JP2009285581A - Ammoxidation catalyst for fluidized-beds and manufacturing method of acrylonitrile or methacrylonitrile using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst which is capable of stably manufacturing acrylonitrile and the like with high yields for a long time under conditions with a reduced amount of ammonia that is excess to propylene and the like when acrylonitrile and the like are manufactured by the ammoxidation reaction using propylene and the like. <P>SOLUTION: The ammoxidation catalyst for the fluidized-bed is used for manufacturing acrylonitrile and the like by the reaction between propylene and the like, molecular oxygen and ammonia, has an element composition represented by general formula (1): Mo<SB>a</SB>Bi<SB>b</SB>Ce<SB>c</SB>Fe<SB>d</SB>E<SB>e</SB>J<SB>f</SB>G<SB>g</SB>L<SB>h</SB>O<SB>i</SB>, wherein E denotes Ni and the like, J denotes Mg and the like, G denotes Sb and the like, and L denotes K and the like and a-i each denotes the atomic ratio (specific numerical range) of each element, and is equipped with an oxide which satisfies the range of α and β: 0.02≤α≤0.08, 0.08≤β≤0.35 wherein α and β are computed by formula (2); α=1.5(b+c)/(1.5d+e+f) and formula (3); β=1.5d/(e+f) from the atomic ration of each element, and a carrier having the oxide supported. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a fluidized bed ammoxidation catalyst for use in producing acrylonitrile or methacrylonitrile by reacting propylene, isobutene or tertiary butanol, molecular oxygen and ammonia, and acrylonitrile or The present invention relates to a method for producing methacrylonitrile.

  A method for producing acrylonitrile or methacrylonitrile by a so-called ammoxidation reaction, which is a reaction of propylene, isobutene or tertiary butanol, molecular oxygen and ammonia, is well known. Many catalysts used for this ammoxidation reaction have also been proposed.

  Various elements are applied to the catalyst used in the production of acrylonitrile or methacrylonitrile, the number of exemplified components is large, and the combination of components and the improvement of the composition can be improved as a multi-element composite oxide catalyst. It is understood from the past literature that it is being advanced. Patent Document 1 includes molybdenum, bismuth, cerium, iron, zinc, one or more elements selected from Ni, Co, Mg, Ca, Sr, Ba, and Cd, and Na, K, Rb, Cs, An ammoxidation catalyst composition containing at least one element selected from Tl as an essential component is described.

  In addition to defining the types of elements and the range of component concentrations, there are also examples in which relational expressions between these elements and other elements are derived. Catalysts containing cerium in addition to molybdenum, bismuth, and iron, and having the atomic ratio of bismuth and cerium within a certain range are disclosed in Patent Document 2, Patent Document 3, and Patent Document 4. . These disclosed techniques are disclosed as methods for obtaining high yields of acrylonitrile or methacrylonitrile and catalysts used to obtain high yields of acrylonitrile or methacrylonitrile in the production of acrylonitrile or methacrylonitrile. It is a thing.

  Patent Documents 1 to 4 show high values for the yields of acrylonitrile and methacrylonitrile obtained when using a recently developed catalyst. However, as is clear from the disclosed examples, by-products in the reaction still exist, and it is also true that the by-products are recovered and processed when the target products acrylonitrile and methacrylonitrile are produced. There is a need for a method and a catalyst that can achieve a high yield with little by-products when producing acrylonitrile and methacrylonitrile without satisfying the conventional techniques.

On the other hand, even if a catalyst capable of obtaining acrylonitrile or methacrylonitrile in high yield is completed, the high yield is limited to the initial reaction performance, and the catalyst is deteriorated in a short time due to catalyst deterioration, Catalysts that have problems in shape and strength and cannot be used in practical processes are virtually unusable. Therefore, it is also necessary that the catalyst is excellent in practicality and handleability.
Japanese Patent No. 3497558 Japanese Patent No. 3214975 Japanese Patent No. 3214984 Japanese Patent No. 3838705

In order to obtain acrylonitrile or methacrylonitrile in a high yield, it is known that the molar ratio of ammonia to propylene or the like as a raw material is increased to improve the yield of the target product. In addition to being consumed for nitrification of the raw material propylene and the like, the raw material ammonia is oxidatively decomposed and converted to nitrogen, or remains unreacted without being consumed in the reaction. When the condition where unreacted ammonia remains, ie, the condition where ammonia is used in excess, is applied, the yield of the target product is increased, but a large amount of sulfuric acid is required to treat the unreacted ammonia. Further, it is necessary to further treat ammonium sulfate produced by the sulfuric acid treatment. For this reason, the present inventor has considered that a catalyst showing a good yield is desirable even under a condition where an excessive amount of ammonia is small.
That is, in the present invention, when acrylonitrile or methacrylonitrile is produced by the ammoxidation reaction of propylene, isobutene or tertiary butanol, acrylonitrile or methacrylonitrile can be stably produced in a high yield for a long period of time under a condition where there is little excess ammonia. An object is to obtain a catalyst that can be produced.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have reacted propylene, isobutene or tertiary butanol with molecular oxygen and ammonia as a catalyst for use in producing acrylonitrile or methacrylonitrile. It has been found that the catalyst shown below exhibits a high reaction yield of acrylonitrile or methacrylonitrile, and exhibits high performance in terms of life stability and handleability. The present inventor has completed the present invention based on this finding. That is, the present invention is as follows.
[1] A catalyst used for producing acrylonitrile or methacrylonitrile by reacting propylene, isobutene or tertiary butanol, molecular oxygen, and ammonia, which is represented by the following general formula (1)
_{Mo a Bi b Ce c Fe d} E e J f G g L h O i ··· (1)
(In the formula (1), E represents at least one element selected from the group consisting of nickel and cobalt, J represents at least one element selected from the group consisting of magnesium, zinc and manganese, and G represents antimony) And L represents at least one element selected from the group consisting of phosphorus, L represents at least one element selected from the group consisting of potassium, rubidium and cesium, and a, b, c, d, e, f, g And h each represent an atomic ratio of each element, 10 ≦ a ≦ 14, 0.03 ≦ b ≦ 1, 0.03 ≦ c ≦ 1, 0.5 ≦ d ≦ 4, 2 ≦ e ≦ 10, 0 ≦ f ≦ 8, 0 ≦ g ≦ 2, 0.02 ≦ h ≦ 1, and i represents an atomic ratio of oxygen atoms satisfying the valence of a constituent element other than oxygen.)
Α and β calculated by the following formulas (2) and (3) from the atomic ratio of each element are 0.02 ≦ α ≦ 0.08, 0.08 ≦ β ≦ A fluidized bed ammoxidation catalyst comprising: an oxide that simultaneously satisfies 0.35; and a carrier that supports the oxide.
α = 1.5 (b + c) / (1.5d + e + f) (2)
β = 1.5d / (e + f) (3)
[2] The fluidized bed ammoxidation catalyst according to [1], wherein γ calculated by the following formula (4) from the atomic ratio of each element satisfies −1 ≦ γ ≦ 1.5.
γ = a−1.5 (b + c + d) + e + f + g (4)
[3] The fluid bed ammoxidation catalyst according to [1] or [2], wherein the carrier contains silica.
[4] The fluidized bed ammoxidation catalyst according to any one of [1] to [3], further comprising a carrier supporting the oxide, wherein the amount of silica in the carrier is 30 to 70% by mass.
[5] Based on the total pore volume occupied by pores having a pore diameter of 1 to 200 nm in the pore distribution measurement, the pore volume occupied by pores having a pore diameter of 8 nm or less is 20% or less. [1] ~ Ammoxidation catalyst for fluidized bed according to any one of [4].
[6] Using the fluidized bed ammoxidation catalyst according to any one of [1] to [5], propylene, isobutene or tertiary butanol, molecular oxygen, and ammonia are reacted to produce acrylonitrile or methacrylonitrile. A method for producing acrylonitrile or methacrylonitrile to be produced.

  When the fluidized bed ammoxidation catalyst of the present invention is used, in the production of acrylonitrile or methacrylonitrile by the ammoxidation reaction of propylene, isobutene or tertiary butanol, a condition in which an excess amount of ammonia is small relative to propylene, isobutene or tertiary butanol Under these conditions, acrylonitrile or methacrylonitrile can be stably produced in a high yield for a long period of time.

  Hereinafter, the best mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail.

The fluidized bed ammoxidation catalyst of this embodiment includes an oxide having an elemental composition represented by the following general formula (1). Α and β calculated by the following formulas (2) and (3) from the atomic ratio of each element constituting the oxide satisfy 0.02 ≦ α ≦ 0.08 and 0.08 ≦ β ≦ 0.35. Meet at the same time.
_{Mo a Bi b Ce c Fe d} E e J f G g L h O i ··· (1)
α = 1.5 (b + c) / (1.5d + e + f) (2)
β = 1.5d / (e + f) (3)
In the formula, Mo represents molybdenum, Bi represents bismuth, Ce represents cerium, Fe represents iron, O represents oxygen, E represents at least one element selected from the group consisting of nickel and cobalt, and J represents magnesium, zinc, and manganese. G represents at least one element selected from the group consisting of antimony and phosphorus, L represents at least one element selected from the group consisting of potassium, rubidium and cesium Represents. a, b, c, d, e, f, g and h represent the atomic ratio of each element, respectively, 10 ≦ a ≦ 14, 0.03 ≦ b ≦ 1, 0.03 ≦ c ≦ 1, 0. 5 ≦ d ≦ 4, 2 ≦ e ≦ 10, 0 ≦ f ≦ 8, 0 ≦ g ≦ 2, 0.02 ≦ h ≦ 1. i represents the atomic ratio of oxygen atoms satisfying the valence of the constituent elements other than oxygen among the elements (constituent elements) constituting the oxide.

For fluidized bed ammoxidation catalyst of the present embodiment has a metal composition of _{Mo a Bi b Ce c Fe d} E e J f G g L h. That is, this catalyst has molybdenum, bismuth, cerium, and iron as essential elements, at least one element selected from the group consisting of nickel and cobalt, and at least one type selected from the group consisting of potassium, rubidium, and cesium. An element is also an essential element, and at least six kinds of metal elements are present. Each element has its own role, and it is selectively added depending on the element composition and composition of the catalyst, such as an element that can substitute for the function of the element, an element that cannot be substituted, and an element that provides an auxiliary function of the function. It is better to change the element and composition ratio.

  For example, cerium acts on the action of bismuth molybdate, an oxide that activates propylene, isobutene or tertiary butanol, and is considered to be effective in stabilizing its structure. Become. Nickel and cobalt also function as iron molybdate (for example, to incorporate molecular oxygen into the structure of the catalyst, supplement the lattice oxygen consumed in the reaction, and prevent the catalyst from being overreduced and deteriorated). It is considered that there is a role of assisting, dilution effect, dispersion effect, and structure stabilization effect of components such as molybdenum, bismuth, and iron that mainly contribute to the reaction. And potassium, rubidium, and cesium act on the acid point formed in the metal composite oxide and the adsorption point of the reaction substrate, and become necessary components for suppressing the decomposition activity.

  Further, in addition to the above essential elements, the following elements are listed as elements to be used as necessary in the composition region proposed by the present inventors. That is, magnesium, zinc, and manganese have functions of further strengthening, weakening, and stabilizing the above-described role of nickel and cobalt. Antimony affects the change in the state of iron, and phosphorus affects the composite oxide of molybdenum with other metals and silica, and acts not only on the composition effect but also on the shape effect.

  In the catalyst of this embodiment, when the atomic ratio of each element in the general formula (1) is substituted into the above formulas (2) and (3), 0.02 ≦ α ≦ 0.08, 0.08 ≦ β It is a catalyst that satisfies ≦ 0.35 at the same time. As described above, each element has its own role, and it is considered that there are elements that can replace the function of the element, elements that cannot be replaced, and elements that provide an auxiliary function of the function. A catalyst having a balance between the functions of these elements is important for stably obtaining the target product in a high yield. Α represented by the above formula (2) represents a balance relationship between the force for activating the reaction substrate and the force for promoting redox, and β represented by the above formula (3) represents the redox This shows the balance between iron, which has strong action, and the element that adjusts its strength. Therefore, these values of α and β are important numerical values as a balance index regarding the catalyst performance.

  α represents a quantitative relationship between an oxide considered to have a role of activating propylene, isobutene or tertiary butanol, and an element having a function of preventing the reduction of the oxide from proceeding excessively by the reaction. . Therefore, α preferably satisfies the condition of 0.02 ≦ α ≦ 0.08, and more preferably satisfies the condition of 0.04 ≦ α ≦ 0.07. When α is less than 0.02, the reaction activity of the catalyst decreases, and the nitrification reaction also does not proceed, so the selectivity of acrylonitrile and methacrylonitrile decreases, and the yield of acrylonitrile and methacrylonitrile is low. Become. On the other hand, when α exceeds 0.08, carbon monoxide and carbon dioxide by-products increase in the reaction, although the activity is not as low as when α is low. From this, the decomposition activity of propylene, isobutene or tertiary butanol increases, resulting in a low yield of acrylonitrile or methacrylonitrile.

