Catalyst and Butadiene Production Method

Abstract

To provide a catalyst capable of producing butadiene with ethanol as a raw material with a higher yield (conversion rate of ethanol and / or selection rate of butadiene), and a producing method of butadiene using such catalyst.SOLUTION: According to one aspect of the present invention, a catalyst is provided for use in producing butadiene directly from ethanol. The catalyst in this catalyst has an active component that exhibits catalytic activity. The active component includes an element A selected from elements belonging to group 3 of the periodic table, an element B selected from elements belonging to group 4 of the periodic table, and an element C selected from elements belonging to group 12 of the periodic table, and an element D selected from elements belonging to groups 5 and 11 of the periodic table.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a catalyst and a method for producing butadiene, and more particularly to a catalyst capable of directly producing butadiene from ethanol, and a method for producing butadiene using such a catalyst.

Background Art

[0002] In recent years, production of butadiene, which is useful as a raw material for synthetic rubber, from ethanol has been studied (see Patent Document 1). The catalyst described in Patent Document 1 is a solid catalyst obtained by supporting a metal (A), a metal (B) and a metal (C) on a carrier. In such a solid catalyst, the metal (A) is a metal selected from Group 12, the metal (B) is a metal selected from Group 4, and the metal (C) is at least one metal selected from the group consisting of Group 2, scandium, cerium, neodymium, gadolinium, Group 6, Group 7, Group 9, palladium, and Group 13.

Prior Art Literature

Patent Literature

[0003]

Patent Document 1

Summary of the Invention

Problem to be Solved by the Invention

[0004] Even with the catalyst described in Patent Document 1, butadiene can be produced with a relatively high yield, and development of a catalyst with a higher butadiene productivity is desired. In view of the above circumstances, the present invention aims to provide a catalyst capable of producing butadiene from ethanol as a raw material at a higher yield (ethanol conversion rate and / or butadiene selectivity), and a method for producing butadiene using such a catalyst.

Means for Solving the Problem

[0005] According to one aspect of the present invention, a catalyst is provided for use in directly producing butadiene from ethanol. The catalyst in this catalyst has an active component that exhibits catalytic activity. The active component includes element A selected from elements belonging to Group 3 of the periodic table, element B selected from elements belonging to Group 4 of the periodic table, element C selected from elements belonging to Group 12 of the periodic table, and element D selected from elements belonging to Groups 5 and 11 of the periodic table.

[0006] According to this embodiment, butadiene can be produced directly from ethanol in a higher yield. [Modes for carrying out the invention]

[0007] The catalyst and the method for producing butadiene of the present invention will be described in detail below based on preferred embodiments. 1.1 Catalyst The catalyst of the present invention is used to directly produce butadiene from ethanol (i.e., used in the butadiene production method of the present invention). Preferably, in this case, ethanol is directly converted to butadiene by passing a gas containing ethanol through a reaction bed (reaction vessel) which is filled with the catalyst of the present invention in a reaction tube.

[0008] The catalyst of the present invention has an active component (catalyst component) that exhibits catalytic activity. This active ingredient contains element A, selected from the elements belonging to Group 3 of the periodic table; element B, selected from the elements belonging to Group 4 of the periodic table; element C, selected from the elements belonging to Group 12 of the periodic table; and element D, selected from the elements belonging to Groups 5 and 11 of the periodic table. A catalyst containing such elements A to D can be used to produce butadiene from ethanol in a sufficiently high yield.

[0009] Here, the yield of butadiene from ethanol is calculated by multiplying the percentage of ethanol converted to other compounds (ethanol conversion rate) by the percentage of butadiene in the other compounds converted (butadiene selectivity). Therefore, a high yield of butadiene includes cases where the conversion rate of ethanol is high, where the selectivity of butadiene is high, and where both the conversion rate of ethanol and the selectivity of butadiene are high.

