KR102663397B1 - Method for preparing 1,3-butadiene - Google Patents

Abstract

One exemplary embodiment of the present application includes filling a catalyst layer containing a ferrite-based catalyst and an isomerization catalyst into a reactor; and introducing a reactant containing butene into a reactor filled with the catalyst layer to perform an oxidative dehydrogenation reaction and an isomerization reaction, wherein the catalyst layer includes the ferrite catalyst and the isomerization catalyst simultaneously with the butene. A method for producing 1,3-butadiene is provided, in which 1,3-butadiene is charged into a reactor so that it comes into contact with a reactant.

Description

Method for producing 1,3-butadiene {METHOD FOR PREPARING 1,3-BUTADIENE}

This application claims the benefit of Korean Patent Application No. 10-2017-0179535 filed with the Korea Intellectual Property Office on December 26, 2017, the entire contents of which are incorporated herein by reference.

This application relates to a method for producing 1,3-butadiene.

1,3-Butadiene is an intermediate in petrochemical products, and its demand and value are gradually increasing worldwide. The 1,3-butadiene is produced using naphtha cracking, direct dehydrogenation reaction of butene, oxidative dehydrogenation reaction of butene, etc.

The oxidative dehydrogenation reaction of butene is a reaction in which butene and oxygen react in the presence of a metal oxide catalyst to produce 1,3-butadiene and water. It has a very thermodynamic advantage because stable water is produced. In addition, unlike the direct dehydrogenation reaction of butene, it is an exothermic reaction, so a high yield of 1,3-butadiene can be obtained even at a lower reaction temperature than the direct dehydrogenation reaction, and no additional heat supply is required, so 1,3-butadiene It can be an effective stand-alone production process to meet demand.

The metal oxide catalyst is generally synthesized by a precipitation method, but due to technological and space constraints, the one-time production volume is small, so the same process must be repeated several times to meet the target amount to manufacture the catalyst. In particular, a ferrite-based catalyst is used as a metal oxide catalyst, and the ferrite-based catalyst increases COx selectivity and reduces butadiene selectivity due to heat generation. Accordingly, research is continuously being conducted to control heat generation and consequently improve performance.

Republic of Korea Patent Publication No. 10-2013-0046214

This application provides a method for producing 1,3-butadiene.

One implementation state of this application is,

Filling a reactor with a catalyst layer containing a ferrite catalyst and an isomerization catalyst; and

Injecting a reactant containing butene into a reactor filled with the catalyst layer and performing an oxidative dehydrogenation reaction and isomerization reaction,

The catalyst layer provides a method for producing 1,3-butadiene, wherein the catalyst layer is filled in a reactor so that the ferrite catalyst and the isomerization catalyst are simultaneously in contact with the reactant containing the butene.

The method for producing 1,3-butadiene according to an exemplary embodiment of the present application controls the heat generated in the oxidative dehydrogenation reaction of butene, and as a result, the selectivity of COx can be lowered and the selectivity of butadiene can be increased. .

Figure 1 is a process diagram showing a reaction scheme for carrying out the manufacturing process of 1,3-butadiene according to an exemplary embodiment of the present application.
Figure 2 is a diagram showing an example of a reactor filled with a ferrite-based catalyst and an isomerization catalyst according to Comparative Example 1 of the present application.
Figure 3 is a diagram showing an example of a reactor filled with a ferrite-based catalyst and an isomerization catalyst according to an exemplary embodiment of the present application.
Figure 4 is a diagram showing an example of a reactor filled with a ferrite-based catalyst and an isomerization catalyst according to an exemplary embodiment of the present application.

Hereinafter, this application will be described in more detail.

In this application, 'yield (%)' is defined as the weight of 1,3-butadiene (BD), a product of oxidative dehydrogenation reaction, divided by the weight of butene (BE), a raw material. For example, the yield can be expressed by the following equation.

Yield (%) = [(moles of 1,3-butadiene produced)/(moles of butene supplied)] × 100

In the present application, 'conversion (%)' refers to the rate at which reactants are converted into products. For example, the conversion rate of butene can be defined by the following equation.

Conversion rate (%) = [(number of moles of reacted butene)/(number of moles of butene supplied)] × 100

In this application, 'selectivity (%)' is defined as the amount of change in butadiene divided by the amount of change in butene. For example, selectivity can be expressed by the following equation.

Selectivity (%) = [(number of moles of 1,3-butadiene or COx produced)/(number of moles of reacted butene)] × 100

In the present application, 'COx' refers to a compound containing carbon monoxide (CO), carbon dioxide (CO ₂ ), etc. formed during an oxidative dehydrogenation reaction.