  On the other hand, β preferably satisfies the condition of 0.08 ≦ β ≦ 0.35. More preferably, β satisfies the condition of 0.15 ≦ β ≦ 0.3. β is an atomic ratio of at least one element selected from the group consisting of nickel and cobalt and an atomic ratio of at least one element selected from the group consisting of magnesium, zinc and manganese to the atomic ratio of iron element in the catalyst composition Represents the sum total. That is, β represents an index in which the ratio of elements that support the function of iron and iron affects the catalyst performance. If β is less than 0.08, the activity becomes too low. On the other hand, when β exceeds 0.35, the yield of the target product decreases.

  As is clear from the above, acrylonitrile or methacrylonitrile can be obtained in high yield in the production of acrylonitrile or methacrylonitrile in the ammoxidation reaction of propylene, isobutene or tertiary butanol, and the reaction performance can be stabilized over a long period of time. In order to be able to maintain the properties, the type and composition of the catalyst component are important. That is, molybdenum, bismuth, cerium, and iron are essential elements, and at least one element selected from the group consisting of nickel and cobalt, and at least one element selected from the group consisting of potassium, rubidium, and cesium are also essential elements. In the elemental composition in which magnesium, zinc, manganese, antimony, phosphorus, etc. are selectively added, when the atomic ratio of each element is substituted into the above formulas (2) and (3), 0.02 ≦ α ≦ 0. It is important to satisfy 08 and 0.08 ≦ β ≦ 0.35 at the same time.

The fluidized bed ammoxidation catalyst of this embodiment satisfies the relationship of γ ≦ −1 ≦ γ ≦ 1.5 when the atomic ratio of each metal element of the component constituting the catalyst is substituted into the following formula (4). It is preferable to do.
γ = a−1.5 (b + c + d) + e + f + g (4)
γ is important for further improving the catalyst performance, as it represents the atomic ratio of molybdenum that does not form a molybdenum composite oxide as molybdenum oxide. When γ is lower than −1, the amount of the metal element that cannot form a complex oxide with molybdenum element increases, the decomposition activity increases, and the reaction selectivity of the target product tends to decrease. On the other hand, when γ is higher than 1.5, the amount of molybdenum oxide increases, the catalyst shape deteriorates, and molybdenum oxide precipitates from the catalyst particles during the reaction, resulting in poor fluidity. Is likely to occur. Therefore, in order to improve both the reactivity and the handleability, γ calculated by the above formula (4) preferably satisfies the relationship of −1 ≦ γ ≦ 1.5, more preferably −0. The relationship 5 ≦ γ ≦ 1 is satisfied. As a result, it becomes a catalyst excellent in industrial practicality with good handling properties such as wear resistance and particle shape, and it becomes possible to maintain the stability of reaction performance for a long period of time.

  The catalyst of the present embodiment is a supported catalyst including a carrier that supports the oxide. Silica is preferably used as the carrier. Silica is inert in itself compared to alumina, silica-alumina, zirconia, and titania, and is good for the oxides that are active catalyst components without reducing the selectivity of the active catalyst component for the desired product of the reaction. Has a binding action. However, the carrier is most preferably all of silica, but is not limited thereto, and is generally common in order to improve the shape, abrasion resistance, and compressive strength of the catalyst, such as zirconia and titania. In addition, it is also possible to use several mass% of the components used for the catalyst support with respect to the silica. The content of silica in the carrier is preferably 90 to 100% by mass with respect to the total mass of the carrier.

  When the whole support | carrier is a silica, content of the support | carrier in a catalyst is preferable in it being 30-70 mass% with respect to the total mass of a catalyst, and it is more preferable in it being 40-60 mass%. When the content of the carrier is within this range, the carrier can be used more effectively. The role of the support is to increase the strength of the catalyst and to improve the crush resistance and the wear resistance under practical conditions. When the content of the carrier is lower than 30% by mass, strengths such as crush resistance and wear resistance are weakened, and it becomes difficult to use practically. On the other hand, when the content of the support is higher than 70% by mass, the apparent specific gravity of the catalyst becomes light and tends to be impractical as a fluidized bed catalyst.

  The apparent specific gravity of the catalyst is preferably in the range of 0.85 to 1.15 g / cc. If the apparent specific gravity of the catalyst is less than 0.85 g / cc, the catalyst to be charged into the reactor becomes bulky, and a huge reactor volume is required, and the amount of catalyst scattered from the reactor to the outside is large. The catalyst loss is likely to occur. On the other hand, when the apparent specific gravity of the catalyst exceeds 1.15 g / cc, the flow state of the catalyst is deteriorated, leading to a decrease in reaction performance.

  The fluidized bed ammoxidation catalyst of the present embodiment has a pore volume occupied by pores having a pore diameter of 8 nm or less based on the total pore volume occupied by pores having a pore diameter of 1 to 200 nm in pore distribution measurement. The accumulated volume is preferably 20% or less. A large pore volume of pores having a pore diameter of 8 nm or less means that there are many such small pores. Such a pore distribution is advantageous for the reaction because the reaction field is increased and the activity is improved, and there is also an advantage that the crushing strength is increased with respect to a catalyst having many larger pores. However, there is also a negative effect that the yield of the desired product such as acrylonitrile or methacrylonitrile is reduced. Considering these balances, as described above, the pore volume occupied by pores having a pore diameter of 8 nm or less is preferably 20% or less.

  The average particle diameter of the fluidized bed ammoxidation catalyst of the present embodiment is preferably 30 to 70 μm, more preferably 40 to 60 μm. As the particle size distribution of the catalyst, the amount of catalyst particles having a particle diameter of 5 to 200 μm is preferably 90 to 100% by mass with respect to the total mass of the catalyst.

  The catalyst of this embodiment is a known method, for example, a first step of preparing a raw material slurry, a second step of spray drying the raw material slurry, and a third method of calcining the dried product obtained in the second step. It can be obtained by a method including the steps of

  In the first step, a catalyst raw material is prepared to obtain a raw material slurry. As an element source of each element of molybdenum, bismuth, cerium, iron, nickel, magnesium, zinc, manganese, antimony, phosphorus, potassium, rubidium, and cesium. Include ammonium salts, nitrates, hydrochlorides, sulfates, and organic acid salts that are soluble in water or nitric acid. In particular, ammonium salt is used as a raw material for molybdenum, nitrate is used as an element source for each element of bismuth, cerium, iron, nickel, magnesium, zinc, manganese, potassium, rubidium, and cesium, and antimony trioxide is used as a raw material for antimony. As a raw material of phosphorus, the alkali metal salt, alkaline-earth metal salt, ammonium salt, or phosphoric acid is mentioned. As a raw material of phosphorus, phosphoric acid is preferable.

  On the other hand, the carrier material is not particularly limited as long as it is a commonly used carrier material. However, when the carrier is silica, it is preferable to use silica sol as a raw material. As the silica sol, various types such as purity, difference in impurities, pH, particle size and the like can be used. Among these, in the case of a silica sol containing aluminum as an impurity, preferably a silica sol containing 0.04 atom or less of aluminum per 100 atoms of silicon, more preferably 0.02 atom or less of aluminum per 100 atoms of silicon is used. Since the pH of silica affects the viscosity of the raw material slurry, it may be appropriately selected depending on the amount of metal salt used and the pH. The silica particle size also affects the specific surface area, pore volume, pore distribution, etc., and also affects the practicality of the catalyst such as crushing strength, compressive strength, and abrasion resistance. What is necessary is just to select suitably by the difference by a composition and a preparation method.

  For example, in this embodiment, in order to obtain a catalyst in which the pore volume having a pore diameter of 8 nm or less is 20% or less based on the total pore volume occupied by pores having a pore diameter of 1 to 200 nm, A method for selecting the primary particle size of silica is exemplified. When the primary particle diameter of silica is relatively small, the pore volume of pores having a pore diameter of 8 nm or less tends to exceed 20%, and when the primary particle diameter of silica is relatively large, the physical strength of the catalyst is reduced. drop down. Therefore, when a silica sol having a silica primary particle diameter of 20 to 100 nm as an average particle diameter of silica primary particles and a silica sol having a particle diameter of 20 nm or less are mixed and used, a catalyst having the above pore distribution can be obtained. Can do.

  The method for preparing the raw slurry is, for example, as follows. First, an ammonium salt of molybdenum dissolved in water is added to the silica sol. Next, a solution in which nitrate of an element source of each element such as bismuth, cerium, iron, nickel, magnesium, zinc, manganese, potassium, rubidium, and cesium is dissolved in water or an aqueous nitric acid solution is added thereto. Antimony is a solution dissolved using a water-soluble chelating agent such as citric acid, succinic acid, tartaric acid, and hydrogen peroxide. Phosphorus is phosphoric acid, and is added to the silica sol before or after adding the above solution as appropriate. Can be thrown in. In this way, a raw slurry is obtained.

  Compared to the raw material slurry preparation method described above, the procedure for adding each element source is changed, and the pH and viscosity of the slurry are modified by adjusting the concentration of nitric acid and adding aqueous ammonia to the slurry (silica sol). Can be. In addition, water-soluble polymers such as polyethylene glycol, methylcellulose, polyvinyl alcohol, polyacrylic acid, polyacrylamide, amines, aminocarboxylic acids, carboxylic acids such as oxalic acid, malonic acid, succinic acid, glycolic acid, malic acid, Organic acids such as tartaric acid and citric acid can be added as appropriate.

  Next, in the second step, the raw material slurry obtained in the first step is spray-dried to obtain spherical particles as a catalyst precursor. The atomization of the raw material slurry can be performed by a method such as a centrifugal method, a two-fluid nozzle method, and a high-pressure nozzle method which are usually carried out industrially. Examples of the heat source for spray drying include steam, an electric heater, and the like. The temperature at the inlet of the dryer using air heated by this heat source is preferably 100 to 400 ° C, more preferably 150 to 300 ° C.

  In the third step, the desired catalyst composition is obtained by calcining the dried particles obtained in the second step. In this third step, the dried particles are pre-baked, for example, at 150 to 500 ° C., if necessary, and then preferably 500 to 730 ° C., more preferably 550 to 730 ° C. for 1 to 20 hours. Firing is performed. Firing can be performed using a firing furnace such as a rotary furnace, a tunnel furnace, or a muffle furnace.

  The method for producing acrylonitrile or methacrylonitrile by the reaction of propylene, isobutene or tertiary butanol, molecular oxygen and ammonia using the catalyst of the present embodiment is carried out in a fluidized bed reactor which is usually used. The raw materials propylene, isobutene, tertiary butanol and ammonia are not necessarily highly pure, and those of industrial grade can be used. As the molecular oxygen source, it is usually preferable to use air, but a gas whose oxygen concentration is increased by mixing oxygen with air can also be used.

For the composition of the feed gas when the molecular oxygen source is air, the molar ratio of ammonia and air to propylene, isobutene or tertiary butanol is (propylene, isobutene or tertiary butanol) / ammonia / air, preferably 1 /(0.8 to 1.4) / (7 to 12), more preferably in the range of 1 / 0.9 to 1.3 / 8 to 11.
Moreover, reaction temperature becomes like this. Preferably it is 350-550 degreeC, More preferably, it is the range of 400-500 degreeC.
The reaction pressure is preferably in the range of slightly reduced pressure to 0.3 MPa.
The contact time between the raw material gas and the catalyst is preferably 0.5 to 20 (sec · g / cc), more preferably 1 to 10 (sec · g / cc).

  As mentioned above, although the best form for implementing this invention was demonstrated, this invention is not limited to the said embodiment. The present invention can be variously modified without departing from the gist thereof.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. Moreover, the evaluation method of various physical properties is as showing below.

(Evaluation of catalyst reaction performance)
The reactor used was a Pyrex (registered trademark) glass fluidized bed reaction tube having an outer diameter of 23 mm. The reaction temperature T was 430 ° C., the reaction pressure P was 0.15 MPa, the packed catalyst amount W was 40-60 g, and the total supply gas amount F was 250-450 cc / sec (NTP conversion). The composition of the supplied raw material gas is such that the molar ratio of propylene / ammonia / air is 1 / (0.7 to 1.4) / (8.0 to 11.0), and the unreacted ammonia concentration in the reaction gas The reaction was carried out by appropriately changing the composition of the supplied gas within the above range so that the unreacted oxygen concentration was 0.2% or less. The composition of the source gas is shown in Tables 2 and 4. The reaction gas 24 hours after the start of raw material supply was analyzed by gas chromatography to determine the reaction performance of the catalyst. In Examples and Comparative Examples, the conversion rate, selectivity, and yield used to represent contact time and reaction results are defined by the following formulas.
Contact time (sec · g / cc) = (W / F) × 273 / (273 + T) × P / 0.10
Propylene conversion rate (%) = M / L × 100
Acrylonitrile selectivity (%) = N / M × 100
Acrylonitrile yield (%) = N / L × 100
Here, L represents the number of moles of propylene supplied, M represents the number of moles of reacted propylene, and N represents the number of moles of acrylonitrile produced. In addition, the number of moles obtained by subtracting the number of moles of propylene in the reaction gas from the number of moles of propylene supplied was defined as the number of moles of propylene reacted.