[0010] [Element A] Element A is an element selected from the elements belonging to Group 3 of the periodic table. In the following, "elements belonging to Group X of the periodic table" will simply be referred to as "Group X elements." Examples of Group 3 elements include scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), samarium (Sm), and gadolinium (Gd). Among these, yttrium and lanthanum are preferred as Group 3 elements because they yield a higher yield of butadiene.

[0011] The amount of yttrium contained in the active ingredient is preferably 2 mol% to 25 mol%, and more preferably 7 mol% to 25 mol%. The amount of lanthanum contained in the active ingredient is preferably 0 mol% to 20 mol%, more preferably 0 mol% to 13 mol%, even more preferably 0 mol% to 12 mol%, and particularly preferably 0 mol% to 10 mol%. Furthermore, the amount of Group 3 elements contained in the active ingredient is preferably 9 mol% to 32% mol%, more preferably 9 mol% to 29 mol%, even more preferably 14 mol% to 29 mol%, and particularly preferably 14 mol% to 25 mol%.

[0012] [Element B] Element B is an element selected from the elements of Group 4. Examples of Group 4 elements include titanium (Ti), zirconium (Zr), and hafnium (Hf). Among these, zirconium and hafnium are preferred as Group 4 elements because they yield a higher yield of butadiene.

[0013] The amount of zirconium contained in the active ingredient is preferably 0 mol% or more and 33 mol% or less, more preferably 0 mol% or more and 18 mol% or less, and even more preferably 0 mol% or more and 14 mol% or less. The amount of hafnium contained in the active ingredient is preferably 0 mol% or more and 24 mol% or less, and more preferably 7 mol% or more and 24 mol% or less. Further, the amount of the Group 4 element contained in the active ingredient is preferably 4 mol% or more and 42 mol% or less, more preferably 7 mol% or more and 38 mol% or less, even more preferably 7 mol% or more and 32 mol% or less, and particularly preferably 7 mol% or more and 27 mol% or less.

[0014] Element C Element C is an element selected from Group 12 elements. Examples of the Group 12 element include zinc (Zn), cadmium (Cd), mercury (Hg), and the like. Among these, zinc is preferred as the Group 12 element because it provides a higher yield of butadiene.

[0015] The amount of zinc contained in the active ingredient is preferably 1 mol% or more and 26 mol% or less, more preferably 6 mol% or more and 26 mol% or less, and even more preferably 6 mol% or more and 16 mol% or less. Further, the amount of the Group 12 element contained in the active ingredient is preferably 1 mol% or more and 26 mol% or less, more preferably 6 mol% or more and 26 mol% or less, and even more preferably 6 mol% or more and 16 mol% or less.

[0016] The total amount of element A, element B, and element C contained in the active ingredient is preferably 40 mol% or more, more preferably 45 mol% or more and 80 mol% or less, even more preferably 50 mol% or more and 75 mol% or less, and particularly preferably 55 mol% or more and 70 mol% or less. In this case, the yield of butadiene (particularly, the conversion rate of ethanol) can be further increased.

[0017] [Element D] Element D is an element selected from Group 5 elements and Group 11 elements. Examples of the Group 5 element include vanadium (V), niobium (Nb), tantalum (Ta), and the like. Examples of the Group 11 element include copper (Cu), silver (Ag), gold (Au), and the like. Among these, niobium is preferable as the Group 5 element, and copper and silver are preferable as the Group 11 element, because these can further increase the yield of butadiene.

[0018] The content of niobium contained in the active ingredient is preferably 0 mol% or more and 12 mol% or less, more preferably 1 mol% or more and 12 mol% or less. Furthermore, the content of the Group 5 element contained in the active ingredient is preferably 0 mol% or more and 12 mol% or less, more preferably 1 mol% or more and 12 mol% or less.