In this application, 'butadiene' means 1,3-butadiene.

An exemplary embodiment of the present application includes filling a catalyst layer containing a ferrite-based catalyst and an isomerization catalyst into a reactor; and introducing a reactant containing butene into a reactor filled with the catalyst layer to perform an oxidative dehydrogenation reaction and an isomerization reaction, wherein the catalyst layer includes the ferrite catalyst and the isomerization catalyst simultaneously with the butene. A method for producing 1,3-butadiene is provided, in which 1,3-butadiene is charged into a reactor so that it comes into contact with a reactant.

Ferrite-based catalysts used in the oxidative dehydrogenation reaction of butene tend to reduce the selectivity of butadiene by generating a large amount of COx due to excessive heat generation during the reaction. Accordingly, in order to reduce the heat generated by the rapid catalytic reaction of the oxidative dehydrogenation reaction, the present inventors control the heat generation by mixing catalysts or substances that can perform a competitive reaction to reduce the reaction rate, resulting in the reduction of COx, a by-product. By suppressing the production, the selectivity of butadiene could be improved.

Specifically, a reaction in which 2-butene is oxidized by a ferrite catalyst to produce 1,3-butadiene and a reaction in which 2-butene is isomerized to 1-butene by an isomerization catalyst occur competitively. Accordingly, the production rate of 1,3-butadiene is slowed, making it possible to control the heat generation of the oxidative dehydrogenation reaction. As a result, most of the reactant butene is converted to butadiene, but the speed is slowed due to competition with the isomerization reaction, and the section of the catalyst layer where heat generation occurs is widely distributed throughout the catalyst layer, which has the effect of dispersing heat generation.

According to an exemplary embodiment of the present application, the step of performing the oxidative dehydrogenation reaction and the isomerization reaction may include performing the oxidative dehydrogenation reaction first and then performing the isomerization reaction. More specifically, when the oxidative dehydrogenation reaction proceeds under a ferrite-based catalyst, 2-butene is converted to butadiene, and when the isomerization reaction is performed, 2-butene, which is a reactant, isomerizes to 1-butene, It can inhibit oxidative dehydrogenation reaction.

According to an exemplary embodiment of the present application, the oxidative dehydrogenation reaction and the isomerization reaction may be performed simultaneously with the oxidative dehydrogenation reaction and the isomerization reaction. More specifically, when the oxidative dehydrogenation reaction proceeds under a ferrite-based catalyst, 2-butene is converted to butadiene, and when an isomerization reaction is performed at the same time, 2-butene, which is a reactant, isomerizes to 1-butene and is oxidized. It can slow down the dehydrogenation reaction rate.

According to an exemplary embodiment of the present application, the catalyst layer may be filled with the ferrite-based catalyst and the isomerization catalyst mixed with each other. More specifically, the ferrite catalyst molded body manufactured by molding the ferrite-based catalyst and the isomerization catalyst molded body manufactured by molding the isomerization catalyst may be mixed with each other and filled as a catalyst layer in the reactor. That is, the catalyst layer filled in the reactor may be provided in a mixed state with the ferrite-based catalyst molded body and the isomerization catalyst molded body, and the ferrite-based catalyst molded body and the isomerization catalyst molded body may be provided in a state in which the ferrite-based catalyst molded body and the isomerization catalyst molded body are uniformly mixed with each other. It is more desirable to be

According to an exemplary embodiment of the present application, the catalyst layer is filled with the ferrite-based catalyst and the isomerization catalyst mixed with each other, and the content of the ferrite-based catalyst and the isomerization catalyst is each 10% by weight based on the total weight of the catalyst layer. It may be from 90% by weight to 90% by weight, and from 30% to 70% by weight. When the content of the ferrite catalyst and the isomerization catalyst satisfies the above range, the competitive reaction to control heat generation can be effectively performed, and the oxidative dehydrogenation reaction for high butadiene selectivity can also be sufficiently performed. . That is, when the content of the ferrite catalyst and the isomerization catalyst satisfies the above range, heat generation can be controlled in the dehydrogenation reaction of butene, the selectivity of COx can be lowered, and the selectivity of butadiene can be increased. there is.

According to an exemplary embodiment of the present application, the molded body may be in the form of a pellet.

According to an exemplary embodiment of the present application, the diameter of the pellet may be 1.0 mm to 8 mm.

