WO2017116153A1

WO2017116153A1 - Method for preparing multicomponent ferrite metal oxide catalyst

Info

Publication number: WO2017116153A1
Application number: PCT/KR2016/015446
Authority: WO
Inventors: 윤용희; 박지원; 김재우; 김윤정; 노경호
Original assignee: 금호석유화학 주식회사
Priority date: 2015-12-30
Filing date: 2016-12-29
Publication date: 2017-07-06
Also published as: KR101792072B1; KR20170079302A

Abstract

An embodiment of the present invention provides a method for preparing a multicomponent ferrite metal oxide catalyst, the method comprising: (a) a step for preparing a precursor solution by dissolving nitrate precursors of each of magnesium, aluminum, iron, and a divalent metal cation in a polar solvent; (b) a step for forming a catalyst powder by thermally decomposing the precursor solution while spraying the precursor solution into a reactor using a carrier gas; and (c) a step for calcining the catalyst powder in a storage tank after transporting the catalyst powder to the storage tank.

Description

Process for preparing multicomponent ferrite metal oxide catalyst

The present invention relates to a method for producing a multicomponent ferrite metal oxide catalyst.

1,3-butadiene, the main raw material of tires, which is growing in demand every year due to the growth of the automotive market, is usually produced by naphtha cracking of saturated hydrocarbons based on naphtha. Pyrolysis of naphtha results in a mixture of methane, ethane, ethylene, acetylene, propane, propylene, butane, butene, 1,3-butadiene and C5 or higher hydrocarbons. The production of 1,3-butadiene through the pyrolysis as described above accounts for most of the total 1,3-butadiene supply, but other olefins, which are by-products as described above, are also synthesized and the energy cost required for the pyrolysis process is increased. It is very inefficient as a method for producing 1,3-butadiene.

Another method for preparing 1,3-butadiene is to directly dehydrogenate n -butene. In this method, the yield of 1,3-butadiene is higher than that of naphtha pyrolysis, but because of the endothermic reaction, a large amount of energy is required to maintain a high temperature reaction temperature, and a carbon coke is formed on the surface of the catalyst to decrease the activity of the catalyst. There is a problem in that a large amount of energy is required for catalyst regeneration.

Overcoming this problem is an oxidative dehydrogenation method for producing 1,3-butadiene by directly reacting n -butene with oxygen. The oxidative dehydrogenation process is carried out in the presence of steam, in which the added steam acts as a heat transporter and promotes vaporization of organic deposits on the catalyst, thus inhibiting carbonization of the catalyst to prevent activity deterioration.

In addition, n -butene reacts with oxygen to be converted into 1,3-butadiene and water, of which the water produced is stable and thermodynamically advantageous and can lower the reaction temperature. In other words, oxidative dehydrogenation is thermodynamically stable and has good selectivity to olefins at low temperatures.

In general, in the oxidative dehydrogenation reaction, radicals generated at the beginning of the reaction are important reaction intermediates, desorb from the surface of the catalyst during the reaction, move to the gas part, and participate in the homogeneous catalytic reaction.

However, the oxidative dehydrogenation method for producing 1,3-butadiene by reacting n -butene and oxygen is accompanied by side reactions such as partial oxidation and complete oxidation because oxygen is used as a reactant, thus suppressing such side reactions. Developing catalysts with high selectivity and yield of 3-butadiene is a key technology.

Among the developed catalysts, the ferrite metal oxide catalyst has a spinel crystal structure, and the yield of 1,3-butadiene varies greatly in the oxidative dehydrogenation of n -butene according to the type of divalent cation. In particular, zinc, manganese and magnesium ferrite are known to have superior selectivity of 1,3-butadiene over other types of metal ferrites.

In carrying out the oxidative dehydrogenation of n -butene, the ferrite metal oxide catalyst is subjected to oxidative dehydrogenation of n -butene using a ferrite metal oxide catalyst having a spinel structure prepared by physical mixing and coprecipitation. As 1,3-butadiene is produced, the coprecipitation method is typically used in the production of a metal oxide catalyst or can not be manufactured through a multi-step, which is uneconomical, and wastewater is generated during filtration and washing after the catalyst is manufactured. There is this.

