JP2010214217A - Catalyst for producing acrolein and method of producing acrolein and/or acrylic acid using the catalyst - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst for producing acrolein and/or acrylic acid with high efficiency in a method of producing acrolein and/or acrylic acid by the catalytic gas phase oxidation of propylene-containing gas. <P>SOLUTION: The catalyst, for producing acrolein by the catalytic gas phase oxidation of propylene in the presence of molecular oxygen or molecular oxygen-containing gas, is an oxide catalyst containing molybdenum, bismuth, and iron as essential components. The catalytic component has an L<SP>*</SP>value, an a<SP>*</SP>value, and a b<SP>*</SP>value in the L<SP>*</SP>a<SP>*</SP>b<SP>*</SP>color system in the ranges of 30≤L<SP>*</SP>≤60, 0≤a<SP>*</SP>≤5, and 5≤b<SP>*</SP>≤14. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a catalyst for producing acrolein by catalytic gas phase oxidation of propylene and a method for producing acrolein and / or acrylic acid using the catalyst.

  Acrylic acid is industrially important as a raw material for various synthetic resins, paints, and plasticizers, and is currently produced on a scale of several million tons / year worldwide. In recent years, the importance has increased as a raw material for water-absorbent resins, and the demand has further increased, and further improvement in the yield of acrylic acid is desired on an industrial scale.

  The most common industrial process for producing acrylic acid is a two-stage oxidation process in which propylene is converted to acrylic acid via acrolein by a catalytic gas-phase oxidation reaction. It is also necessary to improve the yield of acrolein by catalytic vapor phase oxidation of propylene, which is the reaction of the eye. Acrolein itself is also a useful compound as a raw material for synthesis of methionine (raw materials for pharmaceuticals and feeds), glutaraldehyde, pyridine, other synthetic materials such as allyl alcohol and glycerin, and as a crosslinking agent and fiber processing agent. The improvement in yield from propylene to acrolein has great economic significance.

  With regard to such a catalyst for the catalytic gas phase oxidation of propylene, various companies have been studied mainly by molybdenum-bismuth oxide catalysts for the purpose of improving the catalyst performance such as the yield and life of acrolein, and various proposals have been made. ing.

For example, as a molybdenum-bismuth oxide catalyst, a catalyst having a crystal phase of β-X ¹ MoO ₄ as a main component and Fe ₂ (MoO ₄ ) ₃ as a second component and not containing MoO ₃ (Patent Document 1) A catalyst having a crystal phase represented by Bi ₂ Fe ₂ Mo ₂ O ₁₂ in the active phase (Patent Document 2), a catalyst having a loss on drying of water content of 0.5% by weight or less (Patent Document 3), a ratio A catalyst having a surface area of 15 to 18 m ² / g (Patent Document 4), a catalyst having a specific ring shape, and a side compression strength of the catalyst precursor molded body is ≧ 12N and ≦ 23N (Patent Document 5) Etc. have been proposed.

JP 2000-169149 A Japanese Patent Publication No. 56-28180 JP 2005-186065 A JP-T-2006-521916 Special table 2007-505740 gazette

  However, although all of the above-mentioned catalysts have improved somewhat in the catalyst performance such as the yield and life of the target acrolein, there is still room for improvement from the industrial scale.

  Thus, an object of the present invention is to provide a catalyst exhibiting performance excellent in activity, selectivity and the like in a method for producing acrolein and / or acrylic acid by catalytic vapor phase oxidation of propylene.

  Another object of the present invention is to provide a method for producing acrolein and / or acrylic acid in high yield by catalytic gas phase oxidation of propylene.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that molybdenum-bismuth for mainly producing acrolein by catalytic vapor phase oxidation of propylene in the presence of molecular oxygen or a molecular oxygen-containing gas. In the system oxide catalyst, the correlation between the catalyst performance and the color of the catalyst, which has never been noticed at all, was newly found. Specifically, it is an oxide catalyst containing Mo (molybdenum), Bi (bismuth), Fe (iron) as essential components, and the L ^* value in the L ^* a ^* b ^* color system of the catalyst component, a catalyst having an a ^* value and a b ^* value of 30 ≦ L ^* ≦ 60, 0 ≦ a ^* ≦ 5, and 5 ≦ b ^* ≦ 14, respectively, can produce acrolein in a high yield; The present invention has been reached. Although the reason for this is not clear, it has been found by various studies that the catalyst activity and selectivity are reduced when the L ^* value, a ^* value, and b ^* value are outside the above ranges.

