KR102216767B1 - Method for preparing metal complex catalyst and metal complex catalyst prepared thereof - Google Patents

Abstract

(A) a zinc (Zn) precursor, a ferrite (Fe) precursor, and the step of obtaining a precipitate by contacting a metal precursor solution including water with a basic aqueous solution; (B) filtering and firing the precipitate to obtain a zinc ferrite catalyst; And (C) supporting an acid on the zinc ferrite catalyst, and to a metal composite catalyst prepared thereby.

Description

Method of manufacturing a metal complex catalyst and a metal complex catalyst manufactured thereby {METHOD FOR PREPARING METAL COMPLEX CATALYST AND METAL COMPLEX CATALYST PREPARED THEREOF}

The present specification relates to a method of manufacturing a metal composite catalyst and a metal composite catalyst manufactured thereby.

1,3-butadiene is an intermediate of petrochemical products, and its demand and value are gradually increasing worldwide. The 1,3-butadiene is prepared 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 the high reaction temperature, but also has a problem that other basic oils other than 1,3-butadiene are produced in excess because it is not a single process only for the production of 1,3-butadiene. . In addition, the direct dehydrogenation reaction of n-butene is not only thermodynamically disadvantageous, but also requires high temperature and low pressure conditions for the production of high yield 1,3-butadiene as an endothermic reaction, and is commercialized to produce 1,3-butadiene. Not suitable as a process.

On the other hand, 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, and since stable water is produced, it has a very advantageous thermodynamic advantage. In addition, since it is an exothermic reaction unlike the direct dehydrogenation reaction of butene, it is possible to obtain a high yield of 1,3-butadiene even at a lower reaction temperature compared to the direct dehydrogenation reaction, and since it does not require additional heat supply, 1,3-butadiene It can be an effective standalone production process that can meet demand.

The metal oxide catalyst is generally synthesized by a precipitation method. Due to technical and spatial constraints, the amount of one time produced is small, and the same process is repeated several times to prepare a catalyst to fill the target amount. The reactivity of the catalysts produced several times may differ depending on the production cycle, and the reactivity difference of these catalysts is also directly related to the yield of the product (butadiene). Is being carried out.

Korea Public Publication No. 10-2014-0119222

The present specification provides a method of manufacturing a metal composite catalyst and a metal composite catalyst manufactured thereby.

An exemplary embodiment of the present specification is, (A) obtaining a precipitate by contacting a metal precursor solution including a zinc (Zn) precursor, a ferrite (Fe) precursor, and water with a basic aqueous solution; (B) filtering and firing the precipitate to obtain a zinc ferrite catalyst; And (C) it provides a method for producing a metal complex catalyst comprising the step of supporting an acid on the zinc ferrite catalyst.

In addition, an exemplary embodiment of the present specification provides a method for producing butadiene comprising the step of preparing butadiene by using a metal composite catalyst prepared according to the method for producing a metal composite catalyst described above in an oxidative dehydrogenation reaction of butene. do.

An exemplary embodiment of the present specification provides a metal composite catalyst including a zinc ferrite catalyst and an acid.

The method of manufacturing a metal complex catalyst according to an exemplary embodiment of the present specification includes phosphoric acid supported on a zinc ferrite catalyst to suppress a complete oxidation reaction, which is a side reaction of the oxidative dehydrogenation reaction, thereby improving the conversion rate of butene, and the selectivity of butadiene. It has the effect of increasing.

1 is a process chart for carrying out a method of manufacturing a metal composite catalyst according to an exemplary embodiment of the present specification.

Hereinafter, the present specification 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 (BD), a product of an oxidative dehydrogenation reaction, by the weight of butene (BE), a raw material. For example, the yield can be expressed by the following equation.

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

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

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

In the present specification,'selectivity (%)' is defined as a value obtained by dividing the change amount of butadiene by the change amount of butene. For example, the 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 specification,'COx' refers to a compound including carbon monoxide (CO), carbon dioxide (CO ₂ ), etc. formed during an oxidative dehydrogenation reaction.

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

An exemplary embodiment of the present specification is, (A) obtaining a precipitate by contacting a metal precursor solution including a zinc (Zn) precursor, a ferrite (Fe) precursor, and water with a basic aqueous solution; (B) filtering and firing the precipitate to obtain a zinc ferrite catalyst; And (C) it provides a method for producing a metal complex catalyst comprising the step of supporting an acid on the zinc ferrite catalyst.