In order to improve this problem, Korean Patent No. 10-1340621 can be prepared by a simple process using spray pyrolysis, ferrite metal oxide capable of synthesizing high yield 1,3-butadiene with excellent selectivity. A method for preparing a catalyst has been proposed.

However, according to this method, a high temperature treatment is performed in a short time in the process of producing a ferrite metal oxide catalyst, and thus the stability of the catalyst is low, and a large amount of by-products such as moisture and nitrate are present in the prepared catalyst, thereby decreasing the purity of the catalyst. There is a problem that the selectivity of 1,3-butadiene prepared using a catalyst is low.

The present invention is to solve the above problems of the prior art, the object of the present invention is the purity, activity of the ferrite metal oxide catalyst used in the case of producing 1,3-butadiene by oxidative dehydrogenation of n -butene And to provide a method for producing a multi-component ferrite metal oxide catalyst that can improve the stability.

In order to achieve the above object, one aspect of the present invention comprises the steps of (a) dissolving the nitrate precursor of each of magnesium, aluminum, iron, and divalent cation metal in a polar solvent to prepare a precursor solution; (b) pyrolysing the precursor solution with a carrier gas into the reactor to form a catalyst powder; It provides a method for producing a multi-component ferrite metal oxide catalyst represented by the following formula (1); and (c) after transporting the catalyst powder to the reservoir, and calcining in the reservoir.

[Formula 1]

Mg _x M _(1-x) Al _y Fe _(2-y) O ₄

In Formula 1, x and y are real numbers satisfying 0 <x <1 and 0 <y <2, respectively, and M is a divalent cation metal element.

In one embodiment, the molar ratio of magnesium, aluminum, iron, and divalent cation metal in the step (a) is 0.1 to 1: 0.1 to 2: 0.1 to 2: 0.1 to 1, respectively You can mix.

In one embodiment, the divalent cation metal in step (a) may be one or more selected from the group consisting of zinc, manganese, nickel, cobalt, and copper.

In one embodiment, the polar solvent in step (a) may be distilled water.

In one embodiment, the carrier gas in the step (b) may be air.

In one embodiment, the pressure of the air in the step (b) may be 2 to 4 atm.

In one embodiment, the thermal decomposition temperature in step (b) may be 500 ℃ to 900 ℃.

In one embodiment, the calcination temperature in step (c) may be 500 ℃ to 600 ℃.

In one embodiment, the calcination in step (c) may be performed for 1 hour to 4 hours.

According to an aspect of the present invention, when preparing a catalyst, a certain amount of magnesium may be replaced with zinc to improve catalyst activity and yield in the production of 1,3-butadiene, and a certain amount of iron may be replaced with aluminum to replace the catalyst. It can improve the activity.

In addition, in the preparation of the ferrite metal oxide catalyst, by further performing the step of calcining the prepared catalyst powder for a certain temperature and time to improve the activity and stability of the catalyst powder, and to reduce the residual moisture and nitrate in the prepared catalyst Purity of the catalyst can be improved.

In addition, when the catalyst prepared after the calcination step is used for the oxidative dehydrogenation of n -butene, high purity 1,3-butadiene having improved selectivity can be prepared.

It is to be understood that the effects of the present invention are not limited to the above effects, and include all effects deduced from the configuration of the invention described in the detailed description or claims of the present invention.

1 is a diagram illustrating a method for preparing a multicomponent ferrite metal oxide catalyst according to one embodiment of the present invention.

Hereinafter, with reference to the accompanying drawings will be described the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention.

Throughout the specification, when a part is said to "include" a certain component, it means that it may further include other components, without excluding the other components unless otherwise stated.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

Referring to Figure 1, one aspect of the present invention comprises the steps of (a) dissolving the nitrate precursor of each of magnesium, aluminum, iron, and divalent cation metal in a polar solvent to prepare a precursor solution; (b) pyrolysing the precursor solution with a carrier gas into the reactor to form a catalyst powder; It provides a method for producing a multi-component ferrite metal oxide catalyst represented by the following formula (1); and (c) after transporting the catalyst powder to the reservoir, and calcining in the reservoir.

