JP2003230835A - Method for manufacturing compound oxide catalyst - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst in which a catalytic performance such as a material conversion ratio and selectivity is enhanced as a catalyst used for any one reaction of a vapor phase catalytic oxidation reaction for manufacturing acrolein or methacrolein from propylene, isobutene or tert-butanol, a vapor-phase catalytic ammoxidation reaction for manufacturing acrylonitrile or methacrylonitrile from propylene or isobutene and a vapor-phase catalytic oxidative dehydrogenation reaction for manufacturing butadiene from butene. <P>SOLUTION: When a compound oxide catalyst containing at least Mo, Bi and Fe as component elements is manufactured by a step including an integration at an aqueous system of a supply source compound of the respective component elements and heating, the supply source compound of Bi hardly soluble in the aqueous system and having an average grain diameter of 6-50 μm is used. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a gas phase catalytic oxidation reaction for producing acrolein or methacrolein from propylene, isobutene or tertiary butanol, and a gas phase catalytic ammoxidation reaction for producing acrylonitrile or methacrylonitrile from propylene or isobutene. , And a complex oxide catalyst used in a selective reaction such as a gas phase catalytic oxidative dehydrogenation reaction for producing butadiene from butene, and a method for producing the same.

[0002]

2. Description of the Prior Art Gas phase catalytic oxidation reaction for producing acrolein or methacrolein from propylene, isobutene or tertiary butanol, gas phase catalytic ammoxidation reaction for producing acrylonitrile or methacrylonitrile from propylene or isobutene, and butadiene from butene. It is well known that the Mo-Bi-based composite oxide catalyst is a useful catalyst in the selective reaction such as the gas-phase catalytic oxidative dehydrogenation reaction to be produced, and it is industrially widely used. .

Patent documents relating to the composition and manufacturing method of the Mo-Bi type composite oxide in these various reactions include Japanese Patent Publication Nos. 39-3670 and 48-1645.
48-4763, 48-17253,
49-3498, 55-41213,
No. 56-14659, No. 56-23969, No. 56-52013, No. 57-26245, No. 48-503, No. 48-514, No. 48-52713. 48-54027, 48-57916, and 55-20610.
No. 55-47144, No. 55-8454.
1, gazette 59-76541 gazette, gazette 60-122.
Many publications such as the 041 publication are known.

Among these, Japanese Patent Application Laid-Open Nos. 55-47144 and 59-76541 disclose that Mo-Bi or WB should be prepared beforehand when a composite oxide catalyst is produced.
Except for the disclosure of producing i, all others use bismuth nitrate in the examples as a raw material for Bi, and in each description, a water-soluble bismuth compound as a raw material for Bi is used. That is, bismuth nitrate or hydroxide is recommended. The catalysts described in these are considered to be rational formulations considering the uniform dispersion of Bi in the composite oxide catalyst, but sufficient catalyst performance has not been obtained.

Further, Japanese Patent Publication No. 5-87300 discloses that
A composite oxide catalyst using bismuth subcarbonate in which Na is dissolved as a Bi raw material is disclosed, and Japanese Patent Publication No. 6-13096 discloses a bismuth subcarbonate in which any one of Mg, Ca, Zn, Ce and Sm is dissolved. Is disclosed as a Bi raw material, and Japanese Patent Publication No. 6-13097 discloses that
A composite oxide catalyst using bismuth subcarbonate in which any one of Mg, Ca, Zn, Ce and Sm and Na is solid-dissolved is disclosed as a Bi raw material. It is disclosed that these composite oxide catalysts have sufficient catalytic performance.

[0006]

By the way, the catalysts used in these reactions are required to have as high a catalytic performance as possible from the viewpoint of effective utilization of petroleum resources and rationalization of the steps in each of the above reactions. That is, when the raw material conversion rate and the selectivity are improved by 0.1%, the amount of the obtained product is several hundred to
Increase at the level of thousands of tons. Therefore, even if the catalyst performance such as the raw material conversion rate and the selectivity is improved, even if it is a little improvement, it will greatly contribute to the effective utilization of petroleum resources and the rationalization of the process.

Therefore, the present invention provides a gas phase catalytic oxidation reaction for producing acrolein or methacrolein from propylene, isobutene or tertiary butanol, a gas phase catalytic ammoxidation reaction for producing acrylonitrile or methacrylonitrile from propylene or isobutene, and butene. An object of the present invention is to provide, as a catalyst used in any one of the gas phase catalytic oxidative dehydrogenation reactions for producing butadiene from ethylene, a catalyst having further improved catalytic performance such as raw material conversion and selectivity.

