KR20200021064A - Method for preparing metal complex catalyst and metal complex catalyst prepared thereof - Google Patents

Abstract

The present specification relates to a method for manufacturing a metal complex catalyst and the metal complex catalyst manufactured by the same, wherein the method comprises following steps of: (A) obtaining a precipitate by making a basic aqueous solution come in contact with a metal precursor solution containing a zinc (Zn) precursor, a ferrite (Fe) precursor, and water; (B) filtering and calcining the precipitate to obtain a zinc ferrite catalyst; and (C) supporting an acid on the zinc ferrite catalyst. The present invention has an effect of improving a conversion ratio of butene and increasing the selectivity of butadiene.

Description

METHOD FOR PREPARING METAL COMPLEX CATALYST AND METAL COMPLEX CATALYST PREPARED THEREOF

The present specification relates to a method for preparing a metal composite catalyst and a metal composite catalyst produced thereby.

1,3-butadiene is an intermediate of petrochemicals, and its demand and value are 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 has a high energy consumption due to the high reaction temperature, and because it is not a sole process for producing only 1,3-butadiene, there is a problem that other basic oils other than 1,3-butadiene are produced in excess. . In addition, the direct dehydrogenation of n-butene is not only thermodynamically disadvantageous, but also requires commercialization to produce 1,3-butadiene, requiring high temperature and low pressure conditions to produce high yield of 1,3-butadiene as an endothermic reaction. It is not suitable as a process.

On the other hand, the oxidative dehydrogenation of butene is a reaction of butene and oxygen in the presence of a metal oxide catalyst to produce 1,3-butadiene and water, which has a thermodynamically advantageous advantage because stable water is produced. In addition, unlike the direct dehydrogenation of butenes, it is exothermic, so that higher yields of 1,3-butadiene can be obtained at lower reaction temperatures than direct dehydrogenation, and 1,3-butadiene is not required because no additional heat supply is required. It can be an effective stand-alone production process that can meet demand.

The metal oxide catalyst is generally synthesized by a precipitation method, but the production process is small due to technology and space constraints, so that the catalyst may be prepared by repeating the same process several times to fill the target amount. The catalysts produced several times may have different reactivity with reactants according to the production cycle, and the reactivity of these catalysts is directly related to the yield of the product (butadiene). Is being performed.

Korean public publication 10-2014-0119222

The present specification provides a method for preparing a metal complex catalyst and a metal complex catalyst produced thereby.

One embodiment of the present specification, (A) contacting a metal precursor solution containing a zinc (Zn) precursor, a ferrite (Fe) precursor and water with a basic aqueous solution to obtain a precipitate; (B) filtering and calcining the precipitate to obtain a zinc ferrite catalyst; And (C) supporting an acid on the zinc ferrite catalyst.

In addition, an exemplary embodiment of the present specification provides a method for preparing butadiene, including preparing butadiene by using a metal complex catalyst prepared according to the method for preparing a metal complex catalyst in an oxidative dehydrogenation reaction of butene. do.

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

According to one embodiment of the present specification, a method for preparing a metal complex catalyst supports phosphoric acid on a zinc ferrite catalyst, inhibits a complete oxidation reaction as a side reaction of an oxidative dehydrogenation reaction, improves the conversion of butene, and selectivity of butadiene. Has the effect of increasing.

1 is a process chart for carrying out the method for producing a metal complex catalyst according to one embodiment of the present specification.

Hereinafter, this specification is demonstrated in detail.

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

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

In the present specification, 'conversion (%)' refers to the rate at which the reactants convert to the product, for example, the conversion of butene may be defined by the following formula.

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

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

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

In the present specification, 'COx' refers to a compound including carbon monoxide (CO), carbon dioxide (CO ₂ ) and the like formed during the oxidative dehydrogenation reaction.

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

One embodiment of the present specification, (A) contacting a metal precursor solution containing a zinc (Zn) precursor, a ferrite (Fe) precursor and water with a basic aqueous solution to obtain a precipitate; (B) filtering and calcining the precipitate to obtain a zinc ferrite catalyst; And (C) supporting an acid on the zinc ferrite catalyst.