[Formula 1]

Mg _x M _(1-x) Al _y Fe _(2-y) O ₄

In preparing the precursor solution in the step (a), in order to increase the solubility of each precursor, the temperature of the solution is 10 ℃ to 80 ℃, preferably 15 ℃ to 60 ℃, more preferably 25 ℃ to 40 ℃ I can keep it.

In the step (a), the molar ratios of magnesium, aluminum, iron, and divalent cation metal are respectively 0.1 to 1: 0.1 to 2: 0.1 to 2: 0.1 to 1, preferably 0.2 to 0.8: 0.2-1.8: 0.2-1.8: It can mix so that it may be 0.1-0.8. When the molar ratio of magnesium, aluminum, iron, and divalent cationic metal is included in the above range, the surface area of the ferrite metal oxide catalyst produced is 60 m 2 / g to 100 m 2 / g, preferably 90 m 2 / g to 100 m 2 / g, the weight loss may be 20% by weight or less, preferably 4% to 12% by weight.

When the surface area is less than 60 m 2 / g, in preparing 1,3-butadiene, the contact area of n -butene and the catalyst may be reduced to decrease the selectivity of 1,3-butadiene, The contact time may be increased to increase byproduct production.

In addition, when the weight loss is more than 20% by weight, the stability of the catalyst is lowered to produce 1,3-butadiene by oxidative dehydrogenation of n -butene, the activity of the catalyst may be lowered.

Meanwhile, in step (a), one or more selected from the group consisting of sulfate precursor, chloride precursor, and carbonate precursor may be used in place of each nitrate precursor, but is not limited thereto.

In the step (a), the polar solvent may be distilled water, but is not limited thereto. When the polar solvent is distilled water, it is possible to minimize the impurities in the precursor solution to improve the purity of the ferrite metal oxide catalyst as a final product.

In addition, the divalent cation metal may be one or more selected from the group consisting of zinc, manganese, nickel, cobalt, and copper, preferably zinc, but is not limited thereto.

The ferrite metal oxide catalyst prepared by adding the divalent cation metal nitrate precursor is a certain amount of magnesium is replaced by a divalent cation metal such as zinc, so that the activity of the catalyst and 1,3-butadiene compared to the case where magnesium is applied alone The yield can be improved.

On the other hand, when only iron as the trivalent cation metal is present in the ferrite metal oxide catalyst, the activity of the catalyst may be reduced due to the collapse of the spinel structure. On the other hand, the ferrite metal oxide catalyst prepared by adding the aluminum nitrate precursor in step (a) can be replaced by a certain amount of iron aluminum, thereby stabilizing the spinel structure can improve the activity of the catalyst.

In the step (b), the carrier gas may be air, preferably the pressure of the air may be 2 to 4 atm, more preferably 3 atm. If the pressure of the air is less than 2 atm, the physical properties of the catalyst to be produced may be lower than the standard value required for the production of 1,3-butadiene, and the performance of the catalyst may be lowered. In addition to this, the performance of the catalyst may be degraded due to the formation of high melt or the deformation of the crystal structure.

In addition, in the step (b), the pyrolysis temperature may be 500 ° C to 900 ° C, preferably 700 ° C to 800 ° C, and more preferably 750 ° C. When the pyrolysis temperature is less than 500 ° C., catalyst crystals suitable for the standard required for the preparation of 1,3-butadiene may not be obtained, and when it is above 900 ° C., the catalyst may melt to form a high melt or change in the crystal structure of the catalyst. . Therefore, by performing pyrolysis in the above range, it is possible to produce a ferrite metal oxide catalyst prepared by uniformly dispersing an active metal consisting of magnesium, aluminum, iron, and divalent cation metal.

By performing the step (c), it is possible to improve the purity of the catalyst through the process of purifying the ferrite metal oxide catalyst. Accordingly, selectivity and purity of 1,3-butadiene prepared using the catalyst may be improved.

