阅读说明：本技术 金属络合物催化剂的制备方法和由此制备的金属络合物催化剂 (Method for preparing metal complex catalyst and metal complex catalyst prepared thereby ) 是由 黄善焕 车京龙 高东铉 黄叡瑟 韩俊奎 韩相真 金成敃 于 2019-04-10 设计创作，主要内容包括：本说明书涉及一种金属络合物催化剂的制备方法,和由此制备的金属络合物催化剂,所述制备方法包括：(A)通过使包含锌(Zn)前体、铁(Fe)前体和水的金属前体溶液与碱性水溶液接触得到沉淀物；(B)通过过滤并烧制所述沉淀物得到铁酸锌催化剂；(C)在所述铁酸锌催化剂上负载酸。(The present specification relates to a method for preparing a metal complex catalyst, and a metal complex catalyst prepared thereby, the method comprising: (A) obtaining a precipitate by contacting a metal precursor solution including a zinc (Zn) precursor, an iron (Fe) precursor, and water with an alkaline aqueous solution; (B) obtaining a zinc ferrite catalyst by filtering and firing the precipitate; (C) and loading acid on the zinc ferrite catalyst.)

1. A method for preparing a metal complex catalyst, the method comprising:

(A) obtaining a precipitate by contacting a metal precursor solution including a zinc (Zn) precursor, an iron (Fe) precursor, and water with an alkaline aqueous solution;

(B) obtaining a zinc ferrite catalyst by filtering and firing the precipitate; and

(C) and loading acid on the zinc ferrite catalyst.

2. The production method according to claim 1, wherein, in step (a), the content of the zinc precursor is 0.1 to 5% by weight based on 100% by weight of water of the metal precursor solution.

3. The preparation method according to claim 1, wherein, in the step (a), the content of the iron precursor is 1 to 10% by weight based on 100% by weight of water of the metal precursor solution.

4. The production method according to claim 1, wherein, in step (C), the acid is phosphoric acid.

5. The preparation method according to claim 1, wherein, in the step (C), the acid is contained in an amount of 0.05 to 0.2% by weight, based on 100% by weight of the zinc ferrite catalyst.

6. The production method according to claim 1, wherein the zinc precursor and the iron precursor are each independently one or more selected from nitrate, ammonium salt, sulfate, and chloride, or hydrates thereof.

7. The production method according to claim 1, wherein the zinc precursor is zinc chloride (ZnCl)₂)。

8. The method of claim 1, wherein the iron precursor is ferric chloride hydrate (FeCl)₃·6H₂O)。

9. The production method according to claim 1, wherein the pH of the basic aqueous solution is 7 to 11.

10. The production method according to claim 1, wherein the basic aqueous solution is one or more selected from the group consisting of potassium hydroxide, ammonium carbonate, ammonium bicarbonate, an aqueous sodium hydroxide solution, an aqueous sodium carbonate solution, and aqueous ammonia.

11. The method of manufacturing according to claim 1, further comprising:

in the step (B), after filtering the precipitate, the precipitate is dried and then fired.

12. The method of manufacturing according to claim 1, further comprising:

after step (C), firing the acid-loaded zinc ferrite catalyst.

13. A process for preparing butadiene, the process comprising:

in the oxidative dehydrogenation of butene, butadiene is produced by using the metal complex catalyst according to any one of claims 1 to 12.

14. A metal complex catalyst comprising a zinc ferrite catalyst and an acid.

15. The metal complex catalyst of claim 14, wherein the acid is present in an amount of 0.05 to 0.2 wt% based on 100 wt% of the zinc ferrite catalyst.

Technical Field

This application claims priority and benefit from korean patent application No.10-2018-0041559, filed by the korean intellectual property office at 10.04.2018, the entire contents of which are incorporated herein by reference.

The present specification relates to a method for preparing a metal complex catalyst and a metal complex catalyst prepared thereby.

Background

1, 3-butadiene is an intermediate of petrochemical products, and the demand for 1, 3-butadiene and its value are gradually increasing worldwide. 1, 3-butadiene has been produced by cracking using naphtha, direct dehydrogenation of butene, oxidative dehydrogenation of butene, and the like.