[0019] The content of copper contained in the active ingredient is preferably 0 mol% or more and 20 mol% or less, more preferably 5 mol% or more and 8 mol% or less, and even more preferably 7 mol% or more and 8 mol% or less. The content of silver contained in the active ingredient is preferably 0 mol% or more and 12 mol% or less, more preferably 0 mol% or more and 7 mol% or less, and even more preferably 4 mol% or more and 7 mol% or less. Furthermore, the content of the Group 11 element contained in the active ingredient is preferably 0 mol% or more and 27 mol% or less, more preferably 4 mol% or more and 24 mol% or less, even more preferably 7 mol% or more and 15 mol% or less, and particularly preferably 11 mol% or more and 15 mol% or less.

[0020] [Element E] From the viewpoint of further increasing the yield of butadiene, it is preferable that the active ingredient further contains Element E. Element E is an element selected from Group 6 elements. Examples of the Group 6 element include chromium (Cr), molybdenum (Mo), tungsten (W), and the like. Among these, chromium and molybdenum are preferred as Group 6 elements because they yield a higher yield of butadiene.

[0021] The amount of chromium contained in the active ingredient is preferably 0 mol% to 12 mol%, more preferably 0 mol% to 9 mol%, and even more preferably 0 mol% to 1 mol%. The amount of molybdenum contained in the active ingredient is preferably 0 mol% to 14 mol%, more preferably 0 mol% to 12 mol%, and even more preferably 0 mol% to 1 mol%. Furthermore, the amount of Group 6 elements contained in the active ingredient is preferably 0 mol% to 24 mol%, more preferably 1 mol% to 10 mol%, and even more preferably 1 mol% to 2 mol%.

[0022] [Element F] From the viewpoint of further increasing the yield of butadiene, it is preferable that the active ingredient further contains element F. Element F is an element selected from Group 2 elements. Group 2 elements include beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba). Among these, magnesium is preferred as the group 2 element because it yields a higher yield of butadiene.

[0023] The amount of magnesium contained in the active ingredient is preferably 0 mol% to 26 mol%, and more preferably 8 mol% to 26 mol%. Furthermore, the amount of Group 2 elements contained in the active ingredient is preferably 0 mol% to 26 mol%, and more preferably 8 mol% to 26 mol%.

[0024] [Element G] From the viewpoint of further increasing the yield of butadiene, it is preferable that the active ingredient further contains element G. Element G is an element selected from Group 13 elements. Group 13 elements include boron (B), aluminum (Al), gallium (Ga), indium (In), and thallium (Tl). Among these, aluminum and gallium are preferred as Group 13 elements because they yield a higher yield of butadiene.

[0025] The amount of aluminum contained in the active ingredient is preferably 0 mol% to 10 mol%, more preferably 0 mol% to 9 mol%, even more preferably 0 mol% to 8 mol%, and particularly preferably 0 mol% to 7 mol%. The amount of gallium contained in the active ingredient is preferably 0 mol% to 43 mol%, more preferably 0 mol% to 8 mol%, even more preferably 0 mol% to 2 mol%, and particularly preferably 1 mol% to 2 mol%. Furthermore, the amount of Group 13 elements contained in the active ingredient is preferably 0 mol% to 47 mol%, more preferably 0 mol% to 13 mol%, even more preferably 0 mol% to 10 mol%, and particularly preferably 2 mol% to 4 mol%.

[0026] [Element H] From the viewpoint of further increasing the yield of butadiene, it is preferable that the active ingredient further contains the element H. Element H is an element selected from the elements of Group 10. Examples of Group 10 elements include nickel (Ni), palladium (Pd), and platinum (Pt). Among these, nickel is preferred as the Group 10 element because it yields a higher yield of butadiene.

[0027] The amount of nickel contained in the active ingredient is preferably 0 mol% to 16 mol%, and more preferably 0 mol% to 8 mol%. Furthermore, the amount of Group 10 elements contained in the active ingredient is preferably 0 mol% to 16 mol%, and more preferably 0 mol% to 8 mol%.

