KR20220065408A - Method for preparing zinx ferrite-based catalysts and method for preparing butadiene using the same - Google Patents

Abstract

A preparation method of a zinc ferrite-based catalyst according to one exemplary embodiment of the present application comprises the steps of: inducing co-precipitation by contacting a precursor aqueous solution including a zinc precursor, a ferrite precursor, and pure water with a basic aqueous solution; forming a solid sample by performing a drying process and a firing process; and coating the solid sample on a support, wherein the zinc precursor includes zinc nitrate, the ferrite precursor includes ferrite nitrate, and the temperature of the pure water of the co-precipitation step is 20 to 50 ℃.

Description

Manufacturing method of zinc ferritic catalyst and manufacturing method of butadiene using the same

The present application relates to a method for producing a zinc ferritic catalyst and a method for producing butadiene using the same.

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 of butene, oxidative dehydrogenation of butene, and the like.

However, the naphtha cracking process not only consumes a lot of energy due to a high reaction temperature, but is not a single process only for the production of 1,3-butadiene, so there is a problem that other basic oils other than 1,3-butadiene are produced in excess. . In addition, the direct dehydrogenation reaction of n-butene is not only thermodynamically disadvantageous, but also high temperature and low pressure conditions are required to produce 1,3-butadiene in high yield as an endothermic reaction, so commercialization of 1,3-butadiene is produced. The process is not suitable.

On the other hand, the oxidative dehydrogenation of butene is a reaction in which butene and oxygen react to produce 1,3-butadiene and water in the presence of a metal oxide catalyst, and since stable water is produced, it has a thermodynamically very advantageous advantage. In addition, since it is an exothermic reaction unlike the direct dehydrogenation reaction of butene, a high yield of 1,3-butadiene can be obtained even at a lower reaction temperature compared to the direct dehydrogenation reaction, and 1,3-butadiene does not require additional heat supply. It can be an effective standalone production process that can meet the demand.

The metal oxide catalyst is generally synthesized by a co-precipitation method in which a metal solution is simultaneously precipitated with a basic solution. Among the known metal oxide catalysts used in the oxidative dehydrogenation of n-butene, a ferrite-based catalyst is known to have excellent activity and stability. However, the ferrite-based catalyst has a problem in that its activity or durability is lowered due to excessive heat generation due to high temperature/high pressure reaction conditions. There was a problem in that the selectivity of butadiene was decreased as well as the reduction of the .

US Patent Publication No. 2013-0209351

An object of the present application is to provide a method for producing a zinc ferritic catalyst and a method for producing butadiene using the same.

An exemplary embodiment of the present application is,

co-precipitating an aqueous precursor solution comprising a zinc precursor, a ferrite precursor, and pure water in contact with a basic aqueous solution;

forming a solid sample by performing a drying process and a firing process; and

coating the solid sample on a support;

The zinc precursor includes zinc nitrate, the ferrite precursor includes ferrite nitrate,

The temperature of the pure water in the co-precipitation step provides a method for producing a zinc ferritic catalyst that is 20 ℃ to 50 ℃.

In addition, another embodiment of the present application is,

preparing a zinc ferritic catalyst by the above method; and

Preparing butadiene by using the zinc ferritic catalyst for oxidative dehydrogenation of butene

It provides a method for producing butadiene comprising a.

According to an exemplary embodiment of the present application, by using zinc nitrate and ferrite nitrate in the preparation of a zinc ferritic catalyst, filtration and washing processes can be excluded after the co-precipitation step, thereby simplifying the manufacturing process and reducing process costs can do.

In addition, according to an exemplary embodiment of the present application, since zinc chloride and ferrite chloride are not applied as in the prior art, there is a feature that can reduce the emission of corrosive substances such as Cl ^- .

In addition, according to an exemplary embodiment of the present application, by using zinc nitrate and ferrite nitrate in the preparation of a zinc ferritic catalyst, and adjusting the temperature of the pure water in the coprecipitation step to 20° C. to 50° C., the conversion rate of butene and the amount of butadiene It is possible to improve selectivity as well as reduce the amount of heavy oil (heavies) produced as a by-product.

1 is a process diagram for preparing a zinc ferritic catalyst according to Examples 1 to 3 of the present application.
2 is a process diagram for preparing a zinc ferritic catalyst according to Comparative Examples 1 and 2 of the present application.