  Furthermore, it has also been found that a catalyst having a saturation E calculated by the following formula in a range of 7 ≦ E ≦ 14 is more effective.

  According to the present invention, in the method for producing acrolein and / or acrylic acid by catalytic gas phase oxidation of propylene, it becomes possible to produce acrolein and / or acrylic acid in high yield.

  Hereinafter, the acrolein production catalyst according to the present invention and the production method of acrolein and / or acrylic acid using the catalyst will be described in detail. However, the scope of the present invention is not limited to these descriptions, and the following examples are given. Other than the above, the present invention can be changed and implemented as appropriate without departing from the spirit of the present invention.

The catalyst for producing acrolein in the present invention is an oxide catalyst containing molybdenum, bismuth and iron as essential components, and the L ^* value and a ^* value in the L ^* a ^* b ^* color system of the catalyst component. , B ^* values may be in the range of 30 ≦ L ^* ≦ 60, 0 ≦ a ^* ≦ 5, 5 ≦ b ^* ≦ 14, preferably 35 ≦ L ^* ≦ 55, 1 ≦ a ^* ≦ 4, 7 It is a catalyst in the range of ≦ b ^* ≦ 13.
Further, the saturation E calculated by the following formula is preferably in the range of 7 ≦ E ≦ 14, and more preferably in the range of 9 ≦ E ≦ 13.

Here, the L ^* a ^* b ^* color system is color coordinates a ^* , b ^* and lightness L ^* in a three-dimensional approximate uniform color space defined by JIS Z8729. a ^* indicates that the greater the value on the plus side, the stronger the redness, and the greater the value on the minus side, the stronger the greenness. b ^{* the} greater the value on the plus side, the stronger the yellowness and the greater the value on the minus side. It shows that the bluish color is stronger. In addition, the lightness L ^* indicates that the blackness is stronger as the value approaches 0, and the whiteness is stronger as the value approaches 100, and the saturation E indicates that the larger the value is, the brighter the color is.

The catalyst of the present invention is an oxide catalyst containing molybdenum, bismuth and iron as essential components as catalyst components, and it is important that the L ^* value, a ^* value, and b ^* value of the catalyst component satisfy the above ranges. It is. As an oxide catalyst containing molybdenum, bismuth and iron as essential components, the following general formula (1)
_{Mo 12 Bi a Fe b A c} B d C e D f O x (1)
(Where Mo is molybdenum, Bi is bismuth, Fe is iron, A is at least one element selected from cobalt and nickel, B is at least one element selected from alkali metals, alkaline earth metals and thallium, C is at least one element selected from tungsten, silicon, aluminum, zirconium and titanium, D is at least one element selected from phosphorus, tellurium, antimony, tin, cerium, lead, niobium, manganese, arsenic, boron and zinc The element, O is oxygen, a, b, c, d, e, f and x represent the atomic ratios of Bi, Fe, A, B, C, D and O, respectively, and 0 <a ≦ 10, 0 < b ≦ 20, 2 ≦ c ≦ 20, 0 <d ≦ 10, 0 ≦ e ≦ 30, 0 ≦ f ≦ 4, and x is a numerical value determined by the oxidation state of each element. Suitable catalysts are preferred.

  The catalyst of this invention can be manufactured using the method generally used for preparation of this kind of catalyst, and an example is shown below.

  As raw materials for catalytically active components, oxides, hydroxides, ammonium salts, nitrates, carbonates, sulfates, organic acid salts, etc. of each component element, their aqueous solutions, sols, etc., or multiple elements The compound or the like is mixed with water to form an aqueous solution or an aqueous slurry (hereinafter referred to as “starting raw material mixture”).

  Next, if necessary, the obtained starting material mixture is dried by various methods such as heating and decompression to obtain a catalyst precursor. As a drying method by heating, for example, a powdered catalyst precursor can be obtained using a spray dryer, a drum dryer or the like, or heated in an air stream using a box-type dryer, a tunnel-type dryer or the like. Block or flake catalyst precursors can also be obtained. Alternatively, a method of once concentrating and evaporating and drying the mixture of starting materials to obtain a cake-like solid and further subjecting the solid to the above heat treatment can also be employed. As a drying method by reduced pressure, for example, a block or powdery catalyst precursor can be obtained using a vacuum dryer.

