oxide catalyst and method for producing the same, and methods for producing unsaturated aldehyde, di

专利摘要:
OXIDE CATALYST AND METHOD TO PRODUCE THE SAME, AND METHODS TO PRODUCE UNSATURATED ALDEHYDE, DIOLEFINE AND UNSATURATED NITRILLA. An object of the present invention is to provide an oxide catalyst that prevents degradation by reducing the catalyst, even during industrial operation for a long period of time and less reduces unsaturated aldehyde yields, diolefin yields, or unsaturated nitrile yields, and a method for producing the same, and methods for producing unsaturated aldehyde, diolefin, and unsaturated nitrile using the oxide catalyst. The present invention provides an oxide catalyst for use in the production of unsaturated aldehyde, diolefin, or unsaturated nitrile from olefin and / or alcohol, the oxide catalyst meeting the following (1) to (3): (1) the catalyst oxide comprises molybdenum, bismuth, iron, cobalt, and an element A having an ionic radius greater than 0.96 A (except for potassium, cesium and rubidium); (2) an atomic ratio a of bismuth to 12 molybdenum atoms is 1 (less than equal) to (less than equal) 5, an atomic ratio b of iron to 12 molybdenum atoms is 1.5 (less than equal) b (less than equal ) 6, an atomic ratio c of element A to 12 molybdenum atoms is 1 (less than equal) c (less than equal) 5, and a ratio (...).
公开号:BR112015006012B1
申请号:R112015006012-9
申请日:2013-09-27
公开日:2020-11-10
发明作者:Yoshida Jun；Yamaguchi Tatsuo
申请人:Asahi Kasei Chemicals Corporation；
IPC主号:

专利说明:

