Catalyst for producing 1,3-butadiene and method for producing 1,3-butadiene using the same

Abstract

To provide a catalyst for the production of 1,3-butadiene that can efficiently produce, from n-butene, 1,3-butadiene which is industrially useful as the raw material for synthetic rubber, and a method for producing 1,3-butadiene using the same.SOLUTION: A catalyst for the production of 1,3-butadiene comprises a metal component containing a metal element belonging to the groups 8-10 of the periodic table, and zeolite containing the metal component and comprising 12-membered ring pores.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a catalyst for producing 1,3-butadiene and a method for producing 1,3-butadiene using the same. More specifically, the present invention relates to a catalyst for producing 1,3-butadiene that enables efficient production of 1,3-butadiene, which is industrially useful as a raw material for synthetic rubber, using n-butene as a raw material, and a method for producing 1,3-butadiene using the same. [Background technology]

[0002] 1,3-Butadiene is industrially produced by extracting and separating 1,3-butadiene from the C4 fraction (a mixture of 1,3-butadiene, n-butene, iso-butene, n-butane, and iso-butane) produced as a by-product in naphtha cracking (extraction separation method).

[0003] In recent years, due to changes in the environment surrounding basic raw materials, research into catalytic reaction processes that produce 1,3-butadiene as a target product has become active. Specifically, a method for producing butadiene by a dehydrogenation method (see, for example, Patent Document 1) and a method for producing butadiene by an oxidative dehydrogenation method (see, for example, Patent Document 2) have been proposed, in which n-butene contained in the S-C4 fraction (a mixture mainly composed of n-butene, iso-butene, n-butane, and iso-butane) obtained by separating 1,3-butadiene by an extractive separation process is used as a starting material. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2017-165667 [Patent Document 2] Japanese Patent Application Laid-Open No. 2012-082153 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the method proposed in Patent Document 1 involves a dehydrogenation reaction shown in the following formula (1), which is an endothermic reaction and is subject to the constraints of chemical equilibrium, so high temperatures are required for the dehydrogenation reaction to proceed smoothly. Furthermore, the high temperatures pose problems of reactor clogging due to coking, and additional equipment is required to handle the hydrogen produced by dehydrogenation, making the method less economically rational. C4H8 (n-butene) → C4H6 (butadiene) + H2 (hydrogen) (1)

[0006] In the method proposed in Patent Document 2, the oxidative dehydrogenation reaction shown in the following formula (2) is carried out using oxygen as a hydrogen acceptor, and therefore there are no constraints of endothermic heat or chemical equilibrium, and the dehydrogenation reaction proceeds under relatively mild conditions. However, the method is not economically rational because the oxygen used as a raw material is converted into worthless water, the selectivity of the product (butadiene) is insufficient, and additional equipment for handling oxygen is required. C4H8 (n-butene) + 1 / 2O2 (oxygen) → C4H6 (butadiene) + H2O (water) (2)

[0007] Therefore, there has been a need for a catalyst for producing 1,3-butadiene that uses n-butene as a starting material and that enables efficient production of 1,3-butadiene, which is useful as a raw material for synthetic rubber, through a simple catalytic process that does not require the handling of hydrogen or oxygen, and for a method for producing 1,3-butadiene using the catalyst. [Means for solving the problem]

[0008] As a result of intensive investigations to solve the above problems, the present inventors have found that a zeolite containing a specific metal and having 12-membered ring pores can serve as a catalyst for producing 1,3-butadiene, which can efficiently produce 1,3-butadiene from n-butene, and have thus completed the present invention.

[0009] That is, the present invention relates to a catalyst for producing 1,3-butadiene, characterized by comprising a metal component containing a metal element belonging to Groups 8 to 10 of the periodic table, and a zeolite having 12-membered ring pores containing the metal component, and a method for producing 1,3-butadiene using the catalyst. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a catalyst for producing 1,3-butadiene that can efficiently produce 1,3-butadiene using n-butene as a starting material in a simple catalytic process without requiring the handling of hydrogen or oxygen, and a method for producing 1,3-butadiene using the same. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention will be described in detail below.