(Measurement of catalyst pore distribution)
The pore distribution of the catalyst was measured by nitrogen gas adsorption using an autosorb 3MP device manufactured by Yuasa Ionics. For the pore diameter and pore distribution, desorption data by the BJH method was used, and for the pore volume, the adsorption amount at P / P0, Max was adopted.

(Measurement of catalyst particle size)
The particle diameter of the catalyst was measured using a laser diffraction / scattering particle size distribution measuring apparatus LA-300 manufactured by Horiba.

(Shape observation)
The shape of the catalyst was observed using a Hitachi X-650 scanning electron microscope.

(Abrasion resistance strength measurement)
In accordance with the method described in “Test Method for Synthetic Fluid Cracking Catalyst” (American Cyanamid Co. Ltd. 6 / 31-4m−1 / 57) (hereinafter referred to as “ACC method”), the resistance of the catalyst as resistance to wear Abrasion strength (attrition strength) was measured.
Attrition strength is evaluated by friction loss, and this wear loss is defined as follows.
Wear loss (%) = R / (SQ) × 100
In the above formula, Q is the mass (g) of the catalyst that is worn and scattered outside during 0 to 5 hours, and R is the mass (g) of the catalyst that is worn and scattered outside during usually 5 to 20 hours. S is the mass (g) of the catalyst used in the test. It was judged that the value of this wear loss was 3% or less and that it was applicable to industrial use.

(Apparent specific gravity measurement)
Using a powder tester made by Hosokawa Micron KK, drop the catalyst sieved through a funnel into a 100 cc measuring cup container. cc).

(Example 1)
Metal oxidation wherein the metal composition (preparation ratio; the same applies hereinafter) is represented by Mo _12.2 Bi _0.35 Ce _0.23 Fe _1.34 Ni _6.5 Mg _2.6 K _0.2 (α = 0.08, β = 0.22, γ = 0.22) A catalyst in which the product was supported on a 40% by mass silica support was prepared as follows.

666.7 g of an aqueous silica sol containing 30% by mass of SiO ₂ having an average particle diameter of 12 nm of silica primary particles and 492.6 g of an aqueous silica sol containing 40.6% by mass of SiO ₂ having an average particle diameter of 41 nm of silica primary particles. A first mixed solution was obtained by mixing. Next, a solution obtained by dissolving 504.0 g of ammonium paramolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O] in 1008.1 g of water is added to the first mixed solution, and the second mixed solution is added. Got. Next, 416.2 g of nitric acid having a concentration of 16.6% by mass was added with 40.1 g of bismuth nitrate [Bi (NO ₃ ) ₃ .5H ₂ O] and 23.2 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O 128.0 g of iron nitrate [Fe (NO ₃ ) ₃ .9H ₂ O], 448.2 g of nickel nitrate [Ni (NO ₃ ) ₂ .6H ₂ O], 158.0 g of magnesium nitrate [Mg (NO _{3) 2} · 6H ₂ O], potassium nitrate [KNO _3] solution obtained by dissolving the 4.72 g, was obtained aqueous raw material mixture (slurry) was added to the second mixture (first Process). Next, the aqueous raw material mixture was spray-dried under conditions of an inlet temperature of about 250 ° C. and an outlet temperature of about 140 ° C. using a spray device equipped with a dish-shaped rotor installed in the upper center of the dryer (second). Process). The dried catalyst precursor was then pre-baked at 320 ° C. for 2 hours in an air atmosphere using an electric furnace, and then subjected to main baking at 580 ° C. for 2 hours in an air atmosphere (third Step) and finally 815 g of catalyst were obtained.

When a part of the obtained catalyst was taken out and the pore distribution was measured, the pore volume occupied by pores having a pore diameter of 1 to 200 nm was 0.226 cc, and the pore volume occupied by pores having a pore diameter of 8 nm or less was The total volume (pore ratio) of pores having a pore diameter of 80 nm or less with respect to the total pore volume was 3.5%. Further, the shape of the catalyst was a solid sphere, the average particle size was 58 μm, and the apparent specific gravity was 1.10 g / cc. Next, 50 g of this catalyst was used to carry out ammoxidation of propylene with a contact time Θ = 4.4 (sec · g / cc). The conversion rate of propylene after 24 hours from the start of the reaction was 99.3%, the acrylonitrile (indicated as “AN” in Tables 2 and 4) selectivity was 86.3%, and the acrylonitrile yield was 85.7%. became.
Further, when the wear resistance strength of the catalyst 50 g was measured according to the ACC method, the wear loss (%) was 0.8%.
The catalyst composition (metal composition, silica (SiO ₂ ) carrier amount, α, β, γ, the same applies hereinafter) and the firing temperature are shown in Table 1, and the reaction results and physical property measurement results are shown in Table 2.

(Example 2)
Silica carrier having a metal oxide composition represented by Mo _12.4 Bi _0.15 Ce _0.10 Fe _1.51 Ni _6.69 Mg _2.67 K _0.2 (α = 0.03, β = 0.24, γ = 0.40) The catalyst supported on was prepared as follows.

666.7 g of an aqueous silica sol containing 30% by mass of SiO ₂ having an average particle diameter of 12 nm of silica primary particles and 492.6 g of an aqueous silica sol containing 40.6% by mass of SiO ₂ having an average particle diameter of 41 nm of silica primary particles. A first mixed solution was obtained by mixing. Next, a solution prepared by dissolving 514 g of ammonium paramolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O] in 1028 g of water was added to the first mixed solution to obtain a second mixed solution. Subsequently, 17.2 g of bismuth nitrate [Bi (NO ₃ ) ₃ .5H ₂ O] and 10.1 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O are added to 419.6 g of nitric acid having a concentration of 16.6% by mass. 144.7 g of iron nitrate [Fe (NO ₃ ) ₃ .9H ₂ O], 462.9 g of nickel nitrate [Ni (NO ₃ ) ₂ .6H ₂ O], 162.8 g of magnesium nitrate [Mg (NO _{3) 2} · 6H ₂ O], potassium nitrate [KNO _3] solution obtained by dissolving the 4.74 g, was obtained aqueous raw material mixture (slurry) was added to the second mixture (first Process). Next, the aqueous raw material mixture was spray-dried under conditions of an inlet temperature of about 250 ° C. and an outlet temperature of about 140 ° C. using a spray device equipped with a dish-shaped rotor installed in the upper center of the dryer (second). Process). Next, the dried catalyst precursor was pre-baked at 320 ° C. for 2 hours in an air atmosphere using an electric furnace, and then subjected to main baking at 615 ° C. for 2 hours in an air atmosphere (third Step), finally 803 g of catalyst was obtained.

When a part of the obtained catalyst was taken out and the pore distribution was measured, the pore volume occupied by pores having a pore diameter of 1 to 200 nm was 0.218 cc, and the pore volume occupied by pores having a pore diameter of 8 nm or less was The integrated volume (pore ratio) of pores having a pore diameter of 80 nm or less with respect to the total pore volume was 1.8%. Further, the catalyst was a solid sphere, the average particle size was 61 μm, and the apparent specific gravity was 0.94 g / cc. Next, 50 g of this catalyst was used to carry out ammoxidation of propylene with a contact time Θ = 4.1 (sec · g / cc). After 24 hours from the start of the reaction, the propylene conversion was 99.2%, the acrylonitrile selectivity was 86.2%, and the acrylonitrile yield was 85.5%.
Further, when the wear resistance strength of the catalyst 50 g was measured according to the ACC method, the wear loss (%) was 0.9%.
The catalyst composition and calcination temperature are shown in Table 1, and the reaction results and physical property measurement results are shown in Table 2.

(Example 3)
40% by mass of a metal oxide having a metal composition of Mo ₁₂ Bi _0.28 Ce _0.19 Fe _1.8 Ni _6.2 Mg _2.5 Cs _0.08 (α = 0.06, β = 0.31, γ = −0.11) A catalyst supported on a carrier was prepared as follows.

666.7 g of an aqueous silica sol containing 30% by mass of SiO ₂ having an average particle diameter of 12 nm of silica primary particles and 492.6 g of an aqueous silica sol containing 40.6% by mass of SiO ₂ having an average particle diameter of 41 nm of silica primary particles. Thus, a first mixed liquid was obtained. Next, a solution obtained by dissolving 503.5 g of ammonium paramolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O] in 1007 g of water is added to the first mixed solution to obtain a second mixed solution. It was. Next, 412.6 g of nitric acid having a concentration of 16.6% by mass was added with 32.6 g of bismuth nitrate [Bi (NO ₃ ) ₃ .5H ₂ O] and 19.5 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O. 174.6 g of iron nitrate [Fe (NO ₃ ) ₃ .9H ₂ O], 434.2 g of nickel nitrate [Ni (NO ₃ ) ₂ .6H ₂ O], 154.3 g of magnesium nitrate [Mg (NO _{3) 2} · 6H ₂ O], a solution obtained by dissolving cesium nitrate [CsNO _3] of 3.72 g, was obtained aqueous raw material mixture (slurry) was added to the second mixture of (a Step 1). Next, the aqueous raw material mixture was spray-dried under conditions of an inlet temperature of about 250 ° C. and an outlet temperature of about 140 ° C. using a spray device equipped with a dish-shaped rotor installed in the upper center of the dryer (second). Process). Next, the dried catalyst precursor was pre-baked at 320 ° C. for 2 hours in an air atmosphere using an electric furnace, and then subjected to main baking at 590 ° C. for 2 hours in an air atmosphere (third Step), finally 814 g of catalyst was obtained.

When a part of the obtained catalyst was taken out and the pore distribution was measured, the pore volume occupied by pores having a pore diameter of 1 to 200 nm was 0.215 cc, and the pore volume occupied by pores having a pore diameter of 8 nm or less was It was 0.009 cc / g, and the cumulative volume (pore ratio) of pores having a pore diameter of 80 nm or less with respect to the total pore volume was 4.2%. The catalyst was a solid sphere, the average particle size was 66 μm, and the apparent specific gravity was 1.01 g / cc. Next, 50 g of this catalyst was used to carry out ammoxidation of propylene with a contact time Θ = 4.1 (sec · g / cc). After 24 hours from the start of the reaction, the propylene conversion was 99.0%, the acrylonitrile selectivity was 85.4%, and the acrylonitrile yield was 84.5%.
Further, when the wear resistance strength of the catalyst 50g was measured according to the ACC method, the wear loss (%) was 1.5%.
The catalyst composition and calcination temperature are shown in Table 1, and the reaction results and physical property measurement results are shown in Table 2.

Example 4
A metal oxide having a metal composition of Mo ₁₂ Bi _0.22 Ce _0.15 Fe _1.1 Ni _7.0 Mg _2.8 Rb _0.15 (α = 0.05, β = 0.17, γ = 0) is supported on a 50% by mass silica support. The prepared catalyst was prepared as follows.

833.3 g of an aqueous silica sol containing 30% by mass of SiO ₂ having an average particle diameter of 12 nm of silica primary particles, and 615.8 g of an aqueous silica sol containing 40.6% by mass of SiO ₂ having an average particle diameter of 41 nm of silica primary particles. A first mixed solution was obtained by mixing. Next, a solution prepared by dissolving 419.9 g of ammonium paramolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O] in 840 g of water is added to the first mixed solution to obtain a second mixed solution. It was. Subsequently, 21.5 g of bismuth nitrate [Bi (NO ₃ ) ₃ .5H ₂ O] and 12.8 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O are added to 411.5 g of nitric acid having a concentration of 16.6% by mass. ] 89 g of iron nitrate [Fe (NO ₃ ) ₃ .9H ₂ O], 408.8 g of nickel nitrate [Ni (NO ₃ ) ₂ .6H ₂ O], 144.1 g of magnesium nitrate [Mg (NO ₃ ) ₂ · 6H ₂ O], rubidium nitrate [RbNO _3] solution obtained by dissolving a 4.36 g, in addition to the second mixture to obtain an aqueous raw material mixture (raw slurry) (first Process). Next, the aqueous raw material mixture was spray-dried under conditions of an inlet temperature of about 250 ° C. and an outlet temperature of about 140 ° C. using a spray device equipped with a dish-shaped rotor installed in the upper center of the dryer (second). Process). Next, the dried catalyst precursor was pre-baked at 320 ° C. for 2 hours in an air atmosphere using an electric furnace, and then subjected to main baking at 675 ° C. for 2 hours in an air atmosphere (third Step) and finally 802 g of catalyst was obtained.