Hereinafter, the present application will be described in more detail.

In the present specification, 'yield (%)' is defined as a value obtained by dividing the weight of 1,3-butadiene, which is a product of the oxidative dehydrogenation reaction, by the weight of butene, a raw material. For example, the yield may be expressed by the following formula.

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

In the present specification, 'conversion (%)' refers to the rate at which a reactant is converted into a product, for example, the conversion rate of butene may be defined by the following formula.

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

In the present specification, 'selectivity (%)' is defined as a value obtained by dividing the amount of change in butadiene (BD) by the amount of change in butene (BE). For example, selectivity can be expressed by the following formula.

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

In the present specification, 'butadiene' means 1,3-butadiene.

In the preparation of the conventional zinc ferritic catalyst, zinc chloride, which is zinc chloride, was used as a zinc precursor, and ferric chloride hydrate, which is ferrite chloride, was used as a ferrite precursor. As such, in the case of using a metal chloride as a metal precursor, it was essential to perform a filtration process and a washing process in order to reduce Cl ⁻ remaining in the coprecipitation solution and the precipitate after the coprecipitation step. In addition, even when Cl ⁻ is reduced in the filtration process and the washing process step, residual Cl ⁻ is discharged in the calcination step of preparing the zinc ferritic catalyst. Since the residual Cl ⁻ is a corrosive material, it may cause an increase in maintenance cost of a device for manufacturing a zinc ferritic catalyst and the like.

Accordingly, in the present application, it is possible to reduce the emission of corrosive substances such as Cl ⁻ described above, and to provide a method for manufacturing a zinc ferritic catalyst capable of reducing process costs by simplifying the manufacturing process.

A method of manufacturing a zinc ferritic catalyst according to an exemplary embodiment of the present application includes the steps of co-precipitating a zinc precursor, a ferrite precursor, and a precursor aqueous solution including pure water in contact with a basic aqueous solution; forming a solid sample by performing a drying process and a firing process; and coating the solid sample on a support, wherein the zinc precursor includes zinc nitrate, the ferrite precursor includes ferrite nitrate, and the temperature of the pure water in the coprecipitation step is 20° C. to 50° C.

It is known that the activity of a ferritic catalyst having a spinel structure (AFe ₂ O ₄ ) is good as a catalyst for a process of producing 1,3-butadiene through the oxidative dehydrogenation of butene.

On the other hand, in the case of a ferritic catalyst, it is known that the reactivity to 2-butene, especially trans-2-butene, is superior to that of the bismuth-molybdenum catalyst (Mo-Bi catalyst). there is. Therefore, even if the Mo-Bi catalyst is applied to the oxidative dehydrogenation of 2-butene, the same effect as in the present invention, that is, the results such as butene conversion or butadiene selectivity are not obtained.

In this case, the ZnFe ₂ O ₄ catalyst used for the oxidative dehydrogenation of butene may be generally prepared by a co-precipitation method. The co-precipitation method according to the prior art uses zinc chloride and ferrite chloride as metal precursors, and is prepared through processes such as stirring, aging, filtration and washing, drying, and calcination.

However, according to an exemplary embodiment of the present application, by using zinc nitrate and ferrite nitrate in the preparation of the zinc ferritic catalyst, filtration and washing processes can be excluded after the co-precipitation step, and thus the manufacturing process is simplified and process costs can save In addition, according to an exemplary embodiment of the present application, since zinc chloride and ferrite chloride are not applied as in the prior art, there is a feature that can reduce the emission of corrosive substances such as Cl ^- .

In the exemplary embodiment of the present application, the zinc precursor includes zinc nitrate, and the ferrite precursor includes ferrite nitrate. More specifically, the zinc nitrate may be zinc nitrate (Zn(NO ₃ ) ₂ ·6H ₂ O), and the ferrite nitrate may be iron nitrate (Fe(NO ₃ ) ₃ ·9H ₂ O).