Technical Field
[0001] The present invention relates to an oxide catalyst and a method for producing the same, and methods for producing unsaturated aldehyde, diolefin, and unsaturated nitrile using the oxide catalyst. Background Art
[0002] A large number of oxide catalysts for use in the production of unsaturated aldehyde as a major component have been reported so far. For example, the oldest oxide catalyst was discovered by Standard Oil Co., of Ohio, and is known as a composite oxide catalyst comprising Mo and Bi as essential components. Patent literature 1 describes a catalyst, by focusing on Mo, Bi, Ce, K, Fe, Co, Mg, Cs, and Rb as metals constituting the catalyst.
[0003] The method for producing unsaturated aldehyde is used in, for example, a method for producing (meth) acrylate such as methyl acrylate or methyl methacrylate by means of an oxidative esterification reaction using at least one starting material selected from the group consisting of propylene, isobutylene, isobutanol, and t-butyl alcohol and an intermediate unsaturated aldehyde such as acrolein or methacrolein. This method for producing (meth) acrylate is also known as the so-called direct methyl esterification process consisting of two reaction steps or as a process called direct oxidation consisting of three reaction steps. The direct oxidation process produces (meth) acrylate in three stages (see, for example, Non-patent literature 1). The first oxidation step of the direct oxidation process is a step of producing unsaturated aldehyde such as acrolein or methacrolein through the gas catalytic oxidation reaction of at least one starting material selected from the group consisting of propylene, isobutylene, and t-butyl alcohol with molecular oxygen in the presence of a catalyst. The second stage of oxidation of this process is a stage of production of (meth) acrylic acid through the gas catalytic oxidation reaction of the unsaturated aldehyde obtained in the first stage of oxidation with molecular oxygen in the presence of a catalyst. The final esterification stage is a stage of further esterifying the (meth) acrylic acid obtained in the second oxidation stage to obtain (meth) acrylate. Esterification using alcohol such as methanol can give methyl acrylate or methyl methacrylate.
[0004] By contrast, the direct methyl esterification process consists of two catalyst reaction steps: a first reaction step of producing unsaturated aldehyde such as acrolein or methacrolein through the catalytic oxidation reaction in the gas phase of at least one starting material selected from the group consisting of propylene, isobutylene, isobutanol, and t-butyl alcohol with gas containing molecular oxygen; and a second reaction step of reacting the unsaturated aldehyde thus obtained with alcohol such as methanol and molecular oxygen to produce (meth) acrylate such as methyl acrylate or methyl methacrylate at once.
[0005] Reaction systems using such oxide catalysts include fixed bed, fluidized bed, and moving bed reaction systems. Of these, the fixed bed reaction system is often adopted industrially because of the following advantage; high reaction yields can be achieved by feed gas flowing in a state close to the extrusion flow.
[0006] The fixed bed reaction system, however, has low thermal conductivity and is therefore unsuitable for exothermic reaction or endothermic reaction that requires removal of heat or heating. Particularly, severe exothermic reaction, such as oxidation reaction, where a temperature suddenly rises, disadvantageously being beyond the control of the reaction system, possibly resulting in an escape reaction. In addition, this sudden increase in temperature damages the catalyst, resulting in the unfavorable early degradation of the catalyst.
[0007] In contrast, the fluidized bed reaction system has a high heat conductivity, because the catalyst particles flow vigorously into the reactor. Thus, the temperature in the reactor is kept almost constant, even during reaction when heat is generated largely or absorbed. The fluidized bed reaction system can advantageously prevent the reaction from proceeding excessively. This reaction system also has the advantage that, because of the reduced local accumulation of energy, feed gas in an explosive range can be caused to react so that the concentration of starting material is increased to improve productivity. Thus, the fluidized bed reaction system is suitable for the catalytic oxidation reaction of olefin and / or alcohol, which is a high exothermic reaction. Despite these known advantages of the fluidized bed reaction system, patent literature 2 and 3, for example, states that the use of fixed bed catalysts is generally preferred for the conversion of unsaturated hydrocarbon to unsaturated aldehyde. These literature indicates that the catalysts described therein can be used in any of the fixed bed, moving bed, and fluidized bed methods to produce unsaturated aldehyde through the catalytic oxidation reaction of olefin and / or alcohol, but make no mention. specific reaction systems other than the fixed bed.
[0008] Although naphtha pyrolysis is a major method for producing diolefin such as 1,3-butadiene, there is an increasing demand for production based on a gas-phase oxidation reaction along with a recent shift to alternative sources for oil. Examples of the method for producing diolefin using the gas oxidation reaction include methods that involve subjecting the monoolefin having 4 or more carbon atoms, such as n-butene or isopentene, and molecular oxygen for the catalytic oxidative dehydrogenation reaction in the presence of a catalyst to produce conjugated diolefin, such as 1,3-butadiene or isoprene, corresponding to monoolefin. As for the catalyst used in such a reaction, for example, patent literature 4 describes an oxide catalyst comprising Mo, Bi, Fe, Ce, Ni, Mg, and Rb as a catalyst for the monoolefin oxidative dehydrogenation reaction.
[0009] A known method for producing unsaturated nitrile such as acrylonitrile or methacrylonitrile involves reacting one or more selected from the group consisting of propylene, isobutylene, isobutanol, and t-butyl alcohol, with molecular oxygen and ammonia in the presence of a catalyst. This method is widely known as an "amoxidation process" and is currently practiced on an industrial scale.
[0010] Catalysts for use in the amoxidation process were diligently studied with the objective of still efficiently carrying out the method to produce unsaturated nitrile on an industrial scale. For example, composite metal oxide catalysts of Mo-Bi-Fe-Ni or Mo-Bi-Fe-Sb are known as such catalysts for amoxidation. Composition composed of these essential metals supplemented with other components has often been studied in order to improve performance. For example, patent literature 5 describes a catalyst comprising molybdenum, bismuth, iron, cerium, and nickel supplemented with other components. Also, patent literature 6 describes a catalyst comprising molybdenum, bismuth, iron, antimony, nickel, and chromium supplemented with other components.
[0011] According to the non-patent literature 2, the disordered phase, which is a metastable structure, refers to a structure containing Mo sites randomly replaced by Fe, for example, in the case of a 3-component composite oxide Bi -Mo-Fe, and is characterized in that atoms of Mo and Fe form the same tetrahedral structure of oxygen. On the other hand, the ordered phase, which is a stable structure, has the same composition as that of the disordered phase, but differs structurally from it, and is obtained by heat treatment at a higher temperature than for the disordered phase. In the ordered phase, the atoms of Fe and Mo individually form tetrahedrons. This means that the Fe atom forms an oxygen tetrahedron, while the Mo atom forms another oxygen tetrahedron, in addition to the Fe atom. Non-patent literature 2 indicates that a disordered phase Bi3FeiMo2Oi2 is formed at 450 ° C, but suffers transition from phase to ordered phase at a reaction temperature of 475 ° C. 1) Cluttered Bi3FeiMθ2θi2 phase
[0012] Figure 1 shows the crystal structure of the Bi3Fe! Mθ2θi2 of the disordered phase described in the non-patent literature 2. This disordered phase is a tetragonal crystal system of the scheelite type (CaWO4 type) with two equal lateral lengths and three axial angles of 90 degrees in the reticulum constant of a unit cell (A = B * Ceα = β = y = 90 degrees). This phase has two sites: the X sites, which are enclosed in oxygen tetrahedra, and the Y sites, which are not enclosed by oxygen atoms. The X sites are occupied by Mo and Fe either randomly or with a certain probability distribution. Y sites are occupied by Bi and other elements or lattice defects either randomly or with a certain probability distribution. In each layer in the AB plane, the X and Y sites form square planar lattices with lengths equal to the lattice constants in the A and B axis directions, respectively, and occupy offset positions in the A and B axis directions, respectively , for 1/2 of the crosshair constant in the plane. These layers in the AB plane are stacked in the direction of the C axis while repeatedly displaced by (A / 2.0) and (O.B / 2), respectively. In this stack, the oxygen tetrahedrons around the X sites are placed while rotating around the C axis by 90 degrees with their embedded atoms centered.
[0013] Figure 3 shows the X-ray diffraction (XRD) of the disordered phase Bi3Fe1Mo2Oi2. This disordered phase has unique peaks, at least in the planes of 18.30 ° ± 0.2 ° (101), 28.20 ° ± 0.2 ° (112), 33.65 ° ± 0.2 ° (200) , and 46.15 ° ± 0.2 ° (204) in the range of X-ray diffraction angles 20 = 10 ° to 60 ° measured by crystal X-ray diffraction (XRD). 2) Ordered phase of Bi3FeiMo2O12
[0014] For comparison, the crystal structure of the Bi3FeiMo2O12 ordered phase is shown in Figure 2. This ordered phase is a monoclinic crystal system having a distorted scheelite structure with different lateral lengths in the reticulum constant of a unit cell. Two of the three angles formed by basic vectors are 90 degrees and the other angle is different (A # B * C, a = y = 90 degrees, and β * 90 degrees). The ordered phase has three sites: two unequaled sites X1 and X2, which are enclosed in oxygen tetrahedrons, and the Y sites, which are not enclosed by oxygen atoms. The X1 sites are occupied by Mo and other elements or lattice defects. The X2 sites are occupied by Fe and other elements or lattice defects. The Y sites are occupied by Bi and other elements or lattice defects. 3) Structural difference between Bi3FeiMo2Oi2 of disordered phase and the ordered phase of Bi3FeiMo2Oi2
[0015] In Bi3FeiMo2O12 of disordered phase, the X sites or Y sites are equivalent to each other, or elements of different types at random. In the ordered phase, X sites or Y sites are regularly and distinctly occupied by elements of different types or defects so that these two types of sites are differentiated. The ordered phase, therefore, shows peak division in X-ray diffraction, while the disordered phase is characterized in that single peaks are detected (indicated by the arrows in Figure 3). When measuring the diffraction range and X-ray angles 20 = 10 ° to 60 °, the peak in the disordered phase plane of 18.30 ° ± 0.05 ° (101) Bi3FeiMo2O12 is divided into 18.15 ° planes ± 0.05 ° (310) and 18.50 ° ± 0.05 ° (111); the peak in the plane of 28.20 ° ± 0.05 ° (112) of the disordered phase is divided into planes of 28.05 ° ± 0.05 ° (221) and 28.40 ° ± 0.05 ° (42- 1); the peak in the 33.65 ° ± 0.05 ° (200) plane of the disordered phase is divided into 33.25 ° ± 0.05 ° (600) and 34.10 ° ± 0.05 ° (202) planes ; and the peak in the 46.15 ° ± 0.05 ° (204) plane of the disordered phase is divided into 45.85 ° ± 0.05 ° (640) and 46.50 ° ± 0.05 ° (242) planes ). List of citations
[0016] Patent literature Patent literature 1: International publication No.WO 95/35273 Patent literature 2: Japanese patent open for public inspection No. S49-14392 Patent literature 3: Japanese Patent publication No. S61-12488 Patent literature 4: Patent Japanese open to public inspection No. 2010-120933 Patent literature 5: Japanese patent open to public inspection No. 2006-61888 Patent literature 6: Japanese patent open to public inspection No. 2010-253414
[0017] Non-patent literature Non-patent literature 1: Chemical Process of Petroleum, ed. by Japan Petroleum Institute, p. 172-176, Kodansha Scientific Ltd. Non-patent literature 2: Minutes. Cryst (1976). B32, p. 1163-1170 SUMMARY OF THE INVENTION Technical problem
[0018] The oxide catalysts described in patent literature 4, 5, and 6 greatly improve the initial reaction yields, but still cannot produce sufficiently satisfactory yields in industrial operation over a long period of time. These catalysts, when used for a long time in a method to produce unsaturated aldehyde, diolefin, or unsaturated nitrile, are disadvantageously degraded due to the reduction of propylene, isobutylene, isobutanol, n-butene, t-butyl alcohol, and ammonia, etc.
[0019] Reaction conditions of a high concentration of isobutylene and a high reaction temperature are desired from the point of view of unsaturated aldehyde productivity. In this case, catalysts are more susceptible to degradation by reduction. In addition, the unsaturated aldehyde produced can also be decomposed, resulting in an unfavorable decrease in the yield of unsaturated aldehyde.
[0020] The present inventors have formulated the hypothesis, as follows, that the reason why a fixed bed reaction system is adapted in practice, although it is generally accepted that a fluidized bed reaction system, which is advantageous in controlling a reactor temperature, is appropriate in the light of industrial practice: the unsaturated aldehyde that is the product of interest easily undergoes decomposition by combustion in a high temperature atmosphere containing oxygen in the reactor before reaching the reactor outlet, due to its very reactivity high, and is sequentially decomposed into unsaturated carboxylic acid or carbon dioxide. In addition, the fluidized bed reaction system that involves contact between products and catalysts requires: a rich layer, where most of the catalysts are present in a flow state; and a diluted layer that is the space to decrease the linear speed for separating the catalyst. The residence time of the products in the reactor after leaving the catalyst layer (rich layer) is therefore at least 10 times longer than in the fixed bed reactor. This further promotes the decomposition of the unsaturated aldehyde (product of interest) in the reactor, as you can imagine. As a result, reduced unsaturated aldehyde yield is an unavoidable problem for the fluidized bed reaction system.
[0021] Until now, the fluidized bed reaction system, which is supposed to be industrially advantageous from a temperature control point of view, has not been used in practice in the production of unsaturated aldehyde through the catalytic oxidation reaction of olefin and / or alcohol and, conversely, the fixed bed reaction system has been used here. This is probably due to the lack of means to prevent the decomposition of highly reactive unsaturated aldehyde. Presumably, there was no choice but to adopt the excellent fixed bed reaction system in product recovery, although chosen in conflict with industrial efficiency to avoid product decomposition and ensure the necessary yields.
[0022] The present invention was carried out in view of the problems described above, and an object of the present invention is to provide an oxide catalyst that prevents degradation by reduction of the catalyst, even during industrial operation for a long period of time and reduces less the yields of unsaturated aldehyde, yields of diolefin, or yields of unsaturated nitrile, and a method of producing the same, and methods of producing unsaturated aldehyde, diolefin, and unsaturated nitrile using the oxide catalyst. SOLUTION TO THE PROBLEM
[0023] As shown in the non-patent literature 1, the disordered phase is thermally unstable. It was previously considered that the disordered phase carried out by a catalyst for use in the gas phase oxidation reaction, which is carried out at an elevated temperature, has no merit.
[0024] However, studies conducted by the present inventors have revealed that some disordered phases are stably present even at an elevated temperature and can be stably present for a long time, even in a reducing atmosphere. Based on this discovery, the present inventors conducted diligent studies and consequently completed the present invention by verifying that a catalyst, having a disordered phase that is stable even at an elevated temperature and has a high resistance to reduction, can be obtained through incorporation with success of an element having a predetermined ionic radius in the crystal structure.
[0025] Specifically, the present invention is as follows:
[0026] [1] An oxide catalyst for use in the production of unsaturated aldehyde, diolefin, or unsaturated nitrile from olefin and / or alcohol, the oxide catalyst meeting the following (1) to (3): 4)) the oxide catalyst comprises molybdenum, bismuth, iron, cobalt, and an element A having an ionic radius greater than 0.96 Å (except for potassium, cesium and rubidium); 5)) an atomic ratio a of bismuth to 12 molybdenum atoms is 1 <to <5, an atomic ratio b of iron to 12 molybdenum atoms is 1.5 <b <6, an atomic ratio c of element A to 12 molybdenum atoms is 1 <c <5, and an atomic ratio d of cobalt to 12 molybdenum atoms is 1 <d <8; and 6)) the oxide catalyst comprises a disordered phase consisting of a crystal system comprising molybdenum, bismuth, iron and element A.
[0027] [2] The oxide catalyst according to the item above [1], in which the oxide catalyst has a single peak in each range of diffraction angles (29) of 18.30 ° ± 0.2 ° , 28.20 ° ± 0.2 °, 33.65 ° ± 0.2 °, and 46.15 ° ± 0.2 ° in X-ray diffraction, and an intensity ratio (la / lb) of intensity peak (aa) aa 29 = 33.65 ° ± 0.2 ° for peak intensity (lb) ba 29 = 34.10 ° ± 0.2 ° is 2.0 or greater.
[0028] [3] The oxide catalyst according to the item above [1] or [2], in which the oxide catalyst has a composition represented by the following composition formula (1):
where Mo represents molybdenum; Bi represents bismuth; Fe represents iron; element A represents an element having an ionic radius greater than 0.96 A (except for potassium, cesium and rubidium); Co represents cobalt; an element B represents at least one element selected from the group consisting of magnesium, zinc, copper, nickel, manganese, chromium, and tin; an element C represents at least one element selected from the group consisting of potassium, cesium, and rubidium; a to g each represent the atomic ratio of each element to 12 Mo atoms where the atomic ratio a of Bi is 1 <a <5, the atomic ratio b of Fe is 1.5 <b <6, the ratio atomic ratio c of the element A 1 <c <5, and the atomic ratio d of Co is 1 <d <8, the atomic ratio of element B is 0 <e <3, an atomic ratio f of element C is 0 <f <2, and the Fe / Co ratio is 0.8 <b / d; eg represents the atomicity of oxygen determined by a valence of constituent elements other than oxygen.
[0029] [4] The oxide catalyst according to any of the items above [1] to [3], still comprising at least one selected from the group consisting of silica, alumina, titania, and zirconia as a support.
[0030] [5] A method for the production of an oxide catalyst, comprising: a step of mixing the starting material mixture constituting the catalyst, comprising molybdenum, bismuth, iron, cobalt, and an element A having an ionic radius greater than 0.96 A (except for potassium, cesium and rubidium), to obtain a slurry; a drying step of drying the slurry thus obtained to obtain a dried product; and a calcining step of calcining the dried product thus obtained, wherein the step of calcining comprises a step of gradually heating the dried product from 100 ° C to 200 ° C over 1 hour or more.
[0031] [6] The method for producing the oxide catalyst according to the item above [5], in which the slurry has a pH of 8 or less.
[0032] [7] The method for producing the oxide catalyst according to the item above [5] or [6], wherein the calcination step comprises: a preliminary calcination step of preliminarily calcining the dried product at a temperature 200 to 300 ° C to obtain a preliminarily calcined product; and a final calcination step of finally calcining the preliminarily calcined product thus obtained at a temperature of 300 ° C or higher to obtain the catalyst.
[0033] [8] A method for producing unsaturated aldehyde, comprising a step of producing unsaturated aldehyde from oxidation of olefin and / or alcohol using the oxide catalyst according to any of the items above [1] to [4] for get the unsaturated aldehyde.
[0034] [9] The method for producing unsaturated aldehyde according to the item above [8], in which olefin and / or alcohol is at least one selected from the group consisting of propylene, isobutylene, propanol, isopropanol , isobutanol, and t-butyl alcohol.
[0035] [10] The method for producing unsaturated aldehyde according to the item above [8] or [9], wherein the step of producing the unsaturated aldehyde comprises a step of discharging a product gas comprising the unsaturated aldehyde at from a fluidized bed reactor through the catalytic oxidation reaction in gaseous phase of olefin and / or alcohol with an oxygen source in the fluidized bed reactor.
[0036] [11] The method for producing unsaturated aldehyde according to any of the items above [8] to [10], in which the gas phase catalytic oxidation reaction is carried out at a reaction temperature of 400 to 500 ° C, and the product gas discharged from the fluidized bed reactor has an oxygen concentration of 0.03 to 0.5% by volume.
[0037] [12] A method for producing diolefin, comprising a step of producing monoolefin oxidation diolefin having 4 or more carbon atoms using the oxide catalyst according to any of the items above [1] to [4] to obtain the diolefin.
[0038] [13] A method for producing unsaturated nitrile, comprising a step of producing unsaturated nitrile reaction of at least one selected from the group consisting of propylene, isobutylene, propanol, isopropanol, isobutanol, and t-butyl alcohol , with molecular oxygen and ammonia in a fluidized bed reactor using the oxide catalyst according to any of the items above [1] to [4] to obtain unsaturated nitrile. ADVANTAGE EFFECTS OF THE INVENTION
[0039] The present invention can provide an oxide catalyst that prevents degradation by reducing the catalyst, even during industrial operation over a long period of time and reduces less unsaturated aldehyde yields, diolefin yields, or unsaturated nitrile yields , and a method for producing the same, and methods for producing unsaturated aldehyde, diolefin, and unsaturated nitrile using the oxide catalyst. DESCRIPTION OF METHODS
[0040] Figure 1 is a schematic view illustrating the crystal structure of a disordered phase Bi3FeiMθ2θi2;
[0041] Figure 2 is a schematic view illustrating the crystal structure of an ordered phase of Bi3Fe1Mθ2θi2;
[0042] Figure 3A is a graph illustrating the X-ray diffraction of the disordered phase Bi3FeiMo2O12 and Figure 3B is a graph illustrating the X-ray diffraction of the ordered phase of Bi3FeiMo2Oi2;
[0043] Figure 4 is a graph illustrating the relationship between the content rate of the disordered phase and peaks a and b;
[0044] Figure 5 is a graph illustrating the X-ray diffraction of catalysts obtained in Example A1 and Comparative Example A3;
[0045] Figure 6 is an enlarged graph illustrating the range of 20 = 15 to 30 ° in X-ray diffraction in Figure 5;
[0046] Figure 7 is an enlarged graph illustrating the range of 20 = 30 to 50 ° in X-ray diffraction in Figure 5;
[0047] Figure 8 is a graph illustrating the X-ray diffraction (20 = 25 to 27 °) of an oxide catalyst before and after the olefin gas phase catalytic oxidation reaction in Comparative Example A6;
[0048] Figure 9 is a graph illustrating the X-ray diffraction peaks of catalysts obtained in Examples B1 and Comparative Example B1;
[0049] Figure 10 is an enlarged graph illustrating the range of 20 = 15 to 30 ° in X-ray diffraction peaks in Figure 9;
[0050] Figure 11 is an enlarged graph illustrating the range of 20 = 30 to 50 ° in X-ray diffraction peaks in Figure 9;
[0051] Figure 12 is a graph illustrating the XRD (20 = 10 to 60 °) of an oxide catalyst before and after the olefin gas phase catalytic oxidation reaction in Example C1;
[0052] Figure 13 is an enlarged graph illustrating the range of 20 = 25 to 27 ° in Figure 12;
[0053] Figure 14 is a graph illustrating the XRD (20 = 10 to 60 °) of an oxide catalyst before and after the olefin gas phase catalytic oxidation reaction in Comparative Example C1;
[0054] Figure 15 is an enlarged graph illustrating the range of 20 = 25 to 27 ° in Figure 14; and
[0055] Figure 16 is a graph illustrating the X-ray diffraction peaks of the catalysts obtained in Examples C1 and Comparative Example C2. MODE FOR CARRYING OUT THE INVENTION
[0056] In the following, the first to the third embodiments for carrying out the present invention will be described in detail. The present invention is not intended to be limited to the embodiments described below, and various changes or modifications can be made without departing from the spirit of the present invention. [First embodiment] [Oxide catalyst]
[0057] The oxide catalyst according to the first embodiment will be described.
[0058] The oxide catalyst according to the first embodiment is an oxide catalyst for use in the production of unsaturated aldehyde or diolefin from olefin and / or alcohol, the oxide catalyst meeting the following (1) to ( 3): (1) the oxide catalyst comprises molybdenum (here below, also referred to as "Mo"), bismuth (here below, also referred to as "Bi"), iron (here below, also referred to as "Fe"), cobalt (here below, also referred to as "Co"), and an element A having an ionic radius greater than 0.96 A (except for potassium, cesium and rubidium); (2) an atomic ratio a of bismuth to 12 molybdenum atoms is 1 <to <5, an atomic ratio b of iron to 12 molybdenum atoms is 1.5 <b <6, an atomic ratio c of element A to 12 molybdenum atoms is 1 <c <5, and an atomic ratio d of cobalt to 12 molybdenum atoms is 1 <d <8; and (3) the oxide catalyst comprises a disordered phase consisting of a crystal system comprising molybdenum, bismuth, iron and element A. Starting material)
[0059] Examples of the olefin serving as a starting material for use in the production of unsaturated aldehyde or diolefin include, but are not limited to, propylene, n-butene, isobutylene, n-pentene, n-hexene, and cyclohexene. Among them, propylene and isobutylene are preferred.
[0060] Examples of alcohol serving as a starting material for use in the production of unsaturated aldehyde or diolefin include, but are not limited to, propanol, isopropanol, butanol, isobutanol, and t-butyl alcohol. Among them, isobutanol and t-butyl alcohol are preferred.
[0061] In the first embodiment, for example, acrolein or acrylic acid can be produced using propylene, propanol, or isopropanol as a starting material, while methacrolein or methacrylic acid can be produced using isobutylene, isobutanol, or t-butyl alcohol as a starting material.
[0062] Alternatively, butadiene can be produced using n-butene as a starting material. The olefin and alcohol starting materials may contain water, nitrogen, and alkanes such as propane, butane, and isobutane.
[0063] These olefins and / or alcohols can be used alone or in combination. (1) Composition
[0064] The oxide catalyst according to the first embodiment comprises molybdenum, bismuth, iron, cobalt, and element A having an ionic radius greater than 0.96 Å (except for potassium, cesium and rubidium). The presence of Mo, Bi, and Fe is indispensable from the point of view of the composition of the metallic elements in a Bi-Mo catalyst in which Bi and Mo, together, form an active species.
[0065] The atomic ratio a of Bi to 12 atoms of Mo is 1 <to <5. The atomic ratio a is preferably 1 <to <4, more preferably 1 <to <3, from the point of view of further increasing the selectivity of unsaturated aldehyde and / or diolefin.
[0066] From the point of view of increasing the catalytic activity without reducing the selectivity of unsaturated aldehyde and / or diolefin, Fe is an essential element, as with Mo and Bi, to industrially synthesize unsaturated aldehyde and / or diolefin. A high Fe content, however, forms Fe2O3 and tends to increase by-products such as CO or CO2, resulting in reduced selectivity of unsaturated aldehyde and / or diolefin. Alternatively, a high Fe content may not form Fe2O3, but instead form a 2-component Fe-Mo-O composite oxide, which is an inactive component that does not exhibit catalytic activity. From these points of view, the atomic ratio b of Fe to 12 Mo atoms in the oxide catalyst according to the first embodiment is 1.5 <b <6, preferably 1.5 <b <5, more preferably 1.5 <b <4.
[0067] Bi and Mo tend to form a composite oxide such as Bi2Mo3Oi2 or Bi2MoO6, which is, as reported, an active species in gas phase catalytic oxidation, amoxidation, oxidative dehydrogenation reaction, and the like. A catalyst consisting of such a composite oxide gives the high selectivity of unsaturated aldehyde or diolefin, but is poorly active. On the other hand, Fe and Mo form a composite oxide like Fe2Mo3Oi2. A catalyst consisting of such a composite oxide exhibits both low activity and low selectivity. However, the appropriate composition of Mo, Bi, and Fe forms a 3-component composite oxide, comprising the disordered phase Bi3FeiMo2Oi2 with high activity and high selectivity of unsaturated aldehyde and diolefin.
[0068] The present inventors have carried out diligent studies to obtain an excellent oxide catalyst in heat resistance that retains the characteristic structure described above, even at an elevated temperature, and thus found that the heat resistance of the oxide catalyst is improved by incorporation of element A having an ionic radius greater than 0.96 A except for potassium, cesium and rubidium (here below, also simply called an "element A") in the oxide catalyst structure. Specifically, the present inventors have found that a disordered phase consisting of a crystal system comprising molybdenum, bismuth, iron, and element A is useful for improving heat resistance, when contained in the oxide catalyst.
[0069] Element A can be any element having an ionic radius greater than 0.96 Â except for potassium, cesium and rubidium without limitations. Examples of element A include: at least one element selected from the group consisting of lanthanoid elements such as cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium and dysprosium, or a mixture thereof; at least one element selected from the group consisting of elements such as lead and yttrium, or a mixture thereof; and at least one element selected from the group consisting of alkaline earth metals such as calcium, strontium, and barium, or a mixture thereof. Among them, element A is preferably at least one element selected from the group consisting of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, calcium, and lead, or a mixture thereof, more preferably at least an element selected from the group consisting of lanthanum, cerium, praseodymium, neodymium, calcium, and lead, or a mixture of them, from the point of view of balance between stability and reactivity.
[0070] The atomic ratio c of element A to 12 atoms of Mo is 1 <c <5, preferably 1 <c <4, more preferably 1 <c <3. Since the atomic ratio c is within the range described above, a 4-component composite oxide, comprising Bi3.xAxFeiMo2Oi2 of disordered phase, is formed. For example, in the case of using La as element A, a 4-component composite oxide, comprising Bi3.xLaxFeiMθ2θ12 of disordered phase, is formed. La can be appropriately composed into a 3-component composite oxide comprising the disordered phase Bi3FeiMo2Oi2 so that Bi3 + (ionic radius: 0.96 A) is replaced by La3 + having a greater ionic radius to obtain an oxide catalyst that is resistant to heat and has both high activity and high selectivity. A 3-component composite oxide free of La3 + undergoes the phase transition of an ordered phase at an elevated temperature of at least 500 ° C, while, with this, the coexistence of La having a slightly greater ionic radius than Bi inhibits the phase transition to an ordered phase and keeps the phase structure disordered. The element that exerts this inhibitory effect on the phase transition to an ordered phase is not limited to La, and any of the elements A listed above may have similar effects.
[0071] Co is indispensable to provide resistance to reduction for the oxide catalyst according to the first embodiment. In the presence of Co, divalent iron is incorporated into CoMoO4 to form a crystal structure of component Co2 + -Fe2 + -Mo-0 3. This incorporated iron is easily oxidized to trivalent iron, in a reaction atmosphere, due to its metastable structure. Redox is therefore cycled during the reaction, probably avoiding degradation of the reduction.
[0072] Fe in Fe2Mo3Oi2 or a 4-component composite oxide comprising Bi3.xAxFeiMo2Oi2 of disordered phase is trivalent immediately after the start of the reaction, but is reduced to divalent iron through redox cycles during the reaction. In the absence of Co, a composite oxide of divalent iron and molybdenum (FeMoO4) and MoO2 are formed. This FeMoO4 is rarely made trivalent in a reaction atmosphere, due to its stable structure. The formation of these stable compounds stabilizes iron, so that this redox is not cycled during the reaction, probably causing degradation of the reduction.
[0073] The atomic ratio d of Co to 12 atoms of Mo is 1 <d <8, preferably 2 <d <8, more preferably 2 <d <6, still preferably 3 <d <5. At the atomic ratio d exceeding 8 , a 4-component composite oxide comprising Bi3.xAxFeiMθ2θi2 of disordered phase is difficult to form. 2) Crystal structure
[0074] The oxide catalyst according to the first embodiment preferably contains a 4-component composite oxide comprising Bi3. xAxFeiMo2Oi2 of disordered phase. X-ray diffraction (XRD) can be used as an index for the formation of the 4-component composite oxide comprising disordered phase Bi3.xAxFe1Mo2Oi2. The oxide catalyst according to the first embodiment preferably has simple peaks, at least in planes of 18.30 ° ± 0.2 ° (101), 28.20 ° ± 0.2 ° (112), 33, 65 ° ± 0.2 ° (200), and 46.15 ° ± 0.2 ° (204) measured in the range of diffraction angles 20 = 10 ° to 60 ° in X-ray diffraction of the crystal, as in oxide 3-component composite comprising disordered phase Bi3FeiMo2Oi2. Particularly preferably, the oxide catalyst according to the first embodiment has a single peak at a position within each reference value ± 0.05 °.
[0075] The ratio of intensity (la / lb) of intensity (la) of peak aa 20 = 33.65 ° ± 0.2 ° to intensity (lb) of peak ba 20 = 34.10 ° ± 0.2 ° it is preferably 2.0 or greater, more preferably 2.5 or greater, still preferably 3.0 or greater, from the point of view of still preventing decomposition of the catalyst and obtaining the unsaturated aldehyde and / or diolefin in higher yields. The intensity ratio (la / lb) is 1.1 in 100% in the ordered phase and 3.3 in 100% in the disordered phase. A peak intensity (lb) b a 20 = 34.10 ° ± 0.2 ° also comprises peak intensity derived from Fe2Mo3Oi2 present in a trace amount. At an intensity ratio (la / lb) of 2.0 or greater, the oxide catalyst contains a predetermined proportion of the disordered phase and therefore gives a reduced yield of unsaturated carboxylic acid and improves the yield of unsaturated aldehyde and / or diolefin . Figure 4 shows the relationship between the content of the disordered phase with peaks a and b.