[0008]

The present invention is directed to a vapor phase catalytic oxidation reaction for producing acrolein or methacrolein from propylene, isobutene or tertiary butanol, and a vapor phase catalytic ammonia for producing acrylonitrile or methacrylonitrile from propylene or isobutene. A composite containing at least molybdenum (Mo), bismuth (Bi) and iron (Fe) as constituent elements, which is used in any one of an oxidation reaction and a vapor phase catalytic oxidative dehydrogenation reaction for producing butadiene from butene. When the oxide catalyst is produced by a process including integration of a source compound of each component element in an aqueous system and heating, it is hardly soluble in the aqueous system and has an average particle size of 6 to 50 μm. By using a complex oxide catalyst characterized by using a source compound of bismuth (Bi) It was the above-mentioned problems are eliminated.

The complex oxide catalyst is preferably a complex oxide catalyst represented by the following general formula (1). Mo _a Bi _b Co _c Ni _d Fe _e Na _f Q _m Y _g Z _h Si _i X _j O _k (1) (wherein X represents halogen and Y represents at least 1 of K, Rb, Cs or Tl) Indicates the species, Z is B, P, A
at least one of s and W, and Q is M
At least one of g, Ca, Zn, Ce or Sm
Indicates the species. Further, a to k and m represent atomic ratios of respective elements, and when a = 12, b = 0.5 to 7 and c =
0-10, d = 0-10, c + d = 1-10, e = 0.
05-3, f = 0 to 1, m = 0 to 1, g = 0 to 0.4,
h = 0 to 3, i = 0 to 48, j = 0 to 0.5, and k are values satisfying the oxidation states of other elements. )

Since a complex oxide catalyst is produced by using a predetermined Bi source compound such as an oxide containing only Bi as a metal component, a single salt of Bi, or a double salt of Bi, in the integration step, Source compounds of Bi are Mo and F
It is possible to form bismuth molybdate in an environment in which it is dispersed in a predetermined range in a non-uniform manner with respect to e, etc., and is integrated in a predetermined range in a predetermined range with respect to Mo, Fe, etc. It is possible to obtain a complex oxide catalyst. By using this catalyst for a predetermined gas-phase catalytic oxidation reaction or the like, it is possible to further improve the catalyst performance, particularly the raw material conversion rate and selectivity.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. In the present invention, molybdenum (Mo), bismuth (Bi), silicon (Si), cobalt (Co), nickel (Ni), iron (Fe), magnesium (Mg), calcium (Ca), zinc (Zn). , Cerium (Ce), samarium (Sm), sodium (N
a), potassium (K), rubidium (Rb), cesium (Cs), thallium (Tl), boron (B), phosphorus (P), arsenic (As), tungsten (W), fluorine (F), chlorine ( Each element of Cl), bromine (Br), and iodine (I) is described using the element symbol in parentheses.

The complex oxide catalyst according to the present invention is a gas-phase catalytic oxidation reaction for producing acrolein or methacrolein from propylene, isobutene or tertiary butanol, and a gas-phase catalytic ammonia for producing acrylonitrile or methacrylonitrile from propylene or isobutene. Mo, which is used for any one of an oxidation reaction and a gas-phase catalytic oxidative dehydrogenation reaction for producing butadiene from butene.
It is an oxide catalyst containing at least Bi and Fe. When used in these reactions, higher catalyst conversion performance such as raw material conversion and selectivity can be obtained.

The above-mentioned oxide catalyst is produced by a process including integration of a source compound of each component element in an aqueous system and heating.

The above-mentioned source compound of each component element means one or two of the component elements constituting the above composite oxide catalyst.
A compound that contains one or more elements and can be made into an aqueous solution or a water suspension (for example, ammonium paramolybdate for Mo, ammonium phosphomolybdate for Mo and P, etc.).

