 parts by mass of ferric nitrate, 90 parts by mass of cobalt nitrate and 33 parts by mass of nickel nitrate were dissolved in 85 parts by mass of pure water heated to 60 ° C. and added to the mother liquor 1. Subsequently, 16 parts by mass of bismuth nitrate was dissolved in an aqueous nitric acid solution prepared by adding 4.1 parts by mass of nitric acid (60% by mass) to 17 parts by mass of pure water heated to 60 ° C. and added to the mother liquor 1. The mother liquor 1 was dried by a spray-drying method, and the obtained dry powder was pre-baked at 440 ° C. for 4 hours. The pre-baked powder thus obtained (the atomic ratio calculated from the charged raw material is Mo: Bi: Fe: Co: Ni: K = 12: 0.70: 2.0: 6.5: 2.4: 0. After adding 5% by mass of crystalline cellulose to 040) and mixing thoroughly, a 33% by mass glycerin solution was used as a binder by the rolling granulation method, and the carrier was supported on an inert carrier by 50% by mass. It was supported and molded into a spherical shape so as to be%. The spherical molded product having a particle size of 5.3 mm thus obtained was subjected to main firing under the conditions of 550 ° C. for 4 hours, and the X-ray diffraction angle (2θ) was measured.
Further, a product obtained by performing the main firing at 540 ° C. for 4 hours without performing the main firing at 550 ° C. was also prepared, and the X-ray diffraction angle (2θ) was measured.

[Example 2]
100 parts by mass of ammonium heptamolybdate was completely dissolved in 380 parts by mass of pure water heated to 60 ° C. (mother solution 1). Next, 0.17 parts by mass of potassium nitrate was dissolved in 1.6 parts by mass of pure water and added to the mother liquor 1. Next, 37 parts by mass of ferric nitrate, 90 parts by mass of cobalt nitrate and 33 parts by mass of nickel nitrate were dissolved in 85 parts by mass of pure water heated to 60 ° C. and added to the mother liquor 1. Subsequently, 16 parts by mass of bismuth nitrate was dissolved in an aqueous nitric acid solution prepared by adding 4.1 parts by mass of nitric acid (60% by mass) to 17 parts by mass of pure water heated to 60 ° C. and added to the mother liquor 1. The mother liquor 1 was dried by a spray-drying method, and the obtained dry powder was pre-baked at 440 ° C. for 4 hours. The pre-baked powder thus obtained (the atomic ratio calculated from the charged raw material is Mo: Bi: Fe: Co: Ni: K = 12: 0.70: 2.0: 6.5: 2.4: 0. After adding 5% by mass of crystalline cellulose to 10) and mixing thoroughly, a 33% by mass glycerin solution was used as a binder by the rolling granulation method, and the loading ratio was 50% by mass on the inert carrier. It was supported and molded into a spherical shape so as to be%. The spherical molded product having a particle size of 5.3 mm thus obtained was subjected to main firing under the conditions of 550 ° C. for 4 hours, and the respective X-ray diffraction angles (2θ) were measured.
Further, a product obtained by performing the main firing at 540 ° C. for 4 hours without performing the main firing at 550 ° C. was also prepared, and the X-ray diffraction angle (2θ) was measured.

[Comparative Example 1]
100 parts by mass of ammonium heptamolybdate was completely dissolved in 380 parts by mass of pure water heated to 60 ° C. (mother solution 1). Next, 0.37 parts by mass of cesium nitrate was dissolved in 1.6 parts by mass of pure water and added to the mother liquor 1. Next, 37 parts by mass of ferric nitrate, 90 parts by mass of cobalt nitrate and 33 parts by mass of nickel nitrate were dissolved in 85 parts by mass of pure water heated to 60 ° C. and added to the mother liquor 1. Subsequently, 21 parts by mass of bismuth nitrate was dissolved in an aqueous nitric acid solution prepared by adding 5.4 parts by mass of nitric acid (60% by mass) to 23 parts by mass of pure water heated to 60 ° C. and added to the mother liquor 1. The mother liquor 1 was dried by a spray-drying method, and the obtained dry powder was pre-baked at 440 ° C. for 4 hours. The pre-baked powder thus obtained (the atomic ratio calculated from the charged raw material is Mo: Bi: Fe: Co: Ni: Cs = 12: 0.93: 2.0: 6.5: 2.4: 0. After adding 5% by mass of crystalline cellulose to 040) and mixing thoroughly, a 33% by mass glycerin solution was used as a binder by the rolling granulation method, and the carrier was supported on an inert carrier by 50% by mass. It was supported and molded into a spherical shape so as to be%. The spherical molded product having a particle size of 4.7 mm thus obtained was subjected to main firing under the conditions of 550 ° C. for 4 hours, and the respective X-ray diffraction angles (2θ) were measured.
Further, a product obtained by performing the main firing at 540 ° C. for 4 hours without performing the main firing at 550 ° C. was also prepared, and the X-ray diffraction angle (2θ) was measured.