In the exemplary embodiment of the present application, based on the total weight of the precursor solution, the content of the zinc precursor may be 0.1 wt% to 20 wt%, or 0.1 wt% to 15 wt%. In addition, based on the total weight of the precursor solution, the content of the ferrite precursor may be 1 wt% to 35 wt%, and may be 1 wt% to 20 wt%. When the content of the zinc precursor and the ferrite precursor satisfies the above-mentioned ranges, the synthesis of the zinc ferritic catalyst is easy when the precipitate is formed by the co-precipitation method.

In the exemplary embodiment of the present application, pure water (DI water) may be used as the water of the aqueous precursor solution. The temperature of the pure water may be 20 °C to 50 °C, preferably 25 °C to 45 °C, more preferably 25 °C to 30 °C. When the temperature of the pure water satisfies the above range, the catalyst production by the precipitation method is increased, the content of the active catalyst is adjusted, and ultimately, the selectivity and yield of butadiene according to the oxidative dehydrogenation reaction can be improved. In addition, it is possible to reduce the amount of heavy oil (heavies) produced as a by-product during the oxidative dehydrogenation reaction.

In the synthesis process of the zinc ferrite catalyst using the co-precipitation method, an α-Fe ₂ O ₃ phase may be formed. The α-Fe ₂ O ₃ phase shows a low butadiene selectivity in the oxidative dehydrogenation of butene, whereas a high butadiene selectivity in the ZnFe ₂ O ₄ phase. In particular, it is known that the α-Fe ₂ O ₃ phase plays a major role in generating a side product in the oxidative dehydrogenation of butene.

Therefore, the present inventors studied a synthesis method capable of controlling the generation of α-Fe ₂ O ₃ phase to improve butadiene selectivity, and when the temperature of the pure water in the coprecipitation step is 20° C. to 50° C., the zinc produced It was found that the activity of the catalyst can be increased by decreasing the content of the α-Fe ₂ O ₃ phase and increasing the content of the ZnFe ₂ O ₄ phase in the ferritic catalyst.

When the temperature of the pure water is less than 20 ℃ or exceeds 50 ℃, the content of the above-described α-Fe ₂ O ₃ phase increases, the production of by-products such as heavy oil during the oxidative dehydrogenation of butene may be increased. .

In an exemplary embodiment of the present application, the pH of the basic aqueous solution may be 7 to 12. Preferably, the pH may be 7.5 to 10. When the above range is satisfied, there is an effect of stably generating a zinc ferrite catalyst.

In an exemplary embodiment of the present application, the basic aqueous solution may be at least one selected from the group consisting of potassium hydroxide, ammonium carbonate, ammonium hydrogen carbonate, sodium hydroxide aqueous solution, sodium carbonate aqueous solution and aqueous ammonia. Preferably, the basic aqueous solution may be aqueous ammonia. In this case, during the preparation of the zinc ferritic catalyst, precipitation is easy, thereby improving the formation of catalyst particles.

In an exemplary embodiment of the present application, the concentration of the basic aqueous solution may be 3 wt% to 40 wt%, and may be 8 wt% to 20 wt%.

In the exemplary embodiment of the present application, the step of obtaining the precipitate may further include stirring the precursor solution after contacting it with the basic aqueous solution. By further comprising the step of stirring, the formation of precipitates of the metal precursors is facilitated, so that the formation of catalyst particles is advantageous. The stirring step may be performed at room temperature, and the stirring method may be used without limitation as long as it is a method of mixing a liquid phase and a liquid phase. In addition, the stirring time of the stirring step may be 30 minutes to 3 hours, may be 1 hour to 2 hours.

In an exemplary embodiment of the present application, the pH of the co-precipitation solution after the co-precipitation step may be 6 to 10, or 6.5 to 9.2.

A method for manufacturing a zinc ferritic catalyst according to an exemplary embodiment of the present application includes forming a solid sample by performing a drying process and a calcination process.

In the case of using zinc chloride and ferrite chloride as metal precursors as in the prior art, it was essential to perform a filtration process and a washing process in order to reduce Cl ^- remaining in the co-precipitation solution and the precipitate after the co-precipitation step. However, according to an exemplary embodiment of the present application, by using zinc nitrate and ferrite nitrate in the preparation of the zinc ferritic catalyst, filtration and washing processes can be excluded after the co-precipitation step, and thus the manufacturing process is simplified and process costs can save

In an exemplary embodiment of the present application, the drying process may be performed in a dryer or a drying oven after transferring the coprecipitation solution to a drying tray as it is. The drying process may be performed at a temperature of 80 ℃ to 150 ℃.