  The obtained dried product is sent to a subsequent molding step through a pulverization step and a classification step for obtaining a powder having an appropriate particle size as required. The particle size of the catalyst precursor powder is not particularly limited, but is preferably 500 μm or less in terms of excellent moldability.

  As a method for molding the catalyst, a method of molding the catalyst precursor or a mixture of the catalyst precursor and a powdery inert carrier into a certain shape by an extrusion molding method or a tableting molding method, a constant catalyst component is used. There is a supporting method of supporting on an arbitrary inert carrier having the following shape.

  In the case of an extrusion molding method or a tableting molding method, the shape is not particularly limited, and may be any shape such as a spherical shape, a cylindrical shape, a ring shape, and an indeterminate shape. Of course, in the case of a spherical shape, it does not need to be a true sphere, and may be substantially spherical, and the same applies to a cylindrical shape and a ring shape.

  As the loading method, for example, an evaporation to dryness method in which a starting inert liquid mixture or an aqueous slurry is applied to or adhered to a desired inert carrier having a certain shape while being heated or dried while being dried and supported. Alternatively, it can be produced according to a granulation method in which the catalyst precursor is supported in powder form on an inert carrier. Among these, in particular, the centrifugal fluid coating method described in JP-A No. 63-200249, the rolling granulation method described in JP-A No. 10-28877, and the rocking mixer method described in JP-A No. 2004-136267 are used. Thus, a granulation method of supporting on an inert carrier is preferable.

  Examples of the inert carrier include alumina, silica, silica-alumina, titania, magnesia, steatite, cordierite, silica-magnesia, silicon carbide, silicon nitride, zeolite, and the like. When used in the supporting method, the shape is not particularly limited, and known shapes such as a spherical shape, a cylindrical shape, and a ring shape can be used.

  In the molding step, a molding aid or binder for improving moldability, a pore forming agent for forming appropriate pores in the catalyst, or the like can be used. Specific examples include organic compounds such as ethylene glycol, glycerin, propionic acid, maleic acid, benzyl alcohol, propyl alcohol, butyl alcohol or phenols, water, nitric acid, ammonium nitrate, and ammonium carbonate.

  In addition, for the purpose of improving the mechanical strength of the catalyst, reinforcing agents such as ceramic fibers, glass fibers, silicon carbide, and silicon nitride can be used. The reinforcing agent may be added to the starting raw material mixture or may be blended with the catalyst precursor.

  The molded body or carrier obtained in the molding process is sent to the subsequent firing process. The firing temperature is 350 ° C to 600 ° C, preferably 400 ° C to 550 ° C, more preferably 420 ° C to 490 ° C, and the firing time is preferably 1 to 10 hours. The firing atmosphere may be an oxidizing atmosphere, but a molecular oxygen-containing gas atmosphere is preferable, and it is particularly preferable to perform the firing step under the flow of the molecular oxygen-containing gas. Air is suitably used as the molecular oxygen-containing gas.

  In addition, there is no restriction | limiting in particular as a baking furnace used by a baking process, What is necessary is just to use the box-type baking furnace or tunnel type baking furnace etc. which are generally used.

  Here, as a method of obtaining the catalyst of the present invention, for example, in the calcination step, a catalyst is formed by a method of controlling the contact time between the catalyst molded body or the support and the atmosphere gas to be baked, the molecular oxygen concentration of the atmosphere gas, or the like. This is achieved by controlling the amount of molecular oxygen in contact with the molded body or the support.

Specifically, a molecular oxygen-containing gas having a molecular oxygen concentration of 5 to 25% is used as the atmospheric gas, and the mass of catalyst precursor in the catalyst molded body or carrier (W [kg]) and introduced into the firing furnace. The ratio (V / W) to the molecular oxygen gas flow rate (V [L (STP) / min]) is 0.02 to 0.20, preferably 0.04 to 0.15. Adjust it. If the molecular oxygen concentration or the molecular oxygen gas flow rate of the atmospheric gas is out of the above range, it is difficult to obtain a catalyst having a suitable L ^* value, a ^* value, or b ^* value range after firing. This is probably because when the molecular oxygen concentration is less than 5% or when V / W is less than 0.02, components other than the catalytically active component contained in the catalyst molded body or carrier, such as ammonium in the raw material compound This is because the decomposition of roots and nitrates, molding aids and binders used in the molding process, pore forming agents, etc. is insufficient, and the catalytically active components are reduced during decomposition, while the molecular oxygen concentration is 25%. This is probably because the catalytically active component is excessively oxidized or the above components are rapidly oxidized and decomposed when the V / W exceeds 0.20. When air is used as the atmospheric gas, about 0.10 to 0.95 L (STP) / min, preferably 0.19 to 0.72 L (STP) per kg of the mass of the catalyst molded body or catalyst precursor in the carrier. ) / Min at a flow rate.