[Comparative Example 2]
100 parts by mass of ammonium heptamolybdate was completely dissolved in 380 parts by mass of pure water heated to 60 ° C. (mother solution 1). Next, 0.44 parts by mass of potassium nitrate was dissolved in 3.9 parts by mass of pure water and added to the mother liquor 1. Next, 33 parts by mass of ferric nitrate, 71 parts by mass of cobalt nitrate and 38 parts by mass of nickel nitrate were dissolved in 76 parts by mass of pure water heated to 60 ° C. and added to the mother liquor 1. Subsequently, 38 parts by mass of bismuth nitrate was dissolved in an aqueous nitric acid solution prepared by adding 9.7 parts by mass of nitric acid (60% by mass) to 41 parts by mass of pure water heated to 60 ° C. and added to the mother liquor 1. The mother liquor 1 was dried by a spray-drying method, and the obtained dry powder was pre-baked at 440 ° C. for 4 hours. The pre-baked powder thus obtained (the atomic ratio calculated from the charged raw material is Mo: Bi: Fe: Co: Ni: K = 12: 1.7: 1.8: 5.2: 2.8: 0. After adding 5% by mass of crystalline cellulose to 095) and mixing thoroughly, a 33% by mass glycerin solution was used as a binder by the rolling granulation method, and the loading ratio was 50% by mass on the inert carrier. It was supported and molded into a spherical shape so as to be%. The spherical molded product having a particle size of 5.3 mm thus obtained was subjected to main firing under the conditions of 550 ° C. for 4 hours, and the respective X-ray diffraction angles (2θ) were measured.
Further, a product obtained by performing the main firing at 540 ° C. for 4 hours without performing the main firing at 550 ° C. was also prepared, and the X-ray diffraction angle (2θ) was measured.

Using the catalysts obtained in the above Examples and Comparative Examples, the oxidation reaction of propylene was carried out by the following method to determine the raw material conversion rate and the effective yield. 68 ml of each catalyst was filled in a stainless steel reaction tube having an inner diameter of 28.4 mm, and a mixed gas having a gas volume ratio of propylene: oxygen: steam = 1.0: 1.7: 3.0 was introduced at a propylene space velocity of 71 hr- ^1. , Propylene oxidation reaction was carried out. After the aging reaction at a reaction bath temperature of 315 ° C. for 20 hours or more from the start of the reaction, the raw material conversion rate and the effective yield shown in Table 1 were determined by analysis of the reaction tube outlet gas.

Table 2 shows the ratio of the maximum peak intensities within the range of the X-ray diffraction angle 2θ = 28.4 ± 0.15 ° of the catalysts obtained in the above Examples and Comparative Examples and the value of (JL) / 10. ..
The ratio of the maximum peak intensities within the range of 2θ = 28.4 ± 0.15 ° is the maximum peak intensity within the range of 2θ = 28.4 ± 0.15 ° to 2θ = 26.5 ° ± 0.3. It is a value obtained by dividing by the intensity of ° and multiplying by 100.

By using the catalyst of the present invention, it is possible to obtain a high yield at a low reaction bath temperature when an unsaturated aldehyde compound or an unsaturated carboxylic acid compound is oxidatively produced.

Claims (10)

The maximum peak intensity within the range of the X-ray diffraction angle 2θ = 26.5 ± 0.3 ° in the X-ray diffraction pattern when molybdenum, bismuth, and cobalt are contained as essential components and the catalyst is fired at 550 ° C. A catalyst having a maximum peak intensity ratio (J) in the range of 2θ = 28.4 ± 0.15 ° to 36.0 or more and 57.5 or less. The catalyst according to claim 1, wherein the catalyst composition is represented by the following formula (1).
Mo _a1 Bi _b1 Ni _c1 Co _d1 Fe _e1 X _f1 Y _g1 Z _h1 O _i1 ... (1)
(In the formula, Mo, Bi, Ni, Co and Fe represent molybdenum, bismuth, nickel, cobalt and iron, respectively, and X represents tungsten, antimony, tin, zinc, chromium, manganese, magnesium, silica, aluminum, cerium and titanium. At least one element selected from, Y is at least one element selected from sodium, potassium, cesmuth, rubidium, and tarium, Z belongs to groups 1 to 16 of the periodic table, and Mo, Bi, Ni, It means at least one element selected from elements other than Co, Fe, X, and Y, and a1, b1, c1, d1, e1, f1, g1, h1, and i1 are molybdenum, bismuth, and nickel, respectively. , Cobalt, iron, X, Y, Z and oxygen, and when a1 = 12, 0 <b1 ≦ 7, 0 ≦ c1 ≦ 10, 0 <d1 ≦ 10, 0 <c1 + d1 ≦ 20, 0 ≦ e1 ≦ 5, 0 ≦ f1 ≦ 2, 0 ≦ g1 ≦ 3, 0 ≦ h1 ≦ 5, and i1 = values determined by the oxidation state of each element) The catalyst according to claim 2, wherein nickel is an essential component, and b1, c1, and d1 in the above formula (1) are related to the following formula (2).

0.325 ≤ c1 / (b1 + d1) ≤ 0.405 ... (2)
The X-ray diffraction angle in the X-ray diffraction pattern when firing at 540 ° C. is within the range of 2θ = 28.4 ± 0.15 ° with respect to the maximum peak intensity within the range of 2θ = 26.5 ± 0.3 °. The catalyst according to any one of claims 1 to 3, wherein the ratio (L) of the maximum peak intensity and the above (J) have a relationship of the following formula (3).

-0.133 ≤ (J-L) / 10 ≤ 0.869 ... (3)
The catalyst according to any one of claims 1 to 4, which is carried on an inert carrier. The catalyst according to claim 5, wherein the inert carrier is silica and / or alumina. The catalyst according to any one of claims 1 to 6, wherein the catalyst is for producing an unsaturated aldehyde compound and / or an unsaturated carboxylic acid compound. A method for producing an unsaturated aldehyde compound and / or an unsaturated carboxylic acid compound using the catalyst according to any one of claims 1 to 7. The production method according to claim 8, wherein the unsaturated aldehyde compound is acrolein and the unsaturated carboxylic acid compound is acrylic acid. An unsaturated aldehyde compound and / or an unsaturated carboxylic acid compound produced by using the catalyst according to any one of claims 1 to 7.