JP2020157294A - Catalyst precursor, catalyst using the same, and production method of the same - Google Patents

Abstract

To provide a catalyst used for a method for producing unsaturated aldehydes and unsaturated carboxylic acids using propylene, isobutylene, t-butyl alcohol, and the like as a raw material, or a catalyst precursor thereof, the catalyst having high catalytic activity, selectivity, and a high yield of a target product, and enabling a long-term operation of a safe, stable, and low-cost gas phase oxidation method by using the catalyst of the present invention.SOLUTION: Provided is a catalyst precursor represented by the following formula (1), having an average particle diameter of 30 μm to 70 μm and a maximum pore diameter obtained by a mercury penetration method of 0.01 μm to 20 μm. Moa1Bib1 Nic1Cod1Fee1Xf1Yg1Zh1Oi1 (1)SELECTED DRAWING: None

Description

The present invention relates to a novel catalyst having high activity and a high yield to obtain the desired product, and the catalytic activity is particularly high in the oxidative production of unsaturated aldehydes, unsaturated carboxylic acids, or conjugated diene. The present invention relates to a catalyst that enables stable and high-yield production even in a high region.

The method for producing the corresponding unsaturated aldehyde and unsaturated carboxylic acid from propylene, isobutylene, t-butyl alcohol, etc., and the vapor-phase catalytic oxidation method for producing 1,3-butadiene from butenes are industrially widespread. It has been implemented.
In particular, many reports have been made on 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 as a means for improving the yield (for example, patent). Documents 1, 2 etc.).

Even if improvements are made by means as described above, further improvement in yield is required in the production of corresponding unsaturated aldehydes and / or unsaturated carboxylic acids by partial oxidation reaction of propylene, isobutylene, t-butyl alcohol and the like. ing. 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. Further, by continuing the operation with a low yield, a large amount of by-products are produced, which imposes a heavy load on the purification process, and causes a problem that the time required for the purification process and the operation cost increase. Furthermore, depending on the type of by-products, they may deposit on the surface of the catalyst or in the gas flow path near the catalyst. Since these reduce the activity of the catalyst by covering the necessary reaction active sites on the surface of the catalyst, it is necessary to forcibly increase the activity and the reaction bath temperature must be increased. Then, the catalyst is subjected to thermal stress, which causes a decrease in life and a further decrease in selectivity, which also leads to a decrease in yield. In addition, by-products deposited in the system may cause an increase in the internal pressure, which may lead to a decrease in selectivity and a decrease in yield. In the worst case, a sudden increase in internal pressure causes a temperature abnormality and reacts. May run out of control. In that case, it is expected that the operation will be stopped for a long period of time, and it will be necessary to clean the inside of the system and replace the catalyst.

Further, particularly in the case of a gas-phase catalytic oxidation reaction using isobutylene or t-butyl alcohol as a raw material, in addition to the main product methacrolein, compounds having a relatively high boiling point such as maleic acid and terephthalic acid are by-produced. At the same time, it has a unique problem that polymers and tar-like substances are contained in the reaction-producing gas. When the reaction-producing gas containing such substances is directly subjected to the subsequent reaction, these substances cause blockage in the piping or in the latter-stage catalyst packed bed, resulting in an increase in pressure loss, a decrease in catalytic activity, and methacrylic acid. It may cause a decrease in the selectivity of. In addition, industrial production must be stopped in order to remove the blockage, which causes a great decrease in production. Such troubles often occur when the supply amount of isobutylene and / or t-butyl alcohol is increased in order to increase the productivity of methacrylic acid, or the concentration of isobutylene and / or t-butyl alcohol is increased.

As a method generally adopted to prevent such troubles, the reaction is periodically stopped, and the gas inlet side of the post-stage catalyst is filled to prevent clogging in the catalyst layer and reduction of the activity of the catalyst. The active substance can be extracted and replaced, or the metachlorine is once separated from the gas produced in the first stage reaction, and this separated metachlorine is supplied to the second stage reaction to adopt the optimization process of the oxidation reaction, or the concentration of the raw material gas. A method has been proposed in which the reaction is carried out by diluting the gas more than necessary to reduce the concentration of by-products. Patent Document 3 describes a method of keeping the temperature above the boiling point of maleic anhydride and devising a method of keeping the gas ray velocity extremely high in order to prevent blockage of pipes and the like in the intermediate part of the reaction of the first stage and the second stage. Patent Document 4 proposes a method of specifying the shape of the catalyst used in the subsequent reaction, increasing the porosity between the catalysts, and suppressing the clogging of the solid matter from the first-stage reactor. However, these methods are also not sufficiently satisfactory as industrial methods, and it is desired to develop a catalyst capable of further improving the yield.

The process of producing methacrolein and methacrylic acid in order by a two-step vapor-phase catalytic oxidation reaction using isobutylene or t-butyl alcohol as raw materials, and further producing methyl methacrylate by an esterification reaction from methacrylic acid is a direct acid method. It is called, and is expected to be a highly competitive process because it is safer and has less environmental load than other methyl methacrylate production processes, can effectively utilize the reaction heat, and can reduce the catalyst price. In the first-stage reaction of this direct acid method, that is, the reaction for producing methacrolein from isobutylene or t-butyl alcohol, isobutylene becomes a toxic substance in the second-stage reaction in the latter stage, so that the catalytic activity is increased to remain as much as possible. Isobutylene needs to be reduced. In order to increase the catalytic activity, the reaction bath temperature is increased to increase the isobutylene conversion rate, but as mentioned in Non-Patent Document 1, in a generally high isobutylene conversion rate region, the yield or selectivity of methacrolein and / or methacrylic acid is rapidly increased. Is known to decrease. That is, it is desired to develop a catalyst having a high yield of methacrolein and / or methacrylic acid even in a region having high catalytic activity.

International Publication 2016/136882 Japanese Unexamined Patent Publication No. 2017-024009 Japanese Unexamined Patent Publication No. 50-126605 Japanese Unexamined Patent Publication No. 61-22149

Journal of Catalysis 236 No. 282-291 (2005)

The present invention provides a method for producing the corresponding unsaturated aldehyde and unsaturated carboxylic acid using propylene, isobutylene, t-butyl alcohol, etc. as raw materials, and a vapor-phase catalytic oxidation method for producing 1,3-butadiene from butenes. It proposes a catalyst to be used, which has high selectivity and a high yield of a target product even in a region where the catalytic activity is particularly high. 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 studies of the present inventors, the final catalyst performance when the average particle size and the maximum pore diameter of the catalyst precursor obtained by drying the mixed solution of the catalyst active ingredient raw materials or the slurry are in a specific range, In particular, they have found that the catalytic activity is significantly improved, and have completed the present invention.