[0028] Combinations of elements that yield catalysts with particularly high butadiene yields include: I: A combination of elements A (Group 3 elements), B (Group 4 elements), C (Group 12 elements), D (Group 5 elements and / or Group 11 elements), E (Group 6 elements), F (Group 2 elements), and G (Group 13 elements). II: Combinations of elements A (Group 3 elements), B (Group 4 elements), C (Group 12 elements), D (Group 5 and / or Group 11 elements), E (Group 6 elements), F (Group 2 elements), G (Group 13 elements), and H (Group 10 elements). III: Combinations of elements A (Group 3 elements), B (Group 4 elements), C (Group 12 elements), D (Group 5 elements and / or Group 11 elements), F (Group 2 elements), and G (Group 13 elements). IV: Combinations of elements A (Group 3 elements), B (Group 4 elements), C (Group 12 elements), D (Group 5 elements and / or Group 11 elements), E (Group 6 elements), G (Group 13 elements), and H (Group 10 elements). V: A combination of elements A (Group 3 elements), B (Group 4 elements), C (Group 12 elements), D (Group 5 elements and / or Group 11 elements), E (Group 6 elements), F (Group 2 elements), and H (Group 10 elements). These are some examples.

[0029] Among these, the combination of elements II is preferred: element A (group 3 element), element B (group 4 element), element C (group 12 element), element D (group 5 element and / or group 11 element), element E (group 6 element), element F (group 2 element), element G (group 13 element), and element H (group 10 element), and the combination of element A (group 3 element), element B (group 4 element), element C (group 12 element), element D (group 5 and group 11 element), element E (group 6 element), element F (group 2 element), element G (group 13 element), and element H (group 10 element).

[0030] The amount of each element contained in the active ingredient is preferably in the range of 1, more preferably in the range of 2, even more preferably in the range of 3, particularly preferably in the range of 4, and most preferably in the range of 5, as shown in Table 1 below. In Table 1, "Y~Z" indicates a range between Y and Z. The same applies hereafter. [Table 1]

[0031] Preferred combinations of elements include magnesium (Mg), zinc (Zn), copper (Cu), silver (Ag), nickel (Ni), aluminum (Al), lanthanum (La), yttrium (Y), hafnium (Hf), zirconium (Zr), chromium (Cr), gallium (Ga), niobium (Nb), and molybdenum (Mo).

[0032] The amount of each element contained in the active ingredient is preferably in the range of 1, more preferably in the range of 2, even more preferably in the range of 3, particularly preferably in the range of 4, and most preferably in the range of 5, as shown in Table 2 below. [Table 2]

[0033] The catalyst of the present invention may consist of an active component alone, or it may consist of an active component and a carrier supporting the active component. In this case, the shape retention of the catalyst can be further improved, and the specific surface area of ​​the catalyst can be easily adjusted. When the catalyst has a support, the amount of active ingredient loaded onto 1 g of the support (hereinafter also referred to as "loading amount") is preferably 1.05 mmol or more and 1.56 mmol or less, more preferably 1.05 mmol or more and 1.47 mmol or less, and even more preferably 1.05 mmol or more and 1.46 mmol or less. If the loading amount of the active ingredient in the catalyst is within the above range, the yield of butadiene can be further improved while maintaining its high shape retention.

[0034] The constituent material of the support can be any compound that is not easily modified by contact with gases containing ethanol or by reaction conditions, and is not particularly limited. Examples include inorganic materials such as oxides, nitrides, oxynitrides, and carbides, and carbon materials (graphite, graphene, etc.). Among these, the support material is preferably an oxide, more preferably an oxide containing at least one of magnesium (Mg), titanium (Ti), zirconium (Zr), aluminum (Al), and silicon (Si), and even more preferably silicon oxide. These oxides are preferred because they have high thermal stability and can stably support active ingredients.

[0035] The carrier may be a dense material, but it is preferably a porous material. In this case, the average pore diameter of the support is preferably 2 nm to 50 nm, more preferably 2 nm to 30 nm, and even more preferably 2 nm to 15 nm. In this case, the amount of active ingredient supported can be sufficiently increased to further improve the yield of butadiene by catalyst. The total pore volume of the support is preferably 0.1 mL / g or more and 2 mL / g or less, more preferably 0.5 mL / g or more and 2 mL / g or less, and even more preferably 0.75 mL / g or more and 2 mL / g or less. In this case, the gas containing ethanol can be introduced into the interior of the catalyst, and a sufficient contact area between ethanol and the active ingredient can be secured, thereby further increasing the yield of butadiene.