The integration of the source compound of each component element in the aqueous system means that the aqueous solution or dispersion of the source compound of each component element is collectively or stepwise mixed or aged. . That is, (a) a method of collectively mixing the above-mentioned source compounds, (b) a method of collectively mixing the above-mentioned source compounds, and a aging treatment,
(C) A method of stepwise mixing the above-mentioned respective source compounds,
(D) The method of repeating stepwise mixing and aging treatment of each of the above source compounds, and the method of combining (a) to (d) are all integrated in the aqueous system of the above source element compounds. It is included in the concept of conversion. Here, the above-mentioned aging means
"Operation of processing industrial raw materials or semi-finished products under specific conditions such as constant time and constant temperature to obtain necessary physical properties and chemical properties, increase temperature, or progress predetermined reactions" Dictionary / Kyoritsu Publishing). In the present invention, the above-mentioned constant time refers to a range of 10 minutes to 24 hours, and the above-mentioned constant temperature refers to a range of room temperature to the boiling point of an aqueous solution or aqueous dispersion.

Further, the above integration does not mean that the above treatment is performed only on the source compound of each element, and alumina, silica-alumina, refractory oxide, etc., which may be used as necessary. The carrier material of (1) is also included as a target.

The above-mentioned heating means the formation of individual oxides or complex oxides of the source compounds of the above-mentioned respective component elements, formation of complex compound oxides or complex oxides formed by integration, and final formation. A heat treatment for forming a complex oxide. And heating is not necessarily limited to once. That is, this heating can be arbitrarily performed at each stage of the integration shown in the above (A) to (D), and may be additionally performed after the integration if necessary. The above heating temperature is usually 2
It is in the range of 00 ° C to 700 ° C.

Further, in the above integration and heating, other than these, for example, drying, crushing, molding, etc. may be performed before, after, or during the process.

Among the above-mentioned source compounds, the Bi source compound is a compound which is hardly soluble in an aqueous system. The hardly soluble compound in the aqueous system means a compound in which 90% or more of the compound is present in a solid state in an aqueous suspension state in the catalyst production process, or pure water 100 at a temperature of 20 ° C
A compound having a solubility in g of 1 g or less.

Further, the above Bi source compound is preferably a compound which exists stably in an aqueous system. For example, compounds that decompose in aqueous systems such as bismuth chloride are:
It is not preferable because it is difficult to control the particle size.

The average particle size of the Bi source compound in the present invention is preferably 6 to 50 μm, and more preferably 10 to 30 μm. By satisfying this condition, it is possible to further improve the catalyst performance, particularly the raw material conversion rate and selectivity.
The average particle size of the Bi source compound was measured by a laser diffraction type particle size distribution measuring method. LMS-24 manufactured by Seishin Enterprise Co., Ltd. is used as an analytical instrument, and the average particle size is 5 on a volume basis.
It is expressed as a 0% diameter.

Although it is not clear why the catalyst performance is improved by using the Bi source compound having the above-mentioned average particle size, the Bi source compound is added to the M source in the integration step.
It is possible to form bismuth molybdate in an environment in which O and Fe are non-uniformly dispersed in a predetermined range in a predetermined range and integrated, and which is non-uniformly dispersed in a predetermined range in Mo and Fe and the like by a heating process. Therefore, it is presumed that the formation of bismuth molybdate and the formation of the oxide containing other Mo as a constituent can be performed more suitably.

The source compound of Bi in the present invention is M
The oxide of o and Bi, that is, bismuth molybdate is not included. This is because when the bismuth molybdate is present before being subjected to a step including integration and heating in an aqueous system, the Bi source compound, which is the object of the present invention, has a predetermined content with respect to Mo, Fe and the like. This is because it becomes impossible to form bismuth molybdate in an environment in which the bismuth is non-uniformly dispersed within the range of, and the characteristics obtained by the manufacturing method according to the present invention cannot be sufficiently exhibited. Further, a compound that does not form bismuth molybdate in the integration and heating steps in an aqueous system is naturally not included. Specific examples thereof include bismuth tungstate. More preferably, the above Bi source compound, that is, a compound that reacts with Mo to form bismuth molybdate in the integration and heating steps in an aqueous system, is an oxide containing only Bi as a metal component, and Examples thereof include a single salt and a double salt of Bi.

Examples of the oxide containing only Bi as the metal component include bismuth oxide and the like.
Examples of the single salt of i include bismuth subcarbonate and the like, and examples of the double salt of Bi include a complex carbonate compound of Bi and Na.

Examples of the Mo source compound include ammonium paramolybdate, molybdenum trioxide, molybdic acid, ammonium phosphomolybdate, phosphomolybdic acid and the like. Examples of the Fe source compound include ferric nitrate, ferric sulfate, ferric chloride, ferric acetate and the like.