That is, the present invention relates to the following 1) to 11).
1)
A catalyst precursor represented by the following formula (1), which has an average particle diameter of 30 μm or more and 70 μm or less, and a maximum pore diameter obtained by a mercury intrusion method of 0.01 μm or more and 20 μm or less.
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, silicon, 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 ≦ c + d ≦ 20, 0 ≦ e ≦ 5, 0 ≦ f ≦ 2, 0 ≦ g ≦ 3, 0 ≦ h ≦ 5, and i = values determined by the oxidation state of each element)
2)
Further, the catalyst precursor according to 1) above, wherein the cumulative pore volume is 1.05 cc / g or more and 10 cc / g or less.
3)
A catalyst obtained by molding the catalyst precursor according to 1) or 2) above.
4)
A catalyst in which the catalyst precursor according to 1) or 2) above is supported on an inert carrier.
5)
The catalyst according to 4) above, wherein the inert carrier is silica and / or alumina.
6)
The catalyst according to any one of 1) to 5) above, wherein the catalyst is for producing an unsaturated aldehyde compound and / or an unsaturated carboxylic acid compound.
7)
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 6) above.
8)
The method for producing an unsaturated aldehyde compound and / or an unsaturated carboxylic acid compound having a raw material conversion rate of 98.5% or more in 7) above.
9)
The production method in which the unsaturated aldehyde compound is methacrolein and the unsaturated carboxylic acid compound is methacrylic acid in the above 7) to 8).
10)
A method for producing a catalyst using the catalyst precursor according to 1) or 2) above.
11)
The catalyst according to 3) to 6) above, wherein the catalyst precursor is a pre-baked powder obtained by pre-baking a mixed solution or slurry of a catalyst active ingredient raw material at a temperature of 200 to 600 ° C.

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 using propylene, isobutylene, t-butyl alcohol and the like as raw materials. It is particularly useful as an oxidation catalyst and an oxidation dehydrogenation catalyst for producing an acid or for producing a conjugated diolefin by a catalytic redox reaction from a mixed gas containing a monoolefin having 4 or more carbon atoms and molecular oxygen. ..
In particular, it is effectively used when producing the corresponding unsaturated aldehyde from propylene, isobutylene, t-butyl alcohol or the like as a raw material. In addition, the catalyst of the present invention is effective in improving the yield even in a region where the catalytic activity is not high, and the process stability of a partial oxidation reaction accompanied by heat generation such as reduction of ΔT (difference between hot spot temperature and reaction bath temperature). The improvement effect is also seen in.

The present invention relates to a catalyst having particularly high catalytic activity and a method for producing the same, but the catalyst precursor itself can also be produced because the catalyst precursor can be produced via the catalyst precursor or the catalyst precursor can be used as it is as an oxidation catalyst. Described as the present invention.
[Average particle size is 30 μm or more and 70 μm or less]
The catalyst precursor of the present invention has an average particle size of 30 μm or more and 70 μm or less.
The average particle size is obtained by measuring the particle size distribution from a laser diffraction / scattering particle size distribution measuring device (manufactured by Seishin Enterprise Co., Ltd., trade name "LMS-2000e") and calculating the volume average (median size).
When the average particle size is out of the range of 30 μm or more and 70 μm, the performance when used as a catalyst is not stable, and as a result, the catalytic activity may be lowered.
The lower limit of the preferable range of the average particle size is 35 μm, more preferably 38 μm. The upper limit is preferably 60 μm, more preferably 50 μm. That is, the most preferable range for the average particle size is 38 μm or more and 50 μm or less.
Generally, in order to change the above parameters regarding the catalyst precursor, it can be realized by adjusting the pH in the compounding step and setting the temperature in the drying step, but a particularly effective method is a sprayer in the case of spray drying (a sprayer ( It is the optimization of the number of rotations of the atomizer). The rotation of the atomizer varies depending on the composition of the catalyst precursor, but is preferably 12,000 rpm or more and 17,000 rpm or less. A more preferable upper limit of the atomizer rotation speed is 16500 pm, particularly preferably 16000 rpm, and most preferably 15500 rpm. A further preferable lower limit is 12500 rpm, a particularly preferable lower limit is 13000 rpm, and the most preferable lower limit is 13500 rpm. That is, the most preferable range of atomizer rotation speed is 13500 rpm or more and 15500 rpm or less. This rotation speed is also represented by the relative centrifugal acceleration, and is preferably 2000 G or more and 30,000 G or less.

[Maximum pore diameter obtained by mercury injection method is 0.01 μm or more and 20 μm or less]
The catalyst precursor of the present invention has a maximum pore diameter of 0.01 μm or more and 20 μm or less, which is obtained by the mercury intrusion method.
Here, the mercury press-fitting method applies pressure to mercury having a high surface tension and press-fits it into the pores or gaps on the solid surface, and the pore distribution is based on the relationship between the pressure applied at that time and the pushed mercury volume. Is a method of finding. In the present specification, the mercury press-fitting method is not particularly limited as long as it is a general method, but for example, a fully automatic pore distribution measuring device (Pore Master 60-GT (Quanta Chrome)) without pretreatment is performed. Using Co.)), a sample weight of about 0.5 g was placed in a small cell (10 mmΦ × 3 cm) having a cell volume of 0.5 cc, the mercury surface tension was set to 480 dyn / cm, and the mercury contact angle was set to 140 ° for measurement. Measurement was performed under the conditions of a temperature of 20 ° C. and a measurement pore diameter range of 0.0036 μm to 400 μm, and the measurement results were analyzed using the pressure applied at the time of measurement and the Washburn formula, assuming that all pores were cylindrical. There is a method of obtaining the pore distribution of each pore diameter of the catalyst precursor.
The Washburn formula is the following formula (I) showing the relationship between the pressure applied at the time of measurement and the pore diameter at which mercury can penetrate at that pressure.

R = -4 × γ × cos θ ÷ p ÷ 6.9 ... (I)

(In the above formula (I), R is the pore diameter (unit: μm), γ is the mercury surface tension (unit: dyn / cm), θ is the mercury contact angle (unit: °), and p is the pressure applied during measurement. (Unit: psi) is shown.)
From the obtained pore distribution, the maximum pore diameter (D1) can be obtained. The maximum pore diameter (D1) can be obtained from the frequency distribution of the pore distribution as the pore diameter having the largest appearance ratio, that is, the pore diameter having the maximum value of the distribution.
In order to make the effect of the present invention more remarkable, the upper limit of the maximum pore diameter (D1) is preferably 18 μm, more preferably 15 μm, and particularly preferably 14 μm. The lower limit is preferably 0.1 μm, more preferably 1 μm, and particularly preferably 5 μm. That is, the most preferable range is 5 μm or more and 14 μm or less.