[0036] Furthermore, the BET specific surface area of ​​the carrier is 50 m². 2 / g or more 1200m 2 It is preferable that the amount be less than or equal to 50m 2 / g or more 1000m 2 It is more preferable that it be less than or equal to / g, and 100m 2 / g or more 1000m 2 It is even more preferable that the BET specific surface area is less than or equal to / g. If the BET specific surface area is within the above range, the above effect can be further improved. Furthermore, while the shape of the carrier is not particularly limited, granular shape is preferred, for example. Here, "granular" is a concept that includes powder, particulate, lump, pellet, etc., and its form can be spherical, plate-like, polygonal, crushed, columnar, needle-like, or flaky.

[0037] The average particle size of the support material is preferably 1 μm or more and 10 mm or less, more preferably 100 μm or more and 10 mm or less, and even more preferably 100 μm or more and 5 mm or less. With a catalyst having such an average particle size, it is easy to adjust its BET specific surface area to the above range. In this specification, the average particle size refers to the average value of the particle sizes of any 200 carriers within a single field of view observed with an electron microscope. In this case, "particle size" refers to the maximum distance between any two points on the contour line of the carrier. If the carrier is columnar, the maximum distance between any two points on the contour line of its end face is defined as the "particle size." Furthermore, the average particle size refers to the average particle size of secondary particles when primary particles are aggregated, for example, in a clump-like structure.

[0038] The yield of butadiene by the catalyst of the present invention is preferably 40% or more, more preferably 45% or more, more preferably 50% or more, even more preferably 55% or more, even more preferably 60% or more, particularly preferably 65% ​​or more, and most preferably 70% or more. Furthermore, no catalyst has been found to date that can produce such a high yield of butadiene.

[0039] 1.2 Method for producing catalysts Next, we will explain the method for producing the catalyst. The method for producing the catalyst is not particularly limited, but examples include impregnation, sol-gel, coprecipitation, solid-phase, and hydrothermal synthesis. The catalyst can be manufactured, for example, as follows: First, a solution is prepared by dissolving salts of the elements (constituent elements) that make up the active component in a suitable solvent. Next, a support is added to this solution as needed, and then the metal salt is impregnated by heating and drying under reduced pressure while stirring. After that, if necessary, it is dried at a temperature higher than the heating temperature and then calcined. In other words, the catalyst of the present invention can be manufactured easily and reliably by the so-called impregnation method. Furthermore, the solution may contain, for example, citric acid, acetic acid, malic acid, tartaric acid, hydrochloric acid, nitric acid, or mixtures thereof.

[0040] Examples of salts of the constituent elements include nitrates, sulfates, chlorides, hydroxides, carbonates, or compound thereof, but nitrates and chlorides are preferred among these. Hydrates may also be used as elemental salts as needed. In the case of nitrates, water is preferably used as the solvent. In the case of chlorides, alcohols such as ethanol are preferably used as the solvent.

[0041] The temperature during impregnation (drying temperature) is preferably 20°C to 150°C, more preferably 50°C to 100°C. When the solvent is water, the drying temperature is about 90°C, and when the solvent is ethanol, it is about 70°C. Furthermore, the impregnation time (drying time) is preferably 0.5 hours or more and 15 hours or less, more preferably 1 hour or more and 10 hours or less. This drying method allows for uniform drying of the metal salt-impregnated carrier. Drying can be performed under atmospheric pressure or under reduced pressure, but it is preferable to perform it under reduced pressure.