Zinc ferrite catalysts (ZnFe ₂ O ₄ ) used for oxidative dehydrogenation are generally prepared by coprecipitation. Since the catalyst prepared by the coprecipitation method is manufactured in a bulk form, it forms an α-iron oxide (α-Fe ₂ O ₃ ) phase. This α-iron oxide (α-Fe ₂ O ₃ ) phase acts as a cause of reducing the selectivity of the product 1,3-butadiene in the oxidative dehydrogenation of butene.

Accordingly, the present inventors supported phosphoric acid on a zinc ferrite catalyst prepared by a coprecipitation method to suppress a complete oxidation reaction which is a side reaction of an oxidative dehydrogenation reaction of butene. When fully oxidized, 6 oxygen (O ₂ ) is consumed. When the complete oxidation reaction is suppressed, the consumption of oxygen supplied with the reactant butene can be reduced, thereby ultimately improving the butene conversion and butadiene selectivity. . Through this, it was possible to improve the reactivity of the zinc ferrite catalyst prepared by the coprecipitation method.

In addition, in the case of adding an acid in the extrusion process of the catalyst (Korean Patent Publication No. 2014-0082869), this is for the purpose of epoxidizing the inorganic binder, in this case, since the acid is removed in the heat treatment process after extrusion, the acid is used in the reaction It doesn't work. However, when an acid is supported on a catalyst as in the present invention, it is used for oxidative dehydrogenation as a supported catalyst, and thus the purpose of using acid is different.

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

According to an exemplary embodiment of the present specification, the content of the ferrite precursor based on 100wt% of water of the metal precursor solution in the step (A) may be 1wt% to 10wt%, specifically 1wt% to 7wt% Can be. When the content of the zinc precursor and the ferrite precursor satisfies the above range, it is easy to synthesize the metal complex catalyst during the formation of a precipitate by the coprecipitation method.

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

According to an exemplary embodiment of the present specification, the acid content may be 0.05wt% to 0.2wt% based on 100wt% of the zinc ferrite catalyst in step (C), and more specifically 0.05wt% to 0.1wt May be%. If the acid content is less than 0.05wt%, the phosphoric acid is not sufficiently supported to prevent side reactions of the oxidative dehydrogenation reaction. If the acid content is more than 0.2wt%, the acid is excessively supported to inhibit the activity of the catalyst, thereby reducing the conversion of butene. Butadiene selectivity may 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 Hydrates thereof.

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

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

According to an 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 more than 7 11 or less. 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 producing a metal complex catalyst.

According to one embodiment of the present specification, the basic aqueous solution may be one or more selected from the group consisting of potassium hydroxide, ammonium carbonate, ammonium bicarbonate, sodium hydroxide aqueous solution, sodium carbonate aqueous solution, and ammonia water. Preferably it may be ammonia water.

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

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

According to one 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 hour to 2 hours.

According to one embodiment of the present specification, the precipitate may further include a step of washing before calcination after filtration. By further comprising the washing step, it is possible to remove unnecessary ions remaining in the precipitate.

According to an exemplary embodiment of the present specification, in the step (B) may further comprise the step of drying before sintering the precipitate after filtration.

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

According to an exemplary embodiment of the present specification, the drying step may be dried at 80 ℃ to 150 ℃.

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

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

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

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

According to an exemplary embodiment of the present specification, after the step (C) may further comprise the step of calcining the zinc ferrite catalyst loaded with phosphoric acid. Specifically, after heating up to 500 ° C. at a rate of 1 ° C./min, the step may be a 6-hour firing process.

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

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

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

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

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

According to an exemplary embodiment of the present specification, the metal complex catalyst may be in the form of an acid supported on the 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 one 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 initial dose may remain. Specifically, the acid content may be 0.05 wt% to 0.2 wt% based on the total weight of the metal composite catalyst, and more specifically 0.05 wt% to 0.1 wt%. In addition, the zinc ferrite catalyst may be 99.8wt% to 99.95wt% based on the total weight of the metal complex catalyst.