[composition]
The catalyst precursor of the present invention 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, silicon, 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 i = values determined by the oxidation state of each element)

In the above formula (1), the preferable range of b1 to h1 is as follows.
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.
Further preferable ranges are as follows.
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.

[Cumulative pore volume is 1.05 cc / g or more and 10 cc / g or less]
The catalyst precursor of the present invention preferably has a cumulative pore volume of 1.05 cc / g or more and 10 cc / g or less. The cumulative pore volume is one of the parameters indicating fine pore properties, and the measuring method thereof is not particularly limited, but it is preferably measured by the above-mentioned mercury intrusion method. Further, it is preferable to calculate the measured value from the pore distribution data having a pore diameter of 0.0036 μm or more and 400 μm or less.
The preferable range of the cumulative pore volume is 1.08 cc / g or more and 8 cc / g or less, and the more preferable range is 1.10 cc / g or more and 5 cc / g or less.

The catalyst precursor of the present invention is granules before the step of molding the catalyst, and a slurry obtained by mixing raw materials containing each element constituting the catalyst is produced by, for example, drum drying, spray drying, evaporation drying, etc. It is made into granules using. As a drying method, spray drying, which allows the slurry to be dried into granules in a short time, is particularly preferable.
The drying temperature is not particularly limited as long as it can remove water, and when adjusting the pressure and time, it may be at room temperature (25 ° C), but more reliably and in a short time. In order to remove it, it is preferably 80 ° C. or higher, and more preferably 90 ° C. or higher. When the pressure is not adjusted, the temperature is preferably 100 ° C. or higher, more preferably 150 ° C. or higher.
As will be described in detail in the description of the manufacturing process, the catalyst precursor can be further pre-baked, and in this case, firing is performed at a temperature of about 200 ° C to 600 ° C for about 1 to 12 hours. The powder after the pre-baking is also defined as a catalyst precursor in the present application, but may be described as a pre-firing powder in order to express that the pre-baking has been performed.

[About support]
The catalyst in which the catalyst precursor is supported on an inert carrier has high activity 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 catalyst precursor is calculated as the loading ratio from the following formula based on the charged mass of each raw material.
Support rate (mass%) = (mass of catalyst precursor used for molding) / {(mass of catalyst precursor used for molding) + (mass of carrier used for molding)} × 100
The preferred upper limit of the loading ratio is 90%, more preferably 80%.
The lower limit is preferably 20%, more preferably 30%.

[Catalyst manufacturing method, etc.]
The starting material for the catalyst precursor of the present invention and each element constituting the catalyst is not particularly limited, but for example, the raw material for the molybdate component is molybdate oxide such as molybdenum trioxide, molybdic acid, or paramolybdic acid. Molybdic acids such as ammonium and ammonium metamolybdate or salts thereof, heteropolyacids containing molybdenum such as phosphomolybdic acid and silicate molybdate or salts 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.

The raw material of the alkali metal which is the Y component represented by the general formula (1) is not limited to these, but the hydroxides, chlorides and carbonates of the component elements (lithium, sodium, potassium, rubidium, cesium). , Sulfates, nitrates, oxides, acetates and the like. A compound containing cesium is preferable, and examples thereof include cesium hydroxide, cesium chloride, cesium carbonate, cesium sulfate, and cesium oxide. In particular, cesium nitrate is preferably used, and its atomic ratio g1 is 0 ≦. It is g1 ≦ 3, preferably 0.1 ≦ g1 ≦ 2, and more preferably 0.3 ≦ g1 ≦ 1.

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 200 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. Further, the nitrate ion concentration in the slurry liquid immediately before the final drying is 8.0% by mass or more and 50% by mass or less, preferably 9.0% by mass or more and 45% by mass or less, more preferably 10.0% by mass. It is 40% by mass or more, most preferably 11.0% by mass or more and 30% by mass or less, and similarly, the ammonium ion concentration in the slurry liquid immediately before drying is 1.0% by mass or more and 10% by mass or less, preferably 10% by mass or less. It is 1.2% by mass or more and 8% by mass or less, more preferably 1.5% by mass or more and 6% by mass or less, and most preferably 1.7% by mass or more and 4% by mass or less.

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 certain period of time and a certain temperature to acquire, increase, or increase a predetermined physical property or a predetermined reaction. 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.

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 used. 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. Optimal conditions for pre-baking and main firing differ depending on the catalyst raw material used, catalyst composition, preparation method, etc., but are usually 200 ° C. or higher and 600 ° C. or lower, preferably under the flow of an oxygen-containing gas such as air or the flow of an inert gas. Is performed at 300 ° C. or higher and 550 ° C. or lower for 0.5 hours or longer, preferably 1 hour or longer and 40 hours or shorter. 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. In particular, the present firing is an important step in determining the activity of the catalyst in the present invention, but when the activity of the catalyst is low or high, the process parameters of the main firing step, that is, the oxygen content in the atmosphere, the maximum temperature reached, and the like. It is known to those skilled in the art that the activity is adjusted by changing the firing time or the like to bring out the highest yield of the composition, and 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 catalyst of the present invention is preferably used as a catalyst for producing an unsaturated aldehyde compound and 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 preferable to use it as a catalyst for producing methacrolein from isobutylene.

[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 (2).
Mo ₁₀ V _a2 P _b2 Cu _c2 Cs _d2 (NH ₄ ) _e2 X _f2 O _g2 (2)
(In the formula, Mo is molybdenum, V is vanadium, P is phosphorus, Cu is copper, Cs is cesium, (NH4) is an ammonium group, and X is Sb, As, Ag, Mg, Zn, Al, B, Ge, Sn. , Pb, Ti, Zr, Cr, Re, Bi, W, Fe, Co, Ni, Ce, Th, K and Rb, respectively, representing one or more elements selected from the group, and a2 to g2, respectively. A2 is a positive number of 0.1 ≦ a2 ≦ 6.0, b2 is a positive number of 0.5 ≦ b2 ≦ 6.0, and c2 is a positive number of 0 ≦ c2 ≦ 3.0. , D2 is a positive number of 0 ≦ d2 ≦ 3.0, e2 is a positive number of 0 ≦ e2 ≦ 3.0, and f2 is a positive number of 0 ≦ f2 ≦ 3.0. G2 is the valence of each element. It is a value determined by.)