When a part of the obtained catalyst was taken out and the pore distribution was measured, the pore volume occupied by pores having a pore diameter of 1 to 200 nm was 0.211 cc, and the pore volume occupied by pores having a pore diameter of 8 nm or less was It was 0.002 cc / g, and the cumulative volume (pore ratio) of pores having a pore diameter of 80 nm or less with respect to the total pore volume was 0.9%. The catalyst was a solid sphere, the average particle size was 65 μm, and the apparent specific gravity was 0.99 g / cc. Next, 50 g of this catalyst was used to carry out an ammoxidation reaction of propylene with a contact time Θ = 4.7 (sec · g / cc). After 24 hours from the start of the reaction, the propylene conversion was 99.3%, the acrylonitrile selectivity was 86.6%, and the acrylonitrile yield was 86.0%.
Further, when the wear resistance strength of the catalyst 50 g was measured according to the ACC method, the wear loss (%) was 0.8%.
The catalyst composition and calcination temperature are shown in Table 1, and the reaction results and physical property measurement results are shown in Table 2.

(Example 5)
40% by mass of a metal oxide having a metal composition represented by Mo ₁₂ Bi _0.29 Ce _0.20 Fe _1.5 Ni _6.5 Mg _2.6 Rb _0.12 (α = 0.06, β = 0.25, γ = −0.08) A catalyst supported on a carrier was prepared as follows.

985.2 g of aqueous silica sol containing 40.6% by mass of SiO ₂ having an average particle diameter of silica primary particles of 41 nm was prepared. Next, a solution in which 502.2 g of ammonium paramolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O] was dissolved in 1004 g of water was added to the aqueous silica sol to obtain a mixed solution. Next, 33.7 g of bismuth nitrate [Bi (NO ₃ ) ₃ .5H ₂ O] and 20.5 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O are added to 417.3 g of nitric acid having a concentration of 16.6% by mass. 145.1 g of iron nitrate [Fe (NO ₃ ) ₃ .9H ₂ O], 454.0 g of nickel nitrate [Ni (NO ₃ ) ₂ .6H ₂ O], 160.1 g of magnesium nitrate [Mg (NO _{3) 2} · 6H ₂ O], rubidium nitrate [RbNO _3] dissolved in the resulting solution of 4.17 g, was obtained aqueous raw material mixture (slurry) was added to the mixed solution (first step ). Next, the aqueous raw material mixture was spray-dried under conditions of an inlet temperature of about 250 ° C. and an outlet temperature of about 140 ° C. using a spray device equipped with a dish-shaped rotor installed in the upper center of the dryer (second). Process). Next, the dried catalyst precursor was pre-baked at 320 ° C. for 2 hours in an air atmosphere using an electric furnace, and then subjected to main baking at 630 ° C. for 2 hours in an air atmosphere (third Step), and finally 822 g of catalyst was obtained.

When a part of the obtained catalyst was taken out and the pore distribution was measured, the pore volume occupied by pores having a pore diameter of 1 to 200 nm was 0.248 cc, and the pore volume occupied by pores having a pore diameter of 8 nm or less was It was 0.002 cc / g, and the cumulative volume (pore ratio) of pores having a pore diameter of 80 nm or less with respect to the total pore volume was 0.8%. Further, the catalyst was a solid sphere, the average particle size was 64 μm, and the apparent specific gravity was 0.98 g / cc. Next, 50 g of this catalyst was used to carry out ammoxidation of propylene with a contact time Θ = 4.4 (sec · g / cc). After 24 hours from the start of the reaction, the propylene conversion was 99.2%, the acrylonitrile selectivity was 87.3%, and the acrylonitrile yield was 86.6%.
Further, when the wear resistance strength of the catalyst 50 g was measured according to the ACC method, the wear loss (%) was 1.7%.
The catalyst composition and calcination temperature are shown in Table 1, and the reaction results and physical property measurement results are shown in Table 2.

(Example 6)
Silica support having a metal composition represented by Mo _12.2 Bi _0.22 Ce _0.14 Fe _1.45 Ni _6.63 Mg _2.65 K _0.18 (α = 0.05, β = 0.23, γ = 0.21) 40 mass% The catalyst supported on was prepared as follows.

666.7 g of an aqueous silica sol containing 30% by mass of SiO ₂ having an average particle diameter of 12 nm of silica primary particles and 492.6 g of an aqueous silica sol containing 40.6% by mass of SiO ₂ having an average particle diameter of 41 nm of silica primary particles. A first mixed solution was obtained by mixing. Next, a solution prepared by dissolving 509.1 g of ammonium paramolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O] in 1018 g of water is added to the first mixed solution to obtain a second mixed solution. It was. Next, 28.6 g of bismuth nitrate [Bi (NO ₃ ) ₃ .5H ₂ O] and 14.3 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O are added to 418.6 g of nitric acid having a concentration of 16.6% by mass. 139.9 g of iron nitrate [Fe (NO ₃ ) ₃ .9H ₂ O], 461.7 g of nickel nitrate [Ni (NO ₃ ) ₂ .6H ₂ O], 162.7 g of magnesium nitrate [Mg (NO _{3) 2} · 6H ₂ O], potassium nitrate [KNO _3] solution obtained by dissolving the 4.29 g, was obtained aqueous raw material mixture (slurry) was added to the second mixture (first Process). Next, the aqueous raw material mixture was spray-dried under conditions of an inlet temperature of about 250 ° C. and an outlet temperature of about 140 ° C. using a spray device equipped with a dish-shaped rotor installed in the upper center of the dryer (second). Process). Next, the dried catalyst precursor was pre-baked at 320 ° C. for 2 hours in an air atmosphere using an electric furnace, and then subjected to main baking at 610 ° C. for 2 hours in an air atmosphere (third Step), finally 819 g of catalyst was obtained.

When a part of the obtained catalyst was taken out and the pore distribution was measured, the pore volume of pores having a pore diameter of 1 to 200 nm was 0.203 cc, and the pore volume occupied by pores having a pore diameter of 8 nm or less was 0. It was 0.005 cc / g, and the cumulative volume (pore ratio) of pores having a pore diameter of 80 nm or less with respect to the total pore volume was 2.5%. Further, the shape of the catalyst was a solid sphere, the average particle size was 57 μm, and the apparent specific gravity was 1.04 g / cc. Next, 50 g of this catalyst was used to carry out an ammoxidation reaction of propylene with a contact time Θ = 3.3 (sec · g / cc). After 24 hours from the start of the reaction, the propylene conversion was 99.1%, the acrylonitrile selectivity was 86.7%, and the acrylonitrile yield was 85.9%.
Further, when the wear resistance strength of the catalyst 50 g was measured according to the ACC method, the wear loss (%) was 0.8%.
The catalyst composition and calcination temperature are shown in Table 1, and the reaction results and physical property measurement results are shown in Table 2.

(Example 7)
Silica support having a metal composition represented by Mo _12.4 Bi _0.24 Ce _0.16 Fe _1.52 Ni _6.5 Mg _2.6 Rb _0.15 (α = 0.05, β = 0.25, γ = 0.42) 40 mass% The catalyst supported on was prepared as follows.

666.7 g of an aqueous silica sol containing 30% by mass of SiO ₂ having an average particle diameter of 12 nm of silica primary particles and 492.6 g of an aqueous silica sol containing 40.6% by mass of SiO ₂ having an average particle diameter of 41 nm of silica primary particles. A first mixed solution was obtained by mixing. Next, a solution obtained by dissolving 510.2 g of ammonium paramolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O] in 1020 g of water is added to the first mixed solution to obtain a second mixed solution. It was. Then, 27.4 g of bismuth nitrate [Bi (NO ₃ ) ₃ .5H ₂ O] and 16.1 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O are added to 417.7 g of nitric acid having a concentration of 16.6% by mass. 144.6 g of iron nitrate [Fe (NO ₃ ) ₃ .9H ₂ O], 446.4 g of nickel nitrate [Ni (NO ₃ ) ₂ .6H ₂ O], 157.4 g of magnesium nitrate [Mg (NO _{3) 2} · 6H ₂ O], rubidium nitrate [RbNO _3] dissolved in the resulting solution of 5.13 g, was obtained aqueous raw material mixture (slurry) was added to the second mixture of (a Step 1). Next, the aqueous raw material mixture was spray-dried under conditions of an inlet temperature of about 250 ° C. and an outlet temperature of about 140 ° C. using a spray device equipped with a dish-shaped rotor installed in the upper center of the dryer (second). Process). Subsequently, the dried catalyst precursor was pre-baked at 320 ° C. for 2 hours in an air atmosphere using an electric furnace, and then subjected to main baking at 590 ° C. for 2 hours in an air atmosphere (third Step), and finally 821 g of catalyst was obtained.

When a part of the obtained catalyst was taken out and the pore distribution was measured, the pore volume occupied by pores having a pore diameter of 1 to 200 nm was 0.220 cc, and the pore volume occupied by pores having a pore diameter of 8 nm or less was It was 0.006 cc / g, and the cumulative volume (pore ratio) of pores having a pore diameter of 80 nm or less with respect to the total pore volume was 2.7%. Further, the shape of the catalyst was a solid sphere, the average particle size was 60 μm, and the apparent specific gravity was 1.00 g / cc. Next, using 50 g of this catalyst, ammoxidation of propylene was carried out at a contact time Θ = 4.5 (sec · g / cc). After 24 hours from the start of the reaction, the propylene conversion was 99.4%, the acrylonitrile selectivity was 86.5%, and the acrylonitrile yield was 86.0%. Further, the reaction was continued under the same conditions, and the reaction gas was analyzed 1200 hours after the start of the reaction. As a result, the conversion of propylene was 99.6%, the acrylonitrile selectivity was 86.0%, and the acrylonitrile yield. Was 85.7%, and it was confirmed that there was almost no change from the performance after 24 hours. Further, when the wear resistance strength of the catalyst 50 g was measured according to the ACC method, the wear loss (%) was 0.8%.
The catalyst composition and calcination temperature are shown in Table 1, and the reaction results and physical property measurement results are shown in Table 2.

(Example 8)
Silica support having a metal composition represented by Mo _12.3 Bi _0.2 Ce _0.08 Fe _0.7 Ni _7.75 Mg _2.6 Rb _0.08 (α = 0.04, β = 0.10, γ = 0.48) 40 mass% The catalyst supported on was prepared as follows.

666.7 g of an aqueous silica sol containing 30% by mass of SiO ₂ having an average particle diameter of 12 nm of silica primary particles and 492.6 g of an aqueous silica sol containing 40.6% by mass of SiO ₂ having an average particle diameter of 41 nm of silica primary particles. A first mixed solution was obtained by mixing. Next, a solution prepared by dissolving 509.1 g of ammonium paramolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O] in 1018 g of water is added to the first mixed solution to obtain a second mixed solution. It was. Then, 23.0 g of bismuth nitrate [Bi (NO ₃ ) ₃ .5H ₂ O], 8.10 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] in 417 g of nitric acid having a concentration of 16.6% by mass, 67 g of iron nitrate [Fe (NO ₃ ) ₃ .9H ₂ O], 535.4 g of nickel nitrate [Ni (NO ₃ ) ₂ .6H ₂ O], 158.3 g of magnesium nitrate [Mg (NO ₃ ) _2. 6H ₂ O] and 2.75 g of rubidium nitrate [RbNO ₃ ] dissolved therein were added to the second mixed liquid to obtain an aqueous raw material mixture (raw material slurry) (first step). . Next, the aqueous raw material mixture was spray-dried under conditions of an inlet temperature of about 250 ° C. and an outlet temperature of about 140 ° C. using a spray device equipped with a dish-shaped rotor installed in the upper center of the dryer (second). Process). The dried catalyst precursor was then pre-baked at 320 ° C. for 2 hours in an air atmosphere using an electric furnace, and then subjected to main baking at 580 ° C. for 2 hours in an air atmosphere (third Step) and finally 798 g of catalyst were obtained.

When a part of the obtained catalyst was taken out and the pore distribution was measured, the pore volume occupied by pores having a pore diameter of 1 to 200 nm was 0.224 cc, and the pore volume occupied by pores having a pore diameter of 8 nm or less was It was 0.005 cc / g, and the cumulative volume (pore ratio) of pores having a pore diameter of 80 nm or less with respect to the total pore volume was 2.2%. Further, the catalyst was a solid sphere, the average particle size was 55 μm, and the apparent specific gravity was 0.96 g / cc. Next, 50 g of this catalyst was used to carry out ammoxidation of propylene with a contact time Θ = 5 (sec · g / cc). After 24 hours from the start of the reaction, the propylene conversion was 99.5%, the acrylonitrile selectivity was 85.3%, and the acrylonitrile yield was 84.9%. Further, when the wear resistance strength of the catalyst 50g was measured according to the ACC method, the wear loss (%) was 1.1%.
The catalyst composition and calcination temperature are shown in Table 1, and the reaction results and physical property measurement results are shown in Table 2.