[0042] The firing temperature of the carrier impregnated with the metal salt is preferably 200°C to 800°C, and more preferably 300°C to 600°C. The calcination time for the carrier impregnated with the metal salt is preferably 1 hour to 24 hours, more preferably 1.5 hours to 20 hours. The metal salt can be converted into an active component by calcination. Furthermore, calcination under the above conditions can prevent excessive particle growth of the active component (catalyst). Until the above firing temperature is reached, the heating rate should be increased at a rate of 1°C / min to 20°C / min, preferably 2°C / min to 10°C / min. This promotes the growth of the active component (catalyst) particles and also helps to avoid cracking of the crystals (particles).

[0043] Specific examples of salts of constituent elements include, for example, magnesium(II) nitrate hexahydrate, zinc nitrate hexahydrate, copper(II) nitrate trihydrate, silver nitrate, nickel(II) nitrate hexahydrate, aluminum nitrate notahydrate, lanthanum(III) nitrate hexahydrate, yttrium(III) nitrate hexahydrate, hafnium(IV) chloride, zirconium nitrate dihydrate, zirconium(IV) chloride, zirconium oxychloride octahydrate, chromium(III) nitrate notahydrate, chromium(III) chloride hexahydrate, gallium(III) nitrate, niobium(V) chloride, molybdenum(V) chloride, and so on.

[0044] [Method for producing butadiene] The present invention provides a method for producing butadiene by directly producing it by contacting ethanol with a catalyst. Specifically, this method is carried out by supplying a gas containing ethanol to a reaction bed, which is made by filling a reaction tube with the catalyst. The catalyst used in the butadiene production method of the present invention has an active component that exhibits catalytic activity. This active component includes element A selected from group 3 elements, element B selected from group 4 elements, element C selected from group 12 elements, and element D selected from group 5 and group 11 elements. The preferred configuration, shape, and properties of the catalyst are the same as those described above.

[0045] The temperature at which ethanol is brought into contact with the catalyst (reaction temperature) is preferably 200°C to 600°C, and more preferably 300°C to 500°C. The concentration of ethanol in the supplied gas is preferably between 5% by volume and 20% by volume. The flow rate of the supplied gas is preferably 1 mL / min or more and 30 mL / min or less, and more preferably 5 mL / min or more and 25 mL / min or less. By setting these conditions, the yield of butadiene can be sufficiently increased.

[0046] As described above, the present invention provides a catalyst that can produce butadiene from ethanol as a raw material in a higher yield (conversion rate of ethanol and / or selectivity of butadiene), and a method for producing butadiene using such a catalyst. Furthermore, they may be provided in the following embodiments.

[0047] (1) A catalyst used to directly produce butadiene from ethanol, wherein the catalyst has an active component that exhibits catalytic activity, and the active component comprises element A selected from elements belonging to Group 3 of the periodic table, element B selected from elements belonging to Group 4 of the periodic table, element C selected from elements belonging to Group 12 of the periodic table, and element D selected from elements belonging to Groups 5 and 11 of the periodic table.

[0048] (2) A catalyst as described in (1) above, wherein the total amount of element A, element B, and element C contained in the active component is 40 mol% or more.

[0049] (3) A catalyst according to (1) or (2) above, wherein the active component further comprises element E selected from elements belonging to Group 6 of the periodic table.

[0050] (4) A catalyst according to any one of (1) to (3) above, wherein the active component further comprises an element F selected from elements belonging to Group 2 of the periodic table.

[0051] (5) A catalyst according to any one of (1) to (4) above, wherein the active component further comprises element G selected from elements belonging to Group 13 of the periodic table.

[0052] (6) A catalyst according to any one of (1) to (5) above, wherein the active component further comprises an element H selected from the elements belonging to Group 10 of the periodic table.

[0053] (7) The catalyst described in (1) above, wherein the active component further comprises element E selected from elements belonging to Group 6 of the periodic table, element F selected from elements belonging to Group 2 of the periodic table, and element G selected from elements belonging to Group 13 of the periodic table.

[0054] (8) The catalyst described in (1) above, wherein the active component further comprises element E selected from elements belonging to Group 6 of the periodic table, element F selected from elements belonging to Group 2 of the periodic table, element G selected from elements belonging to Group 13 of the periodic table, and element H selected from elements belonging to Group 10 of the periodic table.