As used herein, the term "calcination" refers to a "heat treatment process that heats the solid to cause pyrolysis or phase transition or remove volatile components," which is obtained after completion of step (b). It can be understood as a concept including the purification process for removing the residual moisture and nitrate contained in the prepared catalyst powder to obtain a ferrite metal oxide catalyst with improved purity, and the process of activating the catalyst powder in a storage tank to improve the stability of the catalyst. .

In step (c), the calcination temperature may be 500 ° C. to 600 ° C., preferably 530 ° C. to 570 ° C., and more preferably 550 ° C. When the calcination temperature is less than 500 ℃, it is difficult to expect improved catalyst purity and improved selectivity of 1,3-butadiene compared to the case performed only to the step (b), if the calcination temperature is higher than 600 ℃ 1 Is improved but the yield can be drastically reduced.

In addition, in step (c), the calcination may be performed for 1 hour to 4 hours, preferably 1 hour to 3 hours. If the calcination is carried out in less than 1 hour it is difficult to expect improved purity of the catalyst and improved selectivity of 1,3-butadiene compared to the case performed only to the step (b), and if more than 4 hours the selection of 1,3-butadiene The degree is improved but the conversion rate can be drastically lowered.

And 70% to 90% conversion of butene-ferrite metal oxide catalyst prepared according to the method n - as the catalyst used in the case of producing 1,3-butadiene through oxidative dehydrogenation reaction from butene, n The selectivity of 1,3-butadiene may be 80% to 90%, indicating improved selectivity compared to the conventional manufacturing method.

In addition, the ferrite metal oxide catalyst may have a high durability, life and reaction activity without the support of the catalyst on the powder itself. Therefore, the catalyst itself can be used without a separate support.

If necessary, the ferrite metal oxide catalyst may further include one support selected from the group consisting of alumina, silica, or silica-alumina, but is not limited thereto.

In the oxidative dehydrogenation of n -butene for the production of 1,3-butadiene using a ferrite metal oxide catalyst prepared according to the invention, the reactants further contain a mixture of air and steam in addition to n -butene. N -butene may be used in a C4 mixture having a content of 50 to 75% by weight. The C4 mixture may include 0.5 to 25% by weight of n -butane and include 0.5 to 10% by weight of impurities except n -butene and n -butane.

The mixing ratio of the reactants may preferably be n -butene: air: steam = 4-12 vol%: 15-25 vol%: 45-80 vol%, more preferably 5-9 vol%: 16-30 Volume%: may be 60 to 78 volume%. If the mixing ratio of the reactants is out of the above range, the reaction activity may decrease or the by-products may increase.

The injection amount of n -butene and air may be controlled by a mass flow controller, and the injection amount of steam may be controlled by a fine flow pump.

Injection amount of the reaction product is n - space velocity of 150 h ^-1, based on the butene to ^{700h -1 (GHSV, Gas Hourly Space} Velocity) in, preferably 175 h ^-1 to 600 h ^-1 be injected into a space velocity of It is possible to inject, more preferably at a space velocity of 200 h ^-1 to 500 h ^-1 . If the space velocity is less than 150 h ^−1, the amount of the product per unit time may be low, and thus there may be a problem in profitability. If the space velocity exceeds 700 h ⁻ ¹ , the time for n -butene to react with the catalyst is short, increasing the amount of unreacted product The yield of 1,3-butadiene can be lowered.

The oxidative dehydrogenation may be performed under a temperature range of 300 ° C to 500 ° C, preferably 330 ° C to 470 ° C, more preferably 350 ° C to 450 ° C. If the reaction temperature is less than 350 ℃ may be a problem that the reaction temperature is so low that the catalyst is not activated so that the partial oxidation reaction does not occur well, if it is above 500 ℃ decomposition products or complete oxidation of C1 ~ C3 may occur have.

Hereinafter, embodiments of the present invention will be described in detail.