[0076] The mechanism by which disorderly phase Bi3.xAxFeiMo2O12 is formed is uncertain. A composite oxide of Bi and Mo is formed as an intermediate in a heat treatment phase. The continuation of the heat treatment probably causes the thermal diffusion and solid solution of substitution of Fe and element A in the composite oxide of Bi and Mo to form a disorderly phase composite Bi3.xAxFeiMo2O12. (Single peak)
[0077] The term "single peak" described here should not be understood in the strict sense, and a main peak detected at each diffraction angle can be understood as a single peak unless divided. This means that even if a peak having an inflection point can be considered as a single peak. A peak that is evidently less than a main peak is excluded, if present, and then the main peak is desirably determined to be a single or divided peak. The "smallest peak" refers to a peak with an intensity less than 50% than that of the main peak within a predetermined range of diffraction angle.
[0078] The "main peak" refers to the largest peak among the peaks present in a predetermined diffraction angle range. For example, as for a diffraction angle in the range of 18.30 ° ± 0.2 °, the largest peak can be detected at a position of 18.35 °. In such a case, this peak is determined as a main peak at 18.30 ° ± 0.2 °.
[0079] The oxide catalyst according to the first embodiment preferably has a composition represented by the formula of composition (1) shown below. The oxide catalyst having the composition represented by the formula of composition (1) shown below tends to prevent the formation of unsaturated carboxylic acid or carbon dioxide and further improve the selectivity of unsaturated aldehyde and / or diolefin. Composition formula (1)
where Mo represents molybdenum; Bi represents bismuth; Fe represents iron; element A represents an element having an ionic radius greater than 0.96 Å (except for potassium, cesium and rubidium); Co represents cobalt; element B represents at least one element selected from the group consisting of magnesium, zinc, copper, nickel, manganese, chromium, and tin; element C represents at least one element selected from the group consisting of potassium, cesium, and rubidium; a to g each represent the atomic ratio of each element to 12 Mo atoms where the atomic ratio a of Bi is 1 <a <5, the atomic ratio b of Fe is 1.5 <b <6, the ratio atomic c of element A is 1 <c <5, atomic ratio d of Co is 1 <d <8, atomic ratio and element B is 0 <e <3, atomic ratio f of element C is 0 <f <2, and the Fe / Co ratio is 0.8 <b / d; eg represents the atomicity of oxygen determined by the valences of constituent elements other than oxygen.
[0080] In the composition formula (1), element B represents at least one element selected from the group consisting of magnesium, zinc, copper, nickel, manganese, chromium, and tin and probably replaces some cobalt atoms in the oxide catalyst. The atomic and element B ratio is preferably 0 <and <3, more preferably 0 <and <2, from the point of view of maintaining equilibrium with the formation of disordered phase crystals. Element B is not essential, but it contributes to improving the activity of the catalyst or stabilizing the crystal structure of CoMoO4 in the catalyst. For example, copper has the effect of improving the activity of the catalyst. Nickel, magnesium, zinc, and manganese have the effects of stabilizing the crystal structure of C0M004 and inhibiting, for example, the phase transition attributed to pressure or temperature.
[0081] In the oxide catalyst according to the first embodiment, Co is an essential element, as with Mo, Bi, and Fe, from the point of view of industrial synthesis of unsaturated aldehyde and / or diolefin. Co plays a role as a support to form the composite oxide CoMoO4 and highly disperses the active species like Bi-Mo-0 and also plays a role in absorbing 0 oxygen from the gas phase and supplying this oxygen to Bi-Mo-0 or similar. Co and Mo are preferably composed to form a composite oxide COMOOA, from the point of view of obtaining unsaturated aldehyde and / or diolefin in high yields. The atomic ratio d of Co is preferably 1 <d <8, more preferably 2 <d <8, still preferably 2 <d <7, even more preferably 2 <d <5, from the point of view of reducing the formation of unary oxides like CO3O4 or CoO.
[0082] The Fe / Co ratio is preferably 0.8 <b / d, more preferably 0.8 <b / d <1.5, still preferably 0.9 <b / d <1.2. As long as the Fe / Co ratio is within the range described above, unary oxides such as Co3O4 or CoO tend to be rarely formed.
[0083] Element A represents an element having an ionic radius greater than 0.96 Â except for potassium, cesium and rubidium. The atomic ratio of element A is preferably 1 <c <5, more preferably 1 <c <4, still preferably 1 <c <3.
[0084] Element C represents at least one element selected from the group consisting of potassium, cesium, and rubidium. Element C probably plays a role in neutralizing the non-composite MoO3 acid center or the like in the oxide catalyst. The presence or absence of element C contained therein does not directly influence the crystal structure of the disordered phase described later. The atomic ratio f of element C to 12 Mo atoms is preferably 0 <f <2, more preferably 0.01 <f <2, still preferably 0.01 <f <1, from the point of view of catalytic activity. At the atomic ratio f of 0 or greater, the neutralizing effect tends to be further improved. At the atomic ratio f of 2 or less, the oxide catalyst tends to be processed from basic to neutral. The resulting oxide catalyst easily adsorbs the olefin or alcohol starting material and tends to exhibit greater catalytic activity.
[0085] The oxide catalyst can contain arbitrary components like other metal components without inhibiting the disordered phase formation of B3-xAxFeiMo2Oi2.
[0086] Element B and element C form crystal structures separately from the crystal structure of the disordered phase described below and therefore do not directly influence the crystal structure of the disordered phase. (3) Component other than metal oxide
[0087] The oxide catalyst according to the first embodiment can further comprise a support for supporting the metal oxide. The catalyst still comprising the support is highly preferred due to the dispersion of the metal oxide and conferring a high wear resistance to the supported metal oxide. In this context, the catalyst preferably comprises the support when molded by an extrusion molding method. Alternatively, a catalyst compressed into a tablet for the production of methacrolein in a fixed bed reactor may not need to include the support.
[0088] Examples of the support include, but are not limited to, at least one selected from the group consisting of silica, alumina, titania, and zirconia. The oxide catalyst supported by such support tends to improve the physical properties appropriate for the fluidized bed reaction, such as particle shape, size, distribution, fluidity, and mechanical strength. Among them, silica is preferred as the support. In general, the silica support is preferable in terms of its property of conferring the appropriate physical properties for the fluidized bed reaction to the oxide catalyst, as well as because of being inactive compared to other supports and having a binding effect favorable over metal oxide without reducing selectivity for unsaturated aldehyde and / or diolefin. In addition, the silica support is also preferred because of the ease of providing high wear resistance for the metal oxide thus supported.
[0089] A silica sol is preferred as a source of silica. The concentration of the silica sol in the state of a starting material not mixed with other components is preferably 10 to 50% by mass from the point of view of the dispersibility of silica particles. The silica sol preferably comprises 40 to 100% by mass of at least one silica sol (a) containing primary silica particles having an average particle diameter of 20 nm to less than 55 nm, preferably 20 to 50 nm, and 60 to 0% by mass of at least one silica sol (b) containing primary silica particles having an average particle diameter of 5 nm to less than 20 nm, from the point of view of unsaturated nitrile selectivity.
[0090] The content of the support is preferably 20 to 80% by weight, more preferably 30 to 70% by weight, still preferably 40 to 60% by weight, even more preferably 5 to 10% by weight, relative to 100% by weight. mass in the total of the support and the oxide catalyst. The fixation of the support content being within the range described above, the yield of unsaturated aldehyde and / or diolefin tends to be improved. (4) Molding of oxide catalyst
[0091] The oxide catalyst of the first embodiment can be shaped for use. In such a case, molding is carried out by a method known in the art as tablet compression or extrusion molding. Examples of formats in which the oxide catalyst is shaped include inserts, granules, spheres, computer-designed formats (CDS), trilobules, quadrilobules, rings, high geometric surfaces (HGSS), clover leaf shapes, and beehive shapes. Among them, CDSs and rings are preferred from the standpoint of resistance.
[0092] The specific surface area of the oxide catalyst is preferably 2 to 5 m2 / g, more preferably 2 to 4 m2 / g. In the case of using the support as silica, the specific surface area tends to be greater than 2 to 5 m2 / g. The specific surface area of the unsupported metal oxide is preferably 2 to 5 m2 / g. [2] Method for producing oxide catalyst
[0093] As mentioned above, the present inventors concentrated on obtaining disordered phase B3.xAxFeiMo2Oi2 comprising element A, Bi, Fe, and Mo, and exhaustively studied the compositional ratios of the elements and a method for preparing the disordered phase.
[0094] As is evident from the name catalyst Bi-Mo, both Bi and Mo are essential elements to form an active species. A catalyst rich in Bi and Mo is advantageous from an activity point of view. A large content of Bi, however, has been shown to render the catalyst inhomogeneous. For example, bismuth nitrate, which is a conventional source of Bi used industrially, is a poorly soluble substance in water and therefore requires a large amount of nitric acid for its dissolution. As a result, the catalyst has a non-homogeneous composition after calcination. In this regard, the Bi content is limited within a range in the conventional catalyst preparation technique. This fails to provide a homogeneous catalyst due to the unary oxides formed as BIO2O3, resulting in an unfavorable decrease in the yield of unsaturated aldehyde and / or diolefin.
[0095] From the point of view of increasing catalytic activity without reducing the selectivity of unsaturated aldehyde and / or diolefin, Fe was previously reported to be an essential element, as with Mo and Bi, to industrially synthesize unsaturated aldehyde and / or diolefin. As reported by International Publication No. WO 95/35273, however, a large amount of added Fe tends to increase by-products such as CO or CO2, resulting in reduced selectivity of unsaturated aldehyde and / or diolefin. Fe is therefore optimally added in a small amount.
[0096] After several trial and error procedures to solve this problem, the present inventors have found that disordered phase B3.xAxFeiMo2O12 crystals can be easily formed with the formation of an ordered phase suppressed by a method to produce an oxide catalyst described later.
[0097] The method for producing the oxide catalyst according to the first embodiment comprises: a step of mixing the starting materials mixture constituting the catalyst, comprising molybdenum, bismuth, iron, cobalt, and element A having a radius ionic greater than 0.96 A (except for potassium, cesium and rubidium), to obtain slurry; a drying step of drying the slurry thus obtained to obtain a dried product; and a calcining step of calcining the dried product thus obtained, wherein the step of calcining comprises a step of gradually heating the product dried from 100 ° C to 200 ° C for 1 hour or more. (1) Mixing step
[0098] The mixing step is a step of mixing starting materials of metal elements constituting the catalyst, comprising molybdenum, bismuth, iron, cobalt, and element A having an ionic radius greater than 0.96 A (except for potassium, cesium and rubidium), to obtain slurry. Examples of sources of molybdenum, bismuth, iron, cobalt, element A, rubidium, cesium, potassium, magnesium, copper, nickel, chromium, manganese, lead, alkaline earth metals, and rare earth elements including this element in the form of ammonium salt, nitrate, hydrochloride, salts of organic acids, oxides, hydroxides, and carbonate, which are soluble in water or nitric acid.
[0099] In the case of using an oxide from each element source, a dispersion containing the oxide dispersed in water or in an organic solvent is preferably used, and an oxide dispersion containing the oxide dispersed in water is most preferably used. The dispersion of the oxide in water may further contain a dispersion stabilizer such as a polymer for dispersing the oxide. The particle size of the oxide is preferably 1 to 500 nm, more preferably 10 to 80 nm.
[00100] The slurry can be appropriately supplemented with: water-soluble polymers such as polyethylene glycol, methyl cellulose, polyvinyl alcohol, polyacrylic acid, and polyacrylamide; polyvalent carboxylic acids such as amines, aminocarboxylic acids, oxalic acid, malonic acid and succinic acid; and / or organic acids, such as glycolic acid, malic acid, tartaric acid, and citric acid, from the point of view of uniform dispersion of the catalyst starting materials in the slurry. The amount of water-soluble polymer and / or organic acid added is, but is not limited to, preferably 30% by weight or less compared to 100% by weight of the catalyst starting materials from the point of view of the balance between uniformity and income.
[00101] The slurry can be prepared by any method normally used without limitations and can be prepared, for example, by mixing a solution containing molybdenum ammonium salt dissolved in hot water, with solutions containing metal nitrate components except molybdenum, such as bismuth, iron, cobalt, and element A, dissolved in water or these metallic components dissolved in an aqueous solution of nitric acid. In the case of the oxide catalyst comprising a support, for example, a silica sol can be added before or after mixing a solution containing molybdenum ammonium salt dissolved in hot water, with solutions containing metal components, except molybdenum, dissolved in water or an aqueous solution of nitric acid. The slurry, thus blended, has a metal element concentration of generally 1 to 50% by weight, preferably 10 to 40% by weight, more preferably 20 to 40% by weight, relative to 100% by weight of the slurry. from the point of view of the balance between uniformity and yields.
[00102] The step of preparing the slip described above is provided for illustrative purposes and is not intended to limit the technical scope of the present invention. The order in which element sources are added can be changed, or the pH or viscosity of the slurry can be changed by adjusting the nitric acid concentration or by adding ammonia water to the slurry. Preferably, the slurry is homogeneous to form the disordered phase Bi3.xAxFeiMθ2θi2 crystal structure. From this point of view, the pH of the slurry is preferably 8.0 or less, more preferably 7.0 or less, still preferably 6.0 or less. The slurry having a pH of 8.0 or less can prevent the precipitation of bismuth components and tends to promote the formation of the disordered phase B1-3-xAxFeiMo2O12 crystal structure. (2) Drying step
[00103] The drying step is a step of drying the slurry obtained in the mixing step to obtain a dried product. Drying can be carried out by any method generally used without limitations. Examples of the drying method include arbitrary methods such as evaporation to dryness, spray drying, and drying under reduced pressure. Examples of the spray drying method include, but are not limited to, common methods such as centrifugation systems, two-fluid nozzle systems, and high-pressure nozzle systems, which are carried out industrially. In this drying, air heated with steam, an electric heater, or the like is preferably used as a source of dry heat. The temperature at the dryer inlet of the spray drying apparatus is generally 150 to 400 ° C, preferably 180 to 400 ° C, more preferably 200 to 350 ° C. (3) Calcination step
[00104] The calcination step is a step of calcining the dried product obtained in the drying step. The calcination can be carried out using an oven such as a rotary kiln, a tunnel kiln, or a muffle furnace. The calcination step comprises a step of gradually heating the dried product from 100 to 200 ° C for 1 hour or more. Through this heating step, 4-component elements Bi, Mo, Fe, and element A can be uniformly mixed at the atomic level to easily form the crystal structure of disordered phase BÍ3.xAxFeiMo2Oi2 The term "gradually heating" described here refers to heating to a predetermined temperature usually for 1 h to 10 h, as a heating time. The heating rate does not need to be kept constant. The heating time is generally 1 h to 10 h, preferably 1 h to 5 h, more preferably 2 h to 4 h.
[00105] The method for calcining the dried product may vary depending on the starting materials used. For example, a product dried from the starting materials comprising nitric acid ions is preferably calcined in two stages of preliminary calcination and final calcination. Specifically, calcination is preferably carried out by: a preliminary calcination step of preliminarily calcining a dried product at a temperature of 200 to 300 ° C to obtain a preliminarily calcined product; and a final calcination step of finally calcining the preliminarily calcined product thus obtained at a temperature of 300 ° C or higher to obtain the catalyst. The heating step is carried out before the preliminary calcination step, and then the temperature is increased to the range of 200 ° C to 300 ° C, usually for 1 h or more.
[00106] The preliminary calcination step involves calcining the dried product at a temperature in the range of 200 ° C to 300 ° C. The preliminary calcination time is generally 1 h to 10 h, preferably 2 h to 8 h, more preferably 3 h to 6 h. Preliminary calcination is carried out in order to cause the gradual combustion of nitric acid remaining in the dried product. Preliminary calcination tends to form a homogeneous crystal structure of disordered phase BÍ3.xAxFeiMo2Oi2. In this context, preliminary calcination in a temperature range of 200 ° C to 300 ° C is performed directly without the heating step from 100 to 200 ° C, rarely forming the crystal structure of Bi3.xAxFeiMo2Oi2 of disordered phase and can form, on the contrary, an ordered phase or 2-component oxides, such as Fe2Mθ3θi2, Bi2Mo3Oi2, or A2Mo3Oi2.
[00107] The preliminarily calcined product thus obtained by preliminary calcination is finally calcined in the second phase, in order to facilitate the formation of the crystal structure of the disordered phase. According to the results obtained by the present inventors, the formation of the crystal structure depends on the product of the calcination temperature and the calcination time. Preferably, the calcination temperature and the calcination time are set correctly. The final calcination temperature is higher than the preliminary calcination temperature and is preferably 300 ° C or greater, more preferably 300 ° C or greater and 700 ° C or less, still preferably 300 to 650 ° C, even more preferably 400 ° C to 600 ° C, particularly preferably 450 ° C to 600 ° C. The setting of the final calcination temperature is within the range described above, the crystal structure of the disordered phase Bi-xAxFeiMo2O12 tends to be more easily formed.
[00108] In the case of final calcination at such a temperature, the final calcination time is generally 0.1 to 72 hours, preferably 2 to 48 hours, more preferably 3 to 24 hours, from the point of view of properly setting the temperature of calcination and the calcination time of the product and promote the formation of crystals.
[00109] To form the crystal structure, the final calcination time is preferably, for example, 24 to 72 hours at a final calcination temperature as low as at least 400 ° C from the point of view of properly setting the temperature of calcination x calcination time, and is preferably 3 hours or shorter at a final calcination temperature as high as at least 600 ° C from the point of view of preventing the formation of an ordered phase.
[00110] The crystal structure of Bi3.xAxFeiMo2O12 of disordered phase can be easily formed by carrying out all these steps.
[00111] The successful formation of the Bi3 crystal structure. xAxFeiMo2Oi2 of disordered phase in the final calcination step can be confirmed by structural X-ray analysis in the oxide catalyst obtained by the final calcination. Since the oxide catalyst according to the first embodiment has unique peaks at diffraction angles (20) at least in each plane range of 18.30 ° ± 0.2 ° (101), 28.20 ° ± 0.2 ° (112), 33.65 ° ± 0.2 ° (200), and 46.15 ° ± 0.2 ° (204) in X-ray diffraction analysis and intensity ratio (la / lb) of peak intensity (la) at 20 = 33.65 ° ± 0.2 ° for peak intensity (lb) at 20 = 34.10 ° ± 0.2 ° is 2.0 or greater, can be it is determined that the disordered phase Bi3.xAxFeiMo2Oi2 crystal structure has been formed. [3] Method for producing unsaturated aldehyde
[00112] Unsaturated aldehyde can be produced through the oxidation reaction of at least one olefin selected from the group consisting of propylene and isobutylene and / or at least one alcohol selected from isobutanol and t-butyl alcohol using the oxide catalyst according to the first embodiment. Hereinafter, specific examples of the method will be described, although the method for producing unsaturated aldehyde is not limited to the specific examples below. (1) Method for producing methacrolein
[00113] Methacrolein can be obtained, for example, through the gas phase catalytic oxidation reaction of isobutylene, isobutanol, or t-butyl alcohol using the oxide catalyst according to the first embodiment. The gas phase catalytic oxidation reaction can be carried out by introducing, in a catalyst layer in a fixed bed reactor, a feed gas composed of 1 to 10% by volume of isobutylene, isobutanol, t-butyl alcohol, or a mixed gas supplemented with gas containing molecular oxygen and diluent gas at a molecular oxygen concentration of 1 to 20% by volume in the presence of the oxide catalyst. This reaction can be carried out at a temperature of 250 to 480 ° C, a pressure of normal pressure of 5 atm, and a space speed of 400 to 4000 / h [under conditions of pressure of normal temperature (NTP)]. The molar ratio of oxygen to isobutylene, isobutanol, t-butyl alcohol, or its mixed gas (oxygen / isobutylene, isobutanol, t-butyl alcohol, or its mixed gas) is generally 1.0 to 2.0, preferably 1.1 to 1.8, more preferably 1.2 to 1.8, from the point of view of controlling the oxygen concentration at the reactor outlet, in order to improve the yield of unsaturated aldehyde.
[00114] Examples of the gas containing molecular oxygen include, but are not limited to, gases containing oxygen such as pure oxygen gas, N2O, and air. Among these, air is preferred from an industrial point of view.
[00115] Examples of the diluting gas include, but are not limited to, nitrogen, carbon dioxide, water vapor and mixed gases thereof. The mixing ratio between the gas containing molecular oxygen and the diluent gas is preferably 0.01 <molecular oxygen / (gas containing molecular oxygen + diluent gas) <0.3 in volume. The molecular oxygen content is preferably 1 to 20% by volume relative to 100% by volume of the feed gas.
[00116] Water vapor in the feed gas is effective to avoid coking the catalyst. In contrast, the water vapor concentration in the diluent gas is preferably decreased as much as possible, in order to inhibit the formation of carboxylic acid by-products such as methacrylic acid or acetic acid. The water vapor content is generally 0 to 30% by volume, compared to 100% by volume of the feed gas. (2) Method for producing acrolein
[00117] Acrolein can be produced through the catalytic oxidation in propylene gas phase, for example, under any condition without limitations and can be produced by a method generally used to produce acrolein through the catalytic oxidation in propylene gas phase. For example, a mixed gas containing 1 to 15% by volume of propylene, 3 to 30% by volume of molecular oxygen, 0 to 60% by volume of water vapor, and 20 to 80% by volume of inert gas such as nitrogen and CO2 gas can be introduced at 250 to 450 ° C under pressure of 0.1 to 1 MPa at a spatial speed (SV) of 300 to 5000 h 1 to a catalyst layer in a reactor. The reactor used can be a general fixed bed reactor, fluidized bed reactor, or moving bed reactor. (3) Method for producing diolefin
[00118] The method for producing diolefin according to the first embodiment comprises a step of producing monoolefin oxidation diolefin having 4 or more carbon atoms using the oxide catalyst according to the first embodiment to obtain the diolefin. More specifically, the diolefin production step is a step of obtaining the diolefin through the gas catalytic oxidation reaction of monoolefin having 4 or more carbon atoms with an oxygen source in the presence of the oxide catalyst according to the first embodiment.
[00119] The oxygen source used in the gas phase catalytic oxidation reaction can be, but is not limited to, for example, a mixed gas gas containing molecular oxygen and diluent gas.
[00120] Examples of the monoolefin having 4 or more carbon atoms include, but are not limited to, n-butene.
[00121] The diolefin obtained differs depending on the monoolefin having 4 or more carbon atoms used. For example, butadiene is obtained using n-butene.
[00122] Examples of the gas containing molecular oxygen include, but are not limited to, gases containing oxygen such as pure oxygen gas and air. Among them, air is preferably used as the gas containing molecular oxygen. The use of air tends to be excellent from an industrial point of view as the cost.
[00123] Examples of the diluting gas include, but are not limited to, nitrogen, carbon dioxide, water vapor and mixed gases thereof.
[00124] The feed gas to be supplied for the diolefin production step is preferably supplemented with gas containing molecular oxygen and diluent gas for monoolefin having a concentration of 4 or more carbon atoms of 1 to 10% by volume and a concentration molecular oxygen of 1 to 20% by volume.
[00125] Examples of the reactor include, but are not limited to, fixed bed reactors. The reaction can be carried out at a temperature preferably from 250 to 450 ° C, a pressure preferably from normal pressure to 5 atm, and a spatial speed of preferably 400 to 4000 / h [under normal temperature pressure conditions (NTP)]. [Second embodiment]
[00126] The oxide catalyst according to the second embodiment (here below, also referred to as an "amoxidation catalyst") will be described.
[00127] The oxide catalyst according to the second embodiment is an oxide catalyst for use in the production of unsaturated nitrile from olefin and / or alcohol, the oxide catalyst meeting the following (1) to (3) : (4) the oxide catalyst comprises molybdenum, bismuth, iron, cobalt, and an element A having an ionic radius greater than 0.96 A (except for potassium, cesium and rubidium); (5) an atomic ratio a of bismuth to 12 molybdenum atoms is 1 <to <5, an atomic ratio b of iron to 12 molybdenum atoms is 1.5 <b <6, an atomic ratio c of element A to 12 molybdenum atoms is 1 <c <5, and an atomic ratio d of cobalt to 12 molybdenum atoms is 1 <d <8, and (6) the oxide catalyst comprises a disordered phase consisting of a crystal system comprising molybdenum , bismuth, iron and element A. (Starting material)
[00128] Examples of the olefin serving as a starting material for use in the production of unsaturated nitrile include, but are not limited to, propylene, n-butene, isobutylene, n-pentene, n-hexene, and cyclohexene. Among them, propylene and isobutylene are preferred.
[00129] Examples of alcohol serving as a starting material for use in the production of unsaturated nitrile include, but are not limited to, propanol, butanol, isobutanol, and t-butyl alcohol. Among them, isobutanol and t-butyl alcohol are preferred.
[00130] In the second embodiment, for example, acrylonitrile can be produced using propylene or propanol as a starting material, while methacrylonitrile can be produced using isobutylene, isobutanol, or t-butyl alcohol as a starting material.
[00131] These olefins and / or alcohols can be used alone or in combination.
[00132] Examples of unsaturated nitrile include, but are not limited to, acrylonitrile and methacrylonitrile. (7) Composition
[00133] The oxide catalyst according to the second embodiment comprises molybdenum, bismuth, iron, cobalt, and element A having an ionic radius greater than 0.96 A (except for potassium, cesium and rubidium). The presence of Mo, Bi, and Fe is indispensable from the point of view of the composition of the metallic elements in a Bi-Mo catalyst in which Bi and Mo, together, form an active species.
[00134] The atomic ratio of Bi to 12 Mo atoms is 1 <to <5, preferably 1 <to <4, more preferably 2 <to <4. Since the atomic ratio of Bi falls within the range described above , the selectivity of unsaturated nitrile tends to be improved.
[00135] From the point of view of increasing the catalytic activity without reducing the selectivity of unsaturated nitrile, Fe is an essential element, as with Mo and Bi, to industrially synthesize unsaturated nitrile. A high Fe content, however, forms Fe2O3 and tends to increase by-products such as CO or CO2, resulting in reduced selectivity of unsaturated nitrile. Alternatively, a high Fe content may not form Fe2O3, but instead form a 2-component composite oxide Fe2Mo3Oi2, which is an inactive component that does not exhibit catalytic activity. From these points of view, the atomic ratio b of Fe to 12 Mo atoms in the amoxidation catalyst according to the second embodiment is preferably 1.5 <b <6, more preferably 2.0 <b <5, still preferably 3 <b <5.
[00136] Bi and Mo tend to form composite oxides such as Bi2Mo3O-i2 and Bi2MoO6, which are, as reactivated, species active in amoxidation reaction. A catalyst consisting of such a composite oxide tends to give the high selectivity of unsaturated nitrile, but be somewhat active. On the other hand, Fe and Mo form a composite oxide like Fe2Mo3O12. A catalyst consisting of such a composite oxide exhibits both low activity and low selectivity. The composition of Mo, Bi, and Fe forms ordered phase Bi3FeiMo2Oi2. The industrial amoxidation reaction using, for a long time, a catalyst having this structure has been shown to reduce the activity of the catalyst due to the reduction during reaction, resulting in reduced yield of unsaturated nitrile, although the initial yields are high. The present inventors have formulated the reason for the reduction degradation reason as follows: iron contained in Bi3FeiMo2Oi2 is in a trivalent state immediately after the start of the reaction, but is reduced to divalent iron through redox cycles during reaction to form a composite oxide of divalent iron and molybdenum (FeMoO4). Also, Mo or Bi forms Moθ2, BÍ2O3, or Bi of metal. The formation of these stable compounds stabilizes the iron so that redox is not cycled during the reaction, probably causing degradation by reduction.
[00137] The present inventors carried out diligent studies on an excellent oxide catalyst in resistance to reduction that retains the structure described above, even in a highly reducing atmosphere, and thus found that: Bi3.xAxFeiMθ2θ12 of disordered phase is formed by the other incorporation of element A having an ionic radius greater than 0.96 A in the structure of an oxide catalyst having 3 components of Mo, Bi, and Fe; and the resulting oxide catalyst has improved resistance to reduction. The 4-component composite oxide having this structure is highly active and provides high selectivity for unsaturated nitrile. In addition, this composite oxide has been shown to have resistance to reduction without forming, even during prolonged operation, the stable composite oxide of divalent iron and molybdenum (FeMoO4) responsible for degradation by reduction. Specifically, as a result of the composition of these 3 components (Mo, Bi, and Fe) with element A, element A and Fe cause redox during reaction. Fe is, therefore, present in a slightly reduced form (eg Fe3'δ) compared to trivalent Fe, without being completely made divalent. Therefore, redox is easily achieved, probably resulting in the prevention of degradation by reduction.
[00138] Element A can be any element having an ionic radius greater than 0.96 A except for potassium, cesium and rubidium without limitations. Examples of element A include: at least one element selected from the group consisting of lanthanoid elements consisting of cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium and dysprosium, or a mixture thereof; at least one element selected from the group consisting of tin, lead, and yttrium elements, or a mixture thereof; and at least one element selected from the group consisting of alkaline earth metals calcium, strontium, and barium, or a mixture thereof. Element A is preferably at least one element selected from the group consisting of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, calcium, and lead, or a mixture thereof, more preferably at least one element selected among the group consisting of lanthanum, cerium, praseodymium, neodymium, calcium, and lead, or a mixture of them, from the point of view of the balance between stability and reactivity.
[00139] The atomic ratio c of element A to 12 molybdenum atoms is 1 <c <5, preferably 1 <c <4, more preferably 1.5 <c <3. As long as the atomic ratio c is within the above range described, a 4-component composite oxide comprising the Bi3.xAxFeiMθ2θ12 composite disordered phase is easily formed. For example, in the case of using La as element A, a 4-component composite oxide comprising Bi3.xLaxFeiMθ2θi2 of disordered phase is formed. La can be appropriately composed into a 3-component composite oxide comprising Bi3FβiMθ2θ12 of disordered phase, so that Bi3 + (ionic radius: 0.96 A) is replaced by La3 + having a greater ionic radius to obtain an amoxidation catalyst that has high activity and selectivity as well as resistance to reduction. In the absence of La3 +, ordered phase Bi3FeiMo2O12 is decomposed into FeMoO4, MoO2, Bi2O3, or Bi metal due to the reduction by reaction gas in prolonged industrial operation. In contrast, the coexistence with La having a slightly greater ionic radius than that of Bi causes redox between Fe and La which, in turn, inhibits the decomposition attributed to the reduction by reaction gas. In addition, the disordered phase Bi3.xLaxFeiMθ2θi2 structure is maintained without being decomposed into FeMoO4, Moθ2, Bi2O3, or Bi metal.
[00140] In this context, the ionic beam is described in, for example, "Chemistry of Ceramics", ed., By Hiroaki Yanagida, p. 14-17, Maruzene Co., Ltd. (8) Crystal structure
[00141] The amoxidation catalyst according to the second embodiment preferably contains a 4-component composite oxide comprising the disordered phase Bi3.xAxFeiMo2Oi2. X-ray diffraction (XRD) can be used as an index for the formation of the 4-component composite oxide comprising disordered phase Bi3.xAxFeiMo2O12. As long as the 4-component composite oxide comprising disordered phase Bi3.xAxFeiMo2O12 has been formed, the amoxidation catalyst according to the second embodiment can be confirmed as having single peaks at least at 18.30 ° ± 0 planes, 2 ° (101), 28.20 ° ± 0.2 ° (112), 33.65 ° ± 0.2 ° (200), and 46.15 ° ± 0.2 ° (204) measured in the angle range diffraction 20 = 10 ° to 60 ° in X-ray diffraction of the crystal, as in the 3-component composite oxide comprising disordered phase Bi3FeiMo2O12 Particularly preferably, the amoxidation catalyst according to the second embodiment has a single peak a one position within each reference value ± 0.05 °.