If the acid content is less than 0.05wt%, the phosphoric acid is not sufficiently supported to prevent side reactions of the oxidative dehydrogenation reaction. If the acid content is more than 0.2wt%, the phosphoric acid is excessively supported to inhibit the activity of the catalyst to inhibit the conversion of butene. And butadiene selectivity can be reduced.

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

According to one embodiment of the present specification, the preparing of butadiene may use a reactant including a C4 mixture. The C4 mixture includes, for example, at least one normal butene selected from 2-butene (trans-2-Butene, cis-2-Butene) and 1-butene (1-Butene), optionally normal butane or C4 raffinate. It may further comprise -3. For example, the reactant may further include one or more selected from air, nitrogen, steam, and carbon dioxide, and preferably further include nitrogen and steam. As a specific example, the reactants 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 the advantage of excellent reaction efficiency and low waste water generation even when using a small amount of steam in 1 mol to 10 mol or 5 mol to 10 mol compared to 1 mol of the C4 mixture. This will ultimately reduce the waste water treatment costs as well as the energy consumed in the process. The oxidative dehydrogenation reaction may be carried out at a reaction temperature of, for example, 250 ℃ to 500 ℃, 300 ℃ to 450 ℃, 320 ℃ to 400 ℃, 330 ℃ to 380 ℃ or 350 ℃ to 370 ℃, within this range It is possible to provide 1,3-butadiene with high productivity because the reaction efficiency is excellent without significantly increasing the energy cost.

According to one embodiment of the present specification, the step of preparing the butadiene is carried out at a reaction temperature of 360 ° C., GHSV (Gas Hourly Space Velocity) 120h ⁻¹ in a single reactor, and the reactants are 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 carried out in a two-stage reactor (reaction temperature of 360 ℃ in the oxygen atomization case, GHSV (Gas Hourly Space Velocity) 120h ^-1 , The reactants may comprise a C4 mixture: oxygen: steam: nitrogen in a molar ratio of 1: 0.67: 5: 2.67.

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

According to one embodiment of the present specification, in order to prevent a phenomenon of reducing butadiene selectivity on α-iron oxide (α-Fe ₂ O ₃ ) formed when the catalyst for oxidative dehydrogenation of butene is prepared by coprecipitation method, Phosphoric acid may be supported on the prepared catalyst to suppress a complete oxidation reaction which is a side reaction of the 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 complex catalyst according to the exemplary embodiment of the present specification may increase the conversion of butene and the selectivity of butadiene in the oxidative dehydrogenation of butene, thereby ultimately producing high yield of butadiene.

Hereinafter, the present invention will be described in detail with reference to Examples. However, embodiments according to the present disclosure may be modified in various other forms, and the scope of the present specification is not interpreted to be limited to the embodiments described below. The embodiments of the present specification are provided to more fully describe the present specification to those skilled 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. Aqueous ammonia was added dropwise to the prepared aqueous metal precursor solution to pH 9, and stirred for 1 hour to coprecipitation. Thereafter, the coprecipitate was filtered under reduced pressure to obtain a coprecipitate, which was dried at 90 ° C. for 16 hours, and then heated to 80 ° C. at a temperature increase rate of 1 ° C./min at 80 ° C. under air atmosphere for 6 hours. The zinc-iron oxide (ZnFe ₂ O ₄ ) powder having a spinel structure was prepared. Phosphoric acid was supported by 0.05wt%.

<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 loaded 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 loaded 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 and dissolved in 1,500 g of DI water to prepare a metal precursor solution. 1,500 g DI water was added to the reactor, and the metal precursor solution and 28 to 30 wt% aqueous ammonia were simultaneously added to the reactor, and the pH was maintained at 8 to form a catalyst precipitate.

The precipitate formed was filtered off with filter paper and 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. This?, 1 L / min of air was injected into the calcination furnace and firing was carried out 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 loaded 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 loaded 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 loaded instead of 0.05 wt% of phosphoric acid.