A preferred embodiment of the composite oxide catalyst obtained by the production method according to the present invention is the following general formula (1)
The catalyst represented by is exemplified. Mo _a Bi _b Co _c Ni _d Fe _e Na _f Q _m Y _g Z _h Si _i X _j O _k (1)

However, X represents halogen, Y represents K, R
at least one of b, Cs, and Tl, and Z
Represents at least one of B, P, As or W, and Q represents at least one of Mg, Ca, Zn, Ce or Sm. Further, a to k and m represent atomic ratios of the respective elements, and when a = 12, they are represented by the following range of values. b = 0.5 to 7, c = 0 to 10, d = 0 to 10, c + d = 1 to 10, e = 0.05 to 3, f = 0 to 1, m = 0 to 1, g = 0 to 0 0.4, h = 0 to 3, i = 0 to 48, j = 0 to 0.5, k is a value satisfying the oxidation states of other elements

As shown in the general formula (1), the above composite oxide catalyst may contain halogen as a component element thereof. The mechanism of action of the halogen in the step of producing the complex oxide catalyst and the form of existence in the complex oxide catalyst are not clear, but the introduction amount of the halogen exerts an effect with respect to Bi at a predetermined amount, and remains after the heat treatment. When the bismuth molybdate crystals formed from Mo and Bi are formed in the heating step of the above-mentioned composite oxide catalyst, the amount of halogen that is present is very small and the catalytic performance does not depend on the amount of halogen that remains. Contributes to the heat diffusion of
It is presumed that as a result of increasing the oxygen lattice defects in the bismuth molybdate crystal, the catalyst performance, especially the raw material conversion rate is improved. Examples of the halogen include F, C
l, Br, and I can be mentioned, and among these, Cl is effective.

The halogen content j in the above complex oxide catalyst is 0.0005 with respect to Mo of 12 in atomic ratio.
Is preferably 0.5 to 0.5, more preferably 0.0005 to 0.05. If it is more than 0.5, the catalyst performance may decrease. On the other hand, it may be less than 0.0005, but 0.
0005 is a measurement limit in the combustion absorption ion chromatography analysis method for measuring the amount of halogen, and since it is not possible to measure a smaller amount, it becomes impossible to confirm the presence of halogen.

Examples of the source compounds other than Bi, Mo and Fe are as follows. Examples of the source compound of Co include cobalt nitrate, cobalt sulfate, cobalt chloride, cobalt carbonate, and cobalt acetate. Ni
Examples of the source compound of nickel nitrate, nickel sulfate, nickel chloride, nickel carbonate, nickel acetate and the like.

As the K source compound, potassium nitrate, potassium sulfate, potassium chloride, potassium carbonate,
Potassium acetate etc. can be mentioned. Examples of the source compound of Rb include rubidium nitrate, rubidium sulfate, rubidium chloride, rubidium carbonate, rubidium acetate and the like. Cs source compounds include cesium nitrate, cesium sulfate, cesium chloride, cesium carbonate,
Cesium acetate etc. can be mentioned. As the source compound of Tl, thallium nitrate, thallium chloride,
Examples thereof include thallium carbonate and thallium acetate.

Further, examples of the source compound of B include borax, ammonium borate, boric acid and the like. Examples of the source compound of P include ammonium phosphomolybdate, ammonium phosphate, phosphoric acid, phosphorus pentoxide, and the like. As a source compound of As,
Examples thereof include dialceno ammonium octamolybdate and ammonium dialceno octatungstate. Examples of the W source compound include ammonium paratungstate, tungsten trioxide, tungstic acid, and phosphotungstic acid.

As the Mg source compound, magnesium nitrate, magnesium sulfate, magnesium chloride,
Examples thereof include magnesium carbonate and magnesium acetate.
Examples of the source compound of Ca include calcium nitrate, calcium sulfate, calcium chloride, calcium carbonate, calcium acetate and the like. As a Zn source compound,
Examples thereof include zinc nitrate, zinc sulfate, zinc chloride, zinc carbonate and zinc acetate. Examples of the Ce source compound include cerium nitrate, cerium sulfate, cerium chloride, cerium carbonate, and cerium acetate. Examples of the source compound of Sm include samarium nitrate, samarium sulfate, samarium chloride, samarium carbonate, and samarium acetate.