[00142] The intensity ratio (la / lb) of peak intensity (la) aa 20 = 33.65 ° ± 0.2 ° to peak intensity (lb) ba 20 = 34.10 ° ± 0.2 ° it is preferably 2.0 or greater, more preferably 2.5 or greater, yet preferably 3.0 or greater, from the point of view of preventing degradation by reducing the catalyst. The intensity ratio (la / lb) is 1.1 in 100% of ordered phase and is 3.3 in 100% of disordered phase. Peak intensity (lb) b a 20 = 34.10 ° ± 0.2 ° also comprises peak intensity lb derived from Fe2Mθ3θi2 present in a trace amount. At an intensity ratio (la / lb) of 2.0 or greater, the oxide catalyst contains a predetermined proportion of the disordered phase and is therefore less susceptible to degradation by reduction in prolonged industrial operation. Thus, the yield of unsaturated nitrile tends to be improved. Figure 4 shows the relationship between the content of the disordered phase with peaks a and b.
[00143] The mechanism upon which the disordered phase Bi3.xAxFeiMo2Oi2 is formed is uncertain. A composite oxide of Bi and Mo is formed as an intermediate in a heat treatment phase. In addition, the heat treatment probably causes the thermal diffusion and solid solution of substitution of Fe and element A in the composite oxide of Bi and Mo to form Bi3.xAxFeiMo2O12 of disordered phase composite.
[00144] The "single peak" and the "main peak" are as defined in the first embodiment.
[00145] The amoxidation catalyst according to the second embodiment preferably comprises a metal oxide having composition represented by the formula of composition (2) below. The amoxidation catalyst comprising a metal oxide having composition represented by the formula of composition (2) below tends to improve the selectivity of unsaturated nitrile.
where Mo represents molybdenum; Bi represents bismuth; Fe represents iron; element A represents an element having an ionic radius greater than 0.96 Å (except for potassium, cesium and rubidium); Co represents cobalt; element B represents at least one element selected from the group consisting of magnesium, zinc, copper, nickel, manganese, chromium, and tin; element C represents at least one element selected from the group consisting of potassium, cesium, and rubidium; a to g each represent the atomic ratio of each element to 12 Mo atoms where the atomic ratio a of Bi is 1 <a <5, the atomic ratio b of Fe is 1.5 <b <6, the ratio atomic c of element A is 1 <c <5, atomic ratio d of Co is 1 <d <8, atomic ratio and element B is 0 <e <3, atomic ratio f of element C is 0 <f <2, and the Fe / Co ratio is 0.8 <b / d; eg it represents the atomicity o and oxygen determined by the valences of constituent elements other than oxygen.
[00146] In the amoxidation catalyst according to the second embodiment, Co is an essential element, as with Mo, Bi, and Fe, from the point of view of industrially synthesizing unsaturated nitrile. Co plays a role as a support to form the composite oxide CoMoO4 and highly dispersed active species like Bi-Mo-0 and also plays a role in absorbing oxygen from the gas phase and supplying this oxygen to Bi-Mo-0 or similar. Co and Mo are preferably composed to form a composite oxide CoMoO4, from the point of view of obtaining unsaturated nitrile in high yields. The atomic ratio d of Co is preferably 1 <d <8, more preferably 2 <d <8, still preferably 2 <d <6, even more preferably 2 <d <4, from the point of view of reducing the formation of unary oxides , such as Co3O4 or CoO.
[00147] In composition formula (2), element B represents at least one element selected from the group consisting of magnesium, zinc, copper, nickel, chromium, manganese, and tin and probably replaces some cobalt atoms in the oxide catalyst. The atomic and element B ratio is preferably 0 <and <3, more preferably 0 <and <2, from the point of view of maintaining equilibrium with the formation of disordered phase crystals. Element B is not essential, but it tends to contribute to the stabilization of the crystal structure of CoMoO4 in the catalyst.
[00148] Element A represents an element having an ionic radius greater than 0.96 A, except for potassium, cesium and rubidium. The atomic ratio of element A is preferably 1 <c <5, more preferably 1 <c <4, still preferably 1 <c <3.
[00149] Element C represents at least one element selected from the group consisting of potassium, cesium, and rubidium. Element C probably plays a role in neutralizing the non-composite MoO3 acid center or the like in the amoxidation catalyst. The presence or absence of potassium, cesium, and / or rubidium contained in it does not directly influence the crystal structure of the disordered phase described later. The atomic ratio f of element C to 12 Mo atoms is preferably 0 <f <2, more preferably 0.01 <f <2, still preferably 0.01 <f <1, from the point of view of catalytic activity. At the atomic ratio f of 0 or greater, the neutralizing effect tends to be further improved. At the atomic ratio f of 2 or less, the oxide catalyst tends to be made basic to neutral. The resulting oxide catalyst tends to easily absorb the propylene, isobutylene, isobutanol, or t-butyl alcohol starting material and also tends to exhibit improved catalytic activity.
[00150] Element B and element C form crystal structures separately from the crystal structure of the disordered phase described later and therefore do not directly influence the crystal structure of the disordered phase.
[00151] The amoxidation catalyst can contain arbitrary components like other metal components without inhibiting the formation of disordered phase Bi3.xAxFeiMθ2θ12. (9) Component other than metal oxide
[00152] The amoxidation catalyst according to the second embodiment can further comprise a support for supporting the metal oxide. The catalyst further comprising the support is preferred because it highly disperses the metal oxide and provides high wear resistance for the supported metal oxide.
[00153] Examples of the support include, but are not limited to, at least one selected from the group consisting of silica, alumina, titania, and zirconia. The oxide catalyst supported by such support tends to have another improvement in physical properties suitable for fluidized bed reaction, such as shape, size, distribution, flow capacity, and mechanical resistance of the particle. Among them, silica is preferred as the support. In general, the silica support is preferable in terms of its property of conferring the appropriate physical properties for the fluidized bed reaction to the oxide catalyst, as well as being inactive alone, compared to other supports and having a binding effect favorable effect on metal oxide without reducing selectivity for unsaturated nitrile. In addition, the silica support is also preferred because of the ease of providing high wear resistance for the metal oxide thus supported.
[00154] A silica sol is preferred as a source of silica. The concentration of the silica sol in the state of a starting material not mixed with other components is preferably 10 to 50% by mass from the point of view of the dispersibility of silica particles. The silica sol preferably comprises 40 to 100% by mass of at least one silica sol (a) containing primary silica particles having an average particle diameter of 20 nm to less than 55 nm, preferably 20 to 50 nm, and 60 to 0% by mass of at least one silica sol (b) containing primary silica particles having an average particle diameter of 5 nm to less than 20 nm, from the point of view of unsaturated nitrile selectivity.
[00155] The content of the support is preferably 20 to 80% by weight, more preferably 30 to 70% by weight, still preferably 40 to 60% by weight, in relation to 100% by weight in the total of the support and the oxide catalyst . By fixing the content of the support within the range described above, the yield of unsaturated nitrile tends to be further improved. (10) Method for producing amoxidation catalyst
[00156] The method for producing the amoxidation catalyst according to the second embodiment comprises: a mixing step of mixing starting materials constituting the catalyst, comprising molybdenum, bismuth, iron, cobalt, and an element A having a ionic radius greater than 0.96 A (except for potassium, cesium and rubidium), to obtain slurry; a drying step of drying the slurry thus obtained to obtain a dried product; and a calcining step of calcining the dried product thus obtained, wherein the step of calcining comprises a step of heating the gradual heating of the dried product from 100 ° C to 200 ° C over 1 hour or more. The details of the method for producing the amoxidation catalyst according to the second embodiment are as described in the first embodiment. (11) Method for producing unsaturated nitrile
[00157] The method for producing unsaturated nitrile according to the second embodiment comprises a step of producing unsaturated nitrile from olefin and / or alcohol reaction with molecular oxygen and ammonia in a fluidized bed reactor using the oxide catalyst according to the second embodiment to obtain unsaturated nitrile.
[00158] Examples of the olefin and / or alcohol include, but are not limited to, one or more selected from the group consisting of propylene, isobutylene, propanol, isopropanol, isobutanol, and t-butyl alcohol.
[00159] One or more selected from the group consisting of propylene, isobutylene, isobutanol, and t-butyl alcohol can react with molecular oxygen and ammonia using the amoxidation catalyst, according to the second embodiment, to produce acrylonitrile or methacrylonitrile . The reaction is preferably carried out using a fluidized bed reactor. Propylene, isobutylene, isobutanol, t-butyl alcohol, and ammonia starting materials are not necessarily required to be highly pure, and industrial type starting materials can be used.
[00160] Generally, air is preferably used as a source of molecular oxygen. A gas having a high oxygen concentration, for example, by mixing oxygen with air can also be used. As for the composition of the feed gas, the molar ratio of propylene, isobutylene, isobutanol, and / or t-butyl alcohol to ammonia and molecular oxygen [(propylene, isobutylene, isobutanol, and / or t-butyl alcohol) / ammonia / oxygen molecular] is preferably 1 / 0.8 to 1.4 / 1.4 to 2.4, more preferably 1 / 0.9 to 1.3 / 1.6 to 2.2.
[00161] The reaction temperature is preferably 350 to 550 ° C, more preferably 400 to 500 ° C.
[00162] The reaction pressure is preferably at normal pressure at 0.3 MPa.
[00163] The duration of contact between the feed gas and the catalyst is preferably 0.5 to 20 sg / cm3, more preferably 1 to 10 sg / cm3. [Third embodiment] [Method for producing unsaturated aldehyde]
[00164] The method for producing unsaturated aldehyde according to the third embodiment comprises: a step of producing unsaturated aldehyde from oxidation of olefin and / or alcohol using the oxide catalyst according to the first embodiment to obtain the unsaturated aldehyde.
[00165] The step of producing the unsaturated aldehyde preferably comprises a step of discharging a product gas comprising the unsaturated aldehyde from a fluidized bed reactor through the catalytic oxidation reaction in gas phase of olefin and / or alcohol with an oxygen source in the fluidized bed reactor.
[00166] The olefin and / or alcohol is preferably at least one selected from the group consisting of propylene, isobutylene, propanol, isopropanol, isobutanol, and t-butyl alcohol.
[00167] Preferably, the catalytic oxidation reaction in the gas phase is carried out at a reaction temperature of 400 to 500 ° C, and the product gas discharged from the fluidized bed reactor has an oxygen concentration of 0.03 to 0.5 % by volume.
[00168] Next, the third embodiment will be described in greater detail. [Olefin]
[00169] Examples of the olefin starting material include, but are not limited to, propylene, n-butene, isobutylene, n-pentene, n-hexene, and cyclohexene. Among them, one or more compounds (s) selected from the group consisting of propylene and isobutylene are preferred. Use of such an olefin tends to further improve the yield of unsaturated aldehyde. [Alcohol]
[00170] Examples of the alcohol starting material include, but are not limited to, propanol, butanol, isobutanol, and t-butyl alcohol. Among them, one or more compounds (s) selected from the group consisting of propanol, isobutanol, and t-butyl alcohol are preferred. Use of such alcohol tends to further improve the yield of unsaturated aldehyde.
[00171] The lower limit of the concentration of olefin and / or alcohol introduced into the fluidized bed reactor is preferably 5.0% by volume or greater, more preferably 6.0% by volume or greater, still preferably 7.0% by volume. volume or greater, of all the gas introduced into the fluidized bed reactor. Setting the lower concentration limit is within the range described above, the unsaturated aldehyde productivity tends to be improved. The upper limit of the concentration is preferably 10% by volume or less, more preferably 9.5% by volume or less, still preferably 9.0% by volume or less. Fixing the higher concentration limit is within the range described above, the yield of unsaturated aldehyde tends to be further improved.
[00172] The method for producing unsaturated aldehyde according to the third embodiment can produce, for example, acrolein, using propylene or propanol as a starting material. Alternatively, the method for producing unsaturated aldehyde according to the third embodiment can produce methacroline using isobutylene, isobutanol, or t-butyl alcohol as a starting material. Olefin and alcohol may contain water, nitrogen, and alkanes such as propane, butane, and isobutane. [Oxygen source]
[00173] In the method to produce unsaturated aldehyde according to the third embodiment, unsaturated aldehyde is produced by the catalytic oxidation reaction in the gaseous phase of olefin and / or alcohol with an oxygen source using the oxide catalyst. This gas phase catalytic oxidation reaction is not limited by the oxygen source, and, for example, a gas mixed gas containing molecular oxygen and diluent gas can be used.
[00174] Examples of the gas containing molecular oxygen include, but are not limited to, gases containing oxygen such as pure oxygen gas and air. Among them, air is preferably used as the gas containing molecular oxygen. Air usage tends to be excellent from an industrial point of view with respect to cost.
[00175] Examples of the diluting gas include, but are not limited to, nitrogen, carbon dioxide, water vapor and mixed gases thereof.
[00176] The mixing ratio between the gas containing molecular oxygen and the diluent gas in the mixed gas preferably meets the conditions (in volume) represented by the following inequality: 0.01 <gas containing molecular oxygen / (gas containing molecular oxygen + diluent gas ) <0.3.
[00177] At a high reaction temperature, the gas phase catalytic oxidation reaction easily proceeds and tends to run out of oxygen. For this reason, the oxygen source is preferably supplied to the oxide catalyst in an amount greater than that of olefin and / or alcohol. For the gas phase catalytic oxidation reaction with a high concentration of olefin and / or alcohol, preferably enough oxygen is supplied to the oxide catalyst while a sufficient amount of the oxygen source is also supplied to it in order to avoid reduction excessive use of the oxide catalyst. Excessive feeding of the oxygen source, however, is responsible for the decomposition reaction and combustion reaction of unsaturated aldehyde and, in fact, tends to reduce yields. Thus, the oxygen source is preferably supplied in an appropriate proportion. From these points of view, the oxygen source in the production method according to the third embodiment is supplied to the oxide catalyst in such a way that the molar ratio of the air supplied to the catalyst layer to the olefin and / or the alcohol is preferably 7.0 to 10.5, more preferably 8.0 to 9.5, still preferably 8.0 to 9.0. By setting the molar ratio of the air delivered to the catalyst layer to the olefin and / or alcohol to 7.0 or higher, the concentration of olefin and / or alcohol tends to be low, resulting in another prevention of degradation by reducing the catalyst of oxide. By setting the molar ratio of the air delivered to the catalyst layer to 10.5 or less, the oxygen concentration supplied to the catalyst layer tends to be low, resulting in another prevention of oxidation degradation of the oxide catalyst.
[00178] The olefin, alcohol, and gas containing molecular oxygen may contain water vapor. The water vapor contained here tends to further inhibit the coking of the oxide catalyst.
[00179] The diluent gas may contain water vapor. The lower content of water vapor in the diluent gas is more preferred. The water vapor contained here tends to further inhibit the formation of by-products such as acetic acid.
[00180] The concentration of water vapor contained in the total gas supplied to the reactor is preferably 0.01 to 30% by volume. [Fluidized bed reactor]
[00181] The method for producing unsaturated aldehyde according to the third embodiment preferably employs a fluidized bed reactor (here below, also simply referred to as a "reactor"). The fluidized bed reactor refers to an apparatus that has a gas distributor, an interpolator, and a cyclone as the main constituents in the reactor and has a structure in which the oxide catalyst is contacted with the feed gas while allowed to flow. More specifically, fluidized bed reactors or the like described in, for example, Handbook of Fluidized Bed (published by Baifukan Co., Ltd., 1999) can be used. Among them, a fluidized bed reactor based on a bubbling fluidized bed system is particularly suitable for the method. The generated reaction heat can be removed using a cooling tube installed in the fluidized bed reactor. [Gas catalytic oxidation reaction reaction temperature]
[00182] In the method for producing unsaturated aldehyde according to the third embodiment, the reaction temperature of the gas phase catalytic oxidation reaction is preferably 400 to 500 ° C, more preferably 420 to 470 ° C, still preferably 430 to 450 ° C. At a reaction temperature of 400 ° C or higher, the conversion rate and reaction rate tend to be further improved, resulting in improved unsaturated aldehyde yield. At a reaction temperature of 500 ° C or lower, the combustion decomposition of the formed unsaturated aldehyde tends to be further avoided. The reaction temperature of the gas phase catalytic oxidation reaction can be measured with a thermometer installed in the fluidized bed reactor.
[00183] Since the gas phase catalytic oxidation reaction is generally an exothermic reaction, the fluidized bed reactor is preferably provided with a cooling apparatus for removing heat in order to set an appropriate reaction temperature. The reaction temperature can be adjusted to the range described above, by removing heat from the reaction heat using a cooling pipe or by providing heat using a heating device. [Methods for introducing olefin and / or alcohol and oxygen source]
[00184] The olefin and / or alcohol and the oxygen source can be introduced by any method without limitations. For example, a gas containing olefin and / or alcohol and air or a gas having an increased concentration of oxygen can be mixed in advance and introduced into a fluidized bed reactor filled with the oxide catalyst. Alternatively, each gas can be introduced individually to it. Each gas that is subjected to the reaction can be introduced into the reactor and then heated to a predetermined reaction temperature or can be preheated and then introduced into the reactor. Among these approaches, preheating followed by introduction to the reactor is preferred for continuous and efficient reaction. [Concentration of oxygen in the product gas discharged from the fluidized bed reactor]
[00185] The oxygen concentration in the product gas discharged from the fluidized bed reactor is preferably 0.03 to 0.5% by volume, more preferably 0.03 to 0.2% by volume, still preferably 0.05 to 0.1% by volume. At an oxygen concentration of 0.5% by volume or less at the reactor outlet, excessive reduction of the catalyst tends to be further avoided. At an oxygen concentration of 0.03% by volume or greater, excessive oxidation of the catalyst is prevented. In both cases, the yield of unsaturated aldehyde tends to be improved. The oxygen concentration at the reactor outlet can be adjusted to the range described above, in order to avoid decomposition by burning unsaturated aldehyde without leaving the equilibrium in the degree of redox.
[00186] The product gas containing the unsaturated aldehyde of interest is discharged at the outlet of the reactor. In the following, the oxygen concentration in the product gas discharged from the fluidized bed reactor is also referred to as the "oxygen concentration at the reactor outlet". In this context, the "oxygen concentration at the reactor outlet" refers to the oxygen concentration in the product gas containing unsaturated aldehyde discharged from the reactor outlet. The oxygen concentration at the reactor outlet can be measured in a region where the oxygen ratio in the product gas is constant near the outlet of the fluidized bed reactor. The region need not be a place where the product gas is discharged from or in the vicinity of the fluidized bed reactor in the strict sense. Thus, the oxygen concentration at the reactor outlet can be measured in the gases at any point in the residence time downstream of the reactor or just before the discharge from the reactor and just before the purification operation. For example, the product gas can be quickly cooled and then absorbed in water, and purified by extractive distillation. In such a case, the product gas for measuring the oxygen concentration at the reactor outlet can be sampled in the piping between the reactor and a rapid cooling column disposed downstream of the reactor. The oxygen concentration at the reactor outlet can be measured by gas chromatography equipped with a thermal conductivity detector (TCD).
[00187] It is important to control the oxygen concentration at the reactor outlet within the range described above, because the oxygen concentration at the reactor outlet influences the decomposition of unsaturated aldehyde or secondary reaction in the reactor. The oxygen concentration at the reactor outlet can be adjusted by changing the molar ratio of the oxygen source supplied to the fluidized bed reactor to an olefin and / or alcohol, the amount of gas containing oxygen supplied to the fluidized bed reactor, the temperature of reaction, the internal pressure of the reactor, the duration of contact between the mixed gas of starting material and the oxide catalyst, the amount of the catalyst, and the amount of total gas supplied to the reactor. Among these approaches, control of the amount of gas containing molecular oxygen, for example, air, supplied to the fluidized bed reactor is preferred for adjustment.
[00188] For example, feed gas can be supplied under conditions involving a reaction temperature of 440 ° C, a reaction pressure of 0.05 MPa, and a flow rate of 595 cm2 / min (in terms of NTP) using 40 g of an oxide represented by Mθi2Bi2, oCe2.oFθ3.4Co3.oCso.i6θx as a catalyst. In such a case, the molar ratio composition of the feed gas can be changed from isobutylene / air / helium = 1 / 9.2 / remainder (isobutylene concentration = 8% by volume) to isobutylene / air / helium = 1/8 , 1 / rest (isobutylene concentration = 8% by volume) to change the concentration of oxygen in the gas at the output of the reactor from 0.4% by volume to 0.05% by volume. In this context, "isobutylene / air / helium = 1 / 8.1 / rest (isobutylene concentration = 8% by volume)" means that the amount of helium is determined so that the isobutylene / air ratio meets 1/8 , 1 and the isobutylene concentration meets 8% by volume.
[00189] Examples of conditions for adjusting the oxygen concentration at the reactor outlet include the conversion rate, as well as the amount of the catalyst, the duration of contact, the reaction pressure, and the spatial speed, as described above. These conditions can be fully adjusted to adjust the oxygen concentration at the reactor output to an arbitrary value. For example, the reaction can be carried out at a reaction temperature adjusted to the range of 430 ° C to 500 ° C and an olefin and / or alcohol concentration adjusted to the range of 6 to 10% by volume. In such a case, the duration of contact defined by the following expression to adjust the oxygen concentration at the reactor outlet is preferably 5.0 (gs / cm3) or shorter, more preferably 4.0 (gs / cm3) or shorter, still preferably 3.0 (gs / cm3) or shorter: Contact duration (gs / cm3) = W / F * 60 * 273.15 / (273.15 + T) * (P * 1000 + 101.325) / 101.325 wherein W represents the quantity (g) of the catalyst loaded in the fluidized bed reactor; F represents the flow rate (cm2 / min, in terms of NTP) of the mixed gas of starting material; T represents the reaction temperature (° C); and P represents the reaction pressure (MPa).
[00190] To adjust the oxygen concentration at the reactor outlet in the range described above, the reaction pressure is preferably the normal pressure at 5 atm. The space velocity is preferably 400 to 4000 / h [under conditions of normal temperature pressure (NTP)]. [Oxide catalyst]
[00191] The oxide catalyst according to the first embodiment is used as the oxide catalyst in the third embodiment. Among the oxide catalysts exemplified above, an oxide catalyst comprising molybdenum, bismuth, iron, cobalt, and a lanthanoid element in which the atomic ratio of iron to cobalt (Fe / Co) meets Fe / Co> 1, plus comprising a support is preferably used.
[00192] The presence or absence of each element in the oxide catalyst and the atomic ratio of each element can be identified by X-ray fluorescence analysis (XRF).
[00193] Mo, Bi, Fe, and Co are essential components to form the oxide catalyst. Olefin and / or alcohol undergoes a reaction of oxidation by oxygen in the reticulum in this oxide catalyst to obtain unsaturated aldehyde. When the oxygen reticulum in the oxide catalyst is consumed in an oxidation reaction, oxygen vacancy generally occurs in the oxide catalyst. As a result, the reduction of the oxide catalyst proceeds as the oxidation reaction proceeds. The reduced oxide catalyst is inactivated. Therefore, it is necessary to immediately reoxidate such a reduced oxide catalyst. An oxide containing Mo, Bi, Fe, and Co is reactive with olefin and / or alcohol and with the oxygen source and also appears to be excellent in the reoxidation effect of incorporating molecular oxygen into the gas phase within the oxide by dissociative adsorption and the reticle of oxygen consumed. Thus, it is likely that this reoxidation effect can be maintained even during the oxidation reaction for a long time, so that unsaturated aldehyde is stably produced from olefin and / or alcohol without inactivating the oxide catalyst.
[00194] In a metal oxide Mo-Bi containing Mo, Bi, Fe, and Co, these metal elements can be composite. In the oxide catalyst of the third embodiment, the atomic ratio of Bi to 12 Mo atoms is 1 <to <5, preferably 1.5 <to <4, more preferably 1.8 <to <4. Since the atomic ratio a is within the range described above, the selectivity of the product of interest is further improved. Bi and Mo preferably form composite Bi-Mo-0 oxides such as Bi2Mo3Oi2 and Bi2MoO6, which are, as reported, species active in gas phase catalytic oxidation, amoxidation reaction, and the like.
[00195] Fe is an essential element, as with Mo and Bi, to industrially synthesize unsaturated aldehyde. The atomic ratio b of Fe to 12 Mo atoms in the oxide catalyst is 1.5 <b <6, preferably 2 <b <5.5, more preferably 3 <b <5. As long as the atomic ratio b is within the In the range described above, the solid iron solution in CoMoO4 can occur through the use of redox between trivalent iron and divalent iron to form a catalyst having resistance to reduction even in a reactor containing a small amount of oxygen.
[00196] Co is an essential element, as with the elements described above, to industrially synthesize unsaturated aldehyde. It forms a composite oxide (eg, C0M004) with Mo and probably plays a role in absorbing oxygen from the gas phase and supplying this oxygen to Bi-Mo-0 or similar. From such a point of view, the atomic ratio d of Co is preferably 1 <d <8, more preferably 2 <d <7, still preferably 2.5 <d <6.
[00197] When solid iron solution in C0M004, the resistance to reduction of the oxide catalyst is improved. In this regard, the atomic Fe / Co ratio of iron to cobalt in the oxide catalyst for use in the third embodiment is preferably Fe / Co> 0.8, more preferably Fe / Co> 1, still preferably Fe / Co> 1.05, even more preferably Fe / Co> 1.1.0 higher limit of Fe / Co is preferably 3> Fe / Co, more preferably 2> Fe / Co, still preferably 1.5> Fe / Co. Generally, iron is oxidized to a trivalent form. Trivalent iron is less susceptible to solid solution in C0M004. An oxide catalyst having high resistance to reduction is difficult to obtain even if the iron is only increased. However, the gas phase catalytic oxidation reaction of olefin and / or alcohol at a temperature of 400 ° C or higher and 500 ° C or lower using an oxide catalyst having the Fe / Co composition> 0.8 has been shown to reduce the trivalent iron and thus improve the resistance to reduction of the oxide catalyst by the resulting iron solids solution in CoMoO4. The successful solid solution of iron in CoMoO4 can be determined based on the peak displacement in XRD of CoMoO4. More specifically, the solid iron solution in CoMoO4 can be confirmed by a method described in the Examples.
[00198] The oxide catalyst for use in the third embodiment preferably has a composition represented by the following formula (1):
where Mo represents molybdenum; Bi represents bismuth; Fe represents iron; Co represents cobalt; A represents at least one lanthanoid element selected from the group consisting of lanthanum, cerium, praseodymium, and neodymium; B represents at least one element selected from the group consisting of magnesium, zinc, copper, nickel, manganese, calcium, strontium, barium, tin, and lead; C represents at least one element selected from the group consisting of potassium, cesium, and rubidium; aag represent each atomic ratio of each element to 12 molybdenum atoms and meet 1 <a <5, 1.5 <b <6, 1 <d <6, Fe / Co> 1, 1 <c <5, 0 <and <3, and 0.01 <f <2; eg represents the atomicity of oxygen determined by the valences of constituent elements other than oxygen.
[00199] In formula (1), lanthanoid element A represents at least one element selected from the group consisting of lanthanum, cerium, praseodymium, and neodymium. As mentioned above, Bi and Mo form a composite Bi-Mo-O oxide, which has a high catalytic activity, but a low melting point and low heat resistance. On the other hand, the lanthanoid element and Mo rarely form a composite oxide like A-Mo-0 which, however, has a high melting point and very high heat resistance. The appropriate composition of these oxides forms Bi-A-Mo-0 heat resistant through the composition of Bi, element A, and Mo. The composite oxide formed has both high activity and high heat resistance appropriate as a fluidized bed catalyst.
[00200] In formula (1), element B represents at least one element selected from the group consisting of magnesium, zinc, copper, nickel, manganese, calcium, strontium, barium, tin, and lead. Element B probably replaces some cobalt atoms in the oxide catalyst. Element B is not essential, but it contributes to improving the activity of the catalyst or stabilizing the crystal structure of CoMoO4 in the catalyst. For example, copper has the effect of improving the activity of the catalyst. Nickel, magnesium, zinc, and manganese have the effects of stabilizing the crystal structure of CoMoO4 and inhibiting, for example, the phase transition attributed to pressure or temperature. The atomic ratio of such element B is preferably 0 <and <3, more preferably 0 <and <2, still preferably 0 <and <1.5. By fixing the atomic ratio and being within the range described above, the effects can be exhibited without destroying the structure with the solid iron solution in C0M004.
[00201] In formula (1), C represents at least one element selected from the group consisting of cesium, rubidium, and potassium. Element C probably plays a role in neutralizing the non-composite MoO3 acid center or the like in the oxide catalyst. The atomic ratio f of element C to 12 Mo atoms is preferably 0 <f <2, more preferably 0.01 <f <2, still preferably 0.05 <f <0.5. By fixing the atomic ratio f within the range described above, the catalytic activity tends to be improved. Particularly, at the atomic ratio f of 2 or less, the oxide catalyst is rarely made basic. In addition, the oxide catalyst easily adsorbs the olefin and / or alcohol from the starting material in the oxidation reaction of the olefin and / or alcohol and tends to further improve the catalytic activity. (Support)
[00202] The oxide catalyst for use in the third embodiment is supported by a support. The content of the support is preferably 20 to 80% by weight, more preferably 30 to 70% by weight, still preferably 40 to 60% by weight, in relation to the total weight of the support and the oxide catalyst. Fixing the content of the support being within the range described above, the yield of unsaturated aldehyde tends to be further improved. The supported catalyst comprising an oxide containing atoms of Mo, Bi, Fe, Co, and lanthanoid can be obtained by a method known in the art, for example, a method comprising: a mixing step of mixing starting materials to prepare slurry ; a spray drying drying step of the slurry; and a calcination step of calcining the dried product obtained in the drying step.
[00203] The support is preferably, but not limited to, at least one selected from the group consisting of, for example, silica, alumina, titania, and zirconia. The support of the oxide catalyst by such support tends to improve, in the same, the physical properties appropriate for reaction in fluidized bed, such as particle shape, size, distribution, flow capacity, and mechanical resistance. Among these, silica is preferred as the support. The silica support has the property of conferring the appropriate physical properties by fluidized bed reaction for the oxide catalyst. In addition, the silica support is inactive compared to other supports and has a favorable binding effect on the catalyst without reducing the catalytic activity against the product of interest or its selectivity. [Method to produce oxide catalyst]
[00204] The oxide catalyst for use in the third embodiment can be produced by any method known in the art without limitations. The oxide catalyst for use in the third embodiment can be obtained, for example, by a production method comprising: a step of mixing starting materials to prepare slurry; a spray drying drying step of the slurry to obtain a dried product; and a calcination step of calcining the dried product. In the following, a preferred aspect of the method for producing the oxide catalyst, comprising these steps, will be described.