However, since the naphtha cracking process consumes a large amount of energy due to high reaction temperature and is not a single process for producing only 1, 3-butadiene, there is a problem in that other essential fractions are excessively generated in addition to 1, 3-butadiene. In addition, the direct dehydrogenation reaction of n-butene is thermodynamically disadvantageous as an endothermic reaction, and requires high temperature and low pressure conditions for producing 1, 3-butadiene in high yield, and thus is not suitable as a commercial process for producing 1, 3-butadiene.

Meanwhile, the oxidative dehydrogenation reaction of butene is a reaction in which butene and oxygen react with each other in the presence of a metal oxide catalyst to generate 1, 3-butadiene and water, and has a thermodynamically very advantageous advantage because stable water is generated. In addition, since the oxidative dehydrogenation reaction of butene is an exothermic reaction unlike the direct dehydrogenation reaction of butene, 1, 3-butadiene can be obtained in high yield even at a lower reaction temperature than the direct dehydrogenation reaction, and since an additional heat supply is not required, the oxidative dehydrogenation reaction of butene can become an efficient single production process capable of satisfying the demand for 1, 3-butadiene.

The metal oxide catalyst is generally synthesized by a precipitation method, and the amount of the metal oxide catalyst produced at one time is small due to technical and space limitations, and thus, in order to satisfy the target amount, the catalyst is prepared by repeating the same process several times. Thus, catalysts prepared several times have different reactivities with reactants according to the preparation order, and the difference in reactivity between such catalysts is directly related to the yield of the product (butadiene), and thus, research has been continuously conducted to reduce the difference in reactivity between catalysts.

Disclosure of Invention

Technical problem

The present specification provides a method of preparing a metal complex catalyst and a metal complex catalyst prepared thereby.

Technical scheme

An exemplary embodiment of the present specification provides a method of preparing a metal complex catalyst, the method comprising: (A) obtaining a precipitate by contacting a metal precursor solution including a zinc (Zn) precursor, an iron (Fe) precursor, and water with an alkaline aqueous solution; (B) obtaining a zinc ferrite catalyst by filtering and firing the precipitate; and (C) supporting an acid on the zinc ferrite catalyst.

In addition, an exemplary embodiment of the present description provides a method of preparing butadiene, the method including: in the oxidative dehydrogenation of butene, butadiene is produced by using the metal complex catalyst prepared according to the above-described method for producing a metal complex catalyst.

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

Advantageous effects

The method of preparing a metal complex catalyst according to one exemplary embodiment of the present specification has the effect of increasing the conversion rate of butene and the selectivity of butadiene by supporting phosphoric acid on a zinc ferrite catalyst to inhibit a complete oxidation reaction, which is a side reaction of an oxidative dehydrogenation reaction.

Drawings

Fig. 1 is a process diagram for carrying out a method of making a metal complex catalyst according to an exemplary embodiment of the present description.

Detailed Description

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, which is a product of the oxidative dehydrogenation reaction, by the weight of Butene (BE), which is a raw material. For example, the yield can be represented by the following equation.

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

In the present specification, "conversion (%)" refers to a ratio of a reactant converted into a product, and for example, the conversion of butene can be defined by the following equation.

Conversion (%) ═ number of moles of reacted butene)/(moles of supplied butene) ] x 100

In the present specification, "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 equation.

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

In the present specification, "COx" means a gas containing carbon monoxide (CO), carbon dioxide (CO) formed during an oxidative dehydrogenation reaction₂) And the like.

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

An exemplary embodiment of the present specification provides a method of preparing a metal complex catalyst, the method comprising: (A) obtaining a precipitate by contacting a metal precursor solution including a zinc (Zn) precursor, an iron (Fe) precursor, and water with an alkaline aqueous solution; (B) obtaining a zinc ferrite catalyst by filtering and firing the precipitate; and (C) supporting an acid on the zinc ferrite catalyst.

Zinc ferrite catalyst (ZnFe) for use in oxidative dehydrogenation reactions₂O₄) Since the catalyst prepared by the co-precipitation method is prepared in a bulk form, α -iron oxide (α -Fe) is formed₂O₃) α -iron oxide (α -Fe)₂O₃) The phase serves as a reason for reducing the selectivity of 1, 3-butadiene, which is a product of the oxidative dehydrogenation reaction of butene.