  Here, the mass of the catalyst precursor in the catalyst molded body or the carrier is the mass of the catalyst molded body or the carrier, and the mass of the inert carrier and the reinforcing material contained in the catalyst molded body or the carrier is subtracted. It is a thing. Note that, in the case where firing is performed in advance using only the catalyst precursor before forming the molded body or the support, the mass of the inert carrier and the reinforcing material contained in the catalyst precursor is similarly subtracted.

Further, although the cause is unknown, color unevenness may occur on some catalyst surfaces after calcination. Even in such a case, the L ^* value of the powder obtained by shaving the surface of the catalyst with uneven color using a mortar or the like, and solidifying the homogenized powder If the a ^* value and the b ^* value are within the above ranges, they are included in the present invention.

  There are no particular limitations on the reactor used for producing acrolein and / or acrylic acid by catalytic vapor phase oxidation of propylene with molecular oxygen in the present invention, and there are no particular limitations. Fixed bed reactor, fluidized bed reactor, moving bed Although any of the reactors can be used, a fixed bed reactor is usually used, and a fixed bed multitubular reactor is particularly preferable. The inner diameter of the reaction tube is usually 15 to 50 mm, more preferably 20 to 40 mm, and still more preferably 22 to 38 mm.

Each reaction tube of the fixed bed multitubular reactor does not necessarily need to be filled with a single catalyst, and can be filled with a plurality of types of catalysts. For example, as described in JP-A-4-217932, JP-A-10-168003, and the like, a plurality of types of catalysts having different activities are packed so as to form a layer (hereinafter referred to as “reaction zone”). Preferably, a method of controlling the activity by a method, a method of diluting a part of the catalyst with an inert carrier or the like as described in JP-A-2005-320315, or a method of combining them is preferably used. it can. At this time, the number of reaction zones is appropriately determined depending on the reaction conditions and the scale of the reactor. However, if the number of reaction zones is too large, problems such as complicated packing of the catalyst may occur. About 2-6 is desirable. In the case of using a plurality of kinds of catalyst, at least one said L ^* value of the catalyst used, a ^* value, b ^* as long as it satisfies the range of values, for all catalysts used L ^* value , A ^* value and b ^* value are within the above ranges, which is preferable because the effects of the present invention are sufficiently achieved.

The reaction conditions in the present invention are not particularly limited, and any conditions generally used for this type of reaction can be used. For example, the raw material gas is 1-15% by volume, preferably 4-12% by volume propylene, 0.5-25% by volume, preferably 2-20% by volume molecular oxygen, 0-30% by volume, preferably 0 A mixed gas consisting of ˜25% by volume of water vapor and the balance consisting of an inert gas such as nitrogen is 300 to 5,000 h ⁻¹ (STP) at a temperature of 280 to 450 ° C. under a pressure of 0.1 to 1.0 MPa. What is necessary is just to contact a catalyst with space velocity.

  Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. Hereinafter, for convenience, “parts by mass” may be simply referred to as “parts”.