[00205] The mixing step involves preparing slurry using catalyst starting materials. Examples of the catalyst starting materials include molybdenum, bismuth, iron, cobalt, and lanthanoid elements such as lanthanum, cerium, praseodymium, and neodymium. Other examples of catalyst starting materials include, but are not limited to, manganese, nickel, copper, zinc, lead, alkali elements, magnesium, calcium, strontium, barium, and rare earth elements except those described above. These starting materials can be used in the form of ammonium salt, nitrate, hydrochloride, sulfate, and salts of organic acids, which are soluble in water or nitric acid. In particular, ammonium salt is preferred as a source of molybdenum element. Sources of elements other than molybdenum are preferably nitrates containing each element.
[00206] As mentioned above, silica, alumina, titania, zirconia, or the like can be used as a support for the oxide. Silica is preferably used as the support. A silica sol is preferred as a source of silica.
[00207] The concentration of the silica sol in an unmixed state with other components in the slurry or the like is preferably 10 to 50% by weight, more preferably 15 to 45% by weight, still preferably 20 to 40% by weight. By fixing the concentration within the range described above, the dispersibility of silica particles tends to be improved.
[00208] The silica sol preferably comprises 40 to 100% by mass of at least one silica sol (a) containing primary silica particles having an average particle diameter of 20 to 55 nm, preferably 20 to 50 nm, and 60 to 0% by mass of at least one silica sol (b) containing primary silica particles having an average particle diameter of 5 nm to 20 nm, from the point of view of the selectivity of the product of interest.
[00209] The amount of the silica support to support the obtained oxide catalyst is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, still preferably 40 to 60% by mass, in relation to the total mass of the catalyst of oxide and silica support.
[00210] The slurry can be prepared by adding molybdenum ammonium salt dissolved in water to a silica sol and the subsequent addition of a solution containing nitrate from each source source except molybdenum dissolved in water or an aqueous solution of acid nitric. The order in which these materials are added can be changed accordingly.
[00211] The drying step involves spray drying the slurry thus obtained in the mixing step to obtain a dried product (dry particles). The slurry can be sprayed by any of the common methods like centrifugation systems, two-fluid nozzle systems, and high-pressure nozzle systems, which are industrially made. Among them, a centrifugation system is preferred. Then, the particles obtained by spraying are dried. Air heated with steam, an electric heater, or the like is preferably used as a source of dry heat. The temperature at the inlet of the dryer is preferably 100 to 400 ° C, more preferably 150 to 300 ° C.
[00212] The calcination step involves the calcination of the dried particles thus obtained in the drying step to obtain the desired catalyst. For calcination, preferably, the dried particles are preliminarily calcined, if necessary, at 150 to 400 ° C and then finally calcined at a temperature in the range of 400 to 700 ° C, preferably 500 to 700 ° C, for 1 to 20 hours. The calcination can be carried out using an oven such as a rotary kiln, a tunnel kiln, or a muffle furnace. The particle sizes of the catalyst are preferably distributed in the range of 10 to 150 pm, EXAMPLES [Example A]
[00213] Example A is provided below to further illustrate a first aspect of the present invention, but is not intended to limit the scope of the first aspect of the present invention. Because the atomic ratio of oxygen in an oxide catalyst is determined by the atomic valence conditions of other elements, the atomic ratio of oxygen is omitted in the formula representing the composition of a catalyst in the Examples and Comparative Examples. The composition ratio of each element in an oxide catalyst was calculated from the composition ratio for preparation.
[00214] In Example A and Comparative Example A in the following, aqueous dispersions of various metals were used as catalyst starting materials. Each of the aqueous dispersions of bismuth oxide, iron oxide, and cobalt oxide for use was made by CIK Nanotek Corporation, and each of the aqueous dispersions of lanthanum oxide and cerium oxide for use was made by Taki Chemical Co. , Ltd. <Measurement of average particle size>
[00215] The average particle size was obtained by calculating based on the following equation: Average particle size [nm] = 6000 / (Surface area [m2 / g] x Actual density (8.99 g / cm3). < PH measurement>
[00216] The measurement was performed with a pH meter KR5E made by AS ONE. <X-ray diffraction measurement>
[00217] In XRD measurement, the plane (111) and plane (200) of a LaB6 compound as standard reference material 660 according to the National Institute of Standards & Technology were measured, so that the values were normalized to 37.441 ° and 43.506 °, respectively.
[00218] An XRD Bruker D8 Advance device was used. The XRD measurement conditions were as follows: a 40 kV-40 mA X-ray output, a 0.3 ° divergence gap (DS), a step width of 0.02 ° / step, a 2.0 s counting time, and a measuring range of 20 = 5 ° to 60 °. <Conversion rate, selectivity, and yield>
[00219] In Example A and Comparative Example A, the reaction performance was represented by conversion rate, selectivity, and yield, which are defined by the following expressions. Conversion rate = (number of moles of reacted starting material / number of moles of starting material supplied) x 100 Selectivity = (number of moles of compound produced / number of moles of reacted compound) x 100 Yield = (number of moles of compound produced / number of moles of starting material supplied) x 100 <Reducibility assessment>
[00220] Reducibility was assessed by accelerated evaluation of the reduction resistance of a catalyst. The catalyst was reduced by the reduction treatment in an atmosphere gas without oxygen and re-oxidized under the returned reaction conditions. The process was repeated to achieve accelerated evaluation of the catalyst reduction resistance.
[00221] A mixed gas of 2% by volume of olefin and / or alcohol and 98% by volume of helium was passed at a flow rate of 3.0 cm3 / s (converted to NTP) for 5 minutes for reduction treatment and then the evaluation reaction conditions were restored and the flow was maintained for 5 minutes. This constituted one set and the reaction was evaluated after 100 sets of runs. After more than 100 sets of runs, the reaction and resistance to reduction were evaluated. The reducibility assessment for the methacrolein reaction was carried out at 430 ° C, the reducibility assessment for the acrolein reaction was carried out at 320 ° C, and the reducibility assessment for the diolefin reaction was carried out at 360 ° C.
[00222] When the conversion rate and selectivity are maintained compared to the initial capacity, the absence of degradation by reduction is determined. When the conversion rate and selectivity are reduced, the presence of degradation by reduction is determined.
[00223] Each of elements A for use in Example A and Comparative Example A has an ionic radius in the following: La: 1.14 A, Ce: 1.07 Â, Ca: 1.03 A, Pb: 1.24 A, and V: 0.56 Â, [Example A1]
[00224] In a liquid mixture of 90.5 g of ion exchange water and 127.5 g of water 30% by weight hydrogen peroxide, 54.5 g of molybdenum trioxide were added, which were stirred and mixed at about 70 ° C for dissolution. A solution (liquid A) was thus produced. In addition, 204.75 g of a 10% by weight bismuth oxide water dispersion liquid having an average particle size of 51 nm, 15.3 g of a 15% cobalt oxide water dispersion liquid. mass having an average particle size of 22 nm, 57.1 g of a liquid dispersion liquid in water of 15% iron oxide having an average particle size of 39 nm, 71.9 g of a liquid of dispersion in water of 10 mass% lanthanum oxide having an average particle size of 40 nm, and 4.3 g of 10 mass% cesium hydroxide liquid were mixed to produce a solution (liquid B).
[00225] Liquid A and liquid B were mixed to produce a liquid mixture, to which aqueous ammonia was added to adjust the pH to 3.2. The liquid was then stirred and mixed for about 3 hours to produce a slurry of starting material. The starting material slurry was transported to a spray dryer so as to be spray dried at an inlet temperature of 250 ° C and an outlet temperature of 140 ° C. An oxide catalyst precursor was thus produced. The oxide catalyst precursor produced was heated from 100 ° C to 200 ° C for more than 3 hours in air, then at 250 ° C for 1 hour, and maintained at this temperature for 3 hours in order to produce a preliminarily calcined product. The preliminarily calcined product produced was formed into a ring shape having a diameter of 5 mm, a height of 4 mm, and an internal diameter of 2 mm by tablet compression, which were then finally calcined at 520 ° C for 6 hours to produce a catalyst. The composition of the catalyst is shown in Table 1 and the results of X-ray powder diffraction measurement are shown in Table 2.
[00226] In order to evaluate the reaction of a catalyst, a SUS reaction tube with a jacket having a diameter of 14 mm was filled with 4.0 g of the catalyst. A mixed gas of 8% by volume of isobutylene, 12.8% by volume of oxygen, 3.0% by volume of water vapor, and 76.2% by volume of nitrogen was passed through the tube at 430 ° C at a flow rate of 120 mL / min (NTP) in order to carry out the methacrolein synthesis reaction. The results of the reaction evaluation are shown in Table 3. The results of the reaction evaluation after 100 sets and 200 sets of runs for accelerated reduction evaluation are also shown in Table 3. [Example A2]
[00227] In 202.6 g of hot water at a temperature of about 90 ° C, 67.5 g of ammonium heptamolybdate were dissolved (liquid A). In addition, 37.0 g of bismuth nitrate, 22.0 g of cerium nitrate, 51.3 g of iron nitrate, 0.55 g of cesium nitrate, and 37.2 g of cobalt nitrate were dissolved in 41.9 g of 18% by weight of aqueous nitric acid solution, to which 206.2 g of hot water in about 90 ° C (liquid B) were added.
[00228] Liquid A and liquid B were mixed, to which aqueous ammonia was added to adjust the pH to 4.1. The liquid was then stirred and mixed at about 55 ° C for about 4 hours to produce a slurry of starting material. The starting material slurry was transported to a spray dryer so as to be spray dried at an inlet temperature of 250 ° C and an outlet temperature of 140 ° C. An oxide catalyst precursor was thus produced. The oxide catalyst precursor produced was heated from 100 ° C to 200 ° C for 2 hours in air, then at 250 ° C for 1 hour, and maintained at this temperature for 3 hours in order to produce a preliminarily calcined product. The preliminarily calcined product produced was formed into a ring shape having a diameter of 5 mm, a height of 4 mm, and an internal diameter of 2 mm by tablet compression, which were then finally calcined at 540 ° C for 6 hours in air to produce a catalyst. The composition of the catalyst is shown in Table 1 and the results of X-ray powder diffraction measurement are shown in Table 2.
[00229] In order to evaluate the reaction of a catalyst, a reaction tube was filled with 4.5 g of the catalyst and the methacrolein synthesis reaction was carried out under the same conditions as in Example A1. The results of the reaction evaluation are shown in Table 3. [Example A3]
[00230] In 199.2 g of hot water at a temperature of about 90 ° C, 66.4 g of ammonium heptamolybdate were dissolved (liquid A). In addition, 47.0 g of bismuth nitrate, 13.5 g of cerium nitrate, 7.4 g of calcium nitrate, 42.8 g of iron nitrate, 1.56 g of rubidium nitrate, and 32, The g of cobalt nitrate was dissolved in 41.5 g of 18% by weight aqueous nitric acid solution, to which 209.0 g of hot water at about 90 ° C was added (liquid B). Liquid A and liquid B were mixed, to which aqueous ammonia was added to adjust the pH to 4.0. The liquid was then stirred and mixed at about 55 ° C for about 3 hours to produce a slurry of starting material. The starting material slurry was transported to a spray dryer so as to be spray dried at an inlet temperature of 250 ° C and an outlet temperature of 140 ° C. An oxide catalyst precursor was thus produced. The oxide catalyst precursor produced was heated from 100 ° C to 200 ° C for more than 3 hours in air, then at 250 ° C for 1 hour, and maintained at this temperature for 3 hours in order to produce a preliminarily calcined product. The preliminarily calcined product produced was formed into a ring shape having a diameter of 5 mm, a height of 4 mm, and an internal diameter of 2 mm by tablet compression, which were then finally calcined at 530 ° C for 5 hours in air to produce a catalyst. The composition of the catalyst is shown in Table 1 and the results of X-ray powder diffraction measurement are shown in Table 2.
[00231] In order to evaluate the reaction of a catalyst, a reaction tube was filled with 4.8 g of the catalyst and the methacrolein synthesis reaction was carried out under the same conditions as in Example A1. The results of the reaction evaluation are shown in Table 3. [Example A4]
[00232] In a liquid mixture of 90.6 g of ion exchange water and 127.6 g of water 30% by weight hydrogen peroxide, 54.5 g of molybdenum trioxide were added, which were stirred and mixed at about 70 ° C for dissolution. A solution (liquid A) was thus produced. In addition, 155.48 g of a dispersion liquid in water 10% by weight bismuth oxide having an average particle size of 51 nm, 4.2 g lead nitrate, 62.4 g of a dispersion liquid in water of 15% by weight of cobalt oxide having an average particle size of 22 nm, 50.4 g of a liquid dispersion in water of 15% by weight of iron oxide having an average particle size of 39 nm, 92.6 g of a 10% by weight lanthanum oxide water dispersion liquid having an average particle size of 40 nm, and 4.3 g of 10% by weight cesium hydroxide liquid were mixed to produce a solution (liquid B).
[00233] Liquid A and liquid B were mixed to produce a liquid mixture, to which aqueous ammonia was added to adjust the pH to 3.6. The liquid was then stirred and mixed for about 3 hours to produce a slurry of starting material. The starting material slurry was transported to a spray dryer so as to be spray dried at an inlet temperature of 250 ° C and an outlet temperature of 140 ° C. An oxide catalyst precursor was thus produced. The oxide catalyst precursor produced was heated from 100 ° C to 200 ° C for more than 3 hours in air, then at 250 ° C for 1 hour, and maintained at this temperature for 3 hours in order to produce a preliminarily calcined product. The preliminarily calcined product produced was formed into a ring shape having a diameter of 5 mm, a height of 4 mm, and an internal diameter of 2 mm by tablet compression, which were then finally calcined at 520 ° C for 6 hours in air to produce a catalyst. The composition of the catalyst is shown in Table 1 and the results of X-ray powder diffraction measurement are shown in Table 2.
[00234] In order to evaluate the reaction of a catalyst, a reaction tube was filled with 4.5 g of the catalyst and the methacrolein synthesis reaction was carried out under the same conditions as in Example A1. The results of the reaction evaluation are shown in Table 3. [Example A5]
[00235] In 207.2 g of hot water at a temperature of about 90 ° C, 69.1 g of ammonium heptamolybdate were dissolved (liquid A). In addition, 45.7 g of bismuth nitrate, 14.0 g of cerium nitrate, 2.3 g of manganese nitrate, 48.5 g of iron nitrate, 0.57 g of cesium nitrate, and 27, 6 g of cobalt nitrate were dissolved in 40.9 g of 18% by weight aqueous nitric acid solution, to which 195.4 g of hot water at about 90 ° C were added (liquid B). Liquid A and liquid B were mixed, to which aqueous ammonia was added to adjust the pH to 4.0. The liquid was then stirred and mixed at about 55 ° C for about 3 hours to produce a slurry of starting material. The starting material slurry was transported to a spray dryer so as to be spray dried at an inlet temperature of 250 ° C and an outlet temperature of 140 ° C. An oxide catalyst precursor was thus produced. The oxide catalyst precursor produced was heated from 100 ° C to 200 ° C for more than 5 hours in air, then at 250 ° C for 1 hour, and maintained at this temperature for 3 hours in order to produce a preliminarily calcined product. The preliminarily calcined product produced was formed into a ring shape having a diameter of 5 mm, a height of 4 mm, and an internal diameter of 2 mm by tablet compression, which were then finally calcined at 540 ° C for 5 hours in air to produce a catalyst. The composition of the catalyst is shown in Table 1 and the results of X-ray powder diffraction measurement are shown in Table 2.
[00236] In order to evaluate the reaction of a catalyst, a reaction tube was filled with 4.2 g of the catalyst and the methacrolein synthesis reaction was carried out under the same conditions as in Example A1. The results of the reaction evaluation are shown in Table 3. [Example A6]
[00237] In 211.2 g of hot water at a temperature of about 90 ° C, 70.4 g of ammonium heptamolybdate were dissolved (liquid A). In addition, 34.0 g of bismuth nitrate, 21.6 g of cerium nitrate, 35.0 g of iron nitrate, 0.58 g of cesium nitrate, and 44.8 g of cobalt nitrate were dissolved in 35.3 g of 18% by weight aqueous nitric acid solution, to which 140.8 g of hot water at about 90 ° C were added (liquid B).
[00238] Liquid A and liquid B were mixed, to which aqueous ammonia was added to adjust the pH to 4.1. The liquid was then stirred and mixed at about 55 ° C for about 4 hours to produce a slurry of starting material. The starting material slurry was transported to a spray dryer so as to be spray dried at an inlet temperature of 250 ° C and an outlet temperature of 140 ° C. An oxide catalyst precursor was thus produced. The oxide catalyst precursor produced was heated from 100 ° C to 200 ° C for 2 hours in air, then at 250 ° C for 1 hour, and maintained at this temperature for 3 hours in order to produce a preliminarily calcined product. The preliminarily calcined product produced was formed into a ring shape having a diameter of 5 mm, a height of 4 mm, and an internal diameter of 2 mm by tablet compression, which were then finally calcined at 540 ° C for 6 hours in air to produce a catalyst. The composition of the catalyst is shown in Table 1 and the results of X-ray powder diffraction measurements are shown in Table 2. [Example A7]
[00239] In 193.1 g of hot water at a temperature of about 90 ° C, 64.4 g of ammonium heptamolybdate were dissolved (liquid A). In addition, 37.0 g of bismuth nitrate, 23.7 g of cerium nitrate, 36.9 g of iron nitrate, 0.41 g of cesium nitrate, and 54.3 g of cobalt nitrate were dissolved in 34.1 g of 18% by weight aqueous nitric acid solution, to which 128.7 g of hot water at about 90 ° C were added (liquid B).
[00240] Liquid A and liquid B were mixed, to which aqueous ammonia was added to adjust the pH to 4.0. The liquid was then stirred and mixed at about 55 ° C for about 4 hours to produce a slurry of starting material. The starting material slurry was transported to a spray dryer so as to be spray dried at an inlet temperature of 250 ° C and an outlet temperature of 140 ° C. An oxide catalyst precursor was thus produced. The oxide catalyst precursor produced was heated from 100 ° C to 200 ° C for more than 3 hours in air, then at 250 ° C for 1 hour, and maintained at this temperature for 3 hours in order to produce a preliminarily calcined product. The preliminarily calcined product produced was formed into a ring shape having a diameter of 5 mm, a height of 4 mm, and an internal diameter of 2 mm by tablet compression, which were then finally calcined at 540 ° C for 5 hours in air to produce a catalyst. The composition of the catalyst is shown in Table 1 and the results of X-ray powder diffraction measurements are shown in Table 2. [Comparative Example A1]
[00241] In 208.8 g of hot water at a temperature of about 90 ° C, 69.6 g of ammonium heptamolybdate were dissolved (liquid A). In addition, 28.6 g of bismuth nitrate, 28.3 g of cerium nitrate, 10.9 g of magnesium nitrate, 38.3 g of iron nitrate, 1.43 g of rubidium nitrate, and 38 , 5 g of nickel nitrate were dissolved in 41.9 g of 18% by weight aqueous nitric acid solution, to which 200.3 g of hot water at about 90 ° C were added (liquid B). Liquid A and liquid B were mixed, to which aqueous ammonia was added to adjust the pH to 4.2. The liquid was then stirred and mixed at about 55 ° C for about 3 hours to produce a slurry of starting material. The starting material slurry was transported to a spray dryer so as to be spray dried at an inlet temperature of 250 ° C and an outlet temperature of 140 ° C. An oxide catalyst precursor was thus produced. The oxide catalyst precursor produced was heated from 100 ° C to 200 ° C for more than 5 hours in air, then at 250 ° C for 1 hour, and maintained at this temperature for 3 hours in order to produce a preliminarily calcined product. The preliminarily calcined product produced was formed into a ring shape having a diameter of 5 mm, a height of 4 mm, and an internal diameter of 2 mm by tablet compression, which were then finally calcined at 530 ° C for 5 hours in air to produce a catalyst. The composition of the catalyst is shown in Table 1 and the results of X-ray powder diffraction measurement are shown in Table 2.
[00242] In order to evaluate the reaction of a catalyst, a reaction tube was filled with 5.0 g of the catalyst and the methacrolein synthesis reaction was carried out under the same conditions as in Example A1. The results of the reaction evaluation are shown in Table 3. [Comparative Example A2]
[00243] In 216.9 g of hot water at a temperature of about 90 ° C, 72.3 g of ammonium heptamolybdate were dissolved (liquid A). In addition, 28.1 g of bismuth nitrate, 14.7 g of cerium nitrate, 0.35 g of potassium nitrate, 19.2 g of iron nitrate, 2.0 g of cesium nitrate, and 69.8 g of cobalt nitrate were dissolved in 40.6 g of 18% by weight aqueous nitric acid solution, to which 181.7 g of hot water at about 90 ° C were added (liquid B). Liquid A and liquid B were mixed, to which aqueous ammonia was added to adjust the pH to 4.3. The liquid was then stirred and mixed at about 55 ° C for about 3 hours to produce a slurry of starting material. The starting material slurry was transported to a spray dryer so as to be spray dried at an inlet temperature of 250 ° C and an outlet temperature of 140 ° C. An oxide catalyst precursor was thus produced. The oxide catalyst precursor produced was heated from 100 ° C to 200 ° C for more than 3 hours in air, then at 250 ° C for 1 hour, and maintained at this temperature for 3 hours in order to produce a preliminarily calcined product. The preliminarily calcined product produced was formed into a ring shape having a diameter of 5 mm, a height of 4 mm, and an internal diameter of 2 mm by tablet compression, which were then finally calcined at 520 ° C for 5 hours in air to produce a catalyst. The composition of the catalyst is shown in Table 1 and the results of X-ray powder diffraction measurement are shown in Table 2.
[00244] In order to evaluate the reaction of a catalyst, a reaction tube was filled with 5.2 g of the catalyst and the methacrolein synthesis reaction was carried out under the same conditions as in Example A1. The results of the reaction evaluation are shown in Table 3. [Comparative Example A3]
[00245] In 197.2 g of hot water at a temperature of about 90 ° C, 65.7 g of ammonium heptamolybdate were dissolved (liquid A). In addition, 64.5 g of bismuth nitrate, 42.4 g of iron nitrate, 0.54 g of cesium nitrate, and 30.8 g of cobalt nitrate were dissolved in 40.6 g of aqueous acid solution nitric to 18% by mass, to which 203.6 g of hot water at about 90 ° C was added (liquid B). Liquid A and liquid B were mixed, to which ammonia water was added to adjust the pH to 4.0. The liquid was then stirred and mixed at about 55 ° C for about 3 hours to produce a slurry of starting material. The starting material slurry was transported to a spray dryer so as to be spray dried at an inlet temperature of 250 ° C and an outlet temperature of 140 ° C. An oxide catalyst precursor was thus produced. The oxide catalyst precursor produced was heated from 100 ° C to 200 ° C for more than 3 hours in air, then at 250 ° C for 1 hour, and maintained at this temperature for 3 hours in order to produce a preliminarily calcined product. The preliminarily calcined product produced was formed into a ring shape having a diameter of 5 mm, a height of 4 mm, and an internal diameter of 2 mm by tablet compression, which were then finally calcined at 540 ° C for 5 hours in air to produce a catalyst. The composition of the catalyst is shown in Table 1 and the results of X-ray powder diffraction measurement are shown in Table 2.
[00246] In order to evaluate the reaction of a catalyst, a reaction tube was filled with 6.1 g of the catalyst and the methacrolein synthesis reaction was carried out under the same conditions as in Example A1. The results of the reaction evaluation are shown in Table 3. [Comparative Example A4]
[00247] In 309.9 g of hot water at a temperature of about 90 ° C, 70.0 g of ammonium heptamolybdate and 5.4 g of ammonium metavanadate were dissolved (liquid A). In addition, 46.3 g of bismuth nitrate, 45.2 g of iron nitrate, 0.57 g of cesium nitrate, and 32.8 g of cobalt nitrate were dissolved in 38.6 g of aqueous acid solution nitric to 18% by mass, to which 170.3 g of hot water at about 90 ° C was added (liquid B). Liquid A and liquid B were mixed, to which aqueous ammonia was added to adjust the pH to 4.5. The liquid was then stirred and mixed at about 55 ° C for about 3 hours to produce a slurry of starting material. The starting material slurry was transported to a spray dryer so as to be spray dried at an inlet temperature of 250 ° C and an outlet temperature of 140 ° C. An oxide catalyst precursor was thus produced. The oxide catalyst precursor produced was heated from 100 ° C to 200 ° C for more than 3 hours in air, then at 250 ° C for 1 hour, and maintained at this temperature for 3 hours in order to produce a preliminarily calcined product. The preliminarily calcined product produced was formed into a ring shape having a diameter of 5 mm, a height of 4 mm, and an internal diameter of 2 mm by tablet compression, which were then finally calcined at 460 ° C for 5 hours in air to produce a catalyst. The composition of the catalyst is shown in Table 1 and the results of X-ray powder diffraction measurement are shown in Table 2.
[00248] In order to evaluate the reaction of a catalyst, a reaction tube was filled with 6.0 g of the catalyst and the methacrolein synthesis reaction was carried out under the same conditions as in Example A1. The results of the reaction evaluation are shown in Table 3. [Comparative Example A5]
[00249] In a liquid mixture of 90.2 g of ion exchange water and 127.0 g of water 30% by weight hydrogen peroxide, 54.3 g of molybdenum trioxide were added, which were stirred and mixed at about 70 ° C for dissolution. A solution (liquid A) was thus produced. In addition, 168.9 g of a 10% by weight bismuth oxide dispersion liquid having a mean particle size of 51 nm, 15.7 g of a 15% cobalt oxide dispersion liquid in water by mass having an average particle size of 22 nm, 66.9 g of a liquid dispersion in water 15% iron oxide by mass having an average particle size of 39 nm, 84.9 g of a dispersion liquid in water 10 wt% cerium oxide having an average particle size of 20 nm, and 4.2 g 10 wt% cesium hydroxide liquid were mixed to produce a solution (liquid B).
[00250] Liquid A and liquid B were mixed, to which ammonia water was added to adjust the pH to 3.0. The liquid was then stirred and mixed for about 3 hours to produce a slurry of starting material. The starting material slurry was transported to a spray dryer so as to be spray dried at an inlet temperature of 250 ° C and an outlet temperature of 140 ° C. An oxide catalyst precursor was thus produced. The oxide catalyst precursor produced was heated from 100 ° C to 250 ° C for more than 20 minutes in air, and held at 250 ° C for 3 hours in order to produce a preliminarily calcined product. The preliminarily calcined product produced was formed into a ring shape having a diameter of 5 mm, a height of 4 mm, and an internal diameter of 2 mm by tablet compression, which were then finally calcined at 530 ° C for 5 hours to produce a catalyst. The composition of the catalyst is shown in Table 1 and the results of X-ray powder diffraction measurement are shown in Table 2.
[00251] In order to evaluate the reaction of a catalyst, a reaction tube was filled with 4.2 g of the catalyst and the methacrolein synthesis reaction was carried out under the same conditions as in Example A1. The results of the reaction evaluation are shown in Table 3. [Comparative Example A6]
[00252] A composition of the catalyst MOi2Bit6Ce04Fe10Co8.0Cs0.4K02, which represents atomic ratio relative to 12 Mo atoms, was prepared as follows. In 1820 g of hot water at a temperature of about 50 ° C, 364 g of ammonium heptamolybdate were dissolved (liquid A). In addition, 133 g of bismuth nitrate, 29.8 g of cerium nitrate, 69.4 g of iron nitrate, 13.4 g of cesium nitrate, 3.46 g of potassium nitrate, and 400 g of nitrate of cobalt were dissolved in 290 g of 15% by weight aqueous solution of nitric acid (liquid B). Liquid A and liquid B were stirred and mixed for about 2 hours to produce a slurry of starting material. The starting material slurry was spray dried to produce a spray dried catalyst precursor composition, which was then preliminarily calcined at 200 ° C for 3 hours. The preliminary calcined catalyst precursor composition produced in the form of pseudo-spherical particles was formed in a columnar form having a diameter of 5 mm and a height of 4 mm by tablet compression, which were then finally calcined at 460 ° C for 3 hours to produce a catalyst. The composition of the catalyst is shown in Table 1 and the results of X-ray powder diffraction measurement are shown in Table 2.
[00253] In order to evaluate the reaction of a catalyst, a reaction tube was filled with 4.2 g of the catalyst and the methacrolein synthesis reaction was carried out under the same conditions as in Example A1. The results of the reaction evaluation are shown in Table 3.
[00254] In Figure 8, the XRD (20 = 25 to 27 °) of an oxide catalyst before and after the olefin gas phase catalytic oxidation reaction in Comparative Example A6 is illustrated. The oxide catalyst before the olefin gas phase catalytic oxidation reaction in Comparative Example A6 had an XMD peak of CoMoO4 (002) at 20 = 26.46 °, and the oxide catalyst after reaction had an XRD peak of C0M004 (002) at 20 = 26.46 °. Thus, it was considered that no bivalent Fe was dissolved in solid in CoMoO4. This was attributed to the atomic ratio of iron to cobalt (Fe / Co), not following the expression: Fe / Co> 1. <Acrolein reaction synthesis> [Example A8]
[00255] In a mixed liquid of 90.7 g of ion exchange water and 127.8 g of water 30% by weight hydrogen peroxide, 54.6 g of molybdenum trioxide were added, which were stirred and mixed at about 70 ° C for dissolution. A solution (liquid A) was thus produced. In addition, 205.3 g of a 10% by weight bismuth oxide water dispersion liquid having an average particle size of 51 nm, 54.5 g of a 15 cobalt oxide water dispersion liquid % by mass having an average particle size of 22 nm, 57.2 g of a liquid dispersion in iron oxide water at 15% by mass having an average particle size of 39 nm, 72.1 g of a liquid dispersion in water of 10 mass% lanthanum oxide having an average particle size of 40 nm, and 1.4 g of 10 mass% cesium hydroxide liquid were mixed to produce a solution (liquid B).
[00256] Liquid A and liquid B were mixed to produce a liquid mixture, to which aqueous ammonia was added to adjust the pH to 3.8. The liquid was then stirred and mixed for about 3 hours to produce a slurry of starting material. The starting material slurry was transported to a spray dryer so as to be spray dried at an inlet temperature of 250 ° C and an outlet temperature of 140 ° C. An oxide catalyst precursor was thus produced. The oxide catalyst precursor produced was heated from 100 ° C to 200 ° C for more than 5 hours in air, then at 260 ° C for 1 hour, and maintained at this temperature for 3 hours in order to produce a preliminarily calcined product. The preliminarily calcined product produced was formed into a ring shape having a diameter of 5 mm, a height of 4 mm, and an internal diameter of 2 mm by tablet compression, which were then finally calcined at 510 ° C for 5 hours in air to produce a catalyst. The composition of the catalyst is shown in Table 1 and the results of X-ray powder diffraction measurement are shown in Table 2.
[00257] Using the catalyst produced, acrolein was synthesized from propylene. A jacketed SUS reaction tube having an internal diameter of 15 mm was filled with 20 mL of the catalyst. A gas starting material of 10% by volume of propylene, 17% by volume of water vapor, and 73% by volume of air was passed through the tube at a reaction temperature of 320 ° C in order to perform the acrolein synthesis reaction. The results of the reaction evaluation are shown in Table 4. [Comparative Example A7]
[00258] In 203.1 g of hot water at a temperature of about 90 ° C, 67.7 g of ammonium heptamolybdate were dissolved (liquid A). In addition, 37.1 g of bismuth nitrate, 22.0 g of cerium nitrate, 51.4 g of iron nitrate, 0.19 g of cesium nitrate, and 37.4 g of cobalt nitrate were dissolved in 41.9 g of 18% by weight aqueous nitric acid solution, to which 205.7 g of hot water at about 90 ° C were added (liquid B). Liquid A and liquid B were mixed, to which aqueous ammonia was added to adjust the pH to 4.0. The liquid was then stirred and mixed at about 55 ° C for about 3 hours to produce a slurry of starting material. The starting material slurry was transported to a spray dryer so as to be spray dried at an inlet temperature of 250 ° C and an outlet temperature of 140 ° C. An oxide catalyst precursor was thus produced. The oxide catalyst precursor produced was heated from 100 ° C to 250 ° C for more than 20 minutes in air, and held at 250 ° C for 3 hours in order to produce a preliminarily calcined product. The preliminarily calcined product produced was formed into a ring shape having a diameter of 5 mm, a height of 4 mm, and an internal diameter of 2 mm by tablet compression, which were then finally calcined at 460 ° C for 5 hours in air to produce a catalyst. The composition of the catalyst is shown in Table 1 and the results of X-ray powder diffraction measurement are shown in Table 2.
[00259] In order to evaluate the reaction of a catalyst, a reaction tube was filled with 20 ml of the catalyst and the acrolein synthesis reaction was carried out under the same conditions as in Example A8. The results of the reaction evaluation are shown in Table 4. <Synthesis of butadiene reaction> [Example A9]
[00260] Using the same catalyst as in Example A2, butadiene was synthesized from 1-butene as follows. A jacketed SUS reaction tube having a diameter of 14 mm was filled with 6.0 g of the catalyst. A mixed gas of 8% by volume of 1-butene, 12.8% by volume of oxygen, and 79.2% by volume of nitrogen was passed through the tube at a reaction temperature of 360 ° C at a flow rate 120 mL / min (NTP) in order to perform a butadiene synthesis reaction. The results of the reaction evaluation are shown in Table 5. [Comparative Example A8]
[00261] Using the same catalyst as in Comparative Example A5, a reaction tube was filled with 6.0 g of the catalyst. Butadiene was synthesized from 1-butene under the same reaction conditions as in Example A9 as follows. The results of the reaction evaluation are shown in Table 5.
[Table 2]