Example 1

Iron nitrate (Fe (NO ₃ ) ₃ · 6H ₂ O), 6.297 kg), zinc nitrate (Zn (NO ₃ ) ₂ · 6H ₂ O, 2.379 kg) magnesium nitrate (Mg (NO ₃ ) ₂ · 6H ₂ O, 0.513 kg) and aluminum nitrate (Al (NO ₃ ) ₃ .9H ₂ O, 0.75 kg) were dissolved in distilled water and contained magnesium, aluminum, iron, and zinc in a molar ratio of 0.2: 0.2: 1.8: 0.8, respectively, with stirring. Mixed solution was prepared. Catalyst powder was prepared by pyrolyzing the prepared mixed solution by spraying the air (3 atm) into the reactor at 750 ° C. using a carrier gas at 3 L per hour. The catalyst powder thus prepared was transferred to a storage tank, and then calcined under conditions of 500 ° C. and 3 hours to prepare a ferrite metal oxide catalyst.

Example 2

Except that the calcination temperature was set to 550 ℃, a ferrite metal oxide catalyst was prepared under the same conditions as in Example 1.

Example 3

A ferrite metal oxide catalyst was prepared under the same conditions as in Example 1, except that the calcination temperature was set to 600 ° C.

Example 4

Except that the calcination time was set to 2 hours, a ferrite metal oxide catalyst was prepared under the same conditions as in Example 1.

Example 5

A ferrite metal oxide catalyst was prepared under the same conditions as in Example 1, except that the calcination time was set to 1 hour.

Comparative Example 1

A ferrite metal oxide catalyst was prepared under the same conditions as in Example 1, but the calcination step was omitted.

Comparative Example 2

Except that the calcination temperature was set to 650 ℃, a ferrite metal oxide catalyst was prepared under the same conditions as in Example 1.

Comparative Example 3

Except that the calcination temperature was set to 450 ℃, a ferrite metal oxide catalyst was prepared under the same conditions as in Example 1.

Comparative Example 4

Except that the calcining time was set to 30 minutes, a ferrite metal oxide catalyst was prepared under the same conditions as in Example 1.

Comparative Example 5

Except that the calcination time was set to 5 hours, a ferrite metal oxide catalyst was prepared under the same conditions as in Example 1.

Comparative Example 6

Iron nitrate (Fe (NO ₃ ) ₃ · 6H ₂ O), 20.5 kg) and magnesium nitrate (Mg (NO ₃ ) ₂ · 6H ₂ O, 6.5 kg) were dissolved in distilled water, and magnesium and iron A ferrite metal oxide catalyst was prepared under the same conditions as in Example 1, except that a mixed solution containing a molar ratio was prepared.

Experimental Example 1 Analysis of Physical Properties of Ferrite Metal Oxide Catalyst According to Manufacturing Conditions

In order to analyze the surface area of the ferrite metal oxide catalyst prepared according to Examples 1 to 5 and Comparative Examples 1 to 6, the nitrogen adsorption amount was measured using a volumetric nitrogen adsorption apparatus (Quantachrome, ASiQ AGC / TCD), and then BET The surface area was calculated using the formula, and the results are shown in Table 1 below.

In addition, in order to analyze the weight loss of the ferrite metal oxide catalyst prepared according to Examples 1 to 5 and Comparative Examples 1 to 6 using a thermogravimetric analyzer (PerkinElmer, Pyris 6 TGA) at 900 ℃ at room temperature under an air atmosphere The weight loss was measured while heating up, and the results are shown in Table 1 below.

Table 1

division	Surface area (㎡ / g)	Weight loss
Example 1	96	6.7
Example 2	93	4.4
Example 3	94	4.1
Example 4	92	11.2
Example 5	93	10.9
Comparative Example 1	52	24.7
Comparative Example 2	72	15.1
Comparative Example 3	69	16.3
Comparative Example 4	66	13.8
Comparative Example 5	71	15.2
Comparative Example 6	92	9.0

Referring to Examples 1 to 5 and Comparative Example 1 in which ferrite metal oxide catalysts were prepared by changing whether or not a calcination step was included in Table 1, the ferrite metal oxide catalyst prepared by further including a calcination step had a surface area of 90 to 100. It has been shown that ferrite metal oxide catalysts having a value of m 2 / g but without the calcination step have a surface area of less than 60 m 2 / g. Through this, the ferrite metal oxide catalyst prepared by further comprising the calcination step is analyzed to exhibit improved catalytic activity.