In the firing process, a method may be used in which the temperature is raised from 80° C. at a rate of 1° C./min, and maintained at 600° C. to 800° C. for 5 to 10 hours. In the firing process, specifically, a method of firing at 600° C. to 700° C., more specifically 600° C. to 650° C. may be used. In the firing process, specifically, a method of firing for 5 to 8 hours, more specifically 5 to 6 hours may be used.

The calcination process may use a heat treatment method commonly used in the art, and may be performed by injecting air at 1 L/min into the calcination furnace.

In an exemplary embodiment of the present application, after the drying process and the calcination process to form a solid sample, the step of pulverizing the solid sample may be further included. The step of pulverizing the solid sample is not particularly limited as long as it is a method of pulverizing the solid sample into fine particles, but ball milling may be used.

In an exemplary embodiment of the present application, the coating of the solid sample on the support may include mixing the support, the solid sample, and water.

Based on the total weight of the zinc ferritic catalyst, the content of the coated solid sample may be 10 wt% to 40 wt%, and may be 12 wt% to 35 wt%. Based on the total weight of the zinc ferritic catalyst, when the content of the coated solid sample is less than 10% by weight or exceeds 40% by weight, the effect of improving the catalytic activity is insignificant, and when the above range is satisfied, the catalytic activity It is possible to prepare a zinc ferritic catalyst with improved catalyst strength while maintaining

In the exemplary embodiment of the present application, the support may include at least one of alumina, silica, codeolite, titania, zirconia, siliconite, and silicon carbide. In an exemplary embodiment of the present application, the support is preferably alumina.

The shape of the support is not particularly limited, for example, the support may be a spherical alumina, in which case the diameter may be 2mm to 7mm.

In the exemplary embodiment of the present application, after the step of coating the solid sample on the support, drying the support on which the solid sample is coated may be further included. If necessary, it may further include a step of baking after drying. The drying may be performed under temperature conditions such as room temperature, 50°C to 150°C, 90°C to 120°C, but is not limited thereto.

In addition, an exemplary embodiment of the present application comprises the steps of preparing a zinc ferritic catalyst by the above method; and using the zinc ferritic catalyst for oxidative dehydrogenation of butene to produce butadiene.

The oxidative dehydrogenation reaction refers to a reaction in which an olefin and oxygen react to produce a conjugated diene and water under a zinc ferritic catalyst, and as a specific example, a reaction in which butene and oxygen react to produce 1,3-butadiene and water can

The reactor used for the oxidative dehydrogenation reaction is not particularly limited if it is a reactor that can be used for the oxidative dehydrogenation reaction, but for example, the reaction temperature of the installed catalyst layer is maintained constant and the reactant continuously passes through the catalyst layer to perform oxidative dehydrogenation. It may be a reactor in which the dehydrogenation reaction proceeds, and as a specific example, it may be a tubular reactor, a batch reactor, a fluidized bed reactor, or a fixed bed reactor, and the fixed bed reactor may be, for example, a shell-and-tube reactor or a plate-type reactor.

According to an exemplary embodiment of the present application, the step of preparing the butadiene is 250° C. to 450° C., 300° C. to a raw material containing C4 oil, steam, oxygen (O ₂ ) and nitrogen (N ₂ ) It can be carried out at a reaction temperature of 430 ° C. or 350 ° C. to 425 ° C. Within this range, the reaction efficiency is excellent without significantly increasing the energy cost, so that butadiene can be provided with high productivity, while maintaining high catalytic activity and stability can be

The oxidative dehydrogenation reaction may be performed, for example, at a gas hourly space velocity (GHSV) of 50 to 2000 h ^-1 , 50 to 1500 h ^-1 or 50 to 1000 h ^-1 based on normal butene, Within this range, the reaction efficiency is excellent, and thus there is an excellent effect of conversion rate, selectivity, yield, and the like.

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 may be doing

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 one or a mixture of two or more selected from the group consisting of -butene.

According to an exemplary embodiment of the present application, the steam (steam) or nitrogen (N ₂ ) in the oxidative dehydrogenation reaction, at the same time reducing the risk of explosion of reactants, prevention of coking of the catalyst and removal of reaction heat, etc. It is a diluent gas injected for the purpose.