Furthermore, examples of the Si source compound include silica, granular silica, colloidal silica, fumed silica and the like. As the halogen source compound, ammonium salt, sodium salt,
Examples thereof include potassium salt. In the case of chloride, for example, ammonium chloride, sodium chloride, potassium chloride and the like can be mentioned.

The external shape of the obtained composite oxide catalyst is not particularly limited, but pellets, rings, spheres, granules and the like can be mentioned.

A specific example of the method for producing the composite oxide catalyst represented by the above general formula (1) is shown below. It is considered that those skilled in the art can easily extend from this specific example to other specific examples when the above-mentioned patent documents and the like are known. First, a suitable source compound of Mo, for example, an aqueous solution of ammonium paramolybdate, is mixed with Fe and Co.
And Ni source compounds, for example aqueous solutions of the respective nitrates. Furthermore, Na, K, Cs, Rb, Tl, B,
Each source compound such as P, As, W, Mg, Ca, Zn, Ce, and Sm, for example, each water-soluble salt is added to the above aqueous solution. Further, if necessary, an Si source compound such as granular or colloidal silica and fumed silica is added. Thus, an aqueous solution or suspension of a source compound such as Mo is prepared.

Next, bismuth subcarbonate ground to an average particle size of 6 to 50 μm as a Bi source compound and ammonium chloride as a halogen source compound are mixed. The above-mentioned bismuth subcarbonate is obtained by, for example, preparing an aqueous solution of bismuth nitrate, dropping-mixing it with an aqueous solution of ammonium carbonate or ammonium bicarbonate, and washing the resulting slurry with water, drying and pulverizing. Existing methods can be used for crushing as long as a crushed product having a required average particle diameter can be obtained by adjusting operating conditions.For example, a mortar / pestle, a hammer mill, a cage mill, an impact crusher, a ball mill, or a stirring mill. Etc. can be used. It is also possible to prepare a complex carbonate compound of bismuth and sodium by using sodium carbonate or sodium bicarbonate in place of the above ammonium carbonate or ammonium bicarbonate, and to use this as a Bi source compound.

The resulting suspension or slurry is thoroughly stirred and then dried. The dried granules or cakes are heat-treated in the air in the temperature range of 250 to 350 ° C for a short time.

The primary heat-treated product thus obtained is shaped into an arbitrary shape by a method such as extrusion molding, tablet molding, or carrier molding. Next, this molded body is preferably 45
A final heat treatment is performed for about 1 to 16 hours under a temperature condition of 0 to 650 ° C. As a result, the composite oxide catalyst according to the present invention is manufactured.

The amount of each source compound added in the above production method may be set according to the composition ratio of the constituent elements of the composite oxide catalyst represented by the general formula (1).

The composite oxide catalyst produced by this method is
Various gas phase catalytic oxidation reactions carried out in the presence of molecular oxygen, specifically, gas phase catalytic oxidation reactions for producing acrolein or methacrolein from propylene, isobutene or tertiary butanol, acrylonitrile or methacrylic acid from propylene or isobutene. It can be used for either a gas phase catalytic ammoxidation reaction for producing ronitrile or a gas phase catalytic oxidative dehydrogenation reaction for producing butadiene from butene.

[0042]

The present invention will be described in detail below. Example 1 100 g of bismuth nitrate was dissolved in ion-exchanged water acidified with nitric acid. Also, ammonium carbonate 3
8.1 g was heated and dissolved in ion-exchanged water. The two liquids were gradually mixed with sufficient stirring. After mixing with stirring, the obtained white precipitate was washed, filtered, and dried to prepare bismuth subcarbonate. The obtained bismuth subcarbonate was crushed in a mortar / mortar to have an average particle size of 13.0 μm.

Next, ammonium paramolybdate 9
4.1 g was heated and dissolved in 400 ml of pure water. Next, 7.18 g of ferric nitrate, 25.8 g of cobalt nitrate and 38.7 g of nickel nitrate were heated and dissolved in 60 ml of pure water. The two liquids were gradually mixed with sufficient stirring. Next, to this mixed solution, a solution prepared by dissolving 0.85 g of borax and 0.36 g of potassium nitrate in 40 ml of pure water with heating was added and sufficiently stirred. Next, 58.1 g of the following bismuth carbonate, 0.09 g of ammonium chloride and 64 g of silica were added and mixed with stirring.