(Comparative Example 1)
A metal oxide having a metal composition of Mo _13.0 Bi _0.73 Fe _0.35 Ni _6.23 Mg _4.16 K _0.07 (α = 0.10, β = 0.05, γ = 0.99) is supported on a 50% by mass silica support. The prepared catalyst was prepared as follows.

1666.7 g of an aqueous silica sol containing 30% by mass of SiO ₂ having an average particle diameter of silica primary particles of 12 nm was prepared. Next, a solution obtained by dissolving 427.2 g of ammonium paramolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O] in 854 g of water was added to the silica sol to obtain a mixed solution. Next, 406.5 g of nitric acid having a concentration of 16.6% by mass was added to 66.5 g of bismuth nitrate [Bi (NO ₃ ) ₃ .5H ₂ O] and 26.6 g of iron nitrate [Fe (NO ₃ ) ₃ .9H ₂ O. 341.7 g of nickel nitrate [Ni (NO ₃ ) ₂ .6H ₂ O], 201.1 g of magnesium nitrate [Mg (NO ₃ ) ₂ .6H ₂ O], 1.32 g of potassium nitrate [KNO ₃ ]. The liquid obtained by dissolving was added to the above mixed liquid to obtain an aqueous raw material mixture (raw material slurry). Next, the above aqueous raw material mixture was spray-dried under conditions of an inlet temperature of about 250 ° C. and an outlet temperature of about 140 ° C. using a spray device equipped with a dish-shaped rotor installed in the upper center of the dryer. Next, the dried catalyst precursor was pre-fired at 320 ° C. for 2 hours in an air atmosphere using an electric furnace, and then finally fired at 560 ° C. for 2 hours in an air atmosphere. 811 g of catalyst was obtained.

When a part of the obtained catalyst was taken out and the pore distribution was measured, the pore volume occupied by pores having a pore diameter of 1 to 200 nm was 0.192 cc, and the pore volume occupied by pores having a pore diameter of 8 nm or less was The integrated volume (pore ratio) of pores having a pore diameter of 80 nm or less with respect to the total pore volume was 27.1%. Further, the catalyst was a solid sphere, the average particle size was 64 μm, and the apparent specific gravity was 1.08 g / cc. Next, 50 g of this catalyst was used to carry out an ammoxidation reaction of propylene with a contact time Θ = 6.0 (sec · g / cc). After 24 hours from the start of the reaction, the propylene conversion was 99.3%, the acrylonitrile selectivity was 74.6%, and the acrylonitrile yield was 74.1%.
Further, when the wear resistance strength of the catalyst 50g was measured according to the ACC method, the wear loss (%) was 0.3%.
The catalyst composition and calcination temperature are shown in Table 1, and the reaction results and physical property measurement results are shown in Table 2.

(Comparative Example 2)
50% by mass of a metal oxide having a metal composition of Mo _12.5 Bi _0.3 Fe _2.6 Ni _6.2 Mg _2.5 Cs _0.07 K _0.3 (α = 0.04, β = 0.45, γ = −0.62) A catalyst supported on a carrier was prepared as follows.

1666.7 g of an aqueous silica sol containing 30% by mass of SiO ₂ having an average particle diameter of silica primary particles of 12 nm was prepared. Next, a solution obtained by dissolving 417.0 g of ammonium paramolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O] in 834 g of water was added to the aqueous silica sol to obtain a mixed solution. Next, 27.8 g of bismuth nitrate [Bi (NO ₃ ) ₃ .5H ₂ O] and 200.5 g of iron nitrate [Fe (NO ₃ ) ₃ .9H ₂ O are added to 413.3 g of nitric acid having a concentration of 16.6% by mass. 345.2 g of nickel nitrate [Ni (NO ₃ ) 2 .6H ₂ O], 122.7 g of magnesium nitrate [Mg (NO ₃ ) ₂ .6H ₂ O], 2.59 g of cesium nitrate [CsNO ₃ ] A liquid obtained by dissolving 5.72 g of potassium nitrate [KNO ₃ ] was added to the above mixed liquid to obtain an aqueous raw material mixture (raw material slurry). Next, the above aqueous raw material mixture was spray-dried under conditions of an inlet temperature of about 250 ° C. and an outlet temperature of about 140 ° C. using a spray device equipped with a dish-shaped rotor installed in the upper center of the dryer. Next, the dried catalyst precursor was pre-fired at 320 ° C. for 2 hours in an air atmosphere using an electric furnace, and then finally fired at 640 ° C. for 2 hours in an air atmosphere. 798 g of catalyst was obtained.

When a part of the obtained catalyst was taken out and the pore distribution was measured, the pore volume occupied by pores having a pore diameter of 1 to 200 nm was 0.201 cc, and the pore volume occupied by pores having a pore diameter of 8 nm or less was It was 0.049 cc / g, and the cumulative volume (pore ratio) of pores having a pore diameter of 80 nm or less with respect to the total pore volume was 24.4%. Further, the catalyst was a solid sphere, the average particle size was 62 μm, and the apparent specific gravity was 1.02 g / cc. Next, 50 g of this catalyst was used to carry out an ammoxidation reaction of propylene with a contact time Θ = 5.5 (sec · g / cc). After 24 hours from the start of the reaction, the propylene conversion was 99.4%, the acrylonitrile selectivity was 82.2%, and the acrylonitrile yield was 81.7%. Further, the reaction was continued under the same conditions, and the reaction gas was analyzed 1000 hours after the start of the reaction. As a result, the propylene conversion was 98.3%, the acrylonitrile selectivity was 81.7%, and the acrylonitrile yield. It became 80.3%, and it turned out that it has fallen with respect to the performance after 24 hours.
Further, when the wear resistance strength of the catalyst 50g was measured according to the ACC method, the wear loss (%) was 0.3%.
The catalyst composition and calcination temperature are shown in Table 1, and the reaction results and physical property measurement results are shown in Table 2.

(Comparative Example 3)
A metal oxide having a metal composition of Mo ₁₂ Bi _0.24 Ce _0.16 Fe _2.28 Ni _5.7 Mg _2.3 Rb _0.15 (α = 0.05, β = 0.43, γ = 0) is supported on a 40% by mass silica support. The prepared catalyst was prepared as follows.

666.7 g of an aqueous silica sol containing 30% by mass of SiO ₂ having an average particle diameter of 12 nm of silica primary particles and 492.6 g of an aqueous silica sol containing 40.6% by mass of SiO ₂ having an average particle diameter of 41 nm of silica primary particles. A first mixed solution was obtained by mixing. Next, a solution obtained by dissolving 507.2 g of ammonium paramolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O] in 1014 g of water is added to the first mixed solution to obtain a second mixed solution. It was. Subsequently, 28.1 g of bismuth nitrate [Bi (NO ₃ ) ₃ .5H ₂ O] and 16.5 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] are added to 419 g of nitric acid having a concentration of 16.6% by mass. 222.8 g of iron nitrate [Fe (NO ₃ ) ₃ .9H ₂ O], 402.1 g of nickel nitrate [Ni (NO ₃ ) ₂ .6H ₂ O], 143.0 g of magnesium nitrate [Mg (NO ₃ ) ₂ · 6H ₂ O], rubidium nitrate [RbNO _3] solution obtained by dissolving the 5.27 g, was obtained aqueous raw material mixture (slurry) was added to the second mixture. Next, the above aqueous raw material mixture was spray-dried under conditions of an inlet temperature of about 250 ° C. and an outlet temperature of about 140 ° C. using a spray device equipped with a dish-shaped rotor installed in the upper center of the dryer. Next, the dried catalyst precursor was pre-fired at 320 ° C. for 2 hours in an air atmosphere using an electric furnace, and then finally fired at 580 ° C. for 2 hours in an air atmosphere. 818 g of catalyst was obtained.

When a part of the obtained catalyst was taken out and the pore distribution was measured, the pore volume occupied by pores having a pore diameter of 1 to 200 nm was 0.214 cc, and the pore volume occupied by pores having a pore diameter of 8 nm or less was The total volume (pore ratio) of pores having a pore diameter of 80 nm or less with respect to the total pore volume was 4.7%. Further, the shape of the catalyst was a solid sphere, the average particle size was 61 μm, and the apparent specific gravity was 1.00 g / cc. Next, 50 g of this catalyst was used to carry out ammoxidation of propylene with a contact time Θ = 4.8 (sec · g / cc). After 24 hours from the start of the reaction, the propylene conversion was 99.2%, the acrylonitrile selectivity was 82.9%, and the acrylonitrile yield was 82.2%.
Further, when the wear resistance strength of the catalyst 50g was measured according to the ACC method, the wear loss (%) was 1.0%.
The catalyst composition and calcination temperature are shown in Table 1, and the reaction results and physical property measurement results are shown in Table 2.

(Comparative Example 4)
46 mass% silica support containing a metal oxide having a metal composition of Mo ₁₂ Bi _0.42 Ce _0.1 Fe _2.8 Ni _5.61 Mg _1.4 K _0.25 (α = 0.07, β = 0.60, γ = 0.01) The catalyst supported on was prepared as follows.

766.7 g of an aqueous silica sol containing 30% by mass of SiO ₂ having an average particle diameter of 12 nm of silica primary particles, and 566.5 g of an aqueous silica sol containing 40.6% by mass of SiO ₂ having an average particle diameter of 41 nm of silica primary particles. A first mixed solution was obtained by mixing. Next, a solution obtained by dissolving 451.4 g of ammonium paramolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O] in 903 g of water is added to the first mixed solution to obtain a second mixed solution. It was. Next, 43.8 g of bismuth nitrate [Bi (NO ₃ ) ₃ .5H ₂ O] and 9.20 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] are added to 413 g of nitric acid having a concentration of 16.6% by mass. 243.5 g of iron nitrate [Fe (NO ₃ ) ₃ .9H ₂ O], 352.2 g of nickel nitrate [Ni (NO ₃ ) ₂ .6H ₂ O], 77.5 g of magnesium nitrate [Mg (NO ₃ ) ₂ · 6H ₂ O], a solution obtained by dissolving 5.38 g of potassium nitrate [KNO ₃ ] was added to the second mixed solution to obtain an aqueous raw material mixture (raw material slurry). Next, the above aqueous raw material mixture was spray-dried under conditions of an inlet temperature of about 250 ° C. and an outlet temperature of about 140 ° C. using a spray device equipped with a dish-shaped rotor installed in the upper center of the dryer. Next, the dried catalyst precursor was pre-fired at 320 ° C. for 2 hours in an air atmosphere using an electric furnace, and then finally fired at 590 ° C. for 2 hours in an air atmosphere. 820 g of catalyst was obtained.

When a part of the obtained catalyst was taken out and the pore distribution was measured, the pore volume occupied by pores having a pore diameter of 1 to 200 nm was 0.206 cc, and the pore volume occupied by pores having a pore diameter of 8 nm or less was It was 0.009 cc / g, and the cumulative volume (pore ratio) of pores having a pore diameter of 80 nm or less with respect to the total pore volume was 4.4%. Further, the catalyst was a solid sphere, the average particle diameter was 69 μm, and the apparent specific gravity was 0.96 g / cc. Next, 50 g of this catalyst was used to carry out an ammoxidation reaction of propylene with a contact time Θ = 3.9 (sec · g / cc). After 24 hours from the start of the reaction, the propylene conversion was 99.4%, the acrylonitrile selectivity was 82.8%, and the acrylonitrile yield was 82.3%.
Further, when the wear resistance strength of the catalyst 50 g was measured according to the ACC method, the wear loss (%) was 0.8%.
The catalyst composition and calcination temperature are shown in Table 1, and the reaction results and physical property measurement results are shown in Table 2.

(Comparative Example 5)
46% by mass of a metal oxide having a metal composition of Mo _11.5 Bi _1.94 Ce _0.34 Fe _1.32 Ni _5.27 Mg _1.32 K _0.2 (α = 0.40, β = 0.30, γ = −0.49) A catalyst supported on a carrier was prepared as follows.