The zinc ferrite catalyst (ZnFe ₂ O ₄ ) used in the oxidative dehydrogenation reaction is generally prepared by coprecipitation. Since the catalyst prepared by the co-precipitation method is manufactured in a bulk form, α-iron oxide (α-Fe ₂ O ₃ ) phase is formed. This α-iron oxide (α-Fe ₂ O ₃ ) phase acts as a cause of reducing the selectivity of 1,3-butadiene, a product, in the oxidative dehydrogenation of butene.

Accordingly, the present inventors suppressed the complete oxidation reaction, which is a side reaction of the oxidative dehydrogenation reaction of butene, by supporting phosphoric acid on the zinc ferrite catalyst prepared by the coprecipitation method. When complete oxidation, 6 oxygen (O ₂ ) is consumed. When complete oxidation is inhibited, the consumption of oxygen supplied with butene as a reactant is reduced, ultimately improving the conversion rate of butene and selectivity of butadiene. . Through this, the reactivity of the zinc ferrite catalyst prepared by the coprecipitation method could be improved.

In addition, when an acid is added during the extrusion molding process of the catalyst (Korean Patent Laid-Open Patent 2014-0082869), this is for the purpose of peptizing the inorganic binder.In this case, since the acid is removed in the heat treatment process after extrusion, the acid is used for the reaction. It doesn't work. However, when an acid is supported on a catalyst as in the present invention, the purpose of using the acid is different because it is used in an oxidative dehydrogenation reaction as a supported catalyst.

According to an exemplary embodiment of the present specification, the content of the zinc precursor may be 0.1wt% to 5wt%, specifically 0.1wt% to 3wt% based on 100wt% of water in the metal precursor solution in step (A). It can be %.

According to an exemplary embodiment of the present specification, the content of the ferrite precursor may be 1wt% to 10wt%, specifically 1wt% to 7wt%, based on 100wt% of water in the metal precursor solution in step (A). I can. When the content of the zinc precursor and the ferrite precursor satisfies the above range, it is easy to synthesize a metal composite catalyst when forming a precipitate by co-precipitation.

According to the exemplary embodiment of the present specification, the acid in step (C) may be phosphoric acid. Specifically, when the catalyst is prepared by supporting phosphoric acid on a zinc ferrite catalyst prepared by a coprecipitation method, a complete oxidation reaction, which is a side reaction during the oxidative dehydrogenation reaction of butene, can be suppressed.

According to an exemplary embodiment of the present specification, the content of the acid may be 0.05wt% to 0.2wt%, more specifically 0.05wt% to 0.1wt%, based on 100wt% of the zinc ferrite catalyst in step (C). It can be %. When the content of the acid is less than 0.05 wt%, phosphoric acid is not sufficiently supported, so that side reactions of the oxidative dehydrogenation reaction cannot be sufficiently prevented, and when the content of the acid is more than 0.2 wt%, the acid is excessively supported and the activity of the catalyst is suppressed, resulting in the conversion of butene and Butadiene selectivity can be reduced.

According to an exemplary embodiment of the present specification, the zinc precursor and the ferrite precursor are each independently at least one selected from the group consisting of nitrate, ammonium salt, sulfate, and chloride, or It may be a hydrate thereof.

According to an exemplary embodiment of the present specification, the zinc precursor may be zinc chloride (ZnCl ₂ ).

According to the exemplary embodiment of the present specification, the ferrite precursor may be ferric chloride hydrate (FeCl ₃ · 6H ₂ O).

According to the exemplary embodiment of the present specification, the pH of the basic aqueous solution may be 7 to 11. Specifically, the pH of the basic aqueous solution may be greater than 7 and less than or equal to 11. More specifically, the pH of the basic aqueous solution may be 8 to 11. When the pH of the basic aqueous solution satisfies the above range, there is an effect of stably generating a metal complex catalyst.

According to the exemplary embodiment of the present specification, 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, it may be aqueous ammonia.

According to the exemplary embodiment of the present specification, the concentration of the basic aqueous solution may be 20wt% to 40wt%. Specifically, the concentration of the basic aqueous solution may be 25wt% to 30wt%.