In addition, the ferrite metal oxide catalyst prepared by further comprising a calcination step has a weight loss value of 4 to 12% by weight, but the ferrite metal oxide catalyst prepared without the calcination step has a weight loss of more than 20% by weight. Appeared to be. Through this, in the case of the ferrite metal oxide catalyst prepared by further comprising a calcination step, it was confirmed that the stability of the catalyst is improved.

Furthermore, when the ferrite metal oxide catalyst is prepared by further including a calcination step, referring to Examples 1 to 3 and Comparative Examples 2 and 3, which are differently set, the calcination temperature is higher than 600 ° C or lower than 500 ° C. It can be seen that the surface area of the catalyst decreases and the weight loss increases, thereby degrading the catalyst activity and the stability of the catalyst.

In addition, to prepare a ferrite metal oxide catalyst by further comprising a calcination step, with reference to Examples 1, 4, 5 and Comparative Examples 4, 5 set the calcination time differently, the calcination time is less than 1 hour or 4 hours If exceeded, the surface area of the catalyst was reduced and the weight loss was increased, thereby degrading the catalyst activity and the stability of the catalyst.

Meanwhile, referring to Examples 1 to 5 and Comparative Example 6, in which the active ingredient of the ferrite metal oxide catalyst is differently controlled, the surface area of the catalyst when the magnesium is replaced with zinc and the iron is replaced with aluminum is used as the active ingredient. It can be seen that this increase and the weight loss decreased, the catalyst activity and the stability of the catalyst slightly improved.

Thus, further comprising a calcination step, the calcination temperature is set to 500 ℃ to 600 ℃, the calcination time from 1 hour to 4 hours, ferrite metal prepared to include all magnesium, aluminum, iron, and zinc as the active ingredient It is analyzed that oxide catalysts exhibit improved catalytic activity and stability.

Experimental Example 2 Analysis of Reactivity of 1,3-Butadiene According to Preparation Conditions of Ferrite Metal Oxide Catalyst

Activation in Examples 1 to 5 and Comparative Examples 1 to 6 370 ℃ while filling such that the prepared ferrite metal oxide catalyst in a stainless steel reactor, the space velocity (GHSV, Gas Hourly Space Velocity) 400h -1 and injecting air according to the I was. The activated catalyst was subjected to an oxidative dehydrogenation reaction using a mass flow rate controller and a mixed gas having a mixing ratio of C4 mixture ( n -butene): air: steam: 5.2% by volume: 17.2% by volume: 77.6% by volume. 1,3-butadiene was prepared, n -butene conversion, 1,3-butadiene selectivity, and 1,3-butadiene yield were calculated using the following Equations 1 to 3, and the results are shown in Table 2 below. Shown in

Equation 1: n -butene conversion

Equation 2: 1,3-butadiene selectivity

Equation 3: 1,3-butadiene yield

TABLE 2

division	n -butene conversion (%)	1,3-butadiene selectivity (%)	1,3-butadiene yield (%)
Example 1	79.8	92.1	73.5
Example 2	79.3	92.3	73.2
Example 3	79	92.4	73
Example 4	77.5	91.7	71.1
Example 5	77.1	91.4	70.5
Comparative Example 1	75.3	87.4	65.8
Comparative Example 2	67.2	91.1	61.2
Comparative Example 3	77.5	84.5	65.5
Comparative Example 4	76.5	89.7	68.6
Comparative Example 5	72.5	95.3	69.1
Comparative Example 6	79.7	85.9	68.5

Referring to Examples 1 to 5 and Comparative Example 1 in which ferrite metal oxide catalysts were prepared by changing whether or not a calcination step was included in Table 2, the ferrite metal oxide catalyst prepared by further comprising a calcination step was 1,3-butadiene. Although the selectivity has a value of 91% or more, the ferrite metal oxide catalyst prepared without the calcination step has been shown to have a 1,3-butadiene selectivity of less than 88%. Through this, in the case of the ferrite metal oxide catalyst prepared by further comprising a calcination step, it can be seen that the catalytic activity is increased to improve the 1,3-butadiene selectivity.