[0055] (9) The catalyst described in (1) above, wherein the active component further comprises an element F selected from elements belonging to Group 2 of the periodic table, and an element G selected from elements belonging to Group 13 of the periodic table.

[0056] (10) The catalyst described in (1) above, wherein the active component further comprises element E selected from elements belonging to Group 6 of the periodic table, element G selected from elements belonging to Group 13 of the periodic table, and element H selected from elements belonging to Group 10 of the periodic table.

[0057] (11) The catalyst described in (1) above, wherein the active component further comprises element E selected from elements belonging to Group 6 of the periodic table, element F selected from elements belonging to Group 2 of the periodic table, and element H selected from elements belonging to Group 10 of the periodic table.

[0058] (12) A method for directly producing butadiene by contacting ethanol with a catalyst, wherein the catalyst has an active component that exhibits catalytic activity, and the active component comprises element A selected from elements belonging to Group 3 of the periodic table, element B selected from elements belonging to Group 4 of the periodic table, element C selected from elements belonging to Group 12 of the periodic table, and element D selected from elements belonging to Groups 5 and 11 of the periodic table. Of course, this is not always the case.

[0059] As previously described, various embodiments of the present invention have been explained, but these are merely examples and do not limit the scope of the invention in any way. These novel embodiments can be implemented in various other forms, and various omissions, substitutions, and modifications can be made without departing from the spirit of the invention. These embodiments and their variations are included in the scope and spirit of the invention, as well as in the claims of the invention and its equivalents.

[0060] For example, the catalyst and butadiene production method of the present invention may have any other additional configurations compared to the above embodiment, may be replaced with any configuration (step) that exhibits similar functionality, and some configurations (steps) may be omitted. [Examples]

[0061] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.

[0062] 1. Catalyst manufacturing First, predetermined amounts of the salts of the constituent elements were weighed out. Next, the measured chlorides of the constituent elements were dissolved in 5 mL of ethanol to prepare a solution. Next, silica particles (average particle size: 2 μm, average pore diameter: 9 nm, total pore volume: 1.5 mL / g, specific surface area: 550 m²) are added to this solution as a porous support. 2 The mixture ( / g) was added and stirred at 50°C for 2 hours. Afterward, it was dried under reduced pressure at 70°C for 4 hours.

[0063] Next, the nitrates of the measured constituent elements were dissolved in 5 mL of water to prepare a solution. Next, the sample that had been dried under reduced pressure for 4 hours was added to this solution and stirred at 50°C for 2 hours. Afterward, it was vacuum-dried at 90°C for 4 hours, and then baked at 400°C for 3 hours. In this way, a catalyst was obtained in which the active ingredient was supported on a carrier. The ratios of the elements constituting the active components of each catalyst 1 to 228 are shown in Tables 3 to 12.

[0064] 2. Evaluation of Butadiene Yield First, a reaction bed was prepared by filling a cylindrical glass reaction tube with catalyst to a height of 2 cm. Next, a pretreatment was performed by setting the reaction bed temperature to 400°C, the reaction bed pressure to 0.1 MPa, and passing an oxygen-containing gas through the reaction tube. Subsequently, the reaction temperature was set to between 300°C and 400°C, and a gas containing ethanol was supplied to the reaction tube.

[0065] The gas supplied to the reaction tube was a mixed gas obtained by diluting ethanol with an inert gas. The ethanol concentrations in this mixed gas were 9% by volume and 18% by volume, and the flow rate of the mixed gas was 2 mL / min. The mixed gas prepared to an ethanol concentration of 18% by volume was used to evaluate catalyst 226. The gas effluent from the reaction tube was then collected and analyzed using a mass spectrometer to determine the conversion rate of ethanol, the selectivity of butadiene, and the yield of butadiene. The results are shown in Tables 3 to 12 below. The evaluation examples for catalysts 1-94 correspond to examples, the evaluation examples for catalysts 95, 128, and 226 correspond to comparative examples, and the other evaluation examples correspond to reference examples.