In an exemplary embodiment of the present application, an example of a reactor filled with a catalyst layer in which the ferrite-based catalyst and the isomerization catalyst are mixed with each other is schematically shown in Figure 3 below.

According to an exemplary embodiment of the present application, the catalyst layer may be filled with a hybrid catalyst composite that is a molded product of a mixture of the ferrite-based catalyst and the isomerization catalyst. More specifically, the hybrid catalyst complex can be manufactured by molding a mixture of the ferrite-based catalyst and the isomerization catalyst.

According to an exemplary embodiment of the present application, the catalyst layer is filled with a hybrid catalyst composite that is a molded product of a mixture of the ferrite-based catalyst and the isomerization catalyst, and the content of the ferrite-based catalyst and the isomerization catalyst based on the total weight of the hybrid catalyst complex. may be 10% by weight to 90% by weight, and may be 30% by weight to 70% by weight, respectively. When the content of the ferrite catalyst and the isomerization catalyst satisfies the above range, the competitive reaction to control heat generation can be effectively performed, and the oxidative dehydrogenation reaction for high butadiene selectivity can also be sufficiently performed. . That is, when the content of the ferrite catalyst and the isomerization catalyst satisfies the above range, heat generation can be controlled in the dehydrogenation reaction of butene, the selectivity of COx can be lowered, and the selectivity of butadiene can be increased. there is.

In an exemplary embodiment of the present application, an example of a reactor filled with a hybrid catalyst composite, which is a molded product of a mixture of the ferrite catalyst and the isomerization catalyst, as a catalyst layer is schematically shown in FIG. 4 below.

An example of a reactor filled with a ferrite-based catalyst and an isomerization catalyst according to Comparative Example 1 of the present application, which will be described later, is schematically shown in FIG. 2. More specifically, Figure 2 below shows a case where the ferrite-based catalyst and the isomerization catalyst were alternately charged into the reactor without mixing them or preparing a hybrid catalyst complex, and the ferrite-based catalyst and the isomerization catalyst were separated from each other. This shows a case where it is provided. In this way, when the ferrite catalyst and the isomerization catalyst are separated from each other and come into contact with a reactant containing butene, the isomerization catalyst only has an effect similar to that of the inert material, so oxidative dehydrogenation of butene as in the present application By controlling the heat generated in the reaction, the effect of lowering the selectivity of COx and increasing the selectivity of butadiene cannot be obtained.

According to an exemplary embodiment of the present application, the ferrite-based catalyst may be represented by the following formula (1).

[Formula 1]

AB ₂ O ₄

In Formula 1,

A is copper (Cu), radium (Ra), barium (Ba), strontium (Sr), calcium (Ca), beryllium (Be), iron (Fe(Ⅱ)), zinc (Zn), magnesium (Mg), Selected from the group consisting of manganese (Mn), cobalt (Co) and nickel (Ni),

B is aluminum (Al), iron (Fe(III)), chromium (Cr), silicon (Si), vanadium (V), gallium (Ga), indium (In), lanthanum (La), and cerium (Ce). is selected from the group consisting of

In an exemplary embodiment of the present application, A in Formula 1 is more preferably selected from the group consisting of Zn, Mg, Mn, Co, and Ni.

In an exemplary embodiment of the present application, it is more preferable that B of Formula 1 is selected from the group consisting of Al, Fe(III), and Cr.

In an exemplary embodiment of the present application, A in Formula 1 may be Zn, and B may be Fe(III).

In an exemplary embodiment of the present application, the ferrite-based catalyst may be a zinc ferrite catalyst.

According to an exemplary embodiment of the present application, the ferrite-based catalyst may further include an α-iron oxide (α-Fe ₂ O ₃ ) phase.

According to an exemplary embodiment of the present application, the ferrite-based catalyst may be a composite phase of α-iron oxide (α-Fe ₂ O ₃ ).

According to an exemplary embodiment of the present application, when the ferrite-based catalyst is a composite phase of α-iron oxide (α-Fe ₂ O ₃ ), based on the total weight of the ferrite-based catalyst composite phase, the content of the ferrite-based catalyst is 5 It may range from 5% to 90% by weight, and the content of α-iron oxide (α-Fe ₂ O ₃ ) may range from 5% to 20% by weight.

According to an exemplary embodiment of the present application, the method for producing the ferrite-based catalyst is not limited to this as long as it is a method commonly used in the technical field. Specifically, a production method using a coprecipitation method is preferable.