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

According to an exemplary embodiment of the present application, the oxidative dehydrogenation reaction may 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

The oxidative dehydrogenation reaction removes hydrogen from butane or butene, thereby producing butadiene. On the other hand, in the oxidative dehydrogenation reaction, in addition to the main reaction shown in Schemes 1 or 2, side reaction products including carbon monoxide (CO) or carbon dioxide (CO ₂ ) may be produced. The side reaction product may include a process of being separated and discharged to the outside of the system so that continuous accumulation does not occur in the process.

According to an exemplary embodiment of the present application, in the method for producing butadiene, the butene conversion rate may be 72% or more, 72.5% or more, and 76% or more.

According to an exemplary embodiment of the present application, in the method for producing butadiene, the selectivity of butadiene may be 80% or more, 82% or more, and 83% or more.

Hereinafter, examples will be given to describe the present application in detail. However, the embodiments according to the present application may be modified in 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 of ordinary skill in the art.

<Example>

<Example 1>

A metal precursor aqueous solution containing 16.7 g of zinc nitrate (Zn(NO ₃ ) ₂ ·6H ₂ O), 71.06 g of iron nitrate (Fe(NO ₃ ) ₃ ·9H ₂ O), and 155.59 g of pure water at 25°C was prepared. At this time, the molar ratio of the metal components included in the metal precursor aqueous solution was Fe:Zn=2:1. A target pH (pH 6 to 10) was maintained while adding aqueous ammonia to the aqueous metal precursor solution. To obtain a sample of uniform composition, both the aqueous metal precursor solution and ammonia water were added while stirring for 1 hour using a stirrer, and then aged for 1 hour, and then the solution in which the precipitate was formed was transferred to a drying tray.

After drying in a drying oven at 90° C. for 16 hours, the dried coprecipitate was put into a kiln and heat-treated at 650° C. for 6 hours to prepare a zinc ferrite catalyst. ZnFe ₂ O ₄ powder was obtained. The obtained powder was pulverized and screened by a sieve method to have a size of 45 μm or less.

A ferritic coating catalyst was prepared by mixing the ferritic catalyst with an alumina support in the form of a ball having a diameter of 4 mm to 6 mm and water in a rotating body coating machine. Drying of the coated catalyst was carried out at a temperature of 90°C to 120°C for 12 hours.

<Example 2>

It was carried out in the same manner as in Example 1, except that 30° C. pure water was used.

<Example 3>

The same procedure as in Example 1 was performed, except that 45° C. pure water was used.

<Comparative Example 1>

The same procedure as in Example 1 was performed, except that 15° C. pure water was used.

<Comparative Example 2>

The same procedure as in Example 1 was performed, except that pure water at 60° C. was used.

<Experimental Example 1>

For the zinc ferritic catalysts prepared in Examples and Comparative Examples, XRD (X-ray diffraction) analysis was performed, and the results are shown in Table 1 below. More specifically, in the prepared zinc ferritic catalyst, the content of the zinc ferrite (ZnFe ₂ O ₄ ) crystal structure and the content of the alpha ferrite (α-Fe ₂ O ₃ ) crystal structure are shown in Table 1 below.

The XRD analysis was measured using an X-ray diffraction analyzer (Bruker AXS D4-Endeavor XRD), and the analysis conditions of applied voltage (40kV) and applied current (40mA) were used. The range was 20° to 80°, and measurements were made by scanning at 0.05° intervals.

[Table 1]

As shown in Table 1 above, according to an exemplary embodiment of the present application, the content of the zinc ferrite (ZnFe ₂ O ₄ ) crystal structure can be increased and the content of the alpha ferrite (α-Fe ₂ O ₃ ) crystal structure can be reduced. It can be confirmed that

<Experimental Example 2>

C4 fraction and oxygen were used as reactants, and nitrogen and steam were additionally introduced together. In the reaction composition, the molar ratios of oxygen, nitrogen, and steam based on the C4 fraction were 0.67, 2.67, and 5, respectively. The reaction was carried out under the conditions of 360° C., GHSV=120h ^-1 , OBR=0.67, SBR=5, NBR=2.67. A metal tubular fixed bed reactor was used as the reactor. 200cc of the catalyst prepared in Examples and Comparative Examples was charged in a fixed bed reactor, steam was injected in the form of water, and was vaporized to steam at 120° C. using a vaporizer. was allowed to enter. After the reaction, the product was analyzed using gas chromatography (GC), and butene conversion, butadiene selectivity, butadiene yield and heavy oil selectivity were calculated using the results measured by gas chromatography.