According to an exemplary embodiment of the present specification, the step of obtaining the precipitate may further include a step of stirring after contacting the metal precursor solution with the basic aqueous solution. By further including the step of stirring, the formation of precipitates of metal precursors is facilitated, and catalyst particle formation is advantageous.

According to an exemplary embodiment of the present specification, the stirring may be performed at room temperature.

According to an exemplary embodiment of the present specification, the stirring method may be used without limitation as long as it is a method of mixing a liquid phase and a liquid phase.

According to an exemplary embodiment of the present specification, the stirring time of the stirring step may be 30 minutes to 3 hours. Specifically, the stirring time is preferably 1 to 2 hours.

According to an exemplary embodiment of the present specification, it may further include washing the precipitate after filtering and before firing. By further including the washing step, it is possible to remove unnecessary ions remaining in the precipitate.

According to an exemplary embodiment of the present specification, in step (B), the step of drying the precipitate after filtering and before firing may be further included.

According to an exemplary embodiment of the present specification, the drying may be performed after filtering the precipitate and then washing the precipitate, and before firing.

According to an exemplary embodiment of the present specification, the drying may be performed at 80°C to 150°C.

According to an exemplary embodiment of the present specification, the firing of the precipitate may be a step of raising the temperature to 650° C. at a rate of 1° C./min, followed by a firing process for 6 hours. The firing method may be a heat treatment method commonly used in the art.

According to an exemplary embodiment of the present specification, the firing of the precipitate may be performed by injecting 1L/min of air into the firing furnace.

According to an exemplary embodiment of the present specification, it may further include pulverizing the zinc ferrite catalyst obtained in step (B) before step (C).

According to the exemplary embodiment of the present specification, the size of the metal composite catalyst particles after the step of supporting an acid on the zinc ferrite catalyst in step (C) may be 0.6mm to 0.85mm.

According to an exemplary embodiment of the present specification, after the step (C), the step of sintering the zinc ferrite catalyst on which phosphoric acid is supported may be further included. Specifically, after raising the temperature to 500°C at a rate of 1°C/min, it may be a step of undergoing a firing process for 6 hours.

According to an exemplary embodiment of the present specification, the method of manufacturing the metal complex catalyst may be a method of manufacturing a metal complex catalyst for oxidative dehydrogenation of butene.

An exemplary embodiment of the present specification provides a metal composite catalyst prepared according to the method for producing a metal composite catalyst described above.

An exemplary embodiment of the present specification provides a method for producing butadiene, including the step of preparing butadiene by using the metal composite catalyst according to the method for producing a metal composite catalyst described above in an oxidative dehydrogenation reaction of butene.

Another exemplary embodiment of the present specification provides a metal composite catalyst including a zinc ferrite catalyst and an acid.

According to the exemplary embodiment of the present specification, the acid may be phosphoric acid.

According to an exemplary embodiment of the present specification, the metal composite catalyst may be in a form in which an acid is supported on a zinc ferrite catalyst.

According to an exemplary embodiment of the present specification, the size of the metal composite catalyst particle may be 0.6mm to 0.85mm.

According to an exemplary embodiment of the present specification, a metal complex catalyst including a zinc ferrite catalyst and an acid may be provided. Phosphoric acid is not removed during firing, so the amount initially added may remain as it is. Specifically, the content of the acid based on the total weight of the metal composite catalyst may be 0.05wt% to 0.2wt%, more specifically 0.05wt% to 0.1wt%. In addition, the zinc ferrite catalyst may be 99.8wt% to 99.95wt% based on the total weight of the metal composite catalyst.

When the content of the acid is less than 0.05 wt%, phosphoric acid is not sufficiently supported, so that side reactions of the oxidative dehydrogenation reaction cannot be sufficiently prevented, and when the content of the acid is more than 0.2 wt%, phosphoric acid is excessively supported and the activity of the catalyst is suppressed, resulting in the conversion of butene. And butadiene selectivity may be reduced.

In addition, an exemplary embodiment of the present specification provides a method for producing butadiene, including the step of preparing butadiene by using the above-described metal composite catalyst in an oxidative dehydrogenation reaction of butene.