According to an exemplary embodiment of the present application, the ferrite-based catalyst may refer to a ferrite-based catalyst manufactured by a coprecipitation method. The coprecipitation method includes coprecipitating a metal precursor and a basic aqueous solution; filtering the sediment; washing step; drying step; And it may include the step of baking.

According to an exemplary embodiment of the present application, the isomerization catalyst is one selected from the group consisting of aluminum oxide, silicon oxide, zeolite, modified zeolite, γ-alumina, hydrotalcite, borosilicate, alkali metal oxide, and alkaline earth metal oxide. Alternatively, it may contain two or more components, or a mixture thereof.

According to an exemplary embodiment of the present application, the isomerization catalyst can perform a reversible isomerization reaction of 1-butene and 2-butene.

According to an exemplary embodiment of the present application, the reversible isomerization reaction means that 2-butene may be converted to 1-butene and 1-butene may be converted to 2-butene by the isomerization catalyst. .

Specifically, when an oxidative dehydrogenation reaction proceeds under a ferrite-based catalyst, 2-butene is converted to butadiene, and when an isomerization reaction is performed, 2-butene is isomerized into 1-butene. The isomerization reaction competes with the oxidative dehydrogenation reaction, and when 2-butene, a reactant of the oxidative dehydrogenation reaction, is consumed, 1-butene is isomerized back to 2-butene by the isomerization catalyst (equilibrium reaction) ) can be. As a result, most of the reactant butene is converted to butadiene, but the speed is slowed due to competition with the isomerization reaction, and the section of the catalyst layer where heat generation occurs is widely distributed throughout the catalyst layer, which has the effect of dispersing heat generation.

According to an exemplary embodiment of the present application, the reactant containing the butene may be a raw material containing C4 fraction, steam, oxygen (O ₂ ), and nitrogen (N ₂ ).

According to an exemplary embodiment of the present application, the oxidative dehydrogenation reaction involves reacting raw materials containing C4 oil, steam, oxygen (O ₂ ), and nitrogen (N ₂ ) at a reaction temperature of 300°C to 600°C, The reaction may be carried out under pressure conditions of 0.1 kg _f / cm ² to 1.5 kg _f / cm ² and GHSV (Gas Hourly Space Velocity) 30 h ^-1 to 500 h ^-1 .

The C4 fraction may refer to C4 raffinate-1, 2, and 3 remaining after separating useful compounds from the C4 mixture produced by naphtha cracking, and refers to C4 that can be obtained through ethylene dimerization. It may be.

According to an exemplary embodiment of the present application, the C4 fraction is n-butane, trans-2-butene, cis-2-butene, and 1 -It may be a mixture of 1 or 2 or more selected from the group consisting of 1-butene.

According to an exemplary embodiment of the present application, the steam or nitrogen (N ₂ ) reduces the risk of explosion of the reactant in the oxidative dehydrogenation reaction, while preventing coking of the catalyst and removing reaction heat. It is a diluting gas introduced for this purpose.

According to an exemplary embodiment of the present application, oxygen (O ₂ ) is an oxidant and reacts with C4 fraction to cause a dehydrogenation reaction.

According to an exemplary embodiment of the present application, the oxidative dehydrogenation reaction can be prepared according to Scheme 1 or Scheme 2 below.

[Scheme 1]

C ₄ H ₈ + 1/2O ₂ → C ₄ H ₆ + H ₂ O

[Scheme 2]

C ₄ H ₁₀ + O ₂ → C ₄ H ₆ + 2H ₂ O

Butadiene is produced by removing hydrogen from butane or butene through the oxidative dehydrogenation reaction. Meanwhile, in the oxidative dehydrogenation reaction, in addition to the main reaction as shown in Scheme 1 or 2, side reaction products including carbon monoxide (CO), carbon dioxide (CO ₂ ), etc. may be generated. The side reaction product may include a process in which the side reaction product is separated and discharged to the outside of the system to prevent continuous accumulation within the process.

Figure 1 is an exemplary process diagram showing a reaction scheme showing the production process of 1,3-butadiene according to an exemplary embodiment of the present application.

According to Figure 1, when the oxidative dehydrogenation reaction proceeds under a ferrite-based catalyst, 2-butene is converted to 1,3-butadiene, and when an isomerization reaction is performed, 2-butene is isomerized into 1-butene. I do it. The isomerization reaction competes with the oxidative dehydrogenation reaction, and when 2-butene, a reactant of the oxidative dehydrogenation reaction, is consumed, 1-butene is isomerized back to 2-butene by the isomerization catalyst (equilibrium reaction) ) can be. As a result, most of the reactant 2-butene is converted to butadiene, but the speed is slowed due to competition with the isomerization reaction, and the section of the catalyst layer where heat generation occurs is widely distributed throughout the catalyst layer, which has the effect of dispersing heat generation. .