[Table 4]
[Table 5]
<X-ray diffraction peaks from catalysts obtained in Example A1 and Comparative Example A3>
[00262] In Figure 5, the X-ray diffraction peaks of catalysts obtained in Example A1 and Comparative Example A3 are illustrated. In Figure 6, an enlarged graph of X-ray diffraction peaks for the range of 20 = 15 to 30 ° in Figure 5 is illustrated. In Figure 7, an enlarged graph for the range of 20 = 30 to 50 ° is illustrated. In Figure 6 and Figure 7, it was illustrated that the catalyst obtained in Example A1 has X-ray diffraction peaks at least 20 = 18.34 ° for plane (101), 28.16 ° for plane (112), 33 , 66 ° for plane (200), and 46.10 °, with a peak intensity ratio (la / lb) = 3.3, where la represents the peak intensity at 20 = 33.66 ° and lb represents the peak intensity at 20 = 34.06 °. It can be assumed that the disordered phase crystal structure of Bi3.xAxFeiMo2O12 was formed on the catalyst obtained in Example A1.
[00263] On the other hand, in the X-ray diffraction of the catalyst obtained in Comparative Example A3, no peak was observed at 18.30 ° ± 0.05 ° for plane (101), 28.20 ° ± 0.05 ° for plane (112), 33.65 ° ± 0.05 ° for plane (200), and 46.15 ° ± 0.05 ° for plane (204). It can therefore be assumed that the disordered phase crystal structure of Bi3.xAxFe1Mo2Oi2 was not formed on the catalyst obtained in Comparative Example A3.
[00264] The comparison of X-ray diffraction between the catalysts obtained in Example A1 and Comparative Example A3 are as follows. Corresponding to the peak at 18.34 ° for plane (101) of the catalyst obtained in Example A1, divided peaks were observed at 18.10 ° for (310) plane and at 18.48 ° for plane (111) in the catalyst obtained in Example Comparative A3. Corresponding to the peak at 28.20 ° ± 0.05 ° for plane (112) of the catalyst obtained in Example A1, split peaks were observed at 28.02 ° for plane (221) and 28.35 ° for plane (42- 1) in the catalyst obtained in Comparative Example A3. Corresponding to the peak at 33.65 ° ± 0.05 ° for plane (200) of the catalyst obtained in Example A1, split peaks were observed at 33.30 ° for plane (600) and at 34.06 ° for plane (202) in the catalyst obtained in Comparative Example A3. Corresponding to the peak at 46.15 ° ± 0.05 ° for plane (204) of the catalyst obtained in Example A1, split peaks were observed at 45.90 ° for plane (640) and 46.46 ° for plane (242) in the catalyst obtained in Comparative Example A3. The catalyst obtained in Example A1 has a peak intensity ratio (la / lb) = 1.1, where la represents the peak intensity at 20 = 33.66 ° and lb represents the peak intensity at 20 = 34, 06 °. It can be assumed that the crystal structure of a disordered B3.xAxFeiMo2Oi2 phase was formed on the catalyst obtained in Example A1. On the other hand, it can be assumed that an ordered phase was formed on the catalyst obtained in Comparative Example A3 instead of a disordered phase of BÍ3.xAxFeiMo2Oi2- [Example B]
[00265] Example B is provided in the following to further illustrate a second aspect of the present invention, but is not intended to limit the scope of the second aspect of the present invention to it. Since the atomic ratio of oxygen in an amoxidation catalyst is determined by the atomic valence conditions of other elements, the atomic ratio of oxygen is omitted in the formula representing the composition of a catalyst in Examples and Comparative Examples. The composition ratio of each element in an amoxidation catalyst was calculated from the composition ratio for preparation.
[00266] In Example B and Comparative Example B in the following, aqueous dispersions of various metals were used as catalyst starting materials. Each of the aqueous dispersions of bismuth oxide, iron oxide, and cobalt oxide for use was manufactured by CIK Nanotek Corporation, and each of the aqueous dispersions of lanthanum oxide and cerium oxide for use was manufactured by Taki Chemical Co. , Ltd. <Measurement of average particle size>
[00267] The average particle size was obtained by calculation based on the following equation: Average particle size [nm] = 6000 / (Surface area [m2 / g] x Actual density (8.99 g / cm3). < PH measurement>
[00268] The measurement was performed with a pH meter KR5E made by AS ONE. <X-ray diffraction measurement>
[00269] In XRD measurement, the plane (111) and plane (200) of a LaB6 compound as standard reference material 660 according to the National Institute of Standards & Technology were measured, such that the values were normalized to 37,441 ° and 43.506 °, respectively.
[00270] An XRD Bruker D8 Advance device was used. The XRD measurement conditions were as follows: a 40 kV-40 mA X-ray output, a 0.3 ° divergence gap (DS), a step width of 0.02 ° / step, a 2.0 s counting time, and a measuring range of 20 = 5 ° to 60 °. <Reaction evaluation conditions for amoxidation>
[00271] 40 to 60 g of a catalyst were placed in a Vycor glass fluidized bed reaction tube having an internal diameter of 25 mm in which 12 sheets of 10 mesh wire mesh arranged at 1 cm intervals. A mixed gas (with a volume ratio of propylene or isobutylene: ammonia: oxygen: helium ': 1.2: 1.85: 7.06) was passed through the tube at a reaction temperature of 430 ° C under normal conditions. normal reaction pressure at a flow rate of 3.64 cm3 / s (converted to NTP). <Conversion rate, selectivity, and yield>
[00272] The reaction performance was represented by conversion rate, selectivity, and yield, which are defined by the following expressions. Conversion rate = (number of moles of reacted starting material / number of moles of starting material supplied) x 100 Selectivity = (number of moles of compound produced / number of moles of reacted starting material) x 100 Yield = (number moles of compost produced / number of moles of starting material supplied) x 100 i <Contact time>
[00273] The contact time is defined by the following expression. Contact time (sg / cm3) = (W / F) x 273 / (273 + T) x P / 0.10
[00274] In the expression, W represents the amount of catalyst (g), F represents the flow rate of mixed gas of starting material (N.cm3 / s) in the normal state (0 ° C, 1 atm), T represents reaction temperature (° C), and P represents reaction pressure (MPa). <Reducibility assessment>
[00275] Reducibility was assessed by accelerated assessment of the reduction resistance of a catalyst. The catalyst was reduced to an oxygen-free atmosphere gas and re-oxidized under the returned reaction conditions. The process was repeated to achieve the accelerated evaluation of the reduction resistance of the catalyst.
[00276] A mixed gas of 2% by volume of propylene, isobutylene, isobutanol, and / or t-butyl alcohol and 98% by volume of helium was approved at a temperature of 430 ° C at a flow rate of 3.64 cm3 / s (converted to NTP) for 5 minutes for reduction treatment. Subsequently, the reaction evaluation conditions were restored and the flow was maintained for 5 minutes. This constituted one set, and the reaction was evaluated after 100 sets of runs. After another 100 sets of runs, the reaction and resistance to reduction were evaluated.
[00277] Each of elements A for use in Example B and Comparative Example B has an ionic radius at the following: La: 1.14 A, Ce: 1.07 Â, Pr: 1.06 A, Ca: 1.03 A, Pb: 1.24 A, and V: 0.56 A. [Example B1]
[00278] First, 125.0 g of 40% by weight silica sol containing 26% by weight of primary silica particles having an average diameter of 44 nm, and 147.1 g of aqueous silica sol at 34 wt% containing SiO2a 30 wt% primary silica particles having an average diameter of 12 nm, and 61.3 g of water were mixed to produce 30 wt% silica starting material.
[00279] In 211.0 g of hot water at a temperature of about 90 ° C, 70.3 g of ammonium heptamolybdate were dissolved (liquid A). In addition, 38.6 g of bismuth nitrate, 22.9 g of lanthanum nitrate, 42.7 g of iron nitrate, 0.51 g of cesium nitrate, and 31.4 g of cobalt nitrate were dissolved in 36.4 g of 18% by weight aqueous nitric acid solution, to which 148.1 g of hot water at about 90 ° C were added (liquid B).
[00280] The silica starting material and both liquid A and liquid B were mixed, to which aqueous ammonia was added to adjust the pH to 4.1. The liquid was then stirred and mixed at about 55 ° C for about 4 hours to produce a slurry of starting material. The starting material slurry was transported to a spray dryer so as to be spray dried at an inlet temperature of 250 ° C and an outlet temperature of 140 ° C. An oxide catalyst precursor was thus produced. The oxide catalyst precursor produced was heated from 100 ° C to 200 ° C for 2 hours in air, then at 260 ° C for 1 hour, and maintained at this temperature for 3 hours in order to produce a preliminarily calcined product. The preliminarily calcined product produced was finally calcined at 570 ° C for 3 hours in air to produce a catalyst. The composition of the catalyst is shown in Table 6 and the results of X-ray powder diffraction measurements are shown in Table 7.
[00281] For the reaction evaluation of a catalyst, 55 g of the catalyst were placed in a Vycor glass fluidized bed reaction tube having an internal diameter of 25 mm, and propylene amoxidation was carried out with a contact time of 4.3 (sg / cm3). The results of the reaction evaluation are shown in Table 8. The results of the reaction evaluation after 100 sets and 200 sets of accelerated reduction evaluation runs are also shown in Table 8. [Example B2]
[00282] First, 125.0 g of 40% by weight silica sol containing 26% by weight of primary silica particles having an average diameter of 44 nm, and 147.1 g of aqueous silica sol at 34 wt% containing SiO2 at 30 wt% primary silica particles having an average diameter of 12 nm, and 61.3 g of water were mixed to produce 30 wt% silica starting material.
[00283] In 207.8 g of hot water at a temperature of about 90 ° C, 69.3 g of ammonium heptamolybdate were dissolved (liquid A). In addition, 41.1 g of bismuth nitrate, 19.7 g of cerium nitrate, 44.7 g of iron nitrate, 0.50 g of cesium nitrate, and 32.5 g of cobalt nitrate were dissolved in 40.9 g of 18% by weight aqueous nitric acid solution, to which 194.7 g of hot water at about 90 ° C were added (liquid B).
[00284] The silica starting material and both liquid A and liquid B were mixed, to which aqueous ammonia was added to adjust the pH to 3.3. The liquid was then stirred and mixed at about 55 ° C for about 4 hours to produce a slurry of starting material. The starting material slurry was transported to a spray dryer so as to be spray dried at an inlet temperature of 250 ° C and an outlet temperature of 140 ° C. An oxide catalyst precursor was thus produced. The oxide catalyst precursor produced was heated from 100 ° C to 200 ° C for 2 hours in air, then at 250 ° C for 1 hour, and maintained at this temperature for 3 hours in order to produce a preliminarily calcined product. The preliminarily calcined product produced was finally calcined at 570 ° C for 3 hours in air to produce a catalyst. The composition of the catalyst is shown in Table 6 and the results of X-ray powder diffraction measurements are shown in Table 7.
[00285] To evaluate the reaction of a catalyst, 55 g of the catalyst were placed in a Vycor glass fluidized bed reaction tube having an internal diameter of 25 mm, and propylene amoxidation was carried out with a contact time of 4.2 (sg / cm3). The results of the reaction evaluation are shown in Table 8. The results of the reaction evaluation after 100 sets and 200 sets of accelerated reduction evaluation runs are also shown in Table 8. [Example B3]
[00286] First, 125.0 g of 40% by weight silica sol containing 26% by weight of primary silica particles having an average diameter of 44 nm, and 147.1 g of aqueous silica sol at 34 wt% containing SiO2 at 30 wt% primary silica particles having an average diameter of 12 nm, and 61.3 g of water were mixed to produce 30 wt% silica starting material.
[00287] In 209.1 g of hot water at a temperature of about 90 ° C, 69.7 g of ammonium heptamolybdate were dissolved (liquid A). In addition, 44.6 g of bismuth nitrate, 17.0 g of praseodymium nitrate, 31.8 g of iron nitrate, 0.57 g of cesium nitrate, and 38.4 g of cobalt nitrate were dissolved in 40 , 2 g of 18% by weight aqueous nitric acid solution, to which 188.8 g of hot water at about 90 ° C were added (liquid B).
[00288] The silica starting material and both liquid A and liquid B were mixed, to which aqueous ammonia was added to adjust the pH to 3.6. The liquid was then stirred and mixed at about 55 ° C for about 4 hours to produce a slurry of starting material. The starting material slurry was transported to a spray dryer so as to be spray dried at an inlet temperature of 250 ° C and an outlet temperature of 140 ° C. An oxide catalyst precursor was thus produced. The oxide catalyst precursor produced was heated from 100 ° C to 200 ° C for 2 hours in air, then at 270 ° C for 1 hour, and maintained at this temperature for 3 hours in order to produce a preliminarily calcined product. The preliminarily calcined product produced was finally calcined at 570 ° C for 3 hours in air to produce a catalyst. The composition of the catalyst is shown in Table 6 and the results of X-ray powder diffraction measurements are shown in Table 7.
[00289] For the reaction evaluation of a catalyst, 57 g of the catalyst were placed in a Vycor glass fluidized bed reaction tube having an internal diameter of 25 mm, and propylene amoxidation was carried out with a contact time of 4.4 (sg / cm3). The results of the reaction evaluation are shown in Table 8. The results of the reaction evaluation after 100 sets and 200 sets of accelerated reduction evaluation runs are also shown in Table 8. Example B4
[00290] First, 125.0 g of 40% by weight silica sol containing 26% by weight of primary silica particles having an average diameter of 44 nm, and 147.1 g of aqueous silica sol at 34 wt% containing SiO2 at 30 wt% primary silica particles having an average diameter of 12 nm, and 61.3 g of water were mixed to produce 30 wt% silica starting material.
[00291] In 223.4 g of hot water at a temperature of about 90 ° C, 74.5 g of ammonium heptamolybdate were dissolved (liquid A). In addition, 20.4 g of bismuth nitrate, 30.3 g of lanthanum nitrate, 45.2 g of iron nitrate, 0.54 g of cesium nitrate, 6.6 g of calcium nitrate, and 32.9 g of cobalt nitrate were dissolved in 34.3 g of 18% by weight aqueous nitric acid solution, to which 114.4 g of hot water at about 90 ° C were added (liquid B).
[00292] The silica starting material and both liquid A and liquid B were mixed, to which aqueous ammonia was added to adjust the pH to 3.6. The liquid was then stirred and mixed at about 55 ° C for about 4 hours to produce a slurry of starting material. The starting material slurry was transported to a spray dryer so as to be spray dried at an inlet temperature of 250 ° C and an outlet temperature of 140 ° C. An oxide catalyst precursor was thus produced. The oxide catalyst precursor produced was heated from 100 ° C to 200 ° C for 2 hours in air, then at 240 ° C for 1 hour, and maintained at this temperature for 4 hours in order to produce a preliminarily calcined product. The preliminarily calcined product produced was finally calcined at 580 ° C for 3 hours in air to produce a catalyst. The composition of the catalyst is shown in Table 6 and the results of X-ray powder diffraction measurements are shown in Table 7.
[00293] For the reaction evaluation of a catalyst, 57 g of the catalyst were placed in a Vycor glass fluidized bed reaction tube having an internal diameter of 25 mm, and propylene amoxidation was carried out with a contact time of 4.5 (sg / cm3). The results of the reaction evaluation are shown in Table 8. The results of the reaction evaluation after 100 sets and 200 sets of accelerated reduction evaluation runs are also shown in Table 8. [Example B5]
[00294] First, 125.0 g of 40% by weight silica sol containing 26% by weight of primary silica particles having an average diameter of 44 nm, and 147.1 g of aqueous silica sol at 34 wt% containing SiO2 at 30 wt% primary silica particles having an average diameter of 12 nm, and 61.3 g of water were mixed to produce 30 wt% silica starting material.
[00295] In 202.0 g of hot water at a temperature of about 90 ° C, 67.3 g of ammonium heptamolybdate were dissolved (liquid A). In addition, 21.5 g of bismuth nitrate, 24.6 g of cerium nitrate, 42.2 g of iron nitrate, 0.74 g of cesium nitrate, 8.4 g of lead nitrate, and 47.3 g of cobalt nitrate were dissolved in 39.4 g of 18% by weight aqueous nitric acid solution, to which 182.0 g of hot water at about 90 ° C were added (liquid B).
[00296] The silica starting material and both liquid A and liquid B were mixed, to which aqueous ammonia was added to adjust the pH to 3.6. The liquid was then stirred and mixed at about 55 ° C for about 4 hours to produce a slurry of starting material. The starting Ki / n slurry was transported to a spray dryer in order to be spray dried at an inlet temperature of 250 ° C and an outlet temperature of 140 ° C. An oxide catalyst precursor was thus produced. The oxide catalyst precursor produced was heated from 100 ° C to 200 ° C for 2 hours in air, then at 250 ° C for 1 hour, and maintained at this temperature for 3 hours in order to produce a preliminarily calcined product. The preliminarily calcined product produced was finally calcined at 570 ° C for 3 hours in air to produce a catalyst. The composition of the catalyst is shown in Table 6 and the results of X-ray powder diffraction measurements are shown in Table 7.
[00297] For the reaction evaluation of a catalyst, 57 g of the catalyst were placed in a Vycor glass fluidized bed reaction tube having an internal diameter of 25 mm, and propylene amoxidation was carried out with a contact time of 4.6 (sg / cm3). The results of the reaction evaluation are shown in Table 8. The results of the reaction evaluation after 100 sets and 200 sets of accelerated reduction evaluation runs are also shown in Table 8. [Example B6]
[00298] First, 125.0 g of 40% by weight silica sol containing 26% by weight of primary silica particles having an average diameter of 44 nm, and 147.1 g of aqueous silica sol at 34 wt% containing SiO2 at 30 wt% primary silica particles having an average diameter of 12 nm, and 61.3 g of water were mixed to produce 30 wt% silica starting material.
[00299] In 211.8 g of hot water at a temperature of about 90 ° C, 70.6 g of ammonium heptamolybdate were dissolved (liquid A). In addition, 37.1 g of bismuth nitrate, 21.5 g of cerium nitrate, 41.5 g of iron nitrate, 0.63 g of rubidium nitrate, 10.2 g of magnesium nitrate, 19, 5 g of cobalt nitrate, and 9.8 g of nickel nitrate were dissolved in 41.3 g of 18% by weight aqueous nitric acid solution, to which 193.1 g of hot water at about 90 ° C were added (liquid B).
[00300] The silica starting material and both liquid A and liquid B were mixed, to which aqueous ammonia was added to adjust the pH to 3.6. The liquid was then stirred and mixed at about 55 ° C for about 4 hours to produce a slurry of starting material. The starting material slurry was transported to a spray dryer so as to be spray dried at an inlet temperature of 250 ° C and an outlet temperature of 140 ° C. An oxide catalyst precursor was thus produced. The oxide catalyst precursor produced was heated from 100 ° C to 200 ° C for 2 hours in air, then at 250 ° C for 1 hour, and maintained at this temperature for 3 hours in order to produce a preliminarily calcined product. The preliminarily calcined product produced was finally calcined at 570 ° C for 3 hours in air to produce a catalyst. The composition of the catalyst is shown in Table 6 and the results of X-ray powder diffraction measurements are shown in Table 7.
[00301] To evaluate the reaction of a catalyst, 57 g of the catalyst were placed in a Vycor glass fluidized bed reaction tube having an internal diameter of 25 mm, and propylene amoxidation was carried out with a contact time of 4.7 (sg / cm3). The results of the reaction evaluation are shown in Table 8. The results of the reaction evaluation after 100 sets and 200 sets of accelerated reduction evaluation runs are also shown in Table 8. [Example B7]
[00302] First, 125.0 g of 40% by weight silica sol containing 26% by weight of primary silica particles having an average diameter of 44 nm, and 147.1 g of aqueous silica sol at 34 wt% containing SiO2 at 30 wt% primary silica particles having an average diameter of 12 nm, and 61.3 g of water were mixed to produce 30 wt% silica starting material.
[00303] In 210.8 g of hot water at a temperature of about 90 ° C, 70.3 g of ammonium heptamolybdate were dissolved (liquid A). In addition, 27.3 g of bismuth nitrate, 14.3 g of cerium nitrate, 20.0 g of iron nitrate, 1.94 g of rubidium nitrate, 0.67 g of potassium nitrate, 4.9 g of zinc nitrate, and 72.7 g of cobalt nitrate were dissolved in 40.5 g of 18% by weight aqueous nitric acid solution, to which 186.0 g of hot water at about 90 ° C were added (liquid B).
[00304] The silica starting material and both liquid A and liquid B were mixed, to which aqueous ammonia was added to adjust the pH to 3.6. The liquid was then stirred and mixed at about 55 ° C for about 4 hours to produce a slurry of starting material. The starting material slurry was transported to a spray dryer so as to be spray dried at an inlet temperature of 250 ° C and an outlet temperature of 140 ° C. An oxide catalyst precursor was thus produced. The oxide catalyst precursor produced was heated from 100 ° C to 200 ° C for 2 hours in air, then at 250 ° C for 1 hour, and maintained at this temperature for 3 hours in order to produce a preliminarily calcined product. The preliminarily calcined product produced was finally calcined at 570 ° C for 3 hours in air to produce a catalyst. The composition of the catalyst is shown in Table 6 and the results of X-ray powder diffraction measurements are shown in Table 7.
[00305] For the reaction evaluation of a catalyst, 57 g of the catalyst were placed in a Vycor glass fluidized bed reaction tube having an internal diameter of 25 mm, and propylene amoxidation was carried out with a contact time of 4.6 (sg / cm3). The results of the reaction evaluation are shown in Table 8. The results of the reaction evaluation after 100 sets and 200 sets of accelerated reduction evaluation runs are also shown in Table 8. [Comparative Example B1]
[00306] First, 125.0 g of 40% by weight silica sol containing 26% by weight of primary silica particles having an average diameter of 44 nm, and 147.1 g of aqueous silica sol at 34 wt% containing SiO2 at 30 wt% primary silica particles having an average diameter of 12 nm, and 61.3 g of water were mixed to produce 30 wt% silica starting material.
[00307] In 203.4 g of hot water at a temperature of about 90 ° C, 67.8 g of ammonium heptamolybdate were dissolved (liquid A). In addition, 61.9 g of bismuth nitrate, 46.3 g of iron nitrate, 0.49 g of cesium nitrate, and 26.2 g of cobalt nitrate were dissolved in 40.4 g of aqueous acid solution 18% by weight nitric, to which 195.7 g of hot water at about 90 ° C were added (liquid B).
[00308] The silica starting material and both liquid A and liquid B were mixed, to which aqueous ammonia was added to adjust the pH to 4.1. The liquid was then stirred and mixed at about 55 ° C for about 4 hours to produce a slurry of starting material. The starting material slurry was transported to a spray dryer so as to be spray dried at an inlet temperature of 250 ° C and an outlet temperature of 140 ° C. An oxide catalyst precursor was thus produced. The oxide catalyst precursor produced was heated from 100 ° C to 200 ° C for 2 hours in air, then at 260 ° C for 1 hour, and maintained at this temperature for 4 hours in order to produce a preliminarily calcined product. The preliminarily calcined product produced was finally calcined at 570 ° C for 3 hours in air to produce a catalyst. The composition of the catalyst is shown in Table 6 and the results of X-ray powder diffraction measurements are shown in Table 7.
[00309] For the reaction evaluation of a catalyst, 55 g of the catalyst were placed in a Vycor glass fluidized bed reaction tube having an internal diameter of 25 mm, and propylene amoxidation was carried out with a contact time of 5.6 (sg / cm3). The results of the reaction evaluation are shown in Table 8. The results of the reaction evaluation after 100 sets and 200 sets of accelerated reduction evaluation runs are also shown in Table 8. [Comparative Example B2]
[00310] First, 125.0 g of 40% by weight silica sol containing 26% by weight of primary silica particles having an average diameter of 44 nm, and 147.1 g of aqueous silica sol at 34 wt% containing SiO2 at 30 wt% primary silica particles having an average diameter of 12 nm, and 61.3 g of water were mixed to produce 30 wt% silica starting material.
[00311] In 252.6 g of hot water at a temperature of about 90 ° C, 84.2 g of ammonium heptamolybdate were dissolved (liquid A). In addition, 5.8 g of bismuth nitrate, 3.4 g of cerium nitrate, 24.0 g of iron nitrate, 0.70 g of rubidium nitrate, 26.4 g of magnesium nitrate, and 75 , 6 g of nickel nitrate were dissolved in 41.8 g of 18% by weight aqueous nitric acid solution, to which 150.8 g of hot water at about 90 ° C were added (liquid B).
[00312] The silica starting material and both liquid A and liquid B were mixed, to which aqueous ammonia was added to adjust the pH to 3.6. The liquid was then stirred and mixed at about 55 ° C for about 4 hours to produce a slurry of starting material. The starting material slurry was transported to a spray dryer so as to be spray dried at an inlet temperature of 250 ° C and an outlet temperature of 140 ° C. An oxide catalyst precursor was thus produced. The oxide catalyst precursor produced was heated from 100 ° C to 200 ° C for 2 hours in air, then at 250 ° C for 1 hour, and maintained at this temperature for 3 hours in order to produce a preliminarily calcined product. The preliminarily calcined product produced was finally calcined at 570 ° C for 3 hours in air to produce a catalyst. The composition of the catalyst is shown in Table 6 and the results of X-ray powder diffraction measurements are shown in Table 7.
[00313] For the evaluation of the reaction of a catalyst, 57 g of the catalyst were placed in a Vycor glass fluidized bed reaction tube having an internal diameter of 25 mm, and propylene amoxidation was carried out with a contact time of 5.4 (sg / cm3). The results of the reaction evaluation are shown in Table 8. The results of the reaction evaluation after 100 sets and 200 sets of accelerated reduction evaluation runs are also shown in Table 8. [Comparative Example B3]
[00314] First, 125.0 g of 40% by weight silica sol containing SiC> 2 to 26% by weight of primary silica particles having an average diameter of 44 nm, and 147.1 g of silica sol 34 wt% aqueous containing 30 wt% SiO2 of primary silica particles having an average diameter of 12 nm, and 61.3 g of water were mixed to produce 30 wt% silica starting material.
[00315] In 249.9 g of hot water at a temperature of about 90 ° C, 83.3 g of ammonium heptamolybdate were dissolved (liquid A). In addition, 8.6 g of bismuth nitrate, 15.2 g of cerium nitrate, 26.9 g of iron nitrate, 0.23 g of rubidium nitrate, 20.1 g of magnesium nitrate, 34, 5 g of cobalt nitrate, 0.36 g of potassium nitrate, and 23.0 g of nickel nitrate were dissolved in 40.9 g of 18% by weight aqueous nitric acid solution, to which 148.1 g of hot water at about 90 ° C was added (liquid B).
[00316] The silica starting material and both liquid A and liquid B were mixed, to which aqueous ammonia was added to adjust the pH to 3.6. The liquid was then stirred and mixed at about 55 ° C for about 4 hours to produce a slurry of starting material. The starting material slurry was transported to a spray dryer so as to be spray dried at an inlet temperature of 250 ° C and an outlet temperature of 140 ° C. An oxide catalyst precursor was thus produced. The oxide catalyst precursor produced was heated from 100 ° C to 200 ° C for 2 hours in air, then at 260 ° C for 1 hour, and maintained at this temperature for 3 hours in order to produce a preliminarily calcined product. The preliminarily calcined product produced was finally calcined at 570 ° C for 3 hours in air to produce a catalyst. The composition of the catalyst is shown in Table 6 and the results of X-ray powder diffraction measurements are shown in Table 7.
[00317] For the reaction evaluation of a catalyst, 57 g of the catalyst were placed in a Vycor glass fluidized bed reaction tube having an internal diameter of 25 mm, and propylene amoxidation was carried out with a contact time of 5.3 (sg / cm3). The results of the reaction evaluation are shown in Table 8. The results of the reaction evaluation after 100 sets and 200 sets of accelerated reduction evaluation runs are also shown in Table 8. [Comparative Example B4]
[00318] First, 125.0 g of 40% by weight silica sol containing 26% by weight of primary silica particles having an average diameter of 44 nm, and 147.1 g of aqueous silica sol at 34 wt% containing SiO2 at 30 wt% primary silica particles having an average diameter of 12 nm, and 61.3 g of water were mixed to produce 30 wt% silica starting material.
[00319] In 216.3 g of hot water at a temperature of about 90 ° C, 72.1 g of ammonium heptamolybdate and 5.2 g of ammonium metavanadate were dissolved (liquid A). In addition, 44.4 g of bismuth nitrate, 43.8 g of iron nitrate, 0.46 g of cesium nitrate, and 31.8 g of cobalt nitrate were dissolved in 38.3 g of aqueous acid solution 18% by weight nitric, to which 161.9 g of hot water at about 90 ° C was added (liquid B).
[00320] The silica starting material and both liquid A and liquid B were mixed, to which aqueous ammonia was added to adjust the pH to 4.1. The liquid was then stirred and mixed at about 55 ° C for about 4 hours to produce a slurry of starting material. The starting material slurry was transported to a spray dryer so as to be spray dried at an inlet temperature of 250 ° C and an outlet temperature of 140 ° C. An oxide catalyst precursor was thus produced. The oxide catalyst precursor produced was heated from 100 ° C to 200 ° C for 2 hours in air, then at 250 ° C for 1 hour, and maintained at this temperature for 3 hours in order to produce a preliminarily calcined product. The preliminarily calcined product produced was finally calcined at 580 ° C for 3 hours in air to produce a catalyst. The composition of the catalyst is shown in Table 6 and the results of X-ray powder diffraction measurements are shown in Table 7.
[00321] For the evaluation of the reaction of a catalyst, 55 g of the catalyst were placed in a Vycor glass fluidized bed reaction tube having an internal diameter of 25 mm, and propylene amoxidation was carried out with a contact time of 5.9 (sg / cm3). The results of the reaction evaluation are shown in Table 8. The results of the reaction evaluation after 100 sets and 200 sets of accelerated reduction evaluation runs are also shown in Table 8. [Comparative Example B5]
[00322] The same oxide catalyst precursor as in Example B1 was heated to 250 ° C for 1 hour in air and maintained at this temperature for 3 hours in order to produce a preliminarily calcined product. The preliminarily calcined product produced was finally calcined at 570 ° C for 3 hours in air to produce a catalyst. The composition of the catalyst is shown in Table 6 and the results of X-ray powder diffraction measurements are shown in Table 7.
[00323] For the reaction evaluation of a catalyst, 55 g of the catalyst was placed in a Vycor glass fluidized bed reaction tube having an internal diameter of 25 mm, and propylene amoxidation was carried out with a contact time of 5.8 (sg / cm3). The results of the reaction evaluation are shown in Table 8. The results of the reaction evaluation after 100 sets and 200 sets of accelerated reduction evaluation runs are also shown in Table 8. [Example B8]
[00324] Using the same catalyst as in Example B1, for the reaction evaluation, 57 g of the catalyst was placed in a Vycor glass fluidized bed reaction tube having an internal diameter of 25 mm, and isobutylene amoxidation was performed with a contact time of 5.4 (sg / cm3). The results of the reaction evaluation are shown in Table 9. The results of the reaction evaluation after 100 sets and 200 sets of accelerated reduction evaluation runs are also shown in Table 9. Comparative Example B6
[00325] Using the same catalyst as in Comparative Example B5, for the reaction evaluation, 55 g of the catalyst was placed in a Vycor glass fluidized bed reaction tube having an internal diameter of 25 mm, and the isobutylene amoxidation was performed with a contact time of 6.0 (sg / cm3). The results of the reaction evaluation are shown in Table 9. The results of the reaction evaluation after 100 sets and 200 sets of accelerated reduction evaluation runs are also shown in Table 9. [Table 6]
[Table 7]
[Table 8]
[Table 9]
<X-ray diffraction peaks of the catalysts obtained in Example B1 and Comparative Example B1>
[00326] In Figure 9, the X-ray diffraction peaks of the catalysts obtained in Example B1 and Comparative Example B1 are illustrated. In Figure 10, an enlarged graph of X-ray diffraction peaks for the range of 20 = 15 to 30 ° in Figure 9 is illustrated. In Figure 11, an enlarged graph for the range of 20 = 30 to 50 ° is illustrated. In Figure 9 and Figure 10, it was illustrated that the catalyst obtained in Example B1 has X-ray diffraction peaks at least 20 = 18.28 ° for plane (101), 28.16 ° for plane (112), 33 , 60 ° for plane (200), and 46.00 °, with a peak intensity ratio (la / lb) = 3.3, where la represents the peak intensity at 20 = 33.60 ° and lb represents the peak intensity at 20 = 34.06 °. It can be assumed that the disordered phase Bi3.xAxFe1Mo2Oi2 crystal structure was formed on the catalyst obtained in Example B1.
[00327] On the other hand, in the X-ray diffraction of the catalyst obtained in Comparative Example B1, no peak was observed at 18.30 ° ± 0.05 ° for plane (101), 28.20 ° ± 0.05 ° for plane (112), 33.65 ° ± 0.05 ° for plane (200), and 46.15 ° ± 0.05 ° for plane (204). It can therefore be assumed that the crystal structure of Bi3. disordered phase xAxFeiMo2O12 was not formed in the catalyst obtained in Comparative Example B1.
[00328] The comparison of X-ray diffraction between the catalysts obtained in Example B1 and Comparative Example B1 is as follows. Corresponding to the peak at 18.34 ° for plane (101) of the catalyst obtained in Example B1, divided peaks were observed at 18.10 ° for plane (310) and 18.45 ° for plane (111) in the catalyst obtained in Example Comparison B1. Corresponding to the peak at 28.20 ° ± 0.2 ° for plane (112) of the catalyst obtained in Example B1, divided peaks were observed at 28.00 ° for plane (221) and 28.35 ° for plane (42- 1) in the catalyst obtained in Comparative Example B1. Corresponding to the peak at 33.65 ° ± 0.2 ° for plane (200) of the catalyst obtained in Example B1, split peaks were observed at 33.30 ° for plane (600) and 34.10 ° for plane (202) in the catalyst obtained in Comparative Example B1. Corresponding to the peak at 46.15 ° ± 0.2 ° for plane (204) of the catalyst obtained in Example B1, split peaks were observed at 45.90 ° for plane (640) and 46.45 ° for plane (242) in the catalyst obtained in Comparative Example B1. The catalyst obtained in Example B1 has a peak intensity ratio (la / lb) = 1.0, where la represents the peak intensity at 20 = 33.60 ° and lb represents the peak intensity at 20 = 34, 06 °. It can be assumed that the crystal structure of a disordered B1-3.xAxFeiMo2Oi2 phase was formed on the catalyst obtained in Example B1. On the other hand, it can be assumed that an ordered phase was formed on the catalyst obtained in Comparative Example B1 instead of a disordered phase of B3.xAxFeiMo2Oi2.
[00329] Example C is presented below to further illustrate a third aspect of the present invention, but is not intended to limit the scope of the third aspect of the present invention to the same. Since the atomic oxygen ratio in an oxide catalyst is determined by the atomic valence conditions of other elements, the atomic oxygen ratio is omitted in the formula representing the composition of the catalysts in Example C and Comparative Example C. The composition ratio of each element in an oxide catalyst was calculated from the composition to preparation ratio.
[00330] In Example C and Comparative Example C, the reaction performance was represented by conversion rate, selectivity, and yield, which are defined by the following expressions. The term "number of moles of starting material" refers to the number of moles of olefin and / or alcohol. Conversion rate (%) = (number of moles of reacted olefin and / or alcohol / number of moles of supplied olefin and / or alcohol) x 100 Selectivity (%) = (number of moles of unsaturated aldehyde produced / number of moles of reacted olefin and / or alcohol) x100 Yield (%) = (number of moles of unsaturated aldehyde produced / number of moles of supplied olefin and / or alcohol) x 100 [Example C1]
[00331] First, 125.0 g of 40% by weight silica sol containing 26% by weight of primary silica particles having an average diameter of 44 nm, and 147.1 g of aqueous silica sol at 34 wt% containing SiO2 at 30 wt% primary silica particles having an average diameter of 12 nm, and 61.3 g of water were mixed to produce 30 wt% silica starting material.
[00332] In 211.9 g of hot water at a temperature of about 90 ° C, 70.6 g of ammonium heptamolybdate were dissolved (liquid A). In addition, 32.3 g of bismuth nitrate, 28.7 g of cerium nitrate, 45.6 g of iron nitrate, 1.03 g of cesium nitrate, and 29.2 g of cobalt nitrate were dissolved in 40.9 g of 18% by weight aqueous nitric acid solution, to which 190.3 g of hot water at about 90 ° C were added (liquid B).
[00333] The silica starting material and both liquid A and liquid B were mixed. The liquid was then stirred and mixed at about 55 ° C for about 4 hours to produce a slurry of starting material. The starting material slurry was transported to a spray dryer so as to be spray dried at an inlet temperature of 250 ° C and an outlet temperature of 140 ° C. An oxide catalyst precursor was thus produced. The oxide catalyst precursor produced was heated from 100 ° C to 200 ° C for 1 hour or more in air, then at 250 ° C more than 2 hours in total, and maintained at 250 ° C for 3 hours in order to produce a preliminarily calcined product. The preliminarily calcined product produced was finally calcined at 600 ° C for 3 hours in air to produce an oxide catalyst. The composition of the oxide catalyst is shown in Table 10.
[00334] Using the oxide catalyst thus produced, unsaturated aldehyde was produced. Specifically, 40 g of the oxide catalyst was placed in a Vycor glass fluidized bed reaction tube having an internal diameter of 25 mm. A mixed starting material gas (isobutylene concentration: 8% by volume) with a molar ratio of isobutylene composition / air / helium = 1 / 8.1 / rest was supplied through the reaction tube at a reaction temperature of 440 ° C under a reaction pressure of 0.05 MPa at a flow rate of 595 cm2 / min (converted to NTP) in order to carry out the methacrolein synthesis reaction. The oxygen concentration at the reactor outlet, the contact time between the oxide catalyst and the mixed gas, and reaction evaluation results at that time are shown in Table 11. [Example C2]
[00335] 40 g of the same oxide catalyst as in Example C1 was used. A mixed starting material gas (isobutylene concentration: 8% by volume) with a molar ratio of isobutylene / air / helium composition = 1 / 8.8 / remainder was supplied at a reaction temperature of 430 ° C under a reaction pressure of 0.05 MPa at a flow rate of 725 cm2 / min (converted to NTP) in order to carry out the methacrolein synthesis reaction. The oxygen concentration at the reactor outlet, the contact time between the catalyst and the mixed gas, and reaction evaluation results at that time are shown in Table 11. [Example C3]
[00336] 30 g of the same oxide catalyst as in Example C1 was used. A mixed starting material gas (isobutylene concentration: 8% by volume) with a molar ratio of isobutylene / air / helium composition = 1 / 9.4 / rest was supplied at a reaction temperature of 440 ° C under a reaction pressure of 0.05 MPa at a flow rate of 794 cm2 / min (converted to NTP) in order to carry out the methacrolein synthesis reaction. The oxygen concentration at the reactor outlet, the contact time between the oxide catalyst and the mixed gas, and reaction evaluation results at that time are shown in Table 11. [Example C4]
[00337] 40 g of the same oxide catalyst as in Example C1 was used. A mixed starting material gas (isobutylene concentration: 8% by volume) with a molar ratio of isobutylene / air / helium = 1 / 7.9 / rest was supplied at a reaction temperature of 440 ° C under a reaction pressure of 0.05 MPa at a flow rate of 595 cm2 / min (converted to NTP) in order to carry out the methacrolein synthesis reaction. The oxygen concentration at the reactor outlet, the contact time between the oxide catalyst and the mixed gas, and reaction evaluation results at that time are shown in Table 11. [Example C5]
[00338] 40 g of the same oxide catalyst as in Example C1 was used. A mixed starting material gas (isobutylene concentration: 8% by volume) with a molar ratio of isobutylene / air / helium = 1 / 9.5 / rest was supplied at a reaction temperature of 440 ° C under a reaction pressure of 0.05 MPa at a flow rate of 625 cm2 / min (converted to NTP) in order to carry out the methacrolein synthesis reaction. The oxygen concentration at the reactor outlet, the contact time between the oxide catalyst and the mixed gas, and reaction evaluation results at that time are shown in Table 11. [Example C6]
[00339] 35 g of the same oxide catalyst as in Example C1 was used. A gas of mixed starting material (isobutylene concentration: 8% by volume) with a molar ratio of isobutylene / air / helium = 1 / 8.8 / remainder was supplied at a reaction temperature of 460 ° C under a reaction pressure of 0.05 MPa at a flow rate of 595 cm2 / min (converted to NTP) in order to carry out the methacrolein synthesis reaction. The oxygen concentration at the reactor outlet, the contact time between the oxide catalyst and the mixed gas, and reaction evaluation results at that time are shown in Table 11. [Example C7]
[00340] 40 g of the same oxide catalyst as in Example C1 was used. A mixed starting material gas (isobutylene concentration: 8% by volume) with a molar ratio of isobutylene / air / helium = 1 / 8.1 / remainder was supplied at a reaction temperature of 400 ° C under a reaction pressure of 0.05 MPa at a flow rate of 595 cm2 / min (converted to NTP) in order to carry out the methacrolein synthesis reaction. The oxygen concentration at the reactor outlet, the contact time between the oxide catalyst and the mixed gas, and reaction evaluation results at that time are shown in Table 11. [Example C8]
[00341] First, 125.0 g of 40% by weight silica sol containing 26% by weight of primary silica particles having an average diameter of 44 nm, and 147.1 g of aqueous silica sol at 34 wt% containing SiO2 at 30 wt% primary silica particles having an average diameter of 12 nm, and 61.3 g of water were mixed to produce 30 wt% silica starting material.
[00342] In 211.8 g of hot water at a temperature of about 90 ° C, 70.6 g of ammonium heptamolybdate were dissolved (liquid A). In addition, 25.8 g of bismuth nitrate, 18.6 g of cerium nitrate, 18.7 g of lanthanum nitrate, 42.9 g of iron nitrate, 1.03 g of cesium nitrate, and 31, 1 g of cobalt nitrate was dissolved in 37.5 g of 18% by weight aqueous nitric acid solution, to which 157.5 g of hot water at about 90 ° C was added (liquid B).
[00343] The silica starting material and both liquid A and liquid B were mixed. The liquid was then stirred and mixed at about 55 ° C for about 4 hours to produce a slurry of starting material. The starting material slurry was transported to a spray dryer so as to be spray dried at an inlet temperature of 250 ° C and an outlet temperature of 140 ° C. An oxide catalyst precursor was thus produced. The oxide catalyst precursor produced was heated from 100 ° C to 200 ° C for 1 hour or more in air, then at 250 ° C more than 2 hours in total, and maintained at 250 ° C for 3 hours in order to produce a preliminarily calcined product. The preliminarily calcined product produced was finally calcined at 590 ° C for 3 hours in air to produce an oxide catalyst. The composition of the oxide catalyst is shown in Table 10.
[00344] Using the oxide catalyst so produced, unsaturated aldehyde was produced. Specifically, 40 g of the oxide catalyst was placed in a Vycor glass fluidized bed reaction tube having an internal diameter of 25 mm. A gas of mixed starting material (isobutylene concentration: 8% by volume) with a molar ratio of isobutylene / air / helium composition = 1 / 8.1 / rest was supplied to the reaction tube at a reaction temperature of 440 ° C under a reaction pressure of 0.05 MPa at a flow rate of 595 cm2 / min (converted to NTP) in order to carry out the methacrolein synthesis reaction. The oxygen concentration at the reactor outlet, the contact time between the oxide catalyst and the mixed gas, and reaction evaluation results at that time are shown in Table 11. [Example C9]
[00345] First, 125.0 g of 40% by weight silica sol containing 26% by weight of primary silica particles having an average diameter of 44 nm, and 147.1 g of aqueous silica sol at 34 wt% containing SiO2 at 30 wt% primary silica particles having an average diameter of 12 nm, and 61.3 g of water were mixed to produce 30 wt% silica starting material.
[00346] In 214.5 g of hot water at a temperature of about 90 ° C, 71.5 g of ammonium heptamolybdate were dissolved (liquid A). In addition, 18.0 g of bismuth nitrate, 39.2 g of cerium nitrate, 4.9 g of nickel nitrate, 3.4 g of magnesium nitrate, 43.4 g of iron nitrate, 1, 48 g of rubidium nitrate, and 31.6 g of cobalt nitrate were dissolved in 41.6 g of 18% by weight aqueous nitric acid solution, to which 192.3 g of hot water at about 90 ° C were added (liquid B).
[00347] The silica starting material and both liquid A and liquid B were mixed. The liquid was then stirred and mixed at about 55 ° C for about 4 hours to produce a slurry of starting material. The starting material slurry was transported to a spray dryer so as to be spray dried at an inlet temperature of 250 ° C and an outlet temperature of 140 ° C. An oxide catalyst precursor was thus produced. The oxide catalyst precursor produced was heated from 100 ° C to 200 ° C for 1 hour or more in air, then at 250 ° C more than 2 hours in total, and maintained at 250 ° C for 3 hours in order to produce a preliminarily calcined product. The preliminarily calcined product produced was finally calcined at 580 ° C for 3 hours in air to produce an oxide catalyst. The composition of the oxide catalyst is shown in Table 10.
[00348] Using the oxide catalyst so produced, unsaturated aldehyde was produced. Specifically, 40 g of the oxide catalyst was placed in a Vycor glass fluidized bed reaction tube having an internal diameter of 25 mm. A mixed starting material gas (isobutylene concentration: 8% by volume) with a molar ratio of isobutylene composition / air / helium = 1 / 8.1 / rest was supplied through the reaction tube at a reaction temperature of 440 ° C under a reaction pressure of 0.05 MPa at a flow rate of 595 cm2 / min (converted to NTP) in order to carry out the methacrolein synthesis reaction. The oxygen concentration at the outlet, the contact time between the catalyst and the mixed gas, and reaction evaluation results at that time are shown in Table 11. [Example C10]
[00349] 40 g of the same oxide catalyst as in Example C1 was used. A mixed starting material gas (isobutylene concentration: 8 volume%) with a molar ratio of isobutylene / air / helium composition = 1 / 10.2 / rest was supplied at a reaction temperature of 440 ° C under a reaction pressure of 0.05 MPa at a flow rate of 595 cm2 / min (converted to NTP) in order to carry out the methacrolein synthesis reaction. The oxygen concentration at the reactor outlet, the contact time between the oxide catalyst and the mixed gas, and reaction evaluation results at that time are shown in Table 11. [Comparative Example C1]
[00350] First, 125.0 g of 40% by weight silica sol containing 26% by weight of primary silica particles having an average diameter of 44 nm, and 147.1 g of aqueous silica sol at 34 wt% containing SiO2 at 30 wt% primary silica particles having an average diameter of 12 nm, and 61.3 g of water were mixed to produce 30 wt% silica starting material.
[00351] In 221.4 g of hot water at a temperature of about 90 ° C, 73.8 g of ammonium heptamolybdate were dissolved (liquid A). In addition, 27.0 g of bismuth nitrate, 6.0 g of cerium nitrate, 14.0 g of iron nitrate, 2.68 g of cesium nitrate, 0.70 g of potassium nitrate, and 81.4 g of cobalt nitrate were dissolved in 40.4 g of 18% by weight aqueous nitric acid solution, to which 175.3 g of hot water at about 90 ° C were added (liquid B).
[00352] The silica starting material and both liquid A and liquid B were mixed. The liquid was then stirred and mixed at about 55 ° C for about 4 hours to produce a slurry of starting material. The starting material slurry was transported to a spray dryer so as to be spray dried at an inlet temperature of 250 ° C and an outlet temperature of 140 ° C. An oxide catalyst precursor was thus produced. The oxide catalyst precursor produced was heated at 250 ° C for 2 hours in air, and maintained at 250 ° C for 3 hours in order to produce a preliminarily calcined product. The preliminarily calcined product produced was finally calcined at 570 ° C for 2 hours in air to produce an oxide catalyst. The composition of the oxide catalyst is shown in Table 10.
[00353] Using the oxide catalyst thus produced, unsaturated aldehyde was produced. Specifically, 40 g of the oxide catalyst was placed in a Vycor glass fluidized bed reaction tube having an internal diameter of 25 mm. A mixed starting material gas (isobutylene concentration: 8% by volume) with a molar ratio of isobutylene composition / air / helium = 1 / 8.1 / rest was supplied through the reaction tube at a reaction temperature of 440 ° C under a reaction pressure of 0.05 MPa at a flow rate of 595 cm2 / min (converted to NTP) in order to carry out the methacrolein synthesis reaction. The oxygen concentration at the outlet, the contact time between the catalyst and the mixed gas, and results of reaction evaluation at that time are shown in Table 11. [Comparative Example C2]
[00354] First, 125.0 g of 40% by weight silica sol containing 26% by weight of primary silica particles having an average diameter of 44 nm, and 147.1 g of aqueous silica sol at 34 wt% containing SiO2 at 30 wt% primary silica particles having an average diameter of 12 nm, and 61.3 g of water were mixed to produce 30 wt% silica starting material.
[00355] In 202.8 g of hot water at a temperature of about 90 ° C, 67.6 g of ammonium heptamolybdate were dissolved (liquid A). In addition, 61.7 g of bismuth nitrate, 43.6 g of iron nitrate, 0.98 g of cesium nitrate, and 28.0 g of cobalt nitrate were dissolved in 40.3 g of aqueous acid solution 18% by weight nitric, to which 195.7 g of hot water at about 90 ° C were added (liquid B).
[00356] The silica starting material and both liquid A and liquid B were mixed. The liquid was then stirred and mixed at about 55 ° C for about 4 hours to produce a slurry of starting material. The starting material slurry was transported to a spray dryer so as to be spray dried at an inlet temperature of 250 ° C and an outlet temperature of 140 ° C. An oxide catalyst precursor was thus produced. The oxide catalyst precursor produced was heated at 250 ° C for 2 hours in air, and maintained at 250 ° C for 3 hours in order to produce a preliminarily calcined product. The preliminarily calcined product produced was finally calcined at 600 ° C for 3 hours in air to produce an oxide catalyst. The composition of the oxide catalyst is shown in Table 10.
[00357] Using the oxide catalyst thus produced, unsaturated aldehyde was produced. Specifically, 40 g of the oxide catalyst was placed in a Vycor glass fluidized bed reaction tube having an internal diameter of 25 mm. A mixed starting material gas (isobutylene concentration: 8% by volume) with a molar ratio of isobutylene composition / air / helium = 1 / 8.1 / rest was supplied through the reaction tube at a reaction temperature of 440 ° C under a reaction pressure of 0.05 MPa at a flow rate of 595 cm2 / min (converted to NTP) in order to carry out the methacrolein synthesis reaction. The oxygen concentration at the reactor outlet, the contact time between the oxide catalyst and the mixed gas, and reaction evaluation results at that time are shown in Table 11. [Table 10]
[Table 11]
<X-ray powder diffraction (XRD) measurement>
[00358] The measurement of X-ray diffraction (XRD) of the oxide catalyst was performed by the range of X-ray diffraction angle from 20 = 5 ° to 60 °. A peak resulting from the X-ray diffraction angle (20) to plane (002) of a composite oxide of Co and Mo was shown at 26.46 ° ± 0.02 °. Bivalent Fe solid dissolved in the composite oxide of Co and Mo forms a composite, allowing the peak to be displaced due to the difference in ionic radius between Co2 + and Fe2 +. Because bivalent Fe dissolved in solids constitutes a composite structure, the resulting peak of the composite oxide comprising Co, Mo, and bivalent Fe is not shown at 26.46 ° but at 26.46 ° -a ° (0 <a) , where ° represents the displacement value. The presence of the peak in the range of 26.30 to 26.40 is attributed to the formation of crystals of a ternary component system Co2 + -Fe2 + -Mo-O.
[00359] The XRD measurement was performed based on the above. In XRD measurement, the plane (111) and plane (200) of a LaB6 compound as standard reference material 660 according to the National Institute of Standards & Technology were measured, so that the values were normalized at 37.441 ° and 43.506 °, respectively.
[00360] An XRD Bruker D8 Advance device was used. The XRD measurement conditions were as follows: a 40 kV-40 mA X-ray output, a 0.3 ° divergence slit (DS), a step width of 0.01 ° / step, a 2.0 s counting time, and a measuring range of 20 = 5 ° to 45 °.
[00361] In Figure 12, the XRD (20 = 10 to 60 °) of the oxide catalyst before and after the olefin gas phase catalytic oxidation reaction in Example C1 is illustrated. In Figure 13, an enlarged graph for the range of 20 = 25 to 27 ° in Figure 12 is illustrated. The oxide catalyst prior to the olefin gas phase catalytic oxidation reaction in Example C1 had a CoMoO4 XRD peak (002) at 20 = 26.46 °, and the oxide catalyst after reaction had a CoMoO4 XRD peak (002) at 20 = 26.34 °. It was thus found that the divalent Fe was dissolved in solid in COM004.
[00362] In Figure 14, the XRD (20 = 10 to 60 °) of the oxide catalyst before and after the olefin gas phase catalytic oxidation reaction in Comparative Example C1 is illustrated. In Figure 15, an enlarged graph for the range of 20 = 25 to 27 ° in Figure 14 is illustrated. The oxide catalyst prior to the olefin gas phase catalytic oxidation reaction in Comparative Example C1 had an XMD peak of CoMoO4 (002) at 20 = 26.46 °, and the oxide catalyst after reaction had an XRD peak of CoMoO4 (002) at 20 = 26.46 °. It was thus found that bivalent Fe was not dissolved in solid in CoMoO4. This was attributed to the atomic ratio of iron to cobalt (b / c), not taking into account the following expression: b / c> 1. <X-ray diffraction peaks of the catalysts obtained in Example C1 and Comparative Example C2>
[00363] In Figure 16, the X-ray diffraction peaks of the catalysts obtained in Example C1 and Comparative Example C2 are illustrated. In Figure 16, it was illustrated that the catalyst obtained in Example C1 has X-ray diffraction peaks at least 20 = 18.32 ° for plane (101), 28.18 ° for plane (112), 33.66 ° for plane (200), and 46.12 °, with a peak intensity ratio (la / lb) = 3.2, where la represents the peak intensity at 20 = 33.66 ° and lb represents the intensity of peak at 20 = 34.06 °. It can be assumed that the disordered phase crystal structure of Bi3. xAxFeiMo2O <2 was formed on the catalyst obtained in Example C1.
[00364] In X-ray diffraction of the catalyst obtained in Comparative Example C2, no peak was observed at 18.30 ° ± 0.05 ° for plane (101), 28.20 ° 0.05 ° for plane (112 ), 33.65 ° ± 0.05 ° for plane (200), and 46.15 ° ± 0.05 ° for plane (204). It can therefore be assumed that the disordered phase crystal structure of Bi3.xAxFeiMo2Oi2 was not formed on the catalyst obtained in Comparative Example C2.
[00365] The comparison of X-ray diffraction between the catalysts obtained in Example C1 and Comparative Example C2 are as follows. Corresponding to the peak at 18.30 ° ± 0.05 ° for plane (101) of the catalyst obtained in Example C1, split peaks were observed at 18.06 ° for (310) plane and 18.44 ° for plane (111) in the catalyst obtained in Comparative Example C2. Corresponding to the peak at 28.20 ° ± 0.05 ° for plane (112) of the catalyst obtained in Example C1, split peaks were observed at 28.00 ° for plane (221) and 28.32 ° for plane (42- 1) in the catalyst obtained in Comparative Example C2. Corresponding to the peak at 33.65 ° ± 0.05 ° for plane (200) of the catalyst obtained in Example C1, split peaks were observed at 33.52 ° for plane (600) and 33.98 ° for plane (202) in the catalyst obtained in Comparative Example C2. Corresponding to the peak at 46.15 ° ± 0.05 ° for plane (204) of the catalyst obtained in Example C1, divided peaks were observed at 45.82 ° for plane (640) and 46.40 ° for plane (242) in the catalyst obtained in Comparative Example C2. with a peak intensity ratio (la / lb) = 0.94, where la represents the peak intensity at 20 = 33.52 ° and lb represents the peak intensity at 20 = 33.98 °, you can suppose that an ordered phase was formed on the catalyst obtained in Comparative Example C2 instead of a disordered Bi3.xAxFeiMo2Oi2de phase.
[00366] This application is based on Japanese patent application No. 2012-216071 filed on December 28, 2012, with the Japanese Patent Office, Japanese patent application No. 2012-253243 filed on November 19, 2012, with the Japanese Patent Institute, and Japanese patent application No. 2013-033663 filed on February 22, 2013 with the Japanese Patent Institute, the contents of which are incorporated herein by reference. INDUSTRIAL APPLICABILITY
[00367] The present invention is industrially applicable to an oxide catalyst for use in the production of unsaturated aldehyde or diolefin from olefin and / or alcohol.