The propylene conversion rate, acrolein yield and acrylic acid yield were determined by the following equations.
Propylene conversion [mol%]
= (Number of moles of propylene reacted) / (number of moles of supplied propylene) × 100
Acrolein yield, acrylic acid yield [mol%]
= (Mole number of produced acrolein or acrylic acid) / (Mole number of supplied propylene) × 100
[Measurement of L ^* a ^* b ^* value of catalyst]
The L ^* value, a ^* value, and b ^* value of the catalyst were measured using SZ-Σ80 COLOR MEASURING SYSTEM manufactured by Nippon Denshoku Industries Co., Ltd. Specifically, each value was measured with 20 randomly selected catalysts, and the average value was used as the L ^* value, a ^* value, and b ^* value of the catalyst.
<Example 1>
(Catalyst preparation)
While heating and stirring 2000 parts of distilled water, 500 parts of ammonium molybdate was dissolved (solution A). Separately, 412 parts of cobalt nitrate and 124 parts of nickel nitrate were dissolved in 500 parts of distilled water (Liquid B). Separately, 191 parts of ferric nitrate was dissolved in 100 parts of distilled water (solution C). Separately, 172 parts of bismuth nitrate was dissolved in a solution made acidic by adding 25 parts of concentrated nitric acid (65 wt%) to 150 parts of distilled water (solution D). Liquid B, liquid C, and liquid D were added dropwise to liquid A while heating and stirring. Further, 1.2 parts of potassium nitrate, 48.1 parts of aluminum oxide and 7.4 parts of boron oxide were added to obtain a suspension. The suspension thus obtained was heated, stirred and evaporated. The obtained dried product was dried at 200 ° C. and then pulverized to 250 μm or less to obtain a catalyst precursor. 4 kg of a silica-alumina spherical carrier having an average particle diameter of 5.0 mm was put into a rolling granulator, and then a catalyst precursor was put together with a 30% by mass ammonium nitrate aqueous solution as a binder while passing hot air at 90 ° C. A support was obtained. The entire amount of the obtained carrier was charged in a box-type firing furnace, and heat-treated at 480 ° C. for 6 hours while introducing air into the furnace at 1 L / min, to obtain catalyst 1. The catalyst loading was about 150% by mass, and the composition of metal elements other than oxygen excluding the carrier was as follows in terms of atomic ratio.
_{Mo 12 Bi 1.5 Fe 2 Co 6} Ni 1.8 K 0.05 Al 4 B 0.9
The loading rate was determined by the following formula.
Support rate [mass%] = (catalyst mass [g] −support mass [g]) / support mass [g] × 100
The L ^* value, a ^* value, b ^* value and saturation E value of this catalyst are shown in Table 1.
[Reactor]
A reactor composed of a SUS reaction tube having a total length of 3000 mm and an inner diameter of 25 mm and a shell for flowing a heat medium covering the SUS reaction tube was prepared in the vertical direction. The catalyst 1 was dropped from the upper part of the reaction tube and filled so that the layer length was 2700 mm.
[Oxidation reaction]
Maintaining the heat medium temperature (reaction temperature) at 320 ° C., a reaction tube filled with the catalyst was mixed with 8% by volume of propylene, 15% by volume of oxygen, 8% by volume of water vapor, 69% by volume of inert gas consisting of nitrogen, etc. Introduced at a space velocity of 2000 hr ⁻¹ (STP), a propylene catalytic gas phase oxidation reaction was carried out. The results are shown in Table 2.
<Example 2>
While heating and stirring 2000 parts of distilled water, 500 parts of ammonium molybdate was dissolved (solution A). Separately, 385 parts of cobalt nitrate was dissolved in 500 parts of distilled water (solution B). Separately, 277 parts of ferric nitrate was dissolved in 100 parts of distilled water (solution C). Separately, 115 parts of bismuth nitrate was dissolved in a solution made acidic by adding 25 parts of concentrated nitric acid (65 wt%) to 150 parts of distilled water (solution D). Liquid B, liquid C, and liquid D were added dropwise to liquid A while heating and stirring. Further, 1.84 parts of cesium nitrate, 36.1 parts of aluminum oxide and 128 parts of 20% by mass of silica sol were added to obtain a suspension. The suspension thus obtained was heated, stirred and evaporated. The obtained dried product was dried at 200 ° C. and then pulverized to 250 μm or less to obtain a catalyst precursor. 8 kg of the obtained catalyst precursor was charged into a box-type firing furnace, and heat-treated at 470 ° C. for 6 hours while introducing air into the furnace at 7.5 L / min to obtain catalyst powder. 4 kg of silica-alumina spherical carrier having an average particle size of 5.0 mm is put into a rolling granulator, and then catalyst powder is put together with 35 wt% ammonium nitrate aqueous solution as a binder while passing hot air at 90 ° C. to the carrier. Supported. The obtained carrier was dried at 230 ° C. to obtain catalyst 2. The catalyst loading was about 150% by mass, and the composition of metal elements other than oxygen excluding the carrier was as follows in terms of atomic ratio.
Mo ₁₂ Bi _1.0 Fe _2.9 Co _5.6 Cs _0.04 Al ₃ Si _1.8
The L ^* value, a ^* value, b ^* value and saturation E value of this catalyst are shown in Table 1.