[0066] [Table 3]

[0067] [Table 4]

[0068] [Table 5]

[0069] [Table 6]

[0070] [Table 7]

[0071] [Table 8]

[0072] [Table 9]

[0073] [Table 10]

[0074] [Table 11]

[0075] [Table 12]

[0076] To confirm the effects of the catalysts of the present invention, the results of evaluation examples for catalysts 1-3, 24, 27, 45, 62, 63, 95, 128, and 226 are summarized in Table 13 below.

[0077] [Table 13]

[0078] As shown in Table 13, the catalysts in each example yielded a high yield of butadiene. In contrast, the catalysts in each comparative example yielded a low yield of butadiene. Among the examples, catalysts that did not contain Group 5 elements or Group 11 elements (element D) (Examples 7 and 8) tended to have lower butadiene yields. Furthermore, among the comparative examples, the catalyst that did not contain Group 4 elements (Comparative Example 3) showed an extremely low yield of butadiene. This suggests that Group 4 elements are important elements for catalytic activity.

Claims

1. A catalyst used to directly produce butadiene from ethanol, The catalyst has an active component that exhibits catalytic activity, The aforementioned active ingredient is Element A selected from lanthanum (La), cerium (Ce), and yttrium (Y), Element B selected from hafnium (Hf) and zirconium (Zr), The element C is zinc (Zn), It comprises element D selected from niobium (Nb), tantalum (Ta), copper (Cu), and silver (Ag), The total amount of elements A, B, and C contained in the active ingredient is 40 mol% or more. catalyst.

2. In the catalyst according to claim 1, The catalyst further comprises the active component element E, selected from elements belonging to Group 6 of the periodic table.

3. In the catalyst according to claim 1, The catalyst further comprises an element F selected from elements belonging to Group 2 of the periodic table.

4. In the catalyst according to claim 1, The catalyst further comprises an element G selected from elements belonging to Group 13 of the periodic table.

5. In the catalyst according to claim 1, The catalyst further comprises the active component H, which is selected from elements belonging to Group 10 of the periodic table.

6. In the catalyst according to claim 1, The catalyst further comprises an element E selected from elements belonging to Group 6 of the periodic table, an element F selected from elements belonging to Group 2 of the periodic table, and an element G selected from elements belonging to Group 13 of the periodic table.

7. In the catalyst according to claim 1, The catalyst further comprises the active ingredient element E selected from elements belonging to Group 6 of the periodic table, element F selected from elements belonging to Group 2 of the periodic table, element G selected from elements belonging to Group 13 of the periodic table, and element H selected from elements belonging to Group 10 of the periodic table.

8. In the catalyst according to claim 1, The catalyst further comprises an element F selected from elements belonging to Group 2 of the periodic table, and an element G selected from elements belonging to Group 13 of the periodic table.

9. In the catalyst according to claim 1, The catalyst further comprises an element E selected from elements belonging to Group 6 of the periodic table, an element G selected from elements belonging to Group 13 of the periodic table, and an element H selected from elements belonging to Group 10 of the periodic table.

10. In the catalyst according to claim 1, The catalyst further comprises, as the active component, element E selected from elements belonging to Group 6 of the periodic table, element F selected from elements belonging to Group 2 of the periodic table, and element H selected from elements belonging to Group 10 of the periodic table.

11. A method for directly producing butadiene by contacting ethanol with a catalyst, The catalyst has an active component that exhibits catalytic activity, The aforementioned active ingredient is Element A selected from lanthanum (La), cerium (Ce), and yttrium (Y), Element B selected from hafnium (Hf) and zirconium (Zr), The element C is zinc (Zn), It comprises element D selected from niobium (Nb), tantalum (Ta), copper (Cu), and silver (Ag), The total amount of elements A, B, and C contained in the active ingredient is 40 mol% or more. A method for producing butadiene.

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