[0012] The catalyst for producing 1,3-butadiene of the present invention is a catalyst that enables efficient production of 1,3-butadiene, which is useful as a raw material for synthetic rubber, using n-butene as a starting material in a simple catalytic process that does not require the handling of hydrogen or oxygen.

[0013] The catalyst for producing 1,3-butadiene of the present invention comprises a metal component containing a metal element belonging to Groups 8 to 10 of the periodic table, and a zeolite containing the metal component and having 12-membered ring pores.

[0014] The zeolite constituting the catalyst for producing 1,3-butadiene of the present invention has 12-membered ring pores. Here, zeolite is a crystalline substance consisting of a rigid anionic framework with regular pores and cavities, and the framework structure is formed by an infinite series of T atoms and oxygen (oxygen atoms) in three dimensions. T atoms are generally composed of aluminum and silicon, but aluminum and silicon may be substituted with atoms other than these atoms. Zeolites containing aluminum and silicon in the T atoms are also called aluminosilicates, and the basic structural unit is a tetrahedral structure of SiO4 or AlO4 (collectively referred to as a TO4 tetrahedron).

[0015] The number of T atoms constituting the ring (pore) is sometimes used as a unit to express the pore size of a zeolite. For example, rings surrounded by 8, 10, 12, and 14 T atoms are called 8-membered rings, 10-membered rings, 12-membered rings, and 14-membered rings, respectively. Pores consisting of 8-, 10-, 12-, and 14-membered or more rings are defined as "small pores," "medium pores," "large pores," and "ultra-large pores," respectively (see J.Vac.Soc.Jpn. (Vacuum), Vol. 49, 205 (2006)). Based on these relationships, the zeolite having 12-membered ring pores used in the catalyst for producing 1,3-butadiene of the present invention means a zeolite having large pores of about 0.6 to 1.2 nm.

[0016] In the present invention, the zeolite having 12-membered ring pores is not particularly limited as long as it has a 12-membered ring as a structural unit, and may be not only a zeolite consisting of only 12-membered ring pores, but also a zeolite having pores other than 12-membered ring pores in addition to 12-membered ring pores. Examples of zeolites having 12-membered ring pores include SSZ-24 (a structure code consisting of three capital letters defined by the International Zeolite Association; AFI, one-dimensional 12-membered ring pores), SSZ-31 ( *STO, one-dimensional 12-membered ring pores), ZSM-12 (MTW, one-dimensional 12-membered ring pores), VPI-8 (VFI, one-dimensional 12-membered ring pores), GUS-1 (GON, one-dimensional 12-membered ring pores), L (LTL, one-dimensional 12-membered ring pores), SSZ-42 (IFR, one-dimensional 12-membered ring pores), SSZ-48 (SFE, one-dimensional 12-membered ring pores), SSZ-55 (ATS, one-dimensional 12-membered ring pores), SSZ-60 (SSY, one-dimensional 12-membered ring pores), Mordenite (MOR, two-dimensional 12-8-membered ring pores), MCM-22 (MWW, two-dimensional 12-10-membered ring pores), IM-12 / ITQ-15 (UTL, two-dimensional 14-12-membered ring pores), Gmelinite (GME, three-dimensional 12-8-8-membered ring pores), Y (FAU, three-dimensional 12-12-12-membered ring pores), Beta( * BEA, three-dimensional 12-12-12 membered ring pores), EMC-2 (EMT, three-dimensional 12-12-12 membered ring pores), CIT-1 (CON, three-dimensional 12-12-10 membered ring pores), ITQ-7 (ISV, three-dimensional 12-12-12 membered ring pores), ITQ-17 (BEC, three-dimensional 12-12-12 membered ring pores), MCM-68 (MSE, three-dimensional 12-10-10 membered ring pores), ITQ-21 (-, three-dimensional 12-12-12 membered ring pores), ITQ-22 (IWW, three-dimensional 12-10-8 membered ring pores), ITQ-24 (IWR, three-dimensional 12-12-10 membered ring pores), etc. From the viewpoint of efficiently producing 1,3-butadiene (increasing the selectivity of 1,3-butadiene), Y (FAU, three-dimensional 12-12-12-membered ring pores), Beta ( * BEA (three-dimensional 12-12-12 membered ring pores), MCM-22 (MWW (two-dimensional 12-10 membered ring pores)) are preferably used, and Y (FAU (three-dimensional 12-12-12 membered ring pores)), Beta ( * BEA (three-dimensional 12-12-12 ring pores) is more preferably used.