Therefore, the present inventors inhibited complete oxidation reaction as a side reaction of oxidative dehydrogenation reaction of butene by supporting phosphoric acid on a zinc ferrite catalyst prepared by a coprecipitation method. Six oxygen (O) is consumed in the complete oxidation process₂) And when the complete oxidation reaction is suppressed, the conversion of butene and the selectivity of butadiene can be finally improved by reducing the consumption of oxygen supplied together with butene as a reactant. Thus, the reactivity of the zinc ferrite catalyst prepared by the coprecipitation method can be improved.

Further, when acid is added during the extrusion and molding of the catalyst (korean patent application laid-open No.2014-0082869), the acid is added for the purpose of peptizing the inorganic binder, and in this case, the acid is not used in the reaction because the acid is not removed during the heat treatment process after the extrusion. However, when an acid is supported on the catalyst as in the present invention, the catalyst is used as a supported catalyst in the oxidative dehydrogenation reaction, and thus the purpose of using the acid is different from that in the above case.

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

According to an exemplary embodiment of the present specification, in the step (a), the content of the iron precursor may be 1 to 10 wt%, specifically, 1 to 7 wt%, based on 100 wt% of water of the metal precursor solution. When the contents of the zinc precursor and the iron precursor satisfy the above ranges, the metal complex catalyst is easily synthesized in the process of forming a precipitate by a coprecipitation method.

According to an exemplary embodiment of the present description, 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, in step (C), the acid may be contained in an amount of 0.05 to 0.2 wt%, more specifically, 0.05 to 0.1 wt%, based on 100 wt% of the zinc ferrite catalyst. When the content of the acid is less than 0.05 wt%, the phosphoric acid is not sufficiently supported, so that the side reaction of the oxidative dehydrogenation reaction cannot be sufficiently prevented, and when the content thereof is more than 0.2 wt%, the acid is excessively supported, so that the activity of the catalyst is inhibited, thereby decreasing the conversion of butene and the selectivity of butadiene.

According to an exemplary embodiment of the present specification, the zinc precursor and the iron precursor may each independently be one or more selected from nitrate, ammonium salt, sulfate and chloride, or hydrates thereof.

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

According to an exemplary embodiment of the present description, the iron precursor may be iron chloride hydrate (FeCl)₃·6H₂O)。

According to an exemplary embodiment of the present description, 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 preparing the metal complex catalyst.

According to an exemplary 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, an aqueous sodium hydroxide solution, an aqueous sodium carbonate solution, and aqueous ammonia. Preferably, the basic aqueous solution may be ammonia.

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

According to an exemplary embodiment of the present specification, the obtaining the precipitate may further include contacting the metal precursor solution with the basic aqueous solution, and then stirring the obtained solution. The formation of the precipitate of the metal precursor is promoted by further comprising stirring the resulting solution, thereby advantageously forming catalyst particles.

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

According to an exemplary embodiment of the present specification, a method for stirring the resulting solution may be used without limitation as long as the method mixes a liquid with a liquid.

According to an exemplary embodiment of the present description, the stirring time in stirring the resultant mixture may be 30 minutes to 3 hours. Specifically, the stirring time is preferably 1 hour to 2 hours.

According to an exemplary embodiment of the present description, the preparation method may further include: after filtering the precipitate, the precipitate is washed and then fired. Unnecessary ions remaining in the precipitate may be removed by further comprising washing the precipitate.

According to an exemplary embodiment of the present description, the preparation method may further include: in the step (B), after filtering the precipitate, the precipitate is dried and then fired.

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

According to an exemplary embodiment of the present description, the drying of the precipitate may be performed at 80 ℃ to 150 ℃.

According to an exemplary embodiment of the present description, the firing of the precipitate may increase the temperature to 650 ℃ at a rate of 1 ℃/min, and then fire the precipitate for 6 hours. The method of firing the precipitate may be a heat treatment method generally used in the art.

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

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

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

According to an exemplary embodiment of the present description, the preparation method may further include: after step (C), firing the zinc ferrite catalyst loaded with phosphoric acid. Specifically, the firing of the zinc ferrite catalyst may increase the temperature to 500 ℃ at a rate of 1 ℃/min, and then fire the zinc ferrite catalyst for 6 hours.

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

An exemplary embodiment of the present specification provides a metal complex catalyst prepared by the above-described method of preparing a metal complex catalyst.

An exemplary embodiment of the present description provides a method of preparing butadiene, the method including: in the oxidative dehydrogenation of butene, butadiene is produced by using the metal complex catalyst according to the above-described production method of the metal complex catalyst.