766.7 g of an aqueous silica sol containing 30% by mass of SiO ₂ having an average particle diameter of 12 nm of silica primary particles, and 566.5 g of an aqueous silica sol containing 40.6% by mass of SiO ₂ having an average particle diameter of 41 nm of silica primary particles. A first mixed solution was obtained by mixing. Next, a solution in which 405.2 g of ammonium paramolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O] is dissolved in 810 g of water is added to the first mixed solution to obtain a second mixed solution. It was. Next, 399.5 g of nitric acid with a concentration of 16.6% by mass was added to 189.5 bismuth nitrate [Bi (NO ₃ ) ₃ .5H ₂ O] and 29.3 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O 107.5 g of iron nitrate [Fe (NO ₃ ) ₃ .9H ₂ O], 309.9 g of nickel nitrate [Ni (NO ₃ ) ₂ .6H ₂ O], 68.4 g of magnesium nitrate [Mg (NO _{3) 2} · 6H ₂ O], a solution obtained by dissolving potassium nitrate [KNO _3] of 4.03 g, was obtained aqueous raw material mixture (slurry) was added to the second mixture. Next, the above aqueous raw material mixture was spray-dried under conditions of an inlet temperature of about 250 ° C. and an outlet temperature of about 140 ° C. using a spray device equipped with a dish-shaped rotor installed in the upper center of the dryer. Next, the dried catalyst precursor was pre-baked at 320 ° C. for 2 hours in an air atmosphere using an electric furnace, and then subjected to main baking at 600 ° C. for 2 hours in an air atmosphere to finally obtain 807 g. The catalyst was obtained.

When a part of the obtained catalyst was taken out and the pore distribution was measured, the pore volume occupied by pores having a pore diameter of 1 to 200 nm was 0.217 cc, and the pore volume occupied by pores having a pore diameter of 8 nm or less was The integrated volume (pore ratio) of pores having a pore diameter of 80 nm or less with respect to the total pore volume was 5.5%. The catalyst was a solid sphere, the average particle size was 64 μm, and the apparent specific gravity was 0.97 g / cc. Next, 50 g of this catalyst was used to carry out ammoxidation reaction of propylene with a contact time Θ = 4.3 (sec · g / cc). After 24 hours from the start of the reaction, the propylene conversion was 99.0%, the acrylonitrile selectivity was 83.3%, and the acrylonitrile yield was 82.5%.
Further, when the wear resistance strength of the catalyst 50g was measured according to the ACC method, the wear loss (%) was 0.7%.
The catalyst composition and calcination temperature are shown in Table 1, and the reaction results and physical property measurement results are shown in Table 2.

(Comparative Example 6)
A metal oxide represented by Mo _13.6 Bi _0.03 Ce _0.05 Fe _1.32 Ni _9.9 Cs _0.04 (α = 0.01, β = 0.2, γ = 1.6) is supported on a 50% by mass silica support. The prepared catalyst was prepared as follows.

1667 g of an aqueous silica sol containing 30% by mass of SiO ₂ having an average particle diameter of 12 nm of silica primary particles was prepared. Next, a solution obtained by dissolving 428.2 g of ammonium paramolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O] in 856 g of water was added to the aqueous silica sol to obtain a mixed solution. Next, 2.62 g of bismuth nitrate [Bi (NO ₃ ) ₃ .5H ₂ O] and 3.85 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] are added to 408 g of nitric acid having a concentration of 16.6% by mass. Dissolves 96.08 g of iron nitrate [Fe (NO ₃ ) ₃ · 9H ₂ O], 520.3 g of nickel nitrate [Ni (NO ₃ ) ₂ · 6H ₂ O], 1.395 g of cesium nitrate [CsNO ₃ ] The obtained liquid was added to the above mixed liquid to obtain an aqueous raw material mixture (raw material slurry). Next, the above aqueous raw material mixture was spray-dried under conditions of an inlet temperature of about 250 ° C. and an outlet temperature of about 140 ° C. using a spray device equipped with a dish-shaped rotor installed in the upper center of the dryer. Next, the dried catalyst precursor was pre-fired at 320 ° C. for 2 hours in an air atmosphere using an electric furnace, and then finally fired at 600 ° C. for 2 hours in an air atmosphere. 788 g of catalyst was obtained.

When a part of the obtained catalyst was taken out and the pore distribution was measured, the pore volume occupied by pores having a pore diameter of 1 to 200 nm was 0.197 cc, and the pore volume occupied by pores having a pore diameter of 8 nm or less was The integrated volume (pore ratio) of pores having a pore diameter of 80 nm or less with respect to the total pore volume was 31.0%. Further, the catalyst was a solid sphere, the average particle size was 63 μm, and the apparent specific gravity was 1.01 g / cc. Next, 50 g of this catalyst was used to carry out ammoxidation of propylene with a contact time Θ = 3.5 (sec · g / cc). After 24 hours from the start of the reaction, the propylene conversion was 99.2%, the acrylonitrile selectivity was 45.4%, and the acrylonitrile yield was 45.0%.
Further, when the wear resistance strength of the catalyst 50g was measured according to the ACC method, the wear loss (%) was 0.2%.
The catalyst composition and calcination temperature are shown in Table 1, and the reaction results and physical property measurement results are shown in Table 2.

Example 9
50% by mass of a metal oxide having a metal composition represented by Mo ₁₂ Bi _0.33 Ce _0.22 Fe _1.95 Ni _6.2 Mg _2.5 Sb _0.3 Rb _0.15 (α = 0.07, β = 0.34, γ = −0.75) A catalyst supported on a silica support was prepared as follows.

1232 g of an aqueous silica sol containing 40.6% by mass of SiO ₂ having an average particle diameter of silica primary particles of 41 nm was prepared. Next, a solution obtained by dissolving 407.6 g of ammonium paramolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O] in 815 g of water was added to the aqueous silica sol to obtain a mixed solution. Next, 42. 6 g of nitric acid having a concentration of 16.6% by mass was added to 31.1 g of bismuth nitrate [Bi (NO ₃ ) ₃ .5H ₂ O] and 18.3 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O. 153.1 g of iron nitrate [Fe (NO ₃ ) ₃ .9H ₂ O], 351.4 g of nickel nitrate [Ni (NO ₃ ) ₂ .6H ₂ O], 124.9 g of magnesium nitrate [Mg (NO _{3) 2} · 6H ₂ O], a solution obtained by dissolving a nitrate rubidium 4.23g [RbNO _3] was added to the mixed solution, there further trioxide antimony 8.52g [Sb ₂ O ₃ ] Was finally added to obtain 175 g of a 20% by mass aqueous solution of tartaric acid to obtain an aqueous raw material mixture (raw material slurry) (first step). Using the spray device equipped with a dish-shaped rotor installed in the upper center of the dryer, the aqueous raw material mixture was spray-dried under conditions of an inlet temperature of about 250 ° C. and an outlet temperature of about 140 ° C. (second step) . The dried catalyst precursor was then pre-baked at 320 ° C. for 2 hours in an air atmosphere using an electric furnace, and then subjected to main baking at 655 ° C. for 2 hours in an air atmosphere (third Step) and finally 801 g of catalyst was obtained.

When a part of the obtained catalyst was taken out and the pore distribution was measured, the pore volume occupied by pores having a pore diameter of 1 to 200 nm was 0.209 cc, and the pore volume occupied by pores having a pore diameter of 8 nm or less was The integrated volume (pore ratio) of pores having a pore diameter of 80 nm or less with respect to the total pore volume was 2.9%. The catalyst was a solid sphere, the average particle size was 62 μm, and the apparent specific gravity was 0.90 g / cc. Next, 50 g of this catalyst was used to carry out ammoxidation reaction of propylene with a contact time Θ = 4.3 (sec · g / cc). After 24 hours from the start of the reaction, the propylene conversion was 99.2%, the acrylonitrile selectivity was 85.3%, and the acrylonitrile yield was 84.6%.
Further, when the wear resistance strength of the catalyst 50g was measured according to the ACC method, the wear loss (%) was 1.6%.
The catalyst composition and calcination temperature are shown in Table 3, and the reaction results and physical property measurement results are shown in Table 4.

(Example 10)
50% by mass of a metal oxide whose metal composition is represented by Mo ₁₂ Bi _0.22 Ce _0.15 Fe _1.4 Ni ₇ Mg _2.8 Sb _0.3 Rb _0.15 (α = 0.05, β = 0.21, γ = −0.76) A catalyst supported on a silica support was prepared as follows.

1232 g of an aqueous silica sol containing 40.6% by mass of SiO ₂ having an average particle diameter of silica primary particles of 41 nm was prepared. Next, a solution in which 409.0 g of ammonium paramolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O] was dissolved in 818 g of water was added to the aqueous silica sol to obtain a mixed solution. Subsequently, 20.8 g of bismuth nitrate [Bi (NO ₃ ) ₃ .5H ₂ O] and 12.5 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] in 429 g of nitric acid having a concentration of 16.6% by mass, 110.3 g of iron nitrate [Fe (NO ₃ ) ₃ .9H ₂ O], 398.2 g of nickel nitrate [Ni (NO ₃ ) ₂ .6H ₂ O], 140.4 g of magnesium nitrate [Mg (NO ₃ ) ₂ · 6H ₂ O], a solution obtained by dissolving a nitrate rubidium 4.25g [RbNO _3] was added to the mixed solution, there further trioxide antimony 8.55g [Sb ₂ O _3] Finally, a solution dissolved in 176 g of a 20 mass% tartaric acid aqueous solution was added to obtain an aqueous raw material mixture (raw material slurry) (first step). Using the spray device equipped with a dish-shaped rotor installed in the upper center of the dryer, the aqueous raw material mixture was spray-dried under conditions of an inlet temperature of about 250 ° C. and an outlet temperature of about 140 ° C. (second step) . Next, the dried catalyst precursor was pre-baked at 320 ° C. for 2 hours in an air atmosphere using an electric furnace, and then subjected to main baking at 670 ° C. for 2 hours in an air atmosphere (third Step) and finally 821 g of catalyst was obtained.

When a part of the obtained catalyst was taken out and the pore distribution was measured, the pore volume occupied by pores having a pore diameter of 1 to 200 nm was 0.222 cc, and the pore volume occupied by pores having a pore diameter of 8 nm or less was The integrated volume (pore ratio) of pores having a pore diameter of 80 nm or less with respect to the total pore volume was 3.2%. Further, the shape of the catalyst was a solid sphere, the average particle size was 65 μm, and the apparent specific gravity was 0.91 g / cc. Next, 50 g of this catalyst was used to carry out ammoxidation of propylene with a contact time Θ = 4.2 (sec · g / cc). After 24 hours from the start of the reaction, the propylene conversion was 99.2%, the acrylonitrile selectivity was 85.7%, and the acrylonitrile yield was 85.0%.
Further, when the wear resistance strength of the catalyst 50g was measured according to the ACC method, the wear loss (%) was 0.5%.
The catalyst composition and calcination temperature are shown in Table 3, and the reaction results and physical property measurement results are shown in Table 4.

Example 11
40% by mass of a metal oxide having a metal composition represented by Mo ₁₂ Bi _0.3 Ce _0.27 Fe _1.7 Ni _6.5 Mg _2.6 P _0.3 Rb _0.1 (α = 0.07, β = 0.28, γ = −0.81) A catalyst supported on a silica support was prepared as follows.

7.99 g of phosphoric acid was added dropwise to 985.2 g of an aqueous silica sol containing 40.6% by mass of SiO ₂ having an average particle diameter of 41 nm of silica primary particles to obtain a first mixed solution. Next, a solution in which 492.7 g of ammonium paramolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O] was dissolved in 985 g of water was added to the first mixture to obtain a second mixture. . Further, 416 g of nitric acid having a concentration of 16.6% by mass includes 34.2 g of bismuth nitrate [Bi (NO ₃ ) ₃ .5H ₂ O], 27.1 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O], 161.3 g of iron nitrate [Fe (NO ₃ ) ₃ .9H ₂ O], 445.4 g of nickel nitrate [Ni (NO ₃ ) ₂ .6H ₂ O], 157 g of magnesium nitrate [Mg (NO ₃ ) _2. 6H ₂ O], a solution obtained by dissolving 3.41 g of rubidium nitrate [RbNO ₃ ] was added to the second mixed solution to obtain an aqueous raw material mixture (raw material slurry) (first step). Using the spray device equipped with a dish-shaped rotor installed in the upper center of the dryer, the aqueous raw material mixture was spray-dried under conditions of an inlet temperature of about 250 ° C. and an outlet temperature of about 140 ° C. (second step) . Next, the dried catalyst precursor was pre-baked at 320 ° C. for 2 hours in an air atmosphere using an electric furnace, and then subjected to main baking at 620 ° C. for 2 hours in an air atmosphere (third Step) and finally 797 g of catalyst were obtained.