In the production of the catalyst of the present invention and the catalyst represented by the above formula (2), 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, ammonium molybdate, molybdic acid, molybdenum oxide and the like can be used as the molybdate compound, ammonium metavanadate, vanadium pentoxide and the like can be used as the vanadium compound, and phosphoric acid or a salt thereof and polymerization can be used as the phosphorus compound. Phosphate or a salt thereof can be used, and as the copper compound, copper oxide, copper phosphate, copper sulfate, copper nitrate, copper molybdate, copper metal, etc. can be used, and antimony, arsenic, silver, magnesium, zinc, aluminum, etc. Boron, germanium, tin, lead, titanium, zirconium, chromium, renium, bismuth, tungsten, iron, cobalt, nickel, cerium, thorium, potassium and rubidium compounds include nitrates, sulfates, carbonates and phosphates, respectively. , Organic acid salts, halides, hydroxides, oxides, metals 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, the dried slurry liquid obtained at this time is preferably dried so that the average particle size is 1 to 700 μm, and more preferably 5 to 500 μm.

Among the catalytically active component solids in the second stage of the present invention, particularly preferable ones are catalysts having a heteropolyacid structure. The catalyst having this heteropolyacid structure has limbanado molybdic acid as the basic skeleton, and other constituent elements are incorporated into the heteropolyacid structure, which contributes to the improvement of catalytic activity and selectivity, and the thermal stability of the structure. It is thought that it also contributes to the improvement of sex. The catalyst having this heteropolyacid structure is a catalyst having a particularly long life. A catalyst having a heteropolyacid structure can be easily prepared by a general method for preparing a heteropolyacid.

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.

Further, in the present invention, the compound containing the active ingredient when preparing the slurry of the second stage does not necessarily have to contain all the active ingredients, and some of the ingredients are used before the following coating step. You may.

The shape of the catalyst in the second stage of the present invention is not particularly limited, and in order to reduce the pressure loss of the reaction gas in the oxidation reaction, it is molded into a columnar shape, a tablet, a ring shape, a spherical shape or the like and used. Of these, since improvement in selectivity and removal of heat of reaction can be expected, it is particularly preferable to coat the inert carrier with the catalytically active component solid to serve as a coating catalyst. The rolling granulation method described below is preferable for this coating step. 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 coating a carrier with a binder, a catalyst active ingredient solid, and, if necessary, a coating 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 coating mixture, 2) it is added at the same time as the coating mixture is added into the fixed container, and 3) it is added after the coating mixture is added into the fixed container. 4) Addition before adding the coating mixture into the fixed container, 5) Dividing the coating mixture and the binder, and adding 2) to 4) in appropriate combination can be arbitrarily adopted. .. Of these, in 5), for example, the addition rate is adjusted by using an auto feeder or the like so that the coating mixture does not adhere to the fixed container wall and the coating mixture does not aggregate with each other and a predetermined amount is supported on the carrier. Is preferable. The binder is not particularly limited as long as it is at least one selected from the group consisting of water and an organic compound having a boiling point of 150 ° C. or less at 1 atm or less. Specific examples of binders other than water include alcohols such as methanol, ethanol, propanols and butanols, preferably alcohols having 1 to 4 carbon atoms, ethers such as ethyl ether, butyl ether or dioxane, and esters such as ethyl acetate or butyl acetate. , Acetone, ketones such as methyl ethyl ketone, and aqueous solutions thereof, and ethanol is particularly preferable. When ethanol is used as the binder, ethanol / water = 10/0 to 0/10 (mass ratio), preferably 9/1 to 1/9 (mass ratio) mixed with water. 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 coating mixture.

Specific examples of the carrier in the coating 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 arundum. As these carriers, those having a porosity of 10 to 70% are usually used. The ratio of the carrier to the coating mixture is usually such that the coating mixture / (coating mixture + carrier) = 10 to 75% by mass, preferably 15 to 60% by mass. When the proportion of the coating mixture is large, the reaction activity of the coating catalyst is large, but the mechanical strength tends to be small. On the contrary, when the ratio of the coating 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 coating 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 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 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. By supporting the catalyst used in the present invention on a carrier, favorable effects such as heat resistance, improvement in life, and increase in reaction yield can be expected. As the material of the 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 each crystal phase thereof. There are no particular restrictions on the degree of crystallization and mixing ratio of the material, and an appropriate range should be selected in consideration of the final catalyst performance, moldability, production efficiency, and the like.

A reaction for producing a corresponding unsaturated aldehyde or unsaturated carboxylic acid using the catalyst of the present invention as a raw material of propylene, isobutylene, t-butyl alcohol or the like, particularly isobutylene or t-butyl alcohol containing molecular oxygen or molecular oxygen. In the reaction for producing methacrolein and methacrolein by vapor-phase catalytic oxidation with gas, the by-product of aromatic compounds (particularly terephthalic acid) is effectively suppressed, and the temperature of hot spots is suppressed to have high catalytic activity. As a result, the target product can be produced in a high yield, and as a result, a high yield can be realized in a region where the catalytic activity is high as compared with the known methods, and the price competitiveness of the product can be expected to be improved. In addition, the catalyst of the present invention is effective in improving the yield even in a region where the catalytic activity is not high, and the process stability of a partial oxidation reaction accompanied by heat generation such as reduction of ΔT (difference between hot spot temperature and reaction bath temperature). The improvement effect is also seen in. In addition, the catalyst of the present invention reduces by-products that adversely affect the environment and the quality of the final product methyl methacrylate, such as carbon monoxide (CO) and carbon dioxide (CO ₂ ), acetaldehyde and acetic acid, acrolein and formaldehyde. It is also effective for.

The catalyst of the present invention thus obtained is obtained by vapor-phase catalytic oxidation of at least one raw material selected from, for example, isobutylene and t-butyl alcohol in the presence of an oxidation catalyst composition using a molecular oxygen-containing gas. It can be used in the production of methacrolein and / or methacrylic acid. 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, isobutylene as a starting material is 1 to 10% by volume, preferably 4 to 9% by volume, more preferably 4 to 7.5% by volume, most preferably 4 to 6% by volume, and molecular oxygen is 3 to 3 to 10% by volume at room temperature. 20% by volume, preferably 4 to 18% by volume, water vapor 0 to 60% by volume, preferably 4 to 50% by volume, 20 to 80% by volume of inert gas such as carbon dioxide and nitrogen, preferably 30 to 60% by volume. The reaction is carried out by introducing a mixed gas composed of% in a reaction tube on the catalyst of the present invention at 250 to 450 ° C. under a pressure of normal pressure to 10 atm and a space velocity of 300 to 5000 h- ¹ . When the reaction is carried out in a region having high catalytic activity as in the present invention, the isobutylene concentration in the raw material gas is generally low, the oxygen concentration is high, the water vapor concentration is high, the space velocity is low, the reaction bath temperature is high, and the reaction tube outlet. It is preferable to control the pressure to a high level, but these are often in a trade-off relationship with productivity and / or catalytic performance as an industrial catalyst, and should be provided in an optimum range.