[0017] The composition of the zeolite is not particularly limited, and examples thereof include aluminosilicates; metalloaluminosilicates such as boroaluminosilicate, titanoaluminosilicate, vanadoaluminosilicate, manganoaluminosilicate, iron aluminosilicate, zinc aluminosilicate, galloaluminosilicate, and tin aluminosilicate; and metallosilicates such as borosilicate, titanosilicate, vanadosilicate, manganosilicate, iron silicate, zinc silicate, gallosilicate, and tin silicate. Of these, aluminosilicates are preferably used because of their high stability and ease of industrial availability.

[0018] Here, the above aluminosilicate is generally M 2 / n The zeolite is expressed by the composition O·Al2O3·xSiO2·yH2O (n represents the valence of the cation M, x represents a number equal to or greater than 2, and y represents the amount of adsorbed water (molar ratio)). The cation M is not particularly limited, and examples thereof include sodium, potassium, calcium, ammonium, and proton. However, from the viewpoint of efficiently producing 1,3-butadiene (increasing the selectivity of 1,3-butadiene), proton is preferably used. Furthermore, x is called the SiO2 / Al2O3 ratio, and is a numerical value that serves as an index of the heat resistance, acid resistance, etc. of the zeolite. While the range is not particularly limited, from the viewpoint of efficiently producing 1,3-butadiene, the SiO2 / Al2O3 ratio is preferably 5 to 1000, and more preferably 10 to 500.

[0019] The zeolite constituting the catalyst for producing 1,3-butadiene of the present invention contains a metal component including a metal element belonging to Groups 8 to 10 of the periodic table (hereinafter also simply referred to as "metal element"). The metal component contained in the zeolite is a component contained outside the skeletal structure, and is distinguished from the atoms (T atoms and oxygen atoms) that constitute the skeletal structure of the zeolite. In this specification, the term "metal element" refers to the type of element and does not specify the state of the element. In other words, the metal element includes metal elements in all states, such as metal, ion, and metal compound.

[0020] The state of the metal element contained in the metal component is not particularly limited, and can be metal, metal compound, or ion. The metal element contained in the metal component may be contained in any one of the states of metal, ion, or metal compound, or in two or more of these states (i.e., as a mixture). From the viewpoint of increasing the yield of 1,3-butadiene and increasing the yield of n-butane, which is useful as a naphtha cracking feedstock as a product other than 1,3-butadiene, it is preferable that the metal element be contained in the metal state. When the metal element is contained in the state of a metal compound, examples of the metal compound include metal chlorides, metal bromides, metal nitrates, metal acetates, metal oxides, metal hydroxides, and metal complexes.

[0021] Here, whether a metal element is in the state of a metal or a metal compound can be confirmed by measuring the oxidation state of the metal element using, for example, XPS (X-ray Photoelectron Spectroscopy) (if the valence of the metal element is 0, it is a metal, and if the valence of the metal element is not 0, it can be determined to be a metal compound).

[0022] The metal element contained in the metal component is not particularly limited in type as long as it is an element belonging to Groups 8 to 10 of the periodic table. Examples include iron, ruthenium, cobalt, rhodium, iridium, nickel, palladium, platinum, etc. From the viewpoint of efficiently producing 1,3-butadiene (increasing the selectivity of 1,3-butadiene), the metal element is preferably platinum.