权利要求:
Claims (13)
[0001]
1. Oxide catalyst for use in the production of unsaturated aldehyde, diolefin, or unsaturated nitrile from olefin and / or alcohol, characterized by the fact that it meets the following conditions (1) to (3): (1) the catalyst of oxide comprises molybdenum, bismuth, iron, cobalt and an element A having an ionic radius greater than 0.96 A, with the exception of potassium, cesium and rubidium; (2) the atomic ratio a of bismuth to 12 molybdenum atoms is 1 <to <5, the atomic ratio b of iron to 12 molybdenum atoms is 1.5 <b <6, the atomic ratio c of element A to 12 molybdenum atoms is 1 <c <5, and the atomic ratio d of cobalt to 12 molybdenum atoms is 1 <d <8; and (3) the oxide catalyst comprises a disordered phase consisting of a crystal system comprising molybdenum, bismuth, iron and element A.
[0002]
2. Oxide catalyst according to claim 1, characterized by the fact that the oxide catalyst has a single peak in each range of diffraction angles (20) of 18.30 ° ± 0.2 °, 28.20 ° ± 0.2 °, 33.65 ° ± 0.2 °, and 46.15 ° ± 0.2 ° in X-ray diffraction, and that the intensity ratio (la / lb) of the intensity (la) of peak aa 20 = 33.65 ° ± 0.2 ° for peak intensity (lb) ba 20 = 34.10 ° ± 0.2 ° is 2.0 or greater.
[0003]
3. Oxide catalyst according to claim 1 or 2, characterized in that the oxide catalyst has a composition represented by the following composition formula (1):
[0004]
An oxide catalyst according to any one of claims 1 to 3, characterized in that it further comprises at least one element selected from the group consisting of silica, alumina, titania, and zirconia as a support.
[0005]
5. Method for the production of an oxide catalyst, characterized by the fact that it comprises: a mixing step to mix the starting material constituted by the catalyst, comprising molybdenum, bismuth, iron, cobalt, and element A having an ionic radius greater than 0.96 A, with the exception of potassium, cesium and rubidium, to obtain a slurry; a drying step to dry the slurry thus obtained to obtain a dried product; and a calcination step to calcine the dry product thus obtained, the calcination step comprising a heating step to gradually heat the dry product from 100 ° C to 200 ° C over 1 hour or more.
[0006]
6. Method for producing the oxide catalyst according to claim 5, characterized in that the slurry has a pH of 8 or less.
[0007]
7. Method for producing the oxide catalyst according to claim 5 or 6, characterized by the fact that the calcination step comprises: a preliminary calcination step to preliminarily calcine the dry product at a temperature of 200 to 300 ° C to obtain a preliminarily calcined product; and a final calcination step to finally calcinate the preliminarily calcined product thus obtained at a temperature of 300 ° C or higher to obtain the catalyst.
[0008]
8. Method for producing unsaturated aldehyde, characterized in that it comprises a step of producing unsaturated aldehyde from oxidation of olefin and / or alcohol using the oxide catalyst, defined according to any one of claims 1 to 4, to obtain unsaturated aldehyde.
[0009]
Method for producing unsaturated aldehyde according to claim 8, characterized by the fact that olefin and / or alcohol are at least one compound selected from a group consisting of propylene, isobutylene, propanol, isopropanol, isobutanol, and t alcohol -butyl.
[0010]
Method for producing unsaturated aldehyde according to claim 8 or 9, characterized in that the step of producing the unsaturated aldehyde comprises a discharge step to discharge a product gas comprising the unsaturated aldehyde from a fluidized bed reactor through the gas phase catalytic oxidation reaction of olefin and / or alcohol with an oxygen source in the fluidized bed reactor.
[0011]
Method for producing unsaturated aldehyde according to any one of claims 8 to 10, characterized in that the catalytic oxidation reaction in the gas phase is carried out at a reaction temperature of 400 to 500 ° C, and the product gas discharged The fluidized bed reactor has an oxygen concentration of 0.03 to 0.5%, by volume.
[0012]
12. Method for producing diolefin, characterized in that it comprises a step of production of diolefin by oxidation of mono-olefin having 4 or more carbon atoms using the oxide catalyst, defined according to any one of claims 1 to 4, to obtain the diolefin.
[0013]
13. Method for producing unsaturated nitrile, characterized by the fact that it comprises a step of producing unsaturated nitrile by reacting at least one compound selected from a group consisting of propylene, isobutylene, propanol, isopropanol, isobutanol, and t-butyl alcohol , with molecular oxygen and ammonia in a fluidized bed reactor, using the oxide catalyst, defined according to any one of claims 1 to 4, to obtain unsaturated nitrile.