In the present invention, the region having high catalytic activity refers to a reaction bath temperature region having a high raw material conversion rate unless otherwise specified, and is synonymous with a high raw material conversion rate region. More specifically, the region having high catalytic activity refers to a region having a raw material conversion rate of 98.5% or more. It was found that increasing the reaction bath temperature increases the raw material conversion rate, but for example, in the first-stage reaction of the direct acid method, the methacrolein and / or methacrylic acid yield or selectivity decreases sharply. Was there. However, when the catalyst precursor or the supported catalyst of the present invention is used, a high conversion rate can be realized even if the reaction bath temperature is set low. This is because the activity of the catalyst is high.
In the present invention, the high yield means that the total yield of methacrolein and / or methacrylic acid is high in the region where the catalytic activity is high, unless otherwise specified.
In the present invention, the constituent elements of the catalytically active component refer to all the elements contained in the catalyst raw material solution containing molybdenum as the main component and the catalyst raw material slurry liquid in the catalyst manufacturing step before the drying step, unless otherwise specified. However, raw materials that disappear, sublimate, volatilize, and burn at 200 ° C. or lower and their constituent elements are not included in the constituent elements of the active component of the catalyst. For example, a silicon raw material such as fumed silica added at the time of preparation of a raw material slurry liquid is contained as a constituent element of a catalytically active component, but is an element constituting silicon and other inorganic materials contained in a molding aid and a carrier in a molding process. Is not included as a constituent element of the active component of the catalyst.
In the present invention, ΔT is a value obtained by subtracting the reaction bath temperature (BT) from the catalyst hotspot temperature (PT), and is a guideline for the amount of heat generated at the most heat-generating portion in the partially oxidized catalytic reaction accompanied by heat generation. Is shown. PT is the maximum temperature of the temperature distribution in the catalyst packed bed to be measured by installing a thermocouple in the long axis direction in the multi-tube reaction tube, and BT is used for the purpose of cooling the heat generation of the reaction tube. This is the set temperature of the heat medium. 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. In the present invention, the conjugated diene compound is an organic compound having at least two double bonds in the molecule, for example, 1,3-butadiene and 1,3-pentadiene.

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 t-butyl alcohol or isobutylene) / (number of moles of supplied t-butyl alcohol or isobutylene) x 100
Effective yield (%) = (total number of moles of methacrolein and methacrylic acid produced) / (number of moles of supplied t-butyl alcohol or isobutylene) x 100
Support rate (mass%) = (mass of catalyst precursor used for molding) / {(mass of catalyst precursor used for molding) + (mass of carrier used for molding)} × 100

The properties of the catalyst precursor in Table 2 below were evaluated as follows.

Average particle size of catalyst precursor L1:
The particle size distribution was measured by a laser diffraction / scattering particle size distribution measuring device (manufactured by Seishin Enterprise Co., Ltd., trade name "LMS-2000e"), and the particle size distribution was determined as the volume average (median diameter).

Maximum maximum diameter of catalyst precursor D1:
Using a fully automatic pore distribution measuring device (Pore Master 60-GT (Quanta Chrome Co.)), a sample weight of about 0.5 g is placed in a small cell (10 mmΦ × 3 cm) having a cell volume of 0.5 cc, and the mercury surface tension Is set to 480 dyn / cm, the mercury contact angle is set to 140 °, the measurement is performed under the conditions of a measurement temperature of 20 ° C. and a measurement pore diameter range of 0.0036 μm to 400 μm, and the measurement result is that all pores are cylindrical. The pressure applied at the time of measurement and the Washburn formula were used for analysis, and the pore distribution of each pore diameter of the catalyst precursor was determined.

Cumulative pore volume of catalyst precursor V1:
Using a fully automatic pore distribution measuring device (Pore Master 60-GT (Quanta Chrome Co.)), a sample weight of about 0.5 g is placed in a small cell (10 mmΦ × 3 cm) having a cell volume of 0.5 cc, and the surface tension of mercury. Is set to 480 dyn / cm, the mercury contact angle is set to 140 °, the measurement is performed under the conditions of a measurement temperature of 20 ° C. and a measurement pore diameter range of 0.0036 μm to 400 μm, and during measurement, inside the pores or gaps on the solid surface. The cumulative pore volume was determined by dividing the total volume of the indented mercury by the sample weight.

The CO ₂ yield in Table 2 was calculated according to the following formula.
CO ₂ yield (%) = (number of moles of CO ₂ produced) / (number of moles of supplied t-butyl alcohol or isobutylene) x 100

[Example 1] (Preparation of catalyst 1)
100 parts by mass of ammonium heptamolybdate was completely dissolved in 380 parts by mass of pure water heated to 80 ° C. (mother solution 1). Next, 3.7 parts by mass of cesium nitrate was dissolved in 42 ml 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 ml 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 ml 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 at an atomizer rotation speed of 15,000 rpm, and the obtained dry powder was pre-baked at 440 ° C. for 5 hours. The catalyst precursor thus obtained (the atomic ratio calculated from the charged raw material is Mo: Bi: Fe: Co: Ni: Cs = 12: 0.9: 2.0: 6.5: 2.4: 0.4. ), 5% by mass of crystalline cellulose was added, and the mixture was sufficiently mixed. Then, 40% by mass of a 25% by mass glycerin solution was used as a binder by the rolling granulation method with respect to the catalyst precursor, and the mixture was inert. The carrier was supported and molded into a spherical shape so that the carrying ratio was 40% by mass. The spherical molded product having a particle size of 4.4 mm thus obtained was fired at 550 ° C. for 5 hours to obtain the catalyst 1 of the present invention.