[0023] From the viewpoint of efficiently producing 1,3-butadiene, the content of the metal component is preferably 0.05 to 5.0 wt%, more preferably 0.1 to 3.0 wt%, relative to 100 wt% of the zeolite (zeolite not containing a metal component).

[0024] The method for producing a zeolite containing a metal component is not particularly limited, and any method such as an impregnation method, an ion exchange method, a physical mixing method, or a vapor deposition method may be used using a metal compound such as a metal chloride, a metal bromide, a metal nitrate, a metal acetate, a metal oxide, a metal hydroxide, or a metal complex of a metal element as a raw material. Among these, the impregnation method is preferred because it provides a high yield of 1,3-butadiene.

[0025] The impregnation method is a method in which a solution containing a metal compound of a metal element is impregnated into a zeolite having 12-membered ring pores (hereinafter simply referred to as "zeolite"), and the zeolite impregnated with the solution is dried. The treatment conditions in the impregnation method (solution composition, impregnation conditions, drying conditions, etc.) can be known conditions and are not particularly limited. For example, the solution to be impregnated into the zeolite contains, as metal compounds of the metal element, platinum chloride (IV), platinum bromide (IV), platinum iodide (IV), etc. )of It is possible to dissolve the metal component in the zeolite. For example, the conditions for impregnating the zeolite with the solution include immersing the zeolite in the solution at 5 to 80°C for 0.1 to 48 hours. For example, the conditions for drying the zeolite impregnated with the solution include treating the zeolite at 50 to 100°C for 0.5 to 120 hours. Herein, a zeolite containing a metal component by the impregnation method is referred to as a metal-impregnated zeolite.

[0026] In the zeolite produced by the impregnation method (metal-impregnated zeolite), the metal elements are contained mainly in the form of ions or metal compounds. To convert the metal elements into a metallic state, the zeolite obtained by the impregnation method can be treated at high temperatures of 200 to 600°C or with a reducing agent such as hydrogen or hydrazine. For example, a method of treating a zeolite with a reducing agent can be used, for example, by contacting the zeolite with a fluid containing a reducing agent. The conditions for the reduction treatment (e.g., fluid composition, fluid flow rate, treatment temperature) are not particularly limited and can be any known conditions. For example, the reducing agent-containing fluid may contain a reducing agent, and may also contain an inert gas such as nitrogen in addition to the reducing agent. For example, the flow rate of the reducing agent-containing fluid contacted with the zeolite can be 20 to 500 ml / min g-zeolite. For example, the conditions for contacting the zeolite with the fluid can be 100 to 500°C and 0.1 to 5 hours.

[0027] The catalyst for producing 1,3-butadiene of the present invention comprises a zeolite containing the above-described metal component, and its shape is not particularly limited. The catalyst for producing 1,3-butadiene of the present invention may be, for example, in powder form. However, it is preferable to shape the catalyst into a molded body in order to obtain a catalyst with excellent handleability and catalytic performance. The shaping can be performed by any method, including a method in which zeolite powder is directly molded into a predetermined shape by compression molding or the like to obtain a molded body; a method in which a binder such as silica, alumina, or clay is mixed with zeolite in a predetermined ratio, and optionally further additives are mixed in a predetermined ratio, and the mixture is molded into a predetermined shape to obtain a molded body; or a method in which sintering is performed to obtain a molded body. The blend ratio of the zeolite to the binder is optional, and a zeolite:binder ratio of 50 to 95:50 to 5 (weight ratio) is preferred, with a weight ratio of 60 to 90:40 to 10 being particularly preferred, in order to obtain a conversion catalyst that exhibits particularly excellent catalytic performance, handleability, and catalytic life.