GHSV: Gas Hourly Space Velocity

OBR: O ₂ /butene molar ratio

SBR: Steam/butene molar ratio

NBR: N ₂ /butene molar ratio

<GC analysis conditions>

1) Column: HP-1 (100m × 350㎛ × 0.5㎛)

2) Injection volume: 1 μl

3) Inlet Temp.: 280℃, Pressure: 36.2psi, Total flow: 33.5 ml/min, Split flow: 60 ml/min, spilt ratio: 10:1

4) Column flow: 1.42 ml/min

5) Oven temp.: 50℃/15min-10℃/min-260℃/18min (Total 52min)

6) Detector temp.: 280℃, H ₂ : 35 ml/min, Air: 300 ml/min, He: 20 ml/min

7) GC Model: Agilent 6890

[Table 2]

As described above, according to an exemplary embodiment of the present application, by using zinc nitrate and ferrite nitrate in the preparation of a zinc ferritic catalyst, filtration and washing processes can be excluded after the co-precipitation step, thereby simplifying the manufacturing process This can reduce the process cost.

In addition, according to an exemplary embodiment of the present application, since zinc chloride and ferrite chloride are not applied as in the prior art, there is a feature that can reduce the emission of corrosive substances such as Cl ^- .

In particular, according to an exemplary embodiment of the present application, by using zinc nitrate and ferrite nitrate in the preparation of a zinc ferritic catalyst, and controlling the temperature of the pure water in the coprecipitation step to 20° C. to 50° C., the butene conversion rate and butadiene It is possible to improve selectivity as well as reduce the amount of heavy oil (heavies) produced as a by-product. In addition, when the conversion of butene, the selectivity of butadiene, the yield of butadiene, and the amount of heavy oil as a by-product are comprehensively considered, it is more preferable that the temperature of the pure water is 25° C. to 30° C.

Although preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and it is possible to carry out various modifications within the scope of the claims and the detailed description of the invention, and this also falls within the scope of the invention. .

Claims (10)

co-precipitating an aqueous precursor solution containing a zinc precursor, a ferrite precursor, and pure water into contact with a basic aqueous solution;
forming a solid sample by performing a drying process and a firing process; and
coating the solid sample on a support;
The zinc precursor includes zinc nitrate, the ferrite precursor includes ferrite nitrate,
The temperature of the pure water in the co-precipitation step is a method for producing a zinc ferritic catalyst that is 20 ℃ to 50 ℃. The method of claim 1, wherein the zinc nitrate is zinc nitrate (Zn(NO ₃ ) ₂ .6H ₂ O). The method of claim 1, wherein the ferrite nitrate is iron nitrate (Fe(NO ₃ ) ₃ ·9H ₂ O). The method according to claim 1, wherein the basic aqueous solution is at least one selected from the group consisting of potassium hydroxide, ammonium carbonate, ammonium hydrogen carbonate, sodium hydroxide aqueous solution, sodium carbonate aqueous solution and aqueous ammonia solution. The method according to claim 1, further comprising the step of pulverizing the solid sample after the step of forming the solid sample by performing the drying process and the calcination process. The method according to claim 1, wherein, based on the total weight of the zinc ferritic catalyst, the content of the coated solid sample is 10 wt% to 40 wt%. The method according to claim 1, wherein the support comprises at least one of alumina, silica, codeolite, titania, zirconia, siliconite and silicon carbide. The method according to claim 1, wherein the coating of the solid sample on the support comprises mixing the support, the solid sample, and water. The method according to claim 1, wherein after the step of coating the solid sample on the support, the method for producing a zinc ferritic catalyst further comprising drying the support on which the solid sample is coated. 10. A method for preparing a zinc ferritic catalyst according to any one of claims 1 to 9; and
Preparing butadiene by using the zinc ferritic catalyst for oxidative dehydrogenation of butene
A method for producing butadiene comprising a.

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