When a part of the obtained catalyst was taken out and the pore distribution was measured, the pore volume occupied by pores having a pore diameter of 1 to 200 nm was 0.213 cc, and the pore volume occupied by pores having a pore diameter of 8 nm or less was It was 0.005 cc / g, and the cumulative volume (pore ratio) of pores having a pore diameter of 80 nm or less with respect to the total pore volume was 2.3%. Further, the catalyst was a solid sphere, the average particle size was 60 μm, and the apparent specific gravity was 1.01 g / cc. Next, 50 g of this catalyst was used to carry out an ammoxidation reaction of propylene with a contact time Θ = 3.9 (sec · g / cc). After 24 hours from the start of the reaction, propylene conversion was 99.2%, acrylonitrile selectivity was 85.5%, and acrylonitrile yield was 84.8%.
Further, when the wear resistance strength of the catalyst 50 g was measured according to the ACC method, the wear loss (%) was 1.8%.
The catalyst composition and calcination temperature are shown in Table 3, and the reaction results and physical property measurement results are shown in Table 4.

Example 12
40% by mass of a metal oxide having a metal composition represented by Mo _12.4 Bi _0.24 Ce _0.16 Fe _1.52 Ni _3.9 Co _2.6 Mg _2.65 Rb _0.15 (α = 0.05, β = 0.25, γ = 0.37) A catalyst supported on a silica support was prepared as follows.

666.7 g of an aqueous silica sol containing 30% by mass of SiO ₂ having an average particle diameter of 12 nm of silica primary particles and 492.6 g of an aqueous silica sol containing 40.6% by mass of SiO ₂ having an average particle diameter of 41 nm of silica primary particles. A first mixed solution was obtained by mixing. Next, a solution in which 509.7 g of ammonium paramolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O] is dissolved in 1019 g of water is added to the first mixed solution to obtain a second mixed solution. It was. Furthermore, 27.4 g of bismuth nitrate [Bi (NO ₃ ) ₃ .5H ₂ O] and 16.1 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] are added to 418 g of nitric acid having a concentration of 16.6% by mass. 144.4 g of iron nitrate [Fe (NO ₃ ) ₃ .9H ₂ O], 267.6 g of nickel nitrate [Ni (NO ₃ ) ₂ .6H ₂ O], 178.5 g of cobalt nitrate [Co (NO ₃ ) ₂ · 6H ₂ O], 160.2 g of magnesium nitrate [Mg (NO ₃ ) ₂ · 6H ₂ O], and 5.12 g of rubidium nitrate [RbNO ₃ ] were dissolved in the second solution. In addition to the mixed solution, an aqueous raw material mixture (raw material slurry) was obtained (first step). Next, the aqueous raw material mixture was spray-dried under conditions of an inlet temperature of about 250 ° C. and an outlet temperature of about 140 ° C. using a spray device equipped with a dish-shaped rotor installed in the upper center of the dryer (second). Process). Next, the dried catalyst precursor was pre-baked at 320 ° C. for 2 hours in an air atmosphere using an electric furnace, and then subjected to main baking at 590 ° C. for 2 hours in an air atmosphere (third Step), finally 791 g of catalyst was obtained.

When a part of the obtained catalyst was taken out and the pore distribution was measured, the pore volume occupied by pores having a pore diameter of 1 to 200 nm was 0.199 cc, and the pore volume occupied by pores having a pore diameter of 8 nm or less was It was 0.007 cc / g, and the cumulative volume (pore ratio) of pores having a pore diameter of 80 nm or less with respect to the total pore volume was 3.5%. Further, the shape of the catalyst was a solid sphere, the average particle size was 60 μm, and the apparent specific gravity was 1.00 g / cc. Next, 50 g of this catalyst was used to carry out ammoxidation of propylene with a contact time Θ = 4.8 (sec · g / cc). After 24 hours from the start of the reaction, the propylene conversion was 99.1%, the acrylonitrile selectivity was 85.2%, and the acrylonitrile yield was 84.4%.
Further, when the wear resistance strength of the catalyst 50g was measured according to the ACC method, the wear loss (%) was 1.0%.
The catalyst composition and calcination temperature are shown in Table 3, and the reaction results and physical property measurement results are shown in Table 4.

(Example 13)
45% by mass of a metal oxide having a metal composition of Mo _12.5 Bi _0.22 Ce _0.09 Fe _1.82 Ni _6.17 Mg _1.64 Zn _1.0 Rb _0.13 (α = 0.04, β = 0.31, γ = 0.50) A catalyst supported on a silica support was prepared as follows.

1500 g of an aqueous silica sol containing 30% by mass of SiO ₂ having an average particle diameter of silica primary particles of 12 nm was prepared. Next, a solution in which 464.6 g of ammonium paramolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O] was dissolved in 929 g of water was added to the aqueous silica sol to obtain a mixed solution. Further, 2413 g of bismuth nitrate [Bi (NO ₃ ) ₃ .5H ₂ O] and 8.18 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] are added to 413 g of nitric acid having a concentration of 16.6% by mass. 156.4 g of iron nitrate [Fe (NO ₃ ) ₃ .9H ₂ O], 382.7 g of nickel nitrate [Ni (NO ₃ ) ₂ .6H ₂ O], 89.7 g of magnesium nitrate [Mg (NO ₃ ) ₂ · 6H ₂ O], 62.8 g of zinc nitrate [Zn (NO ₃ ) ₂ · 6H ₂ O] and 4.01 g of rubidium nitrate [RbNO ₃ ] were dissolved in the above mixture. In addition, an aqueous raw material mixture (raw material slurry) was obtained (first step). Next, the aqueous raw material mixture was spray-dried under conditions of an inlet temperature of about 250 ° C. and an outlet temperature of about 140 ° C. using a spray device equipped with a dish-shaped rotor installed in the upper center of the dryer (second). Process). Next, the dried catalyst precursor was pre-baked at 320 ° C. for 2 hours in an air atmosphere using an electric furnace, and then subjected to main baking at 600 ° C. for 2 hours in an air atmosphere (third Step), finally 814 g of catalyst was obtained.

When a part of the obtained catalyst was taken out and the pore distribution was measured, the pore volume occupied by pores having a pore diameter of 1 to 200 nm was 0.206 cc, and the pore volume occupied by pores having a pore diameter of 8 nm or less was The integrated volume (pore ratio) of pores having a pore diameter of 80 nm or less with respect to the total pore volume was 24.8%. Further, the catalyst was a solid sphere, the average particle size was 61 μm, and the apparent specific gravity was 0.99 g / cc. Next, 50 g of this catalyst was used to carry out ammoxidation of propylene with a contact time Θ = 4.2 (sec · g / cc). After 24 hours from the start of the reaction, the propylene conversion was 99.2%, the acrylonitrile selectivity was 84.7%, and the acrylonitrile yield was 84.0%.
Further, when the wear resistance strength of the catalyst 50g was measured according to the ACC method, the wear loss (%) was 0.2%.
The catalyst composition and calcination temperature are shown in Table 3, and the reaction results and physical property measurement results are shown in Table 4.

(Comparative Example 7)
40% by mass of a metal oxide whose metal composition is represented by Mo ₁₂ Bi _0.45 Ce _0.9 Fe _1.80 Ni ₅ Mg ₂ Sb _0.5 Rb _0.15 (α = 0.21, β = 0.39, γ = −0.23) A catalyst supported on a silica support was prepared as follows.

666.7 g of an aqueous silica sol containing 30% by mass of SiO ₂ having an average particle diameter of 12 nm of silica primary particles and 492.6 g of an aqueous silica sol containing 40.6% by mass of SiO ₂ having an average particle diameter of 41 nm of silica primary particles. A first mixed solution was obtained by mixing. Next, a solution obtained by dissolving 480.4 g of ammonium paramolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O] in 961 g of water is added to the first mixed solution, and the second mixed solution is added. Obtained. Subsequently, 50.0 g of bismuth nitrate [Bi (NO ₃ ) ₃ .5H ₂ O] and 88.1 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O are added to 442.7 g of nitric acid having a concentration of 16.6% by mass. 166.6 g of iron nitrate [Fe (NO ₃ ) ₃ .9H ₂ O], 334.1 g of nickel nitrate [Ni (NO ₃ ) ₂ .6H ₂ O], 117.8 g of magnesium nitrate [Mg (NO _{3) 2} · 6H ₂ O], a solution obtained by dissolving potassium nitrate [KNO _3] of 4.99 g, was added to the second mixture, there further antimony trioxide 16.74g [Sb ₂ O ₃ ] dissolved in 344.2 g of a 20% by mass tartaric acid aqueous solution was finally added to obtain an aqueous raw material mixture (raw material slurry). Next, the above aqueous raw material mixture was spray-dried under conditions of an inlet temperature of about 250 ° C. and an outlet temperature of about 140 ° C. using a spray device equipped with a dish-shaped rotor installed in the upper center of the dryer. Next, the dried catalyst precursor was pre-fired at 320 ° C. for 2 hours in an air atmosphere using an electric furnace, and then finally fired at 615 ° C. for 2 hours in an air atmosphere. 793 g of catalyst was obtained.

When a part of the obtained catalyst was taken out and the pore distribution was measured, the pore volume occupied by pores having a pore diameter of 1 to 200 nm was 0.210 cc, and the pore volume occupied by pores having a pore diameter of 8 nm or less was The integrated volume (pore ratio) of pores having a pore diameter of 80 nm or less with respect to the total pore volume was 2.9%. Further, the catalyst was a solid sphere, the average particle size was 56 μm, and the apparent specific gravity was 0.98 g / cc. Next, 50 g of this catalyst was used to carry out ammoxidation of propylene with a contact time of 4.9 (sec · g / cc). After 24 hours from the start of the reaction, the propylene conversion was 99.2%, the acrylonitrile selectivity was 82.2%, and the acrylonitrile yield was 81.5%.
Further, when the wear resistance strength of the catalyst 50 g was measured according to the ACC method, the wear loss (%) was 0.9%.
The catalyst composition and calcination temperature are shown in Table 3, and the reaction results and physical property measurement results are shown in Table 4.

(Comparative Example 8)
40% by mass of a metal oxide whose metal composition is represented by Mo ₁₂ Bi _0.4 Ce _0.26 Fe _2.1 Ni ₆ Mg _2.4 P _0.3 Rb _0.1 (α = 0.09, β = 0.38, γ = −0.84) A catalyst supported on a silica support was prepared as follows.

7.96 g of phosphoric acid was added dropwise to 985.2 g of an aqueous silica sol containing 40.6% by mass of SiO ₂ having an average particle diameter of 41 nm of silica primary particles to obtain a mixed solution. Next, a solution in which 491.2 g of ammonium paramolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O] was dissolved in 982 g of water was added to the above mixture, and further, 16.6% by mass concentration was added thereto. 45.4 g of bismuth nitrate [Bi (NO ₃ ) ₃ .5H ₂ O], 26.0 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O], 198.7 g of iron nitrate [Fe (NO ₃ ) ₃ · 9H ₂ O], 409.9 g of nickel nitrate [Ni (NO ₃ ) ₂ · 6H ₂ O], 144.5 g of magnesium nitrate [Mg (NO ₃ ) ₂ · 6H ₂ O], 3 A liquid obtained by dissolving 40 g of rubidium nitrate [RbNO ₃ ] was added to obtain an aqueous raw material mixture (raw material slurry). Next, the above aqueous raw material mixture was spray-dried under conditions of an inlet temperature of about 250 ° C. and an outlet temperature of about 140 ° C. using a spray device equipped with a dish-shaped rotor installed in the upper center of the dryer. Next, the dried catalyst precursor was pre-fired at 320 ° C. for 2 hours in an air atmosphere using an electric furnace, and then finally fired at 580 ° C. for 2 hours in an air atmosphere. 804 g of catalyst was obtained.

When a part of the obtained catalyst was taken out and the pore distribution was measured, the pore volume occupied by pores having a pore diameter of 1 to 200 nm was 0.221 cc, and the pore volume occupied by pores having a pore diameter of 8 nm or less was The integrated volume (pore ratio) of pores having a pore diameter of 80 nm or less with respect to the total pore volume was 1.8%. Further, the shape of the catalyst was a solid sphere, the average particle size was 60 μm, and the apparent specific gravity was 1.00 g / cc. Next, 50 g of this catalyst was used to carry out ammoxidation of propylene with a contact time Θ = 3.6 (sec · g / cc). After 24 hours from the start of the reaction, the propylene conversion was 99.3%, the acrylonitrile selectivity was 82.1%, and the acrylonitrile yield was 81.5%.
Further, when 50 g of the catalyst was measured for wear resistance strength according to the ACC method, the wear loss (%) was 3.7%, and the strength applicable to industrial use was not shown.
The catalyst composition and calcination temperature are shown in Table 3, and the reaction results and physical property measurement results are shown in Table 4.

(Example 14)
35% by mass of a metal oxide having a metal composition represented by Mo ₁₂ Bi _0.22 Ce _0.15 Fe _1.2 Ni ₇ Mg _2.8 Rb _0.12 (α = 0.05, β = 0.18, γ = −0.16) A catalyst supported on a carrier was prepared as follows.