[0028] When the catalyst for producing 1,3-butadiene is used as a molded body, its shape may be any, such as a cylindrical shape, a polygonal prism such as a triangular prism, a square prism, a pentagonal prism, or a hexagonal prism, a hollow polygonal prism, or a spherical shape. Among these, a cylindrical shape is preferred because it provides a catalyst with excellent continuous productivity and high crushing strength. Furthermore, its size (diameter, width, length, etc.) and density (bulk density, true density, etc.) can be selected arbitrarily taking into consideration factors such as packing efficiency. A cylindrical shape with a diameter of 1.0 to 10 mm or a cylindrical shape with a thickness of 0.5 to 5.0 mm is preferred because it provides a catalyst that enables efficient production of 1,3-butadiene, which is particularly useful as a synthetic rubber raw material.

[0029] The catalyst for producing 1,3-butadiene of the present invention enables highly efficient production of 1,3-butadiene, which is useful as a raw material for synthetic rubber, by contacting a fluid containing n-butene as a raw material. In this specification, n-butene refers to 1-butene (α-butylene), cis-2-butene (cis-β-butylene), and trans-2-butene (trans-β-butylene).

[0030] The n-butene-containing fluid may be either gaseous or liquid, but is preferably gaseous from the viewpoint of efficient production of 1,3-butadiene. Furthermore, the n-butene-containing fluid may contain n-butene and may also contain other components in addition to n-butene. Examples of n-butene-containing fluids include a C4 fraction (a mixture of 1,3-butadiene, n-butene, isobutene, n-butane, and isobutane) by-produced in naphtha cracking, an S-C4 fraction (a mixture mainly composed of n-butene, isobutene, n-butane, and isobutane) obtained by separating butadiene through an extractive separation process, and an SS-C4 fraction (a mixture mainly composed of n-butene, n-butane, and isobutane) obtained by separating isobutene through a hydration reaction or a methanolization reaction. Fluids containing C4 hydrocarbons (hydrocarbons with a carbon number of 4) obtained from petroleum refining may also be used.

[0031] From the viewpoint of efficiently producing 1,3-butadiene, the n-butene concentration in the n-butene-containing fluid (100% by volume of the n-butene-containing fluid) is preferably 5 to 50% by volume in the case of a C4 fraction by-produced in naphtha cracking. It is also preferable to use n-butene itself (100% by volume) obtained by ethylene oligomerization or refining the above-mentioned C4 hydrocarbons as the n-butene-containing fluid.

[0032] The catalyst for producing 1,3-butadiene of the present invention can efficiently produce 1,3-butadiene by contacting it with a fluid containing n-butene. The reaction format is not particularly limited, and the reaction can be carried out in any format. For example, the reaction can be carried out in a fixed-bed gas-phase flow system, a fixed-bed liquid-phase flow system, or a suspension-bed batch system. The reaction temperature is not particularly limited, and is preferably in the range of 300 to 600°C, which results in a more efficient production method, and more preferably in the range of 350 to 550°C, which results in a higher conversion of n-butene. Furthermore, the reaction pressure is also not particularly limited, and operation is possible within a pressure range of, for example, atmospheric pressure to about 5 MPa. Furthermore, the weight hourly space velocity (WHSV) during the fixed-bed flow reaction is not particularly limited, but is preferably 0.01 to 200 h because 1,3-butadiene can be produced efficiently. -1 , and more preferably 0.1 to 50 hours -1 Here, the weight hourly space velocity (WHSV) represents the total weight of the supply amount of the n-butene-containing fluid per unit time (hr) per unit catalyst weight (in other words, the ratio of the supply rate (weight / hour) of the n-butene-containing fluid to the catalyst weight). When the n-butene-containing fluid is supplied, the n-butene-containing fluid may be diluted with a single or mixed gas selected from an inert gas such as nitrogen, hydrogen, carbon monoxide, and carbon dioxide.