As described above, according to an exemplary embodiment of the present application, the method for producing 1,3-butadiene performs an isomerization reaction as a competing reaction of the oxidative dehydrogenation reaction of butene, slows the reaction rate, and controls heat generation. , thereby suppressing COx production and improving butadiene selectivity.

Hereinafter, in order to explain the present application in detail, examples will be given in detail. However, the embodiments according to the present application may be modified into various other forms, and the scope of the present application is not to be construed as being limited to the embodiments described in detail below. The embodiments of the present application are provided to more completely explain the present application to those with average knowledge in the art.

< Example >

< Example 1> Ferrite catalyst and Isomerization Mix the catalyst evenly

< Ferrite type Catalyst Preparation>

2 L of ammonia water with the pH adjusted to 8 was prepared, and a metal precursor solution containing 2 L of distilled water, 288.456 g of zinc chloride (ZnCl ₂ ), and 1132.219 g of iron chloride (FeCl ₃ ) was prepared in a separate container. While adding the prepared metal precursor solution to the prepared ammonia water, 9 wt% ammonia water was also added to maintain the pH at 8. To obtain a sample with a uniform composition, stir for 1 hour using a stirrer, add all of the metal precursor solutions, and age for 1 hour. Then, wash the solution in which the precipitate was formed using 4L of distilled water and filter it to separate the precipitate. did. The separated precipitate was dried for 16 hours and then calcined at 650°C to obtain ZnFe ₂ O ₄ powder. The obtained powder was ground and selected by sieving to have a size of 45㎛ or less.

ZnFe ₂ O ₄ powder was mixed with water and isopropyl-alcohol in a mechanical mixer, then sealed and aged at 80°C for 3 hours to prepare dough. After the dough was heat treated at 80°C for 3 hours, it was extruded using a screw-type rotor and manufactured into pellets of 6 mm in size. The extruded pellets were dried at 120°C for 3 hours and then heat-treated at 500°C to prepare an oxidative dehydrogenation ferrite-based catalyst.

< Isomerization Catalyst Preparation>

The isomerization catalyst used was Y-zeolite from Zeolyst, a commercial product.

<Manufacture of butadiene>

A mixture of 1-butene, trans-2-butene, and cis-2-butene was used as a reactant, and nitrogen, steam, and oxygen were additionally introduced together. The catalyst layer in the reactor was filled by uniformly mixing 90 cc of the ferrite-based catalyst and 60 cc of the isomerization catalyst to make the catalyst layer 150 cc. At this time, the bulk density of both the ferrite-based catalyst and the zeolite was about 1.5 g/cc, and the weight ratio of the mixed packed ferrite:isomerization catalyst was also about 3:2.

GHSV (based on butene mixture) was set to 120h ^-1 . Steam was injected in the form of water, vaporized into steam at 150°C using a vaporizer, mixed with the butene mixture as a reactant, and introduced into the reactor. The reaction temperature was carried out at 350°C. The reaction results and hot spot temperatures due to heat generation inside the reactor are listed in Table 1 below.

< Example 2> Ferrite catalyst and Isomerization Synthesize a ferrite/isomerization catalyst complex by mixing the catalyst in the powder stage.

A reactant of the same composition as in Example 1 was used. For the catalyst, a hybrid-ferrite/isomerization catalyst composite was prepared by mixing and molding the powdered ferrite catalyst of Example 1 and the isomerization catalyst of Example 1 at a volume ratio of ferrite:isomerization catalyst = 3:2. A catalytic reaction layer was formed by filling 150 cc of catalyst complex. At this time, the bulk density of both the ferrite-based catalyst and the zeolite was about 1.5 g/cc, and the weight ratio of the mixed packed ferrite:isomerization catalyst was also about 3:2.

The experiment was conducted at the same temperature and reactant flow rate as in Example 1. The reaction results and hot spot temperatures due to heat generation inside the reactor are listed in Table 1 below.