<Comparative Example 5>

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

Experimental Example 1-1

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

(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 the reaction temperature 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 the reaction temperature 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 complex catalyst prepared in Example 2 was used instead of the metal complex 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 the reaction temperature 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 the reaction temperature 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 complex catalyst prepared in Example 3 was used instead of the metal complex 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 the reaction temperature 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 the reaction temperature 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 complex catalyst prepared in Comparative Example 1 was used instead of the metal complex 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 the reaction temperature 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 the reaction temperature 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 complex catalyst prepared in Comparative Example 2 was used instead of the metal complex 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 the reaction temperature 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 the reaction temperature 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 complex catalyst prepared in Comparative Example 3 was used instead of the metal complex 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 the reaction temperature 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 the reaction temperature 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 complex catalyst prepared in Comparative Example 4 was used instead of the metal complex 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 the reaction temperature 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 the reaction temperature 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 complex catalyst prepared in Comparative Example 5 was used instead of the metal complex catalyst prepared in Example 1.

<Comparative Example 1-14>

In Comparative Examples 1-13, butadiene was prepared in the same manner as in Comparative Examples 1-13 except that the reaction temperature was 400 ° C instead of the reaction temperature 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 the reaction temperature 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 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 carry phosphoric acid on a zinc ferrite catalyst formed by a conventional coprecipitation method, thereby improving butene conversion and butadiene selectivity. This is because it is possible to suppress the complete oxidation reaction which is a side reaction of the oxidative dehydrogenation reaction of butene.

Comparing Experimental Examples 1-1 to 1-9 and Comparative Examples 1-1 to 1-3, Comparative Examples 1-1 to 1- in which an oxidative dehydrogenation reaction 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 high butene conversion and butadiene selectivity in the entire reaction temperature of 380 ° C, 400 ° C, and 440 ° C.

Comparing Experimental Examples 1-1 to 1-9 and Comparative Examples 1-4 to 1-12, 0.05 wt% phosphoric acid 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 It can be seen that Experimental Examples 1-1 to 1-9 carrying% to 0.2wt% have high butene conversion and butadiene selectivity in the entire reaction temperature of 380 ° C, 400 ° C, and 440 ° C.

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

Comparing Experimental Examples 1-1 to 1-6 with Comparative Examples 1-13 to 1-15, compared to Comparative Examples 1-13 to 1-15 in which phosphate was supported on a manganese ferrite catalyst during oxidative dehydrogenation 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 were remarkably excellent.

Although the preferred embodiment of the present invention has been described above, the present invention is not limited thereto, and various modifications and changes can be made within the scope of the claims and the detailed description of the invention, which also belong to the scope of the invention. .

Claims (15)

(A) contacting a metal precursor solution comprising a zinc (Zn) precursor, a ferrite (Fe) precursor and water with a basic aqueous solution to obtain a precipitate;
(B) filtering and calcining the precipitate to obtain a zinc ferrite catalyst; And
(C) supporting an acid on the zinc ferrite catalyst
Method for producing a metal complex catalyst comprising a. The method of claim 1, wherein in the step (A), the content of the zinc precursor is 0.1 wt% to 5 wt% based on 100 wt% of the water of the metal precursor solution. The method of claim 1, wherein the content of the ferrite precursor is 1 wt% to 10 wt% based on 100 wt% of water of the metal precursor solution in step (A). The method of claim 1, wherein in the step (C), the acid is phosphoric acid. The method of claim 1, wherein in the step (C), the acid content is 0.05 wt% to 0.2 wt% based on 100 wt% of the zinc ferrite catalyst. The method according to claim 1, wherein the zinc precursor and the ferrite precursor is each independently one or more selected from the group consisting of nitrate (ammonium salt), ammonium salt (ammonium salt), sulfate (sulfate) and chloride (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 bicarbonate, sodium hydroxide aqueous solution, sodium carbonate aqueous solution, and ammonia water. The method of claim 1, further comprising drying the precipitate in the step (B) before calcination after filtration. The method of claim 1, further comprising calcining the acid-supported zinc ferrite catalyst after the step (C). A method for producing butadiene comprising the step of preparing butadiene by using the metal complex catalyst according to any one of claims 1 to 12 for the oxidative dehydrogenation of butene. A metal composite catalyst comprising a zinc ferrite catalyst and an acid. The method according to claim 14,
The acid is a metal composite catalyst of 0.05wt% to 0.2wt% based on 100wt% zinc ferrite catalyst.

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