According to an exemplary embodiment of the present specification, in the preparing of butadiene, a reactant including a C4 mixture may be used. The C4 mixture includes, for example, at least one normal butene selected from 2-butene (trans-2-Butene, cis-2-Butene) and 1-butene, and optionally normal butane or C4 raffinate. It may further include -3. The reactant may further include at least one selected from air, nitrogen, steam, and carbon dioxide as an example, and preferably further includes nitrogen and steam. As a specific example, the reactant may include a C4 mixture, oxygen, steam, and nitrogen in a molar ratio of 1: 0.1 to 1.5: 1 to 15: 0.5 to 10 or 1: 0.5 to 1.2: 5 to 12: 0.5 to 5. . In addition, the method for producing butadiene according to an exemplary embodiment of the present specification has an advantage of excellent reaction efficiency and less wastewater generation even when using a small amount of steam at 1 mol to 10 mol or 5 mol to 10 mol relative to 1 mol of the C4 mixture. , Ultimately, it provides the effect of reducing the energy consumed in the process as well as the wastewater treatment cost. The oxidative dehydrogenation reaction may be performed at a reaction temperature of 250°C to 500°C, 300°C to 450°C, 320°C to 400°C, 330°C to 380°C, or 350°C to 370°C, for example, and within this range The reaction efficiency is excellent without significantly increasing the energy cost of 1,3-butadiene can be provided with high productivity.

According to an exemplary embodiment of the present specification, the step of preparing the butadiene is carried out in a single reactor at a reaction temperature of 360°C and a condition of GHSV (Gas Hourly Space Velocity) 120h ^-1 , and the reactant is a C4 mixture: oxygen: steam : Nitrogen may be included in a molar ratio of 1:0.67:5:2.67.

In addition, according to an exemplary embodiment of the present specification, the step of preparing the butadiene is performed in a two-stage reactor (a reaction temperature of 360°C in an oxygen fine-division case, a gas hourly space velocity (GHSV) 120h ^-1 ), and the The reactant may contain a C4 mixture: oxygen: steam: nitrogen in a molar ratio of 1:0.67:5:2.67.

1 is an exemplary process diagram for carrying out a method of manufacturing a metal composite catalyst according to an exemplary embodiment of the present specification.

According to an exemplary embodiment of the present specification, in order to prevent the phenomenon of reducing the selectivity of butadiene on α-iron oxide (α-Fe ₂ O ₃ ) formed when preparing a catalyst for oxidative dehydrogenation of butene by a coprecipitation method, Phosphoric acid is supported on the prepared catalyst to suppress complete oxidation reaction, which is a side reaction of oxidative dehydrogenation of butene. Through this, it is possible to improve the reactivity of the zinc ferrite catalyst prepared by the coprecipitation method.

As described above, the metal composite catalyst according to the exemplary embodiment of the present specification increases the conversion rate of butene and the selectivity of butadiene during the oxidative dehydrogenation of butene, thereby ultimately producing butadiene with high yield.

Hereinafter, examples will be described in detail in order to describe the present specification in detail. However, the embodiments according to the present specification may be modified in various forms, and the scope of the present specification is not construed as being limited to the embodiments described below. The embodiments of the present specification are provided to more completely describe the present specification to those of ordinary skill in the art.

<Example 1>

12.019 g of zinc chloride (ZnCl ₂ ) and 37.662 g of ferric chloride (FeCl ₃ ) were dissolved in 404.59 g of distilled water to prepare a metal precursor solution. At this time, the molar ratio of the metal components included in the metal precursor solution was Zn:Fe=1:2. Ammonia aqueous solution was added dropwise to pH 9 to the prepared metal precursor aqueous solution, and stirred for 1 hour to coprecipitate. Thereafter, the co-precipitate was filtered under reduced pressure to obtain a co-precipitate, which was dried at 90° C. for 16 hours, and then heated up to 650° C. at a rate of 1° C./min at 80° C. in an air atmosphere, and then for 6 hours. Maintained to prepare a zinc-iron oxide (ZnFe ₂ O ₄ ) powder having a spinel structure. 0.05wt% of phosphoric acid was supported.

<Example 2>

In Example 1, a metal composite catalyst was prepared in the same manner as in Example 1, except that 0.1 wt% of phosphoric acid was supported instead of 0.05 wt% of phosphoric acid.

<Example 3>

In Example 1, a metal composite catalyst was prepared in the same manner as in Example 1, except that 0.2 wt% of phosphoric acid was supported instead of 0.05 wt% of phosphoric acid.