Next, after heating and drying this slurry, it was subjected to a heat treatment at 300 ° C. for 1 hour in an air atmosphere. The obtained granular solid was tablet-molded with a small molding machine into tablets having a diameter of 5 mm and a height of 4 mm, and then calcined at 500 ° C./4 hours in a muffle furnace to produce a composite oxide catalyst. The catalyst composition calculated from the charged raw materials was as follows. Mo: Bi: Co: Ni: Fe: Na: B: K: Si =
12: 5: 2: 3: 0.4: 0.1: 0.2: 0.0
8:24 On the other hand, when the content of Cl in the catalyst was measured by the following method, the atomic ratio of Cl to Mo12 was 0.01.

20 ml of this composite oxide catalyst was used to obtain an inner diameter of 15 m.
m stainless steel reaction tube with a niter jacket was charged, and a raw material gas having a propylene concentration of 10%, a steam concentration of 17% and an air concentration of 73% was passed under normal pressure for a contact time of 2.3 seconds to obtain propylene. The oxidation reaction was carried out. It was carried out at a reaction temperature of 320 ° C., and the following reaction results were obtained. Propylene conversion 98.9% Acrolein selectivity 93.6% Acrylic acid selectivity 2.8% Acrolein yield 92.6% Acrylic acid yield 2.8% Total yield 95.4%

Here, the definitions of propylene conversion, acrolein selectivity, acrylic acid selectivity, acrolein yield, acrylic acid yield, and total yield are as follows. Propylene conversion rate (mol%) = (mol number of reacted propylene / mol number of supplied propylene) × 100 Acrolein selectivity (mol%) = (mol number of acrolein produced / mol number of reacted propylene) × 100 ・ Acrylic acid selectivity (mol%) = (mol of generated acrylic acid / mol of reacted propylene) × 100 ・ Acrolein yield (mol%) = (mol of generated acrolein / supplied propylene) No. of mols) × 100 ・ Acrylic acid yield (mol%) = (moles of acrylic acid produced / moles of propylene fed) × 100 ・ Total yield (mol%) = acrolein yield (mol%) +
Acrylic acid yield (mol%)

[Measurement Method of Cl Content] It was measured by the combustion absorption ion chromatography method. That is, a combustion improver was added to the analysis sample, heated to 1100 ° C., the generated gas was absorbed in pure water, and quantified by ion chromatography.

[Measurement Method of Average Particle Diameter] The average particle diameter was measured by a laser diffraction type particle size distribution measuring method. LMS-24 manufactured by Seishin Enterprise Co., Ltd. is used as an analytical instrument, and the average particle size is 50 on a volume basis.
It is expressed in% diameter.

(Comparative Example 1) The bismuth subcarbonate used in Example 1 was further ground in a mortar / mortar to give an average particle diameter of 5.5 μm.
And A composite oxide catalyst was produced in the same manner as in Example 1 except that the above bismuth subcarbonate was used, and the propylene oxidation reaction was carried out. The catalyst composition calculated from the charged raw materials and the measured Cl content in the catalyst are shown in Example 1.
Was similar to. The following reaction results were obtained at a reaction temperature of 320 ° C. Propylene conversion 98.4% Acrolein selectivity 87.5% Acrylic acid selectivity 8.5% Acrolein yield 86.1% Acrylic acid yield 8.4% Total yield 94.5%

(Comparative Example 2) The bismuth subcarbonate used in Example 1 was finely pulverized with a jet mill. The finely pulverized bismuth subcarbonate had an average particle diameter of 0.8 μm. A composite oxide catalyst was produced in the same manner as in Example 1 except that the above bismuth subcarbonate was used, and the propylene oxidation reaction was carried out. The catalyst composition calculated from the charged raw materials and the measured Cl content in the catalyst were the same as in Example 1. The following reaction results were obtained at a reaction temperature of 320 ° C. Propylene conversion 97.9% Acrolein selectivity 88.9% Acrylic acid selectivity 5.9% Acrolein yield 87.0% Acrylic acid yield 5.8% Total yield 92.8%

(Comparative Example 3) The bismuth subcarbonate used in Example 1 was classified with a sieve to obtain bismuth subcarbonate having a mesh of 140 to 280. The average particle size of bismuth subcarbonate is 5
It was 7 μm. A composite oxide catalyst was produced in the same manner as in Example 1 except that the bismuth subcarbonate was used.
The propylene oxidation reaction was carried out. The catalyst composition calculated from the charged raw materials and the measured Cl content in the catalyst were the same as in Example 1. The following reaction results were obtained at a reaction temperature of 320 ° C. Propylene conversion 98.8% Chlorine selectivity 84.8% Acrylic acid selectivity 10.2% Acrolein yield 83.8% Acrylic acid yield 10.1% Total yield 93.9%