[0033] In the method for producing 1,3-butadiene using the catalyst for producing 1,3-butadiene of the present invention, n-butane can be produced along with 1,3-butadiene by using n-butene as a raw material, as shown in formula (3) below. That is, a hydrogen atom in n-butene transfers between molecules of n-butene, enabling highly efficient conversion to 1,3-butadiene, which is useful as a raw material for synthetic rubber, while also producing n-butane, which is useful as a raw material for naphtha cracking. As a result, the process using the catalyst for producing 1,3-butadiene of the present invention is a simple catalytic process that does not require the handling of hydrogen or oxygen, making it highly economically rational. On the other hand, the conventional dehydrogenation method (formula (1) above) produces hydrogen, and the oxidative dehydrogenation method (formula (2) above) requires the use of oxygen as an auxiliary raw material. Therefore, industrial production requires additional facilities for handling hydrogen and oxygen in addition to the 1,3-butadiene production facility. C4H8 (n-butene) → 1 / 2C4H6 (butadiene) + 1 / 2C4H 10 (n-butane) (3) [Example]

[0034] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0035] Example 1 0.20 g of proton-type beta zeolite powder (manufactured by Tosoh Corporation, product name: HSZ-931HOA, SiO2 / Al2O3 molar ratio 27) was suspended in 20 ml of pure water, and 0.023 g of a chloroplatinate (IV) acid solution was added to the suspension. The mixture was stirred at room temperature for 1 hour, and a metal introduction treatment was performed by impregnation. After stirring, the powder was filtered and dried at 80°C under reduced pressure (300 hPa), and then dried overnight at 100°C under normal pressure to obtain a zeolite catalyst precursor containing 1.0 wt% Pt. The Pt content (1.0 wt%) in the zeolite catalyst precursor represents the content relative to 100 wt% of the Pt-free zeolite catalyst precursor, and was determined from the change in the amount of Pt in the solution in which the zeolite was immersed. The zeolite catalyst precursor was then packed into a quartz glass reaction tube equipped with mass flow controllers for supplying nitrogen and hydrogen gases, and reduction treatment was carried out at 300°C for 1 hour under a flow of hydrogen (6 ml / min) and nitrogen (14 ml / min) to prepare a beta zeolite catalyst containing 1.0 wt% of Pt element (metallic state).

[0036] A fixed-bed gas-phase flow reactor equipped with mass flow controllers for supplying nitrogen and 1-butene gases and having a quartz glass reaction tube was packed with 0.05 g of 1.0 wt% Pt-containing beta zeolite catalyst, and 1-butene (6 ml / min) and nitrogen (14 ml / min) were fed into the stainless steel reaction tube and brought into contact with the 1.0 wt% Pt-containing beta zeolite catalyst at 500°C to produce 1,3-butadiene. The weight hourly space velocity (WHSV) was 18 hr -1 It was.

[0037] The reaction outlet gas and reaction liquid (trapped with decane solvent) were collected and analyzed for gas and liquid components separately using a gas chromatograph (Shimadzu Corporation, product name: GC-8A (gas component analysis), Shimadzu Corporation, product name: GC-14B (liquid component analysis)). The results are shown in Table 1.

[0038] The conversion shown in Table 1 was calculated from the following formula (4), and the selectivity shown in Table 1 was calculated from the following formula (5). Furthermore, butadiene shown in Table 1 below represents 1,3-butadiene. Conversion rate (%) = {(AB) / A} × 100 (4) (In the above formula (4), A represents the weight of 1-butene in the supplied gas, and B represents the weight of 1-butene in the discharged gas and liquid.) Selection rate (%) = {C / D} × 100 (5) (In the above formula (5), C represents the weight of the substance in the discharged gas and liquid for which the selectivity is to be determined, and D represents the total weight of the substances in the discharged gas and liquid excluding nitrogen and 1-butene.)

[0039] Example 2 A Y-type zeolite catalyst containing 1.0 wt% of Pt element (metallic state) was prepared in the same manner as in Example 1, except that proton-type Y-type zeolite (manufactured by Tosoh Corporation, product name: HSZ-372HUA, SiO2 / Al2O3 molar ratio 28) was used instead of proton-type beta zeolite powder, and 1,3-butadiene was produced (and its performance evaluated). The results are shown in Table 1.