Another exemplary embodiment of the present description provides a metal complex catalyst comprising a zinc ferrite catalyst and an acid.

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

According to an exemplary embodiment of the present description, the metal complex catalyst may be in the form of an acid supported on a zinc ferrite catalyst.

According to an exemplary embodiment of the present specification, the metal complex catalyst may have a particle size of 0.6mm to 0.85 mm.

According to an exemplary embodiment of the present description, there may be provided a metal complex catalyst comprising a zinc ferrite catalyst and an acid. Since phosphoric acid is not removed during firing, the amount of phosphoric acid initially added may be maintained as it is. Specifically, the acid may be contained in an amount of 0.05 to 0.2 wt%, more specifically 0.05 to 0.1 wt%, based on the total weight of the metal complex catalyst. In addition, the zinc ferrite catalyst may be contained in an amount of 99.8 to 99.95% by weight, based on the total weight of the metal complex catalyst.

When the content of the acid is less than 0.05 wt%, phosphoric acid is not sufficiently supported, so that a side reaction of the oxidative dehydrogenation reaction cannot be sufficiently prevented, and when the content thereof is more than 0.2 wt%, phosphoric acid is excessively supported, so that the activity of the catalyst is inhibited, thereby reducing the conversion of butene and the selectivity of butadiene.

Further, an exemplary embodiment of the present description provides a method of preparing butadiene, the method including: in the oxidative dehydrogenation of butene, butadiene is produced by using the above-mentioned metal complex catalyst.

According to an exemplary embodiment of the present description, a reactant comprising a mixture of C4 may be used to prepare butadiene. As an example, the C4 mixture comprises one or more n-butenes selected from the group consisting of 2-butene (trans-2-butene, cis-2-butene) and 1-butene, and optionally, n-butane or C4 raffinate-3. As an example, the reactant may further include one or more selected from the group consisting of air, nitrogen, steam, and carbon dioxide, and preferably, further include nitrogen and steam. As a specific example, the reactants may comprise a mixture of C4, 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. Further, the method of preparing butadiene according to one exemplary embodiment of the present specification is advantageous in that even if a small amount of steam of 1mol to 10mol or 5mol to 10mol is used based on 1mol of the C4 mixture, reaction efficiency is excellent and a small amount of wastewater is generated, and finally, an effect of not only reducing wastewater treatment costs but also reducing energy consumed by the process is provided. As an example, the oxidative dehydrogenation reaction may be performed at a reaction temperature of 250 ℃ to 500 ℃, 300 ℃ to 450 ℃, 320 ℃ to 400 ℃, 330 ℃ to 380 ℃, or 350 ℃ to 370 ℃, in which the reaction efficiency is excellent without significantly increasing the energy cost, so that 1, 3-butadiene may be provided in high yield.

According to an exemplary embodiment of the present description, the preparation of butadiene may be carried out in a single reactor at a reaction temperature of 360 ℃ and 120h^-1And the reactants may comprise a mixture of C4 in a molar ratio of 1:0.67:5:2.67, oxygen, steam, nitrogen.

Further, according to an exemplary embodiment of the present description, the preparation of butadiene may be in two stagesIn a reactor at (reaction temperature of 360 ℃ C. and 120h^-1Under conditions of Gas Hourly Space Velocity (GHSV)) (oxygen not split) and the reactants may comprise a mixture of C4: oxygen: steam: nitrogen in a molar ratio of 1:0.67:5: 2.67.

Fig. 1 is an exemplary process diagram for performing a method of making a metal complex catalyst according to one exemplary embodiment of the present description.

According to an exemplary embodiment of the present specification, in order to prevent α -iron oxide (α -Fe) formed when a catalyst for the oxidative dehydrogenation of butene is prepared by a co-precipitation method₂O₃) And a phenomenon of lowering the selectivity of butadiene, and a complete oxidation reaction, which is a side reaction of the oxidative dehydrogenation of butene, can be suppressed by supporting phosphoric acid on the prepared catalyst. Thus, the reactivity of the zinc ferrite catalyst prepared by the coprecipitation method can be improved.

As described above, the metal complex catalyst according to an exemplary embodiment of the present specification may ultimately produce butadiene in high yield by increasing the conversion of butene and the selectivity of butadiene in the oxidative dehydrogenation of butene.