[Example 2] (Preparation of catalyst 2)
100 parts by mass of ammonium heptamolybdate was completely dissolved in 380 parts by mass of pure water heated to 80 ° C. (mother solution 1). Next, 3.7 parts by mass of cesium nitrate was dissolved in 42 ml 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 ml 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 ml 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 at an atomizer rotation speed of 15,000 rpm, and the obtained dry powder was pre-baked at 440 ° C. for 5 hours. The catalyst precursor thus obtained (the atomic ratio calculated from the charged raw material is Mo: Bi: Fe: Co: Ni: Cs = 12: 0.9: 2.0: 6.5: 2.4: 0.4. ), 5% by mass of crystalline cellulose was added, and the mixture was sufficiently mixed. Then, 40% by mass of a 25% by mass glycerin solution was used as a binder by the rolling granulation method with respect to the catalyst precursor, and the mixture was inert. The carrier was supported and molded into a spherical shape so that the carrying ratio was 40% by mass. The spherical molded product having a particle size of 4.4 mm thus obtained was fired at 545 ° C. for 5 hours to obtain the catalyst 2 of the present invention.

[Example 3] (Preparation of catalyst 3)
100 parts by mass of ammonium heptamolybdate was completely dissolved in 380 parts by mass of pure water heated to 80 ° C. (mother solution 1). Next, 3.7 parts by mass of cesium nitrate was dissolved in 42 ml 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 ml 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 ml 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 at an atomizer rotation speed of 15,000 rpm, and the obtained dry powder was pre-baked at 440 ° C. for 5 hours. The catalyst precursor thus obtained (the atomic ratio calculated from the charged raw material is Mo: Bi: Fe: Co: Ni: Cs = 12: 0.9: 2.0: 6.5: 2.4: 0.4. ), 5% by mass of crystalline cellulose was added, and the mixture was sufficiently mixed. Then, 40% by mass of a 25% by mass glycerin solution was used as a binder by the rolling granulation method with respect to the catalyst precursor, and the mixture was inert. The carrier was supported and molded into a spherical shape so that the carrying ratio was 40% by mass. The spherical molded product having a particle size of 4.4 mm thus obtained was fired at 555 ° C. for 5 hours to obtain the catalyst 3 of the present invention.

[Example 4] (Preparation of catalyst 4)
100 parts by mass of ammonium heptamolybdate was completely dissolved in 380 parts by mass of pure water heated to 80 ° C. (mother solution 1). Next, 3.7 parts by mass of cesium nitrate was dissolved in 42 ml 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 ml 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 ml 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 at an atomizer rotation speed of 15,000 rpm, and the obtained dry powder was pre-baked at 440 ° C. for 5 hours. The catalyst precursor thus obtained (the atomic ratio calculated from the charged raw material is Mo: Bi: Fe: Co: Ni: Cs = 12: 0.9: 2.0: 6.5: 2.4: 0.4. ), 5% by mass of crystalline cellulose was added, and the mixture was sufficiently mixed. Then, 40% by mass of a 25% by mass glycerin solution was used as a binder by the rolling granulation method with respect to the catalyst precursor, and the mixture was inert. The carrier was supported and molded into a spherical shape so that the carrying ratio was 50% by mass. The spherical molded product having a particle size of 4.4 mm thus obtained was fired at 540 ° C. for 5 hours to obtain the catalyst 4 of the present invention.

[Example 5] (Preparation of catalyst 5)
100 parts by mass of ammonium heptamolybdate was completely dissolved in 380 parts by mass of pure water heated to 80 ° C. (mother solution 1). Next, 3.7 parts by mass of cesium nitrate was dissolved in 42 ml 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 ml 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 ml 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 at an atomizer rotation speed of 13000 rpm, and the obtained dry powder was pre-baked at 440 ° C. for 5 hours. The catalyst precursor thus obtained (the atomic ratio calculated from the charged raw material is Mo: Bi: Fe: Co: Ni: Cs = 12: 0.9: 2.0: 6.5: 2.4: 0.4. ), 5% by mass of crystalline cellulose was added, and the mixture was sufficiently mixed. Then, a 25% by mass glycerin solution was used as a binder by the rolling granulation method in an inert manner using 40% by mass with respect to the catalyst precursor. The carrier was supported and molded into a spherical shape so that the carrying ratio was 40% by mass. The spherical molded product having a particle size of 4.4 mm thus obtained was fired at 545 ° C. for 5 hours to obtain the catalyst 5 of the present invention.

[Example 6] (Preparation of catalyst 6)
100 parts by mass of ammonium heptamolybdate was completely dissolved in 380 parts by mass of pure water heated to 80 ° C. (mother solution 1). Next, 3.7 parts by mass of cesium nitrate was dissolved in 42 ml 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 ml 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 ml 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 at an atomizer rotation speed of 13000 rpm, and the obtained dry powder was pre-baked at 440 ° C. for 5 hours. The catalyst precursor thus obtained (the atomic ratio calculated from the charged raw material is Mo: Bi: Fe: Co: Ni: Cs = 12: 0.9: 2.0: 6.5: 2.4: 0.4. ), 5% by mass of crystalline cellulose was added, and the mixture was sufficiently mixed. Then, 40% by mass of a 25% by mass glycerin solution was used as a binder by the rolling granulation method with respect to the catalyst precursor, and the mixture was inert. The carrier was supported and molded into a spherical shape so that the carrying ratio was 40% by mass. The spherical molded product having a particle size of 4.4 mm thus obtained was fired at 535 ° C. for 5 hours to obtain the catalyst 6 of the present invention.

[Comparative Example 1] (Preparation of catalyst 7)
100 parts by mass of ammonium heptamolybdate was completely dissolved in 380 parts by mass of pure water heated to 80 ° C. (mother solution 1). Next, 3.7 parts by mass of cesium nitrate was dissolved in 42 ml 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 ml 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 ml 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 at an atomizer rotation speed of 11000 rpm, and the obtained dry powder was pre-baked at 440 ° C. for 5 hours. The catalyst precursor thus obtained (the atomic ratio calculated from the charged raw material is Mo: Bi: Fe: Co: Ni: Cs = 12: 0.9: 2.0: 6.5: 2.4: 0.4. ), 5% by mass of crystalline cellulose was added, and the mixture was sufficiently mixed. Then, 40% by mass of a 25% by mass glycerin solution was used as a binder by the rolling granulation method with respect to the catalyst precursor, and the mixture was inert. The carrier was supported and molded into a spherical shape so that the carrying ratio was 40% by mass. The spherical molded product having a particle size of 4.4 mm thus obtained was fired at 545 ° C. for 5 hours to obtain the catalyst 7 of the present invention.