[0040] Comparative Example 1 0.114 g of sodium aluminate, 0.107 g of sodium hydroxide, and 8.68 g of an aqueous solution of tetrabutylammonium hydroxide were mixed and stirred at room temperature for 10 minutes, and 6.93 g of tetraethoxysilane was added to the mixture and stirred for another 2 hours.

[0041] The resulting white gel was sealed in a stainless steel autoclave and crystallized for 72 hours with stirring at 170°C to obtain a slurry mixture. The white solid was filtered from the crystallized slurry mixture, washed with a sufficient amount of purified water, and dried at 110°C to obtain a dry powder. This was then calcined at 550°C for 20 hours in an air stream to obtain a white powder. This white powder was identified as ZSM-11 (SiO2 / Al2O3 molar ratio 31) by XRD analysis (JEOL, trade name: JDX-3530, conditions: Cu-Kα, 45 eV, 200 mA). ZSM-11 is a zeolite consisting solely of 10-membered ring pores.

[0042] A ZSM-11 zeolite catalyst containing 1.0 wt% of Pt element (metallic state) was prepared in the same manner as in Example 1, except that the ZSM-11 was used instead of the proton type beta zeolite powder, and 1,3-butadiene was produced (and its performance evaluated). The results are shown in Table 1.

[0043] [Table 1]

[0044] As shown in Table 1, the catalysts of Examples 1 and 2 produced butadiene (1,3-butadiene), which is useful as a synthetic rubber raw material, at a higher conversion rate and higher selectivity than the catalyst of Comparative Example 1. Furthermore, as a product other than butadiene (1,3-butadiene), the catalysts of Examples 1 and 2 produced only n-butane, which is useful as a naphtha cracking raw material, whereas in Comparative Example 1, mainly propane and propylene were produced, and the amount of n-butane produced was significantly lower than in Examples 1 and 2. [Industrial Applicability]

[0045] The catalyst for producing 1,3-butadiene of the present invention and the process for producing 1,3-butadiene using the same exhibit excellent catalytic performance when converting n-butene to 1,3-butadiene, and the industrial value of the catalyst is extremely high.

Claims

1. A method for producing a catalyst comprising: a platinum metal; and a zeolite having 12-membered ring pores containing the platinum metal; The zeolite is a Y-type zeolite or a Beta-type zeolite, The SiO 2 / Al 2 O 3 ratio of the zeolite is 10 to 500; A catalyst for producing 1,3-butadiene.

2. The catalyst for producing 1,3-butadiene according to claim 1, wherein the platinum metal content is 0.05 to 5.0 wt % relative to 100 wt % of the zeolite not containing the platinum metal.

3. The catalyst for producing 1,3-butadiene according to claim 1, wherein the platinum metal content is 0.1 to 3.0 wt % relative to 100 wt % of the zeolite not containing the platinum metal.

4. 4. The catalyst for producing 1,3-butadiene according to any one of claims 1 to 3, which is a catalyst for producing 1,3-butadiene and n-butane.

5. A method for producing 1,3-butadiene, comprising contacting a fluid containing n-butene with the catalyst for producing 1,3-butadiene according to any one of claims 1 to 4.

6. 6. The method for producing 1,3-butadiene according to claim 5, wherein the n-butene concentration in the fluid is 5 to 50% by volume.

7. The method for producing 1,3-butadiene according to claim 5, wherein the fluid consists of only n-butene.

8. The method for producing 1,3-butadiene according to any one of claims 5 to 7, characterized in that n-butane is produced together with 1,3-butadiene.

9. A method for producing a catalyst for producing 1,3-butadiene according to any one of claims 1 to 4, comprising the steps of: The method includes contacting a zeolite having 12-membered ring pores containing platinum by an impregnation method with a fluid containing a reducing agent, The zeolite is a Y-type zeolite or a Beta-type zeolite, The SiO 2 / Al 2 O 3 ratio of the zeolite is 10 to 500; A method for producing a catalyst for producing 1,3-butadiene, comprising:

10. The method for producing a catalyst for producing 1,3-butadiene according to claim 9, wherein the reducing agent is hydrogen.

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