<Comparative Example 1>

20.865 g of ZnCl ₂ and 81.909 g of FeCl ₃ ·6H ₂ O were added to 1,500 g of DI water and completely dissolved to prepare a metal precursor solution. 1,500 g of DI water was put into the reactor, the metal precursor solution and 28 to 30 wt% of ammonia water were simultaneously added to the reactor, and the pH was maintained at 8 to form a catalyst precipitate.

The formed precipitate was filtered off using a filter paper and then dried in an oven at 90°C. Thereafter, the temperature was raised to 650° C. at a rate of 1° C./min, and then calcined at 650° C. for 6 hours was performed. This ?, 1 L/min of air was injected into the kiln and firing was performed to prepare a metal composite catalyst.

<Comparative Example 2>

In Example 1, a metal composite catalyst was prepared in the same manner as in Example 1, except that 0.3 wt% of phosphoric acid was supported instead of 0.05 wt% of phosphoric acid.

<Comparative Example 3>

In Example 1, a metal composite catalyst was prepared in the same manner as in Example 1, except that 0.4 wt% of phosphoric acid was supported instead of 0.05 wt% of phosphoric acid.

<Comparative Example 4>

In Example 1, a metal composite catalyst was prepared in the same manner as in Example 1, except that 0.6 wt% of phosphoric acid was supported instead of 0.05 wt% of phosphoric acid.

<Comparative Example 5>

After the manganese ferrite catalyst (MnFe ₂ O ₄ ) was pulverized, the temperature was raised to 500°C at a rate of 1°C/min, and then calcined at 500°C for 6 hours to prepare a metal composite catalyst.

<Experimental Example 1-1>

2-butene reactant of 40wt% cis-2-butene and 60wt% trans-2-butene, metal composite catalyst prepared in Example 1 0.1g, GHSV=262h ^-1 , OBR=1, SBR=5, NBR= 4, under conditions of a reaction temperature of 380°C, butadiene was prepared by oxidative dehydrogenation of butene.

(GHSV = Gas houly space velocity, OBR = Oxygen/total 2-butene ratio, SBR = Steam/total 2-butene ratio, NBR = Nitrogen/total 2-butene ratio)

<Experimental Example 1-2>

In Experimental Example 1-1, butadiene was prepared in the same manner as in Experimental Example 1-1, except that the reaction temperature was 400°C instead of 380°C.

<Experimental Example 1-3>

In Experimental Example 1-1, butadiene was prepared in the same manner as in Experimental Example 1-1, except that the reaction temperature was 440°C instead of 380°C.

<Experimental Example 1-4>

In Experimental Example 1-1, butadiene was prepared in the same manner as in Experimental Example 1-1, except that the metal composite catalyst prepared in Example 2 was used instead of the metal composite catalyst prepared in Example 1.

<Experimental Example 1-5>

In Experimental Example 1-4, butadiene was prepared in the same manner as in Experimental Example 1-4, except that the reaction temperature was 400°C instead of 380°C.

<Experimental Example 1-6>

In Experimental Example 1-4, butadiene was prepared in the same manner as in Experimental Example 1-4, except that the reaction temperature was 440°C instead of 380°C.

<Experimental Example 1-7>

In Experimental Example 1-1, butadiene was prepared in the same manner as in Experimental Example 1-1, except that the metal composite catalyst prepared in Example 3 was used instead of the metal composite catalyst prepared in Example 1.

<Experimental Example 1-8>

In Experimental Example 1-7, butadiene was prepared in the same manner as in Experimental Example 1-4, except that the reaction temperature was 400°C instead of 380°C.

<Experimental Example 1-9>

In Experimental Example 1-7, butadiene was prepared in the same manner as in Experimental Example 1-4, except that the reaction temperature was 440°C instead of 380°C.

<Comparative Example 1-1>

In Experimental Example 1-1, butadiene was prepared in the same manner as in Experimental Example 1-1, except that the metal composite catalyst prepared in Comparative Example 1 was used instead of the metal composite catalyst prepared in Example 1.

<Comparative Example 1-2>

In Comparative Example 1-1, butadiene was prepared in the same manner as in Comparative Example 1-1, except that the reaction temperature was 400°C instead of 380°C.