Furthermore, in order to prepare a ferrite metal oxide catalyst by further comprising a calcination step, referring to Examples 1 to 3 and Comparative Examples 2 and 3, wherein the calcination temperature is set differently, the calcination step is less than 500 ° C. 1,3-butadiene selectivity was not improved compared to the ferrite metal oxide catalyst (Comparative Example 1) prepared without. When the calcination temperature is higher than 600 ℃, the 1,3-butadiene selectivity is improved but n -butene It was found that the conversion and 1,3-butadiene yield dropped sharply.

In addition, to prepare a ferrite metal oxide catalyst by further comprising a calcination step, referring to Examples 1, 4, 5 and Comparative Examples 4, 5, the calcination time is set differently, the calcination step is less than 1 hour The 1,3-butadiene selectivity did not appear to be improved compared to the ferrite metal oxide catalyst prepared without the (Comparative Example 1), and the 1,3-butadiene selectivity is improved when the calcination time exceeds 4 hours. It was found that the n -butene conversion was drastically lowered.

Meanwhile, referring to Examples 1 to 5 and Comparative Example 6, in which the active ingredient of the ferrite metal oxide catalyst is differently controlled, when magnesium is replaced with zinc and iron is replaced with aluminum as active ingredient, 1,3 It can be seen that the yield of butadiene is improved, which is a result of suppression of side reactions as the oxidative dehydrogenation reaction proceeds.

Thus, further comprising a calcination step, the calcination temperature is set to 500 ℃ to 600 ℃, the calcination time from 1 hour to 4 hours, ferrite metal prepared to include all magnesium, aluminum, iron, and zinc as the active ingredient It can be seen that the oxide catalyst can improve the 1,3-butadiene selectivity and yield while maintaining the n -butene conversion.

The foregoing description of the present invention is intended for illustration, and it will be understood by those skilled in the art that the present invention may be easily modified in other specific forms without changing the technical spirit or essential features of the present invention. will be. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.

The scope of the invention is indicated by the following claims, and it should be construed that all changes or modifications derived from the meaning and scope of the claims and their equivalents are included in the scope of the invention.

Claims

(a) dissolving a nitrate precursor of each of magnesium, aluminum, iron, and divalent cation metal in a polar solvent to prepare a precursor solution;

(b) pyrolysing the precursor solution with a carrier gas into the reactor to form a catalyst powder; And

(c) transporting the catalyst powder to a storage tank, and then calcining in the storage tank; a method of preparing a multi-component ferrite metal oxide catalyst represented by the following Chemical Formula 1;

[Formula 1]

Mg x M (1-x) Al y Fe (2-y) O 4

In Chemical Formula 1,

x and y are real numbers satisfying 0 <x <1 and 0 <y <2, respectively, and M is a divalent cation metal element.
The method of claim 1,

Mixing the nitrate precursor in the step (a) so that the molar ratio of magnesium, aluminum, iron, and divalent cation metal is 0.1 to 1: 0.1 to 2: 0.1 to 2: 0.1 to 1, respectively. Method for producing multicomponent ferrite metal oxide catalyst.
The method of claim 2,

In the step (a) is characterized in that the divalent cation metal is at least one selected from the group consisting of zinc, manganese, nickel, cobalt, and copper, multi-component ferrite metal oxide catalyst production method.
The method of claim 1,

In the step (a), the polar solvent is distilled water, characterized in that the manufacturing method of the multi-component ferrite metal oxide catalyst.
The method of claim 1,

In the step (b), the carrier gas is air, characterized in that the manufacturing method of the multi-component ferrite metal oxide catalyst.
The method of claim 5,

In the step (b), characterized in that the pressure of the air is 2 to 4 atm, multi-component ferrite metal oxide catalyst.
The method of claim 1,

In the step (b), the pyrolysis temperature is 500 ℃ to 900 ℃, characterized in that the manufacturing method of the multi-component ferrite metal oxide catalyst.
The method of claim 7, wherein

In the step (c), the calcination temperature is 500 ℃ to 600 ℃, characterized in that the manufacturing method of the multi-component ferrite metal oxide catalyst.
The method of claim 8,

In the step (c), the calcination is carried out for 1 to 4 hours, characterized in that the method for producing a multi-component ferrite metal oxide catalyst.