[0052]

EFFECTS OF THE INVENTION Oxides containing only bismuth (Bi) as a metal component, and predetermined Bi such as Bi single salt or double salt.
Since the composite oxide catalyst is produced by using the source compound of Bi, the source compound of Bi is mixed with M in the integration step.
Bi and bismuth molybdate can be integrated in a predetermined range with respect to o and Fe in a non-uniform distribution by heating, and in a predetermined range with Mo and Fe in a non-uniform distribution. The formed complex oxide catalyst can be obtained. Therefore, by using this catalyst for a predetermined gas phase catalytic oxidation reaction or the like, it is possible to further improve the catalyst performance, particularly the raw material conversion rate and the selectivity.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C07C 57/05 C07C 57/05 // C07B 61/00 300 C07B 61/00 300 (72) Inventor Iwakura tool Atsushi Tokamachi, Yokkaichi-shi, Mie Mitsubishi Chemical Co., Ltd. F-term within the company (reference) 4G069 AA03 AA08 BA02B BB08B BB16C BC02B BC03B BC25A BC25B BC59A BC59B BC66B BC67B BC68B BD03 AC06 BA06 AC45 BA06 AC45 BA02 AC45A02 A45A02 A45A02 AH4A06 AH4 BA09 BA13 BA14 BA19 BA20 BA21 BA30 BA31 BA35 BA37 BA81 BC32 BE30 BS10 4H039 CA62 CA65 CC30

Claims (9)

[Claims] 1. A gas phase catalytic oxidation reaction for producing acrolein or methacrolein from propylene, isobutene or tertiary butanol, a gas phase catalytic ammoxidation reaction for producing acrylonitrile or methacrylonitrile from propylene or isobutene, and butadiene from butene. A composite oxide catalyst containing at least molybdenum (Mo), bismuth (Bi), and iron (Fe) as constituent elements, which is used for any one of the vapor-phase catalytic oxidative dehydrogenation reactions to be produced, When produced by a process including the integration of the source compound of (1) in an aqueous system and heating, it is hardly soluble in the aqueous system and has an average particle size of 6 to 50 μm.
A method for producing a composite oxide catalyst, characterized in that a source compound of bismuth (Bi) is used. 2. The bismuth (Bi) source compound is an oxide containing only bismuth (Bi) as a metal component, a single salt of bismuth (Bi) or bismuth (Bi).
2. The method for producing a complex oxide catalyst according to claim 1, wherein the complex oxide is a double salt. 3. Bismuth (Bi) as the metal component
The method for producing a composite oxide catalyst according to claim 2, wherein the oxide containing only is bismuth oxide. 4. The method for producing a composite oxide catalyst according to claim 2, wherein the single salt of bismuth (Bi) is bismuth subcarbonate. 5. The method for producing a complex oxide catalyst according to claim 2, wherein the double salt of bismuth (Bi) is a complex carbonate compound of bismuth and sodium. 6. The method for producing a composite oxide catalyst according to claim 1, which is represented by the following general formula (1). Mo _a Bi _b Co _c Ni _d Fe _e Na _f Q _m Y _g Z _h Si _i X _j O _k (1) (wherein X represents halogen and Y represents at least 1 of K, Rb, Cs or Tl) Indicates the species, Z is B, P, A
at least one of s and W, and Q is M
At least one of g, Ca, Zn, Ce or Sm
Indicates the species. Further, a to k and m represent atomic ratios of respective elements, and when a = 12, b = 0.5 to 7 and c =
0-10, d = 0-10, c + d = 1-10, e = 0.
05-3, f = 0 to 1, m = 0 to 1, g = 0 to 0.4,
h = 0 to 3, i = 0 to 48, j = 0 to 0.5, and k are values satisfying the oxidation states of other elements. ) 7. The method for producing a composite oxide catalyst according to claim 6, wherein the halogen is chlorine. 8. The halogen atom ratio j in the general formula (1) is 0.0005 to 0.5.
A method for producing the composite oxide catalyst according to 1. 9. A method for producing acrolein or acrylic acid from propylene by a gas phase catalytic oxidation reaction, using the composite oxide catalyst prepared by the production method according to claim 1.