Hereinafter, the present specification will be described in detail with reference to examples for specifically describing the present specification. However, the embodiments according to the present specification may be modified in various forms, and should not be construed that the scope of the present specification is limited to the embodiments described in detail below. The embodiments of the present description are provided to more fully explain the present description to those of ordinary skill in the art.

< example 1>

By mixing 12.019g of zinc chloride (ZnCl)₂) And 37.662g of ferric chloride (FeCl)₃) The metal precursor solution was prepared by dissolving in 404.59g of distilled water. In this case, Zn: Fe is 1:2 with respect to the molar ratio of the metal components contained in the metal precursor solution. To the prepared metal precursor solution, an aqueous ammonia solution was added dropwise so that the pH was 9, and the resulting solution was stirred for 1 hour and coprecipitated. Thereafter, the coprecipitate was obtained by filtering the coprecipitated solution under reduced pressure, and the coprecipitate was then added at 90 deg.fAfter drying at 80 ℃ for 16 hours, the temperature was then raised to 650 ℃ at a ramp rate of 1 ℃/min under an air atmosphere at 80 ℃, and zinc-iron oxide having a spinel structure (ZnFe) was prepared by maintaining the temperature for 6 hours₂O₄) And (3) powder. Phosphoric acid was supported in an amount of 0.05 wt%.

< example 2>

A metal complex catalyst was prepared in the same manner as in example 1, except that in example 1, phosphoric acid was supported in an amount of 0.01 wt% instead of 0.05 wt%.

< example 3>

A metal complex catalyst was prepared in the same manner as in example 1, except that in example 1, phosphoric acid was supported in an amount of 0.2 wt% instead of 0.05 wt%.

< comparative example 1>

By mixing 20.865g of ZnCl₂And 81.909g of FeCl₃·6H₂O was added to 1,500g of deionized water and the resulting mixture was dissolved to prepare a metal precursor solution. A catalyst precipitate was formed by adding 1,500g of deionized water to the reactor while adding the metal precursor solution and 28 to 30 wt% of aqueous ammonia to the reactor, and maintaining the pH at 8.

The precipitate formed was filtered using filter paper and then dried in an oven at 90 ℃. Thereafter, the precipitate was heated to 650 ℃ at a rate of 1 ℃/min and then fired at 650 ℃ for 6 hours. In this case, firing was performed while injecting air into the firing furnace at a rate of 1L/min, thereby preparing a metal complex catalyst.

< comparative example 2>

A metal complex catalyst was prepared in the same manner as in example 1, except that in example 1, phosphoric acid was supported in an amount of 0.3 wt% instead of 0.05 wt%.

< comparative example 3>

A metal complex catalyst was prepared in the same manner as in example 1, except that in example 1, phosphoric acid was supported in an amount of 0.4 wt% instead of 0.05 wt%.

< comparative example 4>

A metal complex catalyst was prepared in the same manner as in example 1, except that in example 1, phosphoric acid was supported in an amount of 0.6 wt% instead of 0.05 wt%.

< comparative example 5>

Grinding of manganese ferrite catalyst (MnFe)₂O₄) Thereafter, the catalyst was heated to 500 ℃ at a rate of 1 ℃/min, and then fired at 500 ℃ for 6 hours, thereby preparing a metal complex catalyst.

< Experimental examples 1-1>

The oxidative dehydrogenation of butene was carried out under the following conditions: the composition of the 2-butene reactant was: 40% by weight of cis-2-butene and 60% by weight of trans-2-butene, 0.1g of the metal complex catalyst prepared in example 1, GHSV 262h^-1Butadiene was prepared with OBR ═ 1, SBR ═ 5, NBR ═ 4, and a reaction temperature of 380 ℃.

(GHSV: gas hourly space velocity, OBR: oxygen/total 2-butene ratio, SBR: steam/total 2-butene ratio, NBR: nitrogen/total 2-butene ratio)

< Experimental examples 1 and 2>

Butadiene was produced in the same manner as in Experimental example 1-1, except that in Experimental example 1-1, the reaction temperature was 400 ℃ instead of 380 ℃.

< Experimental examples 1 to 3>

Butadiene was produced in the same manner as in Experimental example 1-1, except that in Experimental example 1-1, the reaction temperature was 440 ℃ instead of 380 ℃.