[Comparative Example 2] (Preparation of catalyst 8)
100 parts by mass of ammonium heptamolybdate was completely dissolved in 380 parts by mass of pure water heated to 80 ° C. (mother solution 1). Next, 3.7 parts by mass of cesium nitrate was dissolved in 42 ml 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 ml 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 ml 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 at an atomizer rotation speed of 11000 rpm, and the obtained dry powder was pre-baked at 440 ° C. for 5 hours. The catalyst precursor thus obtained (the atomic ratio calculated from the charged raw material is Mo: Bi: Fe: Co: Ni: Cs = 12: 0.9: 2.0: 6.5: 2.4: 0.4. ), 5% by mass of crystalline cellulose was added, and the mixture was sufficiently mixed. Then, 40% by mass of a 25% by mass glycerin solution was used as a binder by the rolling granulation method with respect to the catalyst precursor, and the mixture was inert. The carrier was supported and molded into a spherical shape so that the carrying ratio was 40% by mass. The spherical molded product having a particle size of 4.4 mm thus obtained was fired at 550 ° C. for 5 hours to obtain the catalyst 8 of the present invention.

[Comparative Example 3] (Preparation of catalyst 9)
100 parts by mass of ammonium heptamolybdate was completely dissolved in 380 parts by mass of pure water heated to 80 ° C. (mother solution 1). Next, 3.7 parts by mass of cesium nitrate was dissolved in 42 ml 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 ml 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 ml 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 at an atomizer rotation speed of 11000 rpm, and the obtained dry powder was pre-baked at 440 ° C. for 5 hours. The catalyst precursor thus obtained (the atomic ratio calculated from the charged raw material is Mo: Bi: Fe: Co: Ni: Cs = 12: 0.9: 2.0: 6.5: 2.4: 0.4. ), 5% by mass of crystalline cellulose was added, and the mixture was sufficiently mixed. Then, 40% by mass of a 25% by mass glycerin solution was used as a binder by the rolling granulation method with respect to the catalyst precursor, and the mixture was inert. The carrier was supported and molded into a spherical shape so that the carrying ratio was 40% by mass. The spherical molded product having a particle size of 4.4 mm thus obtained was fired at 540 ° C. for 5 hours to obtain the catalyst 9 of the present invention.

[Comparative Example 4] (Preparation of catalyst 10)
100 parts by mass of ammonium heptamolybdate was completely dissolved in 380 parts by mass of pure water heated to 80 ° C. (mother solution 1). Next, 3.7 parts by mass of cesium nitrate was dissolved in 42 ml 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 ml 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 ml 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 at an atomizer rotation speed of 11000 rpm, and the obtained dry powder was pre-baked at 440 ° C. for 5 hours. The catalyst precursor thus obtained (the atomic ratio calculated from the charged raw material is Mo: Bi: Fe: Co: Ni: Cs = 12: 0.9: 2.0: 6.5: 2.4: 0.4. ), 5% by mass of crystalline cellulose was added, and the mixture was sufficiently mixed. Then, 40% by mass of a 25% by mass glycerin solution was used as a binder by the rolling granulation method with respect to the catalyst precursor, and the mixture was inert. The carrier was supported and molded into a spherical shape so that the carrying ratio was 40% by mass. The spherical molded product having a particle size of 4.4 mm thus obtained was fired at 535 ° C. for 5 hours to obtain the catalyst 10 of the present invention.

[Example 7] (Preparation of catalyst 11)
100 parts by mass of ammonium heptamolybdate was completely dissolved in 380 parts by mass of pure water heated to 80 ° C. (mother solution 1). Next, 3.7 parts by mass of cesium nitrate was dissolved in 42 ml 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 ml 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 ml 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 at an atomizer rotation speed of 17,000 rpm, and the obtained dry powder was pre-baked at 440 ° C. for 5 hours. The catalyst precursor thus obtained (the atomic ratio calculated from the charged raw material is Mo: Bi: Fe: Co: Ni: Cs = 12: 0.9: 2.0: 6.5: 2.4: 0.4. ), 5% by mass of crystalline cellulose was added, and the mixture was sufficiently mixed. Then, 40% by mass of a 25% by mass glycerin solution was used as a binder by the rolling granulation method with respect to the catalyst precursor, and the mixture was inert. The carrier was supported and molded into a spherical shape so that the carrying ratio was 40% by mass. The spherical molded product having a particle size of 4.4 mm thus obtained was fired at 540 ° C. for 5 hours to obtain the catalyst 11 of the present invention.

[Example 8] (Preparation of catalyst 12)
100 parts by mass of ammonium heptamolybdate was completely dissolved in 380 parts by mass of pure water heated to 80 ° C. (mother solution 1). Next, 3.7 parts by mass of cesium nitrate was dissolved in 42 ml 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 ml 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 ml 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 at an atomizer rotation speed of 17,000 rpm, and the obtained dry powder was pre-baked at 440 ° C. for 5 hours. The catalyst precursor thus obtained (the atomic ratio calculated from the charged raw material is Mo: Bi: Fe: Co: Ni: Cs = 12: 0.9: 2.0: 6.5: 2.4: 0.4. ), 5% by mass of crystalline cellulose was added, and the mixture was sufficiently mixed. Then, 40% by mass of a 25% by mass glycerin solution was used as a binder by the rolling granulation method with respect to the catalyst precursor, and the mixture was inert. The carrier was supported and molded into a spherical shape so that the carrying ratio was 40% by mass. The spherical molded product having a particle size of 4.4 mm thus obtained was fired at 545 ° C. for 5 hours to obtain the catalyst 12 of the present invention.

[Example 9] (Preparation of catalyst 13)
100 parts by mass of ammonium heptamolybdate was completely dissolved in 380 parts by mass of pure water heated to 80 ° C. (mother solution 1). Next, 3.7 parts by mass of cesium nitrate was dissolved in 42 ml 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 ml 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 ml 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 at an atomizer rotation speed of 16000 rpm, and the obtained dry powder was pre-baked at 440 ° C. for 5 hours. The catalyst precursor thus obtained (the atomic ratio calculated from the charged raw material is Mo: Bi: Fe: Co: Ni: Cs = 12: 0.9: 2.0: 6.5: 2.4: 0.4. ), 5% by mass of crystalline cellulose was added, and the mixture was sufficiently mixed. Then, 40% by mass of a 25% by mass glycerin solution was used as a binder by the rolling granulation method with respect to the catalyst precursor, and the mixture was inert. The carrier was supported and molded into a spherical shape so that the carrying ratio was 40% by mass. The spherical molded product having a particle size of 4.4 mm thus obtained was fired at 535 ° C. for 5 hours to obtain the catalyst 13 of the present invention.