< Comparative example 1> Ferrite catalyst layer and Isomerization catalyst layer taking turns catalyst layer Configuration (configuration in Figure 2)

A reactant of the same composition as in Example 1 was used. The catalyst layer was filled alternately with the ferrite catalyst layer of Example 1 and the isomerization catalyst layer of Example 1 to form a catalytic reaction layer. From the top of the reactor, the ferrite/isomerization/ferrite/isomerization/ferrite catalyst layer was filled to 30cc/30cc/30cc/30cc/30cc. The experiment was conducted at the same temperature and reactant flow rate as in Example 1. The reaction results and hot spot temperatures due to heat generation inside the reactor are listed in Table 1 below.

< Comparative example 2> Ferrite catalyst layer and inert layer taking turns catalyst layer composition

A reactant of the same composition as in Example 1 was used. The catalyst layer was filled with alumina balls, an inert material, instead of the isomerization catalyst of Comparative Example 1, so that the inert layer had the same shape. The ferrite catalyst layer and the alumina ball layer were filled alternately to form a catalyst reaction layer. Starting from the top of the reactor, the ferrite/alumina ball/ferrite/alumina ball/ferrite catalyst layer was filled to 30cc/30cc/30cc/30cc/30cc. The experiment was conducted at the same temperature and reactant flow rate as in Example 1. The reaction results and hot spot temperatures due to heat generation inside the reactor are listed in Table 1 below.

< Comparative example 3> Ferrite catalyst and Alumina ball Catalyst mixed evenly reaction layer composition

A reactant of the same composition as in Example 1 was used. The catalyst layer in the reactor was filled by uniformly mixing 90 cc of the ferrite catalyst of Example 1 and 60 cc of alumina balls to make the catalyst layer 150 cc. The experiment was conducted at the same temperature and reactant flow rate as in Example 1. The reaction results and hot spot temperatures due to heat generation inside the reactor are listed in Table 1 below.

< Comparative example 4> Synthesize ferrite-shaped catalyst by mixing ferrite catalyst and inert material in the powder stage

A reactant of the same composition as in Example 1 was used. A ferrite/bentonite catalyst composite was prepared by uniformly mixing the ferrite-based catalyst powder of Example 1 and bentonite powder, which is an inert material. When mixing alumina powder, the formability was poor, so bentonite was used instead. A catalyst complex was prepared by mixing and molding ferrite catalyst: bentonite at a volume ratio of 3:2. A catalytic reaction layer was formed by filling 150 cc of the catalyst complex. The experiment was conducted at the same temperature and reactant flow rate as in Example 1. The reaction results and hot spot temperatures due to heat generation inside the reactor are listed in Table 1 below.

[Table 1]

As shown above, the method for producing 1,3-butadiene according to an exemplary embodiment of the present application controls the heat generated in the oxidative dehydrogenation reaction of butene, consequently lowering the selectivity of COx and increasing the selection of butadiene. The degree can be increased.

Claims (10)

Filling a reactor with a catalyst layer containing a ferrite catalyst and an isomerization catalyst; and
Injecting a reactant containing butene into a reactor filled with the catalyst layer and performing an oxidative dehydrogenation reaction and isomerization reaction,
The catalyst layer is filled in the reactor so that the ferrite-based catalyst and the isomerization catalyst are simultaneously in contact with the reactant containing the butene,
A method for producing 1,3-butadiene, wherein the ferrite-based catalyst is a zinc ferrite catalyst. The method of claim 1, wherein the oxidative dehydrogenation reaction and the isomerization reaction are performed simultaneously with the oxidative dehydrogenation reaction and the isomerization reaction. The method for producing 1,3-butadiene according to claim 1, wherein the catalyst layer is filled with the ferrite-based catalyst and the isomerization catalyst mixed with each other. The method for producing 1,3-butadiene according to claim 3, wherein the contents of the ferrite-based catalyst and the isomerization catalyst are each 10% by weight to 90% by weight based on the total weight of the catalyst layer. The method for producing 1,3-butadiene according to claim 1, wherein the catalyst layer is filled with a hybrid catalyst complex that is a molded product of a mixture of the ferrite catalyst and the isomerization catalyst. The method for producing 1,3-butadiene according to claim 5, wherein the contents of the ferrite-based catalyst and the isomerization catalyst are each 10% by weight to 90% by weight based on the total weight of the hybrid catalyst complex. delete delete The method according to claim 1, wherein the isomerization catalyst is one or two or more components selected from the group consisting of aluminum oxide, silicon oxide, zeolite, modified zeolite, γ-alumina, hydrotalcite, borosilicate, alkali metal oxide, and alkaline earth metal oxide. , or a mixture thereof. The method for producing 1,3-butadiene according to claim 1, wherein the isomerization catalyst performs a reversible isomerization reaction of 1-butene and 2-butene.