<Comparative Example 1-3>

In Comparative Example 1-1, butadiene was prepared in the same manner as in Comparative Example 1-1, except that the reaction temperature was 440°C instead of 380°C.

<Comparative Example 1-4>

In Experimental Example 1-1, butadiene was prepared in the same manner as in Experimental Example 1-1, except that the metal composite catalyst prepared in Comparative Example 2 was used instead of the metal composite catalyst prepared in Example 1.

<Comparative Example 1-5>

In Comparative Example 1-4, butadiene was prepared in the same manner as in Comparative Example 1-4, except that the reaction temperature was 400°C instead of 380°C.

<Comparative Example 1-6>

In Comparative Example 1-4, butadiene was prepared in the same manner as in Comparative Example 1-4, except that the reaction temperature was 440°C instead of 380°C.

<Comparative Example 1-7>

In Experimental Example 1-1, butadiene was prepared in the same manner as in Experimental Example 1-1, except that the metal composite catalyst prepared in Comparative Example 3 was used instead of the metal composite catalyst prepared in Example 1.

<Comparative Example 1-8>

In Comparative Example 1-7, butadiene was prepared in the same manner as in Comparative Example 1-7, except that the reaction temperature was 400°C instead of 380°C.

<Comparative Example 1-9>

In Comparative Example 1-7, butadiene was prepared in the same manner as in Comparative Example 1-7, except that the reaction temperature was 440°C instead of 380°C.

<Comparative Example 1-10>

In Experimental Example 1-1, butadiene was prepared in the same manner as in Experimental Example 1-1, except that the metal composite catalyst prepared in Comparative Example 4 was used instead of the metal composite catalyst prepared in Example 1.

<Comparative Example 1-11>

In Comparative Example 1-10, butadiene was prepared in the same manner as in Comparative Example 1-10, except that the reaction temperature was 400°C instead of 380°C.

<Comparative Example 1-12>

In Comparative Example 1-10, butadiene was prepared in the same manner as in Comparative Example 1-10, except that the reaction temperature was 440°C instead of 380°C.

<Comparative Example 1-13>

In Experimental Example 1-1, butadiene was prepared in the same manner as in Experimental Example 1-1, except that the metal composite catalyst prepared in Comparative Example 5 was used instead of the metal composite catalyst prepared in Example 1.

<Comparative Example 1-14>

In Comparative Example 1-13, butadiene was prepared in the same manner as in Comparative Example 1-13, except that the reaction temperature was 400°C instead of 380°C.

<Comparative Example 1-15>

In Comparative Example 1-13, butadiene was prepared in the same manner as in Comparative Example 1-13, except that the reaction temperature was 440°C instead of 380°C.

In the oxidative dehydrogenation of butenes of Experimental Examples 1-1 to 1-9 and Comparative Examples 1-1 to 1-15, the results of measuring butene conversion and butadiene selectivity are shown in Table 1 below.

division catalyst Reaction temperature
(℃) Butene
Conversion rate (%) butadiene
Selectivity (%) Experimental Example 1-1 Example 1 380 79.3 92.0 Experimental Example 1-2 Example 1 400 79.6 92.3 Experimental Example 1-3 Example 1 440 72.3 89.6 Experimental Example 1-4 Example 2 380 80.6 91.5 Experimental Example 1-5 Example 2 400 79.5 91.1 Experimental Example 1-6 Example 2 440 75.4 89.9 Experimental Example 1-7 Example 3 380 78.6 91.6 Experimental Example 1-8 Example 3 400 79.2 90.5 Experimental Example 1-9 Example 3 440 74.1 88.9 Comparative Example 1-1 Comparative Example 1 380 77.9 91.7 Comparative Example 1-2 Comparative Example 1 400 79.0 90.3 Comparative Example 1-3 Comparative Example 1 440 70.7 89.1 Comparative Example 1-4 Comparative Example 2 380 39.9 75.4 Comparative Example 1-5 Comparative Example 2 400 45.0 74.7 Comparative Example 1-6 Comparative Example 2 440 51.7 72.9 Comparative Example 1-7 Comparative Example 3 380 7.4 64.5 Comparative Example 1-8 Comparative Example 3 400 13.1 59.9 Comparative Example 1-9 Comparative Example 3 440 29.6 57.2 Comparative Example 1-10 Comparative Example 4 380 8.0 50.4 Comparative Example 1-11 Comparative Example 4 400 13.1 44.4 Comparative Example 1-12 Comparative Example 4 440 23.4 53.5 Comparative Example 1-13 Comparative Example 5 380 29.1 47.3 Comparative Example 1-14 Comparative Example 5 400 26.8 46.5 Comparative Example 1-15 Comparative Example 5 440 22.2 40.2