[Example 10] (Preparation of catalyst 14)
100 parts by mass of ammonium heptamolybdate was completely dissolved in 380 parts by mass of pure water heated to 80 ° C. (mother solution 1). Next, 3.7 parts by mass of cesium nitrate was dissolved in 42 ml 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 ml 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 ml 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 at an atomizer rotation speed of 16000 rpm, and the obtained dry powder was pre-baked at 440 ° C. for 5 hours. The catalyst precursor thus obtained (the atomic ratio calculated from the charged raw material is Mo: Bi: Fe: Co: Ni: Cs = 12: 0.9: 2.0: 6.5: 2.4: 0.4. ), 5% by mass of crystalline cellulose was added, and the mixture was sufficiently mixed. Then, 40% by mass of a 25% by mass glycerin solution was used as a binder by the rolling granulation method with respect to the catalyst precursor, and the mixture was inert. The carrier was supported and molded into a spherical shape so that the carrying ratio was 40% by mass. The spherical molded product having a particle size of 4.4 mm thus obtained was fired at 545 ° C. for 5 hours to obtain the catalyst 14 of the present invention.

[Example 11] (Preparation of catalyst 15)
100 parts by mass of ammonium heptamolybdate was completely dissolved in 380 parts by mass of pure water heated to 80 ° C. (mother solution 1). Next, 3.7 parts by mass of cesium nitrate was dissolved in 42 ml 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 ml 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 ml 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 at an atomizer rotation speed of 15500 rpm, and the obtained dry powder was pre-baked at 440 ° C. for 5 hours. The catalyst precursor thus obtained (the atomic ratio calculated from the charged raw material is Mo: Bi: Fe: Co: Ni: Cs = 12: 0.9: 2.0: 6.5: 2.4: 0.4. ), 5% by mass of crystalline cellulose was added, and the mixture was sufficiently mixed. Then, 40% by mass of a 25% by mass glycerin solution was used as a binder by the rolling granulation method with respect to the catalyst precursor, and the mixture was inert. The carrier was supported and molded into a spherical shape so that the carrying ratio was 40% by mass. The spherical molded product having a particle size of 4.4 mm thus obtained was fired at 545 ° C. for 5 hours to obtain the catalyst 15 of the present invention.

[Comparative Example 5] (Preparation of catalyst 16)
100 parts by mass of ammonium heptamolybdate was completely dissolved in 380 parts by mass of pure water heated to 80 ° C. (mother solution 1). Next, 3.7 parts by mass of cesium nitrate was dissolved in 42 ml 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 ml 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 ml 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 at an atomizer rotation speed of 17,000 rpm, and the obtained dry powder was pre-baked at 440 ° C. for 5 hours. The catalyst precursor thus obtained (the atomic ratio calculated from the charged raw material is Mo: Bi: Fe: Co: Ni: Cs = 12: 0.9: 2.0: 6.5: 2.4: 0.4. ) Is sieved with an opening of 45 μm, 5% by mass of crystalline cellulose is added to the catalyst precursor that has passed through the sieve, and after sufficient mixing, a 25% by mass glycerin solution is used as a binder by the rolling granulation method. Was used in an amount of 40% by mass based on the catalyst precursor, and was supported and molded into an inert carrier so that the carrying ratio was 40% by mass. The spherical molded product having a particle size of 4.4 mm thus obtained was fired at 545 ° C. for 5 hours to obtain the catalyst 16 of the present invention.

The catalysts obtained in the above Examples and Comparative Examples were evaluated for reaction by the following methods. 34 ml of each catalyst is filled in a stainless steel reaction tube, and a mixed gas having a gas volume ratio of isobutylene: oxygen: nitrogen: water vapor = 1: 2.2: 12.5: 1.0 is used, and under an outlet pressure of 50 kPaG, GHSV1200 hr ^{− Under} the condition of ¹ , after the aging reaction of TOS 20 hours or more at the reaction bath temperature of 350 ° C., the condensate component and the gas component are separated by a condenser at the outlet of the reaction tube, and the gas and each component in the condensate are ionized by hydrogen flame. Quantitative analysis was performed with a gas chromatograph equipped with a detector and a thermal conductivity detector. Each data obtained by gas chromatography was factor-corrected to calculate the raw material conversion rate and effective yield.

Table 1 shows the results of the reaction bath temperature, effective yield, etc. at a raw material conversion rate of 98.5% or more according to Examples, Comparative Examples, and the corresponding Test Examples and Comparative Test Examples. As is clear from Table 1, it can be seen that according to the present invention, a highly competitive catalyst can be obtained particularly in the direct acid method without losing the effective yield even in the region where the catalytic activity is high. Furthermore, it can be seen that the catalyst of the present invention reduces the yields of ΔT and CO ₂ , which is effective in improving process stability and reducing by-products.

From the results of Examples 1 to 11 and Comparative Examples 1 to 5, the catalyst of the present invention can obtain the target compounds methacrolein and methacrylic acid in a higher yield than the conventional catalyst even in a region where the catalytic activity is particularly high. Was confirmed. In particular, in Examples 1 to 4 and 7 to 11, it was clarified that the CO ₂ yield was low and that a high raw material conversion rate could be realized even if the reaction bath temperature was lowered.

By using the catalyst of the present invention, when an unsaturated aldehyde compound, an unsaturated carboxylic acid compound, or a conjugated diene compound is oxidatively produced, it is possible to obtain a high yield in a region having high catalytic activity. ..

Claims (11)

A catalyst precursor represented by the following formula (1), which has an average particle diameter of 30 μm or more and 70 μm or less, and a maximum pore diameter obtained by a mercury intrusion method of 0.01 μm or more and 20 μm or less.
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, silicon, 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 ≦ c + d ≦ 20, 0 ≦ e ≦ 5, 0 ≦ f ≦ 2, 0 ≦ g ≦ 3, 0 ≦ h ≦ 5, and i = values determined by the oxidation state of each element) The catalyst precursor according to claim 1, wherein the cumulative pore volume is 1.05 cc / g or more and 10 cc / g or less. A catalyst obtained by molding the catalyst precursor according to claim 1 or 2. A catalyst in which the catalyst precursor according to claim 1 or 2 is supported on an inert carrier. The catalyst according to claim 4, wherein the inert carrier is silica and / or alumina. The catalyst according to any one of claims 1 to 5, 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 6. The method for producing an unsaturated aldehyde compound and / or an unsaturated carboxylic acid compound, wherein the raw material conversion rate is 98.5% or more according to claim 7. The production method in which the unsaturated aldehyde compound is methacrolein and the unsaturated carboxylic acid compound is methacrylic acid in claims 7 to 8. A method for producing a catalyst using the catalyst precursor according to claim 1 or 2. The catalyst according to claim 3 to 6, wherein the catalyst precursor is a pre-baked powder obtained by pre-baking a mixed solution or slurry of a catalyst active ingredient raw material at a temperature of 200 to 600 ° C.