类似技术:

---

公开号 | 公开日 | 专利标题

---

BR112015006012B1|2020-11-10|oxide catalyst and method for producing the same, and methods for producing unsaturated aldehyde, diolefin and unsaturated nitrile

---

Madeira et al.2004|Nickel molybdate catalysts and their use in the selective oxidation of hydrocarbons

---

KR100373572B1|2003-04-21|Dehydrogenation catalyst and process

---

US5885922A|1999-03-23|Multimetal oxide materials

---

KR20140108264A|2014-09-05|Zinc and/or manganese aluminate catalyst useful for alkane dehydrogenation

---

EP2922633B1|2020-05-06|Process for the preparation of mixed metal oxide ammoxidation catalysts

---

CN102625793A|2012-08-01|Catalyst and method for partially oxidizing hydrocarbons

---

EP3263213B1|2020-02-12|Catalyst for manufacturing unsaturated aldehyde and/or unsaturated carboxylic acid and manufacturing method of same, and manufacturing method of unsaturated aldehyde and/or unsaturated carboxylic acid

---

JP2009220008A|2009-10-01|Catalyst for acrylonitrile synthesis and manufacturing method of acrylonitrile

---

WO2017069119A1|2017-04-27|Catalyst for conjugated diolefin production, and method for producing same

---

JP4588533B2|2010-12-01|Catalyst for acrylonitrile synthesis

---

EP3233272B1|2020-07-29|Improved mixed metal oxide ammoxidation catalysts

---

JP6672556B2|2020-03-25|Method for producing butadiene with excellent catalyst reproducibility

---

JP6526062B2|2019-06-05|Improved selective ammoxidation catalyst

---

CN107614106B|2020-10-30|Catalyst for oxidative dehydrogenation and preparation method thereof

---

JP6758514B2|2020-09-23|Catalyst, catalyst manufacturing method, acrylonitrile manufacturing method

---

JP6973828B2|2021-12-01|Method of filling catalyst and method of producing butadiene using this

---

JP2008194634A|2008-08-28|Production method of catalyst for producing acrylonitrile and production method of acrylonitrile

---

JP4606897B2|2011-01-05|Method for producing composite oxide catalyst for fluidized bed ammoxidation process

---

WO2016140263A1|2016-09-09|Conjugated-diolefin-producing catalyst, and production method therefor

---

JP6994807B2|2022-02-21|Method for producing a catalyst for producing a conjugated diolefin

---

US10647638B2|2020-05-12|Method for producing butadiene

---

JP2021000610A|2021-01-07|Catalyst and production method thereof

---

JP2021133272A|2021-09-13|Catalyst precursor and complex oxide catalyst

---

KR20180048353A|2018-05-10|Catalyst for reducing selectively inhibitor in purification system and method for producing same

同族专利:

---

公开号 | 公开日

---

BR112015006012A2|2017-07-04|

---

TW201420185A|2014-06-01|

---

US20150238939A1|2015-08-27|

---

KR101741930B1|2017-05-30|

---

EP2902106A4|2015-10-21|

---

KR20150046224A|2015-04-29|

---

RU2615762C2|2017-04-11|

---

JP5908595B2|2016-04-26|

---

TWI511784B|2015-12-11|

---

CN104661747B|2017-02-15|

---

US9364817B2|2016-06-14|

---

EP2902106A1|2015-08-05|

---

JPWO2014051090A1|2016-08-25|

---

MY177749A|2020-09-23|

---

RU2015109709A|2016-11-20|

---

CN104661747A|2015-05-27|

---

SG11201501592QA|2015-05-28|

---

WO2014051090A1|2014-04-03|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

JPS5222359B2|1972-05-23|1977-06-16|

---

GB2033775B|1978-10-13|1983-02-09|Asahi Chemical Ind|Catalysts and process for the production of methacrolein catalysts|

---

US4424141A|1981-01-05|1984-01-03|The Standard Oil Co.|Process for producing an oxide complex catalyst containing molybdenum and one of bismuth and tellurium|

---

US4388223A|1981-04-06|1983-06-14|Euteco Impianti S.P.A.|Catalyst for the conversion of unsaturated hydrocarbons into diolefins or unsaturated aldehydes and nitriles, and process for preparing the same|

---

JPS6126419B2|1981-10-20|1986-06-20|Asahi Chemical Ind|

---

JPS6112488A|1984-06-28|1986-01-20|Nippon Kokan Kk <Nkk>|Method of building living quarter in ship|

---

JP3154798B2|1992-03-12|2001-04-09|三菱レイヨン株式会社|Method for producing catalyst for synthesizing unsaturated aldehydes and unsaturated carboxylic acids|

---

RU2077528C1|1992-06-22|1997-04-20|Дзе Стандарт Ойл Компани|Method for production of unsaturated nitriles and catalyst for their production|

---

US5728894A|1994-06-22|1998-03-17|Ashahi Kasei Kogyo Kabushiki Kaisha|Method for producing methacrolein|

---

JP4995373B2|2001-02-20|2012-08-08|三菱レイヨン株式会社|Reaction tube, method for producing catalyst, method for producing unsaturated aldehyde and unsaturated carboxylic acid|

---

US7012039B2|2001-12-21|2006-03-14|Asahi Kasei Chemicals Corporation|Oxide catalyst composition|

---

MY139735A|2003-11-18|2009-10-30|Basf Ag|Preparation of acrolein by heterogeneously catalyzed partial gas phase oxidation of propene|

---

JP5188005B2|2004-08-30|2013-04-24|旭化成ケミカルズ株式会社|Metal oxide catalyst, method for producing the catalyst, and method for producing nitrile|

---

US8088947B2|2006-04-03|2012-01-03|Nippon Kayaku Kabushiki Kaisha|Method for producing methacrolein and/or methacrylic acid|

---

CN101385978B|2007-09-12|2011-04-20|上海华谊丙烯酸有限公司|Catalyst for synthesizing methylacrolein and preparation method thereof|

---

JP5371692B2|2008-10-24|2013-12-18|旭化成ケミカルズ株式会社|Method for producing conjugated diolefin|

---

JP5409100B2|2009-04-27|2014-02-05|旭化成ケミカルズ株式会社|Catalyst for producing acrylonitrile and method for producing the same|

---

JP5547922B2|2009-07-31|2014-07-16|住友化学株式会社|Method for producing composite oxide containing molybdenum and cobalt|

---

JP5387297B2|2009-09-30|2014-01-15|住友化学株式会社|Method for producing composite oxide catalyst|

---

JP5586382B2|2010-08-30|2014-09-10|株式会社日本触媒|Method for producing catalyst for producing unsaturated aldehyde and / or unsaturated carboxylic acid, catalyst therefor, and method for producing acrolein and / or acrylic acid using the catalyst|

---

JP5253480B2|2010-11-01|2013-07-31|日立オートモティブシステムズ株式会社|Fuel injection valve|

---

KR101603394B1|2011-06-28|2016-03-14|아사히 가세이 케미칼즈 가부시키가이샤|Oxide catalyst|

---

US9433929B2|2011-09-21|2016-09-06|Ineos Europe Ag|Mixed metal oxide catalysts|

---

JP6501799B2|2014-05-29|2019-04-17|イネオス ユーロープ アクチェンゲゼルシャフト|Improved selective ammoxidation catalyst|EP2837422B1|2013-05-06|2021-02-24|LG Chem, Ltd.|Oxidation catalyst for preparing butadiene and method for preparing same|

---

KR101495478B1|2013-05-06|2015-02-23|주식회사 엘지화학|oxidation catalyst for production of butadiene and method of preparing the same|

---

CN103949262A|2014-04-21|2014-07-30|武汉凯迪工程技术研究总院有限公司|Structured iron-based catalyst for preparing alpha-alkene by synthesis gas as well as preparation method and application of structured iron-based catalyst|

---

JP6526062B2|2014-05-29|2019-06-05|イネオス ユーロープ アクチェンゲゼルシャフト|Improved selective ammoxidation catalyst|

---

US9815045B2|2015-03-23|2017-11-14|Clariant Corporation|Metal oxide catalyst material and processes for making and using same|

---

JP6559039B2|2015-10-19|2019-08-14|日本化薬株式会社|Conjugated diolefin production catalyst and production method thereof|

---

JP6579010B2|2016-03-23|2019-09-25|三菱ケミカル株式会社|Composite oxide catalyst and method for producing conjugated diene|

---

CN107921428B|2016-04-27|2019-07-09|旭化成株式会社|The manufacturing method of ammoxydation catalyst and the manufacturing method of acrylonitrile|

---

JP6722284B2|2016-06-14|2020-07-15|旭化成株式会社|Method for producing ammoxidation catalyst and method for producing acrylonitrile|

---

JP6392488B1|2016-12-26|2018-09-19|日本化薬株式会社|Catalyst for producing conjugated diolefin and method for producing the same|

---

US10640458B2|2017-06-09|2020-05-05|Asahi Kasei Kabushiki Kaisha|Process for producing unsaturated nitrile|

---

EP3470392B1|2017-07-03|2021-06-30|Asahi Kasei Kabushiki Kaisha|Method for producing unsaturated nitrile|

---

EP3778012A4|2018-03-30|2021-06-09|Asahi Kasei Kabushiki Kaisha|Catalyst, method for manufacturing catalyst, method for manufacturing acrylonitrile|

---

JP6758514B2|2018-04-13|2020-09-23|旭化成株式会社|Catalyst, catalyst manufacturing method, acrylonitrile manufacturing method|

---

WO2020039985A1|2018-08-24|2020-02-27|旭化成株式会社|Method for producing ammoxidation catalyst, and method for producing acrylonitrile|

---

WO2021044918A1|2019-09-02|2021-03-11|Jsr株式会社|Method for producing 1,3-butadiene|

---

WO2021066411A1|2019-09-30|2021-04-08|주식회사 엘지화학|Catalyst for ammoxidation of propylene, preparation method therefor, and method for ammoxidation of propylene using same|

---

JP6932292B1|2020-01-10|2021-09-08|日本化薬株式会社|Catalysts, catalyst filling methods, and methods for producing compounds using catalysts.|

---

EP3967398A1|2020-01-10|2022-03-16|Nippon Kayaku Kabushiki Kaisha|Catalyst, method for producing compound using same, and compound|

法律状态:
2018-11-21| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

---

2019-08-27| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

---

2020-06-09| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

---

2020-11-10| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 27/09/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

---

申请号 | 申请日 | 专利标题

---

JP2012216071|2012-09-28|

---

JP2012-216071|2012-09-28|

---

JP2012-253243|2012-11-19|

---

JP2012253243|2012-11-19|

---

JP2013-033663|2013-02-22|

---

JP2013033663|2013-02-22|

---

PCT/JP2013/076364|WO2014051090A1|2012-09-28|2013-09-27|Oxide catalyst, method for producing same, and method for producing unsaturated aldehyde, diolefin or unsaturated nitrile|

---