< Experimental examples 1 to 4>

Butadiene was produced in the same manner as in experimental example 1-1, except that in experimental example 1-1, the metal complex catalyst prepared in example 2 was used instead of the metal complex catalyst prepared in example 1.

< Experimental examples 1 to 5>

Butadiene was produced in the same manner as in experimental examples 1-4, except that in experimental examples 1-4, the reaction temperature was 400 ℃ instead of 380 ℃.

< Experimental examples 1 to 6>

Butadiene was produced in the same manner as in experimental examples 1-4, except that in experimental examples 1-4, the reaction temperature was 440 ℃ instead of 380 ℃.

< Experimental examples 1 to 7>

Butadiene was produced in the same manner as in experimental example 1-1, except that in experimental example 1-1, the metal complex catalyst prepared in example 3 was used instead of the metal complex catalyst prepared in example 1.

< Experimental examples 1 to 8>

Butadiene was produced in the same manner as in examples 1 to 4, except that in examples 1 to 7, the reaction temperature was 400 ℃ instead of 380 ℃.

< Experimental examples 1 to 9>

Butadiene was produced in the same manner as in examples 1 to 4, except that in examples 1 to 7, the reaction temperature was 440 ℃ instead of 380 ℃.

< comparative example 1-1>

Butadiene was produced in the same manner as in experimental example 1-1, except that in experimental example 1-1, the metal complex catalyst prepared in comparative example 1 was used instead of the metal complex catalyst prepared in example 1.

< comparative examples 1 and 2>

Butadiene was produced in the same manner as in comparative example 1-1, except that in comparative example 1-1, the reaction temperature was 400 ℃ instead of 380 ℃.

< comparative examples 1 to 3>

Butadiene was produced in the same manner as in comparative example 1-1, except that in comparative example 1-1, the reaction temperature was 440 ℃ instead of 380 ℃.

< comparative examples 1 to 4>

Butadiene was produced in the same manner as in experimental example 1-1, except that in experimental example 1-1, the metal complex catalyst prepared in comparative example 2 was used instead of the metal complex catalyst prepared in example 1.

< comparative examples 1 to 5>

Butadiene was produced in the same manner as in comparative examples 1 to 4, except that in comparative examples 1 to 4, the reaction temperature was 400 ℃ instead of 380 ℃.

< comparative examples 1 to 6>

Butadiene was produced in the same manner as in comparative examples 1 to 4, except that in comparative examples 1 to 4, the reaction temperature was 440 ℃ instead of 380 ℃.

< comparative examples 1 to 7>

Butadiene was produced in the same manner as in experimental example 1-1, except that in experimental example 1-1, the metal complex catalyst prepared in comparative example 3 was used instead of the metal complex catalyst prepared in example 1.

< comparative examples 1 to 8>

Butadiene was produced in the same manner as in comparative examples 1 to 7, except that in comparative examples 1 to 7, the reaction temperature was 400 ℃ instead of 380 ℃.

< comparative examples 1 to 9>

Butadiene was produced in the same manner as in comparative examples 1 to 7, except that in comparative examples 1 to 7, the reaction temperature was 440 ℃ instead of 380 ℃.

< comparative examples 1 to 10>

Butadiene was produced in the same manner as in experimental example 1-1, except that in experimental example 1-1, the metal complex catalyst produced in comparative example 4 was used instead of the metal complex catalyst produced in example 1.

< comparative examples 1 to 11>

Butadiene was produced in the same manner as in comparative examples 1 to 10, except that in comparative examples 1 to 10, the reaction temperature was 400 ℃ instead of 380 ℃.

< comparative examples 1 to 12>

Butadiene was produced in the same manner as in comparative examples 1 to 10, except that in comparative examples 1 to 10, the reaction temperature was 440 ℃ instead of 380 ℃.

< comparative examples 1 to 13>

Butadiene was produced in the same manner as in experimental example 1-1, except that in experimental example 1-1, the metal complex catalyst produced in comparative example 5 was used instead of the metal complex catalyst produced in example 1.

< comparative examples 1 to 14>

Butadiene was produced in the same manner as in comparative examples 1 to 13, except that in comparative examples 1 to 13, the reaction temperature was 400 ℃ instead of 380 ℃.

< comparative examples 1 to 15>

Butadiene was produced in the same manner as in comparative examples 1 to 13, except that in comparative examples 1 to 13, the reaction temperature was 440 ℃ instead of 380 ℃.