862.1 g of an aqueous silica sol containing 40.6% by mass of SiO ₂ having an average particle diameter of silica primary particles of 41 nm was prepared. Next, a solution obtained by dissolving 544.7 g of ammonium paramolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O] in 1089 g of water was added to the aqueous silica sol to obtain a mixed solution. Next, 27.7 g of bismuth nitrate [Bi (NO ₃ ) ₃ .5H ₂ O] and 16.6 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O are added to 421.4 g of nitric acid having a concentration of 16.6% by mass. 125.9 g of iron nitrate [Fe (NO ₃ ) ₃ .9H ₂ O], 530.4 g of nickel nitrate [Ni (NO ₃ ) ₂ .6H ₂ O], 187.0 g of magnesium nitrate [Mg (NO _{3) 2} · 6H ₂ O], rubidium nitrate [RbNO _3] dissolved in the resulting solution of 4.52 g, was obtained aqueous raw material mixture (slurry) was added to the mixed solution (first step ). Next, the aqueous raw material mixture was spray-dried under conditions of an inlet temperature of about 250 ° C. and an outlet temperature of about 140 ° C. using a spray device equipped with a dish-shaped rotor installed in the upper center of the dryer (second). Process). The dried catalyst precursor was then pre-baked at 320 ° C. for 2 hours in an air atmosphere using an electric furnace, and then subjected to main baking at 640 ° C. for 2 hours in an air atmosphere (third Step) and finally 811 g of catalyst was obtained.

When a part of the obtained catalyst was taken out and the pore distribution was measured, the pore volume occupied by pores having a pore diameter of 1 to 200 nm was 0.229 cc, and the pore volume occupied by pores having a pore diameter of 8 nm or less was It was 0.005 cc / g, and the cumulative volume (pore ratio) of pores having a pore diameter of 80 nm or less with respect to the total pore volume was 2.2%. The catalyst was a solid sphere, the average particle size was 66 μm, and the apparent specific gravity was 1.02 g / cc. Next, 50 g of this catalyst was used to carry out ammoxidation of propylene with a contact time Θ = 4.9 (sec · g / cc). After 24 hours from the start of the reaction, the propylene conversion was 99.2%, the acrylonitrile selectivity was 86.9%, and the acrylonitrile yield was 86.2%.
Further, when the wear resistance strength of the catalyst 50 g was measured according to the ACC method, the wear loss (%) was 1.7%.
The catalyst composition and calcination temperature are shown in Table 3, and the reaction results and physical property measurement results are shown in Table 4.

(Example 15)
Silica support having a metal composition of Mo _12.2 Bi _0.24 Ce _0.16 Fe _1.52 Ni _6.5 Mg _2.6 K _0.19 (α = 0.05, β = 0.25, γ = 0.22) and 65% by mass The catalyst supported on was prepared as follows.

1083 g of an aqueous silica sol containing 30% by mass of SiO ₂ having an average particle diameter of 12 nm of silica primary particles and 800.5 g of an aqueous silica sol containing 40.6% by mass of SiO ₂ having an average particle diameter of 41 nm of silica primary particles were mixed. Thus, a first mixed solution was obtained. Next, a solution obtained by dissolving 296.7 g of ammonium paramolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O] in 593 g of water is added to the first mixed solution, and the second mixed solution is added. Obtained. Next, 402.5 g of nitric acid having a concentration of 16.6% by mass is mixed with 16.2 g of bismuth nitrate [Bi (NO ₃ ) ₃ .5H ₂ O] and 9.51 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O 85.4 g of iron nitrate [Fe (NO ₃ ) ₃ .9H ₂ O], 263.8 g of nickel nitrate [Ni (NO ₃ ) ₂ .6H ₂ O], 93.01 g of magnesium nitrate [Mg (NO _{3) 2} · 6H ₂ O], potassium nitrate [KNO _3] solution obtained by dissolving the 2.64 g, was obtained aqueous raw material mixture (slurry) was added to the second mixture (first Process). Next, the aqueous raw material mixture was spray-dried under conditions of an inlet temperature of about 250 ° C. and an outlet temperature of about 140 ° C. using a spray device equipped with a dish-shaped rotor installed in the upper center of the dryer (second). Process). Next, the dried catalyst precursor was pre-baked at 320 ° C. for 2 hours in an air atmosphere using an electric furnace, and then subjected to main baking at 590 ° C. for 2 hours in an air atmosphere (third Step), and finally 788 g of catalyst was obtained.

When a part of the obtained catalyst was taken out and the pore distribution was measured, the pore volume occupied by pores having a pore diameter of 1 to 200 nm was 0.219 cc, and the pore volume occupied by pores having a pore diameter of 8 nm or less was It was 0.008 cc / g, and the cumulative volume (pore ratio) of pores having a pore diameter of 80 nm or less with respect to the total pore volume was 3.7%. Further, the catalyst was a solid sphere, the average particle size was 59 μm, and the apparent specific gravity was 1.04 g / cc. Next, 50 g of this catalyst was used to carry out ammoxidation of propylene with a contact time Θ = 4.1 (sec · g / cc). After 24 hours from the start of the reaction, the propylene conversion was 99.4%, the acrylonitrile selectivity was 86.9%, and the acrylonitrile yield was 86.4%.
Further, when the wear resistance strength of the catalyst 50g was measured according to the ACC method, the wear loss (%) was 0.4%.
The catalyst composition and calcination temperature are shown in Table 3, and the reaction results and physical property measurement results are shown in Table 4.

(Comparative Example 9)
80% by mass of a metal oxide having a metal composition represented by Mo _11.2 Bi _0.35 Ce _0.35 Fe _0.15 Ni _8.92 Mg _2.24 K _0.13 (α = 0.09, β = 0.02, γ = −1.24) A catalyst supported on a carrier was prepared as follows.

2667 g of an aqueous silica sol containing 30% by mass of SiO ₂ having an average particle diameter of silica primary particles of 12 nm was prepared. Next, a solution obtained by dissolving 157.7 g of ammonium paramolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O] in 315 g of water was added to the aqueous silica sol to obtain a mixed solution. Next, 391 g of nitric acid having a concentration of 16.6% by mass was charged with 13.66 g of bismuth nitrate [Bi (NO ₃ ) ₃ .5H ₂ O], 12.05 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O], 4.88 g of iron nitrate [Fe (NO ₃ ) ₃ .9H ₂ O], 209.6 g of nickel nitrate [Ni (NO ₃ ) ₂ .6H ₂ O], 46.39 g of magnesium nitrate [Mg (NO ₃ ) ₂ · 6H ₂ O], a solution obtained by dissolving potassium nitrate [KNO _3] of 1.05 g, was obtained aqueous raw material mixture (slurry) was added to the above mixture. Next, the above aqueous raw material mixture was spray-dried under conditions of an inlet temperature of about 250 ° C. and an outlet temperature of about 140 ° C. using a spray device equipped with a dish-shaped rotor installed in the upper center of the dryer. Next, the dried catalyst precursor was pre-fired at 320 ° C. for 2 hours in an air atmosphere using an electric furnace, and then finally fired at 600 ° C. for 2 hours in an air atmosphere. 781 g of catalyst was obtained.
It was confirmed that the catalyst was a solid sphere, a hole, or a powder having a distorted shape with depressions on the surface of the sphere. Further, when the average particle diameter of this catalyst was measured, it was 60 μm, but the apparent specific gravity was as low as 0.83 g / cc.
Next, an attempt was made to carry out an ammoxidation reaction of propylene using 50 g of this catalyst, but the reaction was stopped at all even if the contact time Θ = 6 (sec · g / cc). The pore distribution measurement was not performed.
Table 3 shows the catalyst composition and calcination temperature, and Table 4 shows the physical property measurement results.

(Comparative Example 10)
A metal oxide having a metal composition of Mo _11.6 Bi _1.85 Fe _2.05 Ni _6.15 K _0.3 (α = 0.30, β = 0.50, γ = −0.40) was supported on a 25% by mass silica support. The catalyst was prepared as follows.

833.3 g of an aqueous silica sol containing 30% by mass of SiO ₂ having an average particle diameter of silica primary particles of 12 nm was prepared. Next, a solution in which 565.0 g of ammonium paramolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O] was dissolved in 1130 g of water was added to the aqueous silica sol to obtain a mixed solution. Next, 249.8 g of bismuth nitrate [Bi (NO ₃ ) ₃ .5H ₂ O] and 230.8 g of iron nitrate [Fe (NO ₃ ) ₃ .9H ₂ O are added to 401.3 g of nitric acid having a concentration of 16.6% by mass. ] A solution obtained by dissolving 499.9 g of nickel nitrate [Ni (NO ₃ ) ₂ .6H ₂ O] and 8.35 g of potassium nitrate [KNO ₃ ] is added to the above mixture to add an aqueous raw material mixture ( A raw slurry) was obtained. The aqueous raw material mixture was spray-dried under conditions of an inlet temperature of about 250 ° C. and an outlet temperature of about 140 ° C. using a spray device equipped with a dish-shaped rotor installed in the upper center of the dryer. Next, the dried catalyst precursor was pre-fired at 320 ° C. for 2 hours in an air atmosphere using an electric furnace, and then finally fired at 600 ° C. for 2 hours in an air atmosphere. 808 g of catalyst was obtained. The shape of the catalyst was a solid sphere, and the average particle diameter was measured to be 63 μm. The apparent specific gravity was 1.10 g / cc. Next, 50 g of this catalyst was used to carry out ammoxidation of propylene with a contact time Θ = 4.4 (sec · g / cc). After 24 hours from the start of the reaction, the propylene conversion was 99.2%, the acrylonitrile selectivity was 80.6%, and the acrylonitrile yield was 80.0%.
However, when the abrasion resistance strength of the catalyst 50g was measured according to the ACC method, the wear loss (%) was 4.2%, and the strength applicable to industrial use was not shown.
The catalyst composition and calcination temperature are shown in Table 3, and the reaction results and physical property measurement results are shown in Table 4.

  The ammoxidation catalyst for a fluidized bed of the present invention has a high yield of the target product under conditions where the amount of ammonia is small relative to propylene, isobutene or tertiary butanol, and is resistant to industrial use. Good handleability such as wear, apparent specific gravity, particle size, etc., and excellent reaction stability. By carrying out the ammoxidation reaction of propylene, isobutene or tertiary butanol in a fluidized bed reactor using the catalyst of the present invention, acrylonitrile or methacrylonitrile can be produced stably in a high yield. It is advantageous.

Claims (6)

A catalyst used for producing acrylonitrile or methacrylonitrile by reacting propylene, isobutene or tertiary butanol, molecular oxygen, and ammonia, which is represented by the following general formula (1)
_{Mo a Bi b Ce c Fe d} E e J f G g L h O i ··· (1)
(In the formula (1), E represents at least one element selected from the group consisting of nickel and cobalt, J represents at least one element selected from the group consisting of magnesium, zinc and manganese, and G represents antimony) And L represents at least one element selected from the group consisting of phosphorus, L represents at least one element selected from the group consisting of potassium, rubidium and cesium, and a, b, c, d, e, f, g And h each represent an atomic ratio of each element, 10 ≦ a ≦ 14, 0.03 ≦ b ≦ 1, 0.03 ≦ c ≦ 1, 0.5 ≦ d ≦ 4, 2 ≦ e ≦ 10, 0 ≦ f ≦ 8, 0 ≦ g ≦ 2, 0.02 ≦ h ≦ 1, and i represents an atomic ratio of oxygen atoms satisfying the valence of a constituent element other than oxygen.)
Α and β calculated by the following formulas (2) and (3) from the atomic ratio of each element are 0.02 ≦ α ≦ 0.08, 0.08 ≦ β ≦ A fluidized bed ammoxidation catalyst comprising: an oxide that simultaneously satisfies 0.35; and a carrier that supports the oxide.
α = 1.5 (b + c) / (1.5d + e + f) (2)
β = 1.5d / (e + f) (3) The ammoxidation catalyst for fluidized beds according to claim 1, wherein γ calculated from the atomic ratio of each element according to the following formula (4) satisfies −1 ≦ γ ≦ 1.5.
γ = a−1.5 (b + c + d) + e + f + g (4)   The ammoxidation catalyst for fluidized beds according to claim 1 or 2, wherein the carrier contains silica.   The ammoxidation catalyst for fluidized beds according to any one of claims 1 to 3, wherein the amount of silica in the carrier is 30 to 70% by mass.   The pore volume occupied by pores having a pore diameter of 8 nm or less is 20% or less, based on the total pore volume occupied by pores having a pore diameter of 1 to 200 nm, according to any one of claims 1 to 4. The ammoxidation catalyst for fluidized beds as described.   Using the ammoxidation catalyst for fluidized bed according to any one of claims 1 to 5, acrylonitrile or methacrylonitrile is produced by reacting propylene, isobutene or tertiary butanol, molecular oxygen and ammonia. A method for producing acrylonitrile or methacrylonitrile.