Using the obtained catalyst 2, a catalytic gas phase oxidation reaction of propylene was carried out in the same manner as in Example 1. The results are shown in Table 2.
<Example 3>
While heating and stirring 2000 parts of distilled water, 500 parts of ammonium molybdate was dissolved (solution A). Separately, 206 parts of cobalt nitrate and 275 parts of nickel nitrate were dissolved in 500 parts of distilled water (Liquid B). Separately, 143 parts of ferric nitrate was dissolved in 100 parts of distilled water (solution C). Separately, 115 parts of bismuth nitrate was dissolved in a solution made acidic by adding 25 parts of concentrated nitric acid (65 wt%) to 150 parts of distilled water (solution D). Liquid B, liquid C, and liquid D were added dropwise to liquid A while heating and stirring. Further, 2.4 parts of potassium nitrate, 240 parts of aluminum oxide and 71.1 parts of tungsten oxide were added to obtain a suspension. The suspension thus obtained was heated, stirred and evaporated. The obtained dried product was dried at 200 ° C. and then pulverized to 250 μm or less to obtain a catalyst precursor. 4 kg of a silica-alumina spherical carrier having an average particle diameter of 5.0 mm was put into a rolling granulator, and then a catalyst precursor was put together with a 30% by mass ammonium nitrate aqueous solution as a binder while passing hot air at 90 ° C. A support was obtained. The entire amount of the obtained carrier was charged into a box-type firing furnace, and heat-treated at 480 ° C. for 6 hours while introducing air into the furnace at 1 L / min to obtain Catalyst 3. The catalyst loading was about 150% by mass, and the composition of metal elements other than oxygen excluding the carrier was as follows in terms of atomic ratio.
Mo ₁₂ Bi _1.0 Fe _1.5 Co ₃ Ni ₄ K _0.10 Al ₂₀ W _1.3
The L ^* value, a ^* value, b ^* value and saturation E value of this catalyst are shown in Table 1.

Table 2 shows the results of catalytic vapor phase oxidation reaction of propylene using the obtained catalyst 3 in the same manner as in Example 1.
<Examples 4-7, Comparative Examples 1-3>
In Example 1, catalysts 4 to 10 were obtained in the same manner as in Example 1 except that the type and amount of atmospheric gas introduced into the firing furnace in the firing step were changed as shown in Table 1. Table 1 shows the L ^* value, a ^* value, b ^* value and chroma E value of these catalysts.

  Using the obtained catalysts 4 to 10, a propylene catalytic gas phase oxidation reaction was carried out in the same manner as in Example 1. The results are shown in Table 2.

Claims (5)

A catalyst for producing acrolein by catalytic vapor phase oxidation of propylene in the presence of molecular oxygen or a molecular oxygen-containing gas, an oxide catalyst containing molybdenum, bismuth and iron as essential components; and The L ^* value, a ^* value, and b ^* value in the L ^* a ^* b ^* color system of the catalyst component are in the range of 30 ≦ L ^* ≦ 60, 0 ≦ a ^* ≦ 5, and 5 ≦ b ^* ≦ 14, respectively. A catalyst for producing acrolein, wherein The catalyst according to claim 1, wherein the saturation E calculated by the following formula is in the range of 7≤E≤14.

  The catalyst according to claim 1 or 2, wherein the catalyst component is supported on an inert carrier. The catalyst component is represented by the following general formula (1)
_{Mo 12 Bi a Fe b A c} B d C e D f O x (1)
(Where Mo is molybdenum, Bi is bismuth, Fe is iron, A is at least one element selected from cobalt and nickel, B is at least one element selected from alkali metals, alkaline earth metals and thallium, C is at least one element selected from tungsten, silicon, aluminum, zirconium and titanium; D is at least one element selected from phosphorus, tellurium, antimony, tin, cerium, lead, niobium, manganese, arsenic and zinc; O is oxygen, and a, b, c, d, e, f and x represent the atomic ratio of Bi, Fe, A, B, C, D and O, respectively, and 0 <a ≦ 10, 0 <b ≦ 20, 2 ≦ c ≦ 20, 0 <d ≦ 10, 0 ≦ e ≦ 30, 0 ≦ f ≦ 4, and x is a value determined by the oxidation state of each element. The catalyst according to any one of claims 1 to 3.   In the method for producing acrolein and / or acrylic acid by catalytic vapor phase oxidation of propylene, the contact of propylene with molecular oxygen or a molecular oxygen-containing gas in the presence of the catalyst according to any one of claims 1 to 4. A method for producing acrolein and / or acrylic acid, comprising performing a gas phase oxidation reaction.