The measurement results of the conversion rate of butene and the selectivity of butadiene in the oxidative dehydrogenation of butene in each of experimental example 1-1 to experimental example 1-9 and comparative example 1-1 to comparative example 1-15 are shown in the following table 1.

[ Table 1]

Classification	Catalyst and process for preparing same	Reaction temperature (. degree.C.)	Conversion of butene (%)	Butadiene selectivity (%)
					Experimental example 1-1	Example 1	380	79.3	92.0
Experimental examples 1 to 2	Example 1	400	79.6	92.3
					Experimental examples 1 to 3	Example 1	440	72.3	89.6
Experimental examples 1 to 4	Example 2	380	80.6	91.5
					Experimental examples 1 to 5	Example 2	400	79.5	91.1
Experimental examples 1 to 6	Example 2	440	75.4	89.9
					Experimental examples 1 to 7	Example 3	380	78.6	91.6
Experimental examples 1 to 8	Example 3	400	79.2	90.5
					Experimental examples 1 to 9	Example 3	440	74.1	88.9
Comparative example 1-1	Comparative example 1	380	77.9	91.7
					Comparative examples 1 to 2	Comparative example 1	400	79.0	90.3
Comparative examples 1 to 3	Comparative example 1	440	70.7	89.1
					Comparative examples 1 to 4	Comparative example 2	380	39.9	75.4
Comparative examples 1 to 5	Comparative example 2	400	45.0	74.7
					Comparative examples 1 to 6	Comparative example 2	440	51.7	72.9
Comparative examples 1 to 7	Comparative example 3	380	7.4	64.5
					Comparative examples 1 to 8	Comparative example 3	400	13.1	59.9
Comparative examples 1 to 9	Comparative example 3	440	29.6	57.2
					Comparative examples 1 to 10	Comparative example 4	380	8.0	50.4
Comparative examples 1 to 11	Comparative example 4	400	13.1	44.4
					Comparative examples 1 to 12	Comparative example 4	440	23.4	53.5
Comparative examples 1 to 13	Comparative example 5	380	29.1	47.3
					Comparative examples 1 to 14	Comparative example 5	400	26.8	46.5
Comparative examples 1 to 15	Comparative example 5	440	22.2	40.2

According to table 1, the metal complex catalysts prepared according to examples 1 to 3 can improve the conversion of butene and the selectivity of butadiene by supporting phosphoric acid on a zinc ferrite catalyst formed by the existing coprecipitation method. This is because complete oxidation reaction, which is a side reaction of oxidative dehydrogenation of butene, can be suppressed.

When comparing experimental example 1-1 to experimental example 1-9 with comparative example 1-1 to comparative example 1-3, it can be confirmed that experimental example 1-1 to experimental example 1-9 using a zinc ferrite catalyst having phosphoric acid supported thereon have a higher conversion rate of butene and a higher selectivity of butadiene in the entire range of reaction temperatures of 380 ℃, 400 ℃ and 440 ℃ than comparative example 1-1 to comparative example 1-3 performing an oxidative dehydrogenation reaction using a zinc ferrite catalyst formed by a conventional coprecipitation method.

When comparing experimental example 1-1 to experimental example 1-9 with comparative example 1-4 to comparative example 1-12, it can be confirmed that experimental example 1-1 to experimental example 1-9, in which 0.05 wt% to 0.2 wt% of phosphoric acid is supported on a zinc ferrite catalyst, have a higher conversion rate of butene and a higher selectivity of butadiene in the entire range of reaction temperatures of 380 ℃, 400 ℃ and 440 ℃, than comparative example 1-4 to comparative example 1-12, in which 0.3 wt% or more of phosphoric acid is supported on a zinc ferrite catalyst.

Specifically, in comparative examples 1-7 to 1-12 in which 0.4 wt% or more of phosphoric acid was supported, it was confirmed that the conversion of butene and the selectivity of butadiene were significantly reduced.

When comparing experimental examples 1-1 to 1-6 with comparative examples 1-13 to 1-15, it can be confirmed that the conversion of butene and the selectivity of butadiene in the oxidative dehydrogenation of butene in experimental examples 1-1 to 1-6 in which phosphoric acid is supported on a zinc ferrite catalyst are significantly better than those in comparative examples 1-13 to 1-15 in which phosphoric acid is supported on a manganese ferrite catalyst.

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