According to Table 1, the metal composite catalyst prepared according to Examples 1 to 3 may improve the conversion rate of butene and the selectivity of butadiene by supporting phosphoric acid on a zinc ferrite catalyst formed by a conventional coprecipitation method. This is because the complete oxidation reaction, which is a side reaction of the oxidative dehydrogenation reaction of butene, can be suppressed.

Comparing Experimental Examples 1-1 to 1-9 and Comparative Examples 1-1 to 1-3, Comparative Examples 1-1 to 1- in which oxidative dehydrogenation was performed with a zinc ferrite catalyst formed by a conventional coprecipitation method. Compared to 3, it can be seen that Experimental Examples 1-1 to 1-9 using a zinc ferrite catalyst supported on phosphoric acid have higher butene conversion and butadiene selectivity in the entire range of reaction temperatures of 380°C, 400°C and 440°C.

Comparing Experimental Examples 1-1 to 1-9 and Comparative Examples 1-4 to 1-12, compared to Comparative Examples 1-4 to 1-12 in which 0.3 wt% or more of phosphoric acid was supported on a zinc ferrite catalyst, phosphoric acid was 0.05 wt. It can be seen that in Experimental Examples 1-1 to 1-9 carrying% to 0.2wt%, butene conversion and butadiene selectivity are high in the entire range of reaction temperatures of 380°C, 400°C, and 440°C.

Particularly, when 0.4wt% or more of phosphoric acid of Comparative Examples 1-7 to 1-12 is supported, it can be seen that the butene conversion rate and the butadiene selectivity are significantly lower.

Comparing Experimental Examples 1-1 to 1-6 and Comparative Examples 1-13 to 1-15, compared to Comparative Examples 1-13 to 1-15 in which phosphoric acid was supported on a manganese ferrite catalyst during the oxidative dehydrogenation reaction of butene. , It was confirmed that the butene conversion and butadiene selectivity of Experimental Examples 1-1 to 1-6 in which phosphoric acid was supported on a zinc ferrite catalyst was remarkably excellent.

Although preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and various modifications can be made within the scope of the claims and detailed description of the invention, and this also belongs to the scope of the invention. .

Claims (15)

(A) obtaining a precipitate by contacting a metal precursor solution including a zinc (Zn) precursor, a ferrite (Fe) precursor, and water with a basic aqueous solution;
(B) filtering the precipitate and performing primary firing to obtain a zinc ferrite catalyst; And
(C) including the step of supporting phosphoric acid on the zinc ferrite catalyst,
In the step (B) further comprising the step of drying the precipitate after filtering and before the first firing,
After the step (C) further comprising the step of secondary firing the zinc ferrite catalyst supported with phosphoric acid,
In the step (C), the content of phosphoric acid is 0.05wt% to 0.2wt% based on 100wt% of the zinc ferrite catalyst. The method of claim 1, wherein the content of the zinc precursor is 0.1 wt% to 5 wt% based on 100 wt% of water in the metal precursor solution in step (A). The method of claim 1, wherein the content of the ferrite precursor is 1 wt% to 10 wt% based on 100 wt% of water in the metal precursor solution in step (A). delete delete The method according to claim 1, wherein the zinc precursor and the ferrite precursor are each independently at least one selected from the group consisting of nitrate, ammonium salt, sulfate, and chloride, or a hydrate thereof. Method for producing a metal composite catalyst characterized in that. The method of claim 1, wherein the zinc precursor is zinc chloride (ZnCl ₂ ). The method of claim 1, wherein the ferrite precursor is ferric chloride hydrate (FeCl ₃ 6H ₂ O). The method of claim 1, wherein the basic aqueous solution has a pH of 7 to 11. The method of 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. delete delete A method for producing butadiene, comprising the step of preparing butadiene by using a metal composite catalyst prepared by the method for producing a metal composite catalyst according to any one of claims 1 to 3 and 6 to 10 in an oxidative dehydrogenation reaction of butene . delete delete

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