KR20180076835A - Catalyst for oxidative dehydrogenation, method of preparing the same and method for preparing butadien using the same - Google Patents

Abstract

The present disclosure relates to a catalyst for oxidative dehydrogenation reaction of butane, a preparation method thereof, and a method of producing butadiene using the same, and more specifically, to a reaction catalyst used in oxidative dehydrogenation reaction of butane, as a metal oxide represented by chemical formula 1, A_xZn_(1-x)Fe_2O_4, a preparation method of the catalyst, and a method of producing butadiene using the catalyst. In chemical formula 1, A is one or more selected from the group consisting of Cu, Ra, Ba, Sr, Ca, Be, Fe(II), Mg, Mn, Co, Ni, Al, Cr, Si, V, Ga, In, La and Ce, and x satisfies 0 <= x < 1. Accordingly, the present disclosure has effects of providing a catalyst for oxidative dehydrogenation reaction of butane, the catalyst which has uniform particle size distribution while including metals other than iron and zinc metal, has a high reactivity at low temperatures compared to the prior art, and obtains effects such as high yield of butadiene, lifetime extension of the catalyst and reduction of energy costs accordingly; a preparation method of the catalyst; and a method of producing butadiene using the catalyst.

Description

TECHNICAL FIELD The present invention relates to a catalyst for oxidative dehydrogenation of butene, a method for producing the same, and a method for preparing butadiene using the same. BACKGROUND ART &lt; RTI ID = 0.0 &gt;

The present invention relates to a catalyst for oxidative dehydrogenation of butene, a process for producing the same, and a process for producing butadiene using the same, and more particularly, to a process for preparing butadiene from a catalyst having a uniform particle size distribution, To a catalyst for oxidative dehydrogenation of butene which has high reactivity at a low temperature and thereby has a high butadiene yield, an extended catalyst life and an energy cost reduction effect, a process for producing the same, and a process for preparing butadiene using the same.

Conventionally, ferrite catalysts have been used for butadiene production through oxidative dehydrogenation of butene.

The ferrite-based catalysts, particularly zinc ferrite catalysts, are synthesized by coprecipitation. When a metal other than zinc and iron is added for the purpose of improving yield, etc., it is difficult to obtain a uniform ZnFe ₂ O ₄ phase. There was a phenomenon that the temperature decreased.

In addition, ferrite based catalysts synthesized by coprecipitation have a disadvantage of short catalyst life and high energy cost due to high reaction temperature.

Therefore, it is necessary to develop a catalyst having uniform particles by adding metals other than zinc and iron to improve the butadiene yield and to have a high reactivity even at a lower temperature than the prior art.

KR Patent Publication No. 2013-0046458

In order to solve the problems of the prior art as described above, the present invention is to provide a catalyst having a uniform particle size distribution including iron and a metal of a zinc metal, having high reactivity even at a lower temperature than the prior art, An oxidative dehydrogenation catalyst of butene which has an effect of prolonging the service life and reducing energy costs, a process for producing the same, and a process for producing butadiene using the same.

These and other objects of the present disclosure can be achieved by all of the present invention described below.

In order to achieve the above object, the present invention provides a reaction catalyst for use in the oxidative dehydrogenation reaction of butene, which is a metal oxide represented by the following general formula (1).

[Chemical Formula 1]

A _x Zn _{1 - x} Fe ₂ O ₄

(Wherein A is at least one element selected from the group consisting of Cu, Ra, Ba, Sr, Ca, Be, Fe (II), Mg, Mn, Co, Ni, Al, Cr, Si, V, Ga, In, And x satisfies 0 < x &lt; 1.

The present invention also relates to a process for the preparation of an organosilicon compound having i) a Fe (III) precursor, a Zn precursor and an A precursor in a molar ratio of 2: x-1: x (x satisfies 0 & ^Adding and dissolving Fe ^{3+ in} a solvent such that the molar concentration of Fe ³⁺ is 0.05 to 10 mol / L to prepare a reaction solution; Ii) heat-treating the reaction solution at 200 to 300 ° C for 3 to 12 hours; And (iii) separating, washing and drying the reaction product after the solvent thermal reaction. The present invention also provides a process for preparing an oxidative dehydrogenation catalyst of butene.

The present invention also provides a method for producing butadiene, wherein the butadiene is produced by an oxidative dehydrogenation reaction of a raw material containing butene under a catalyst, wherein the catalyst is an oxidative dehydrogenation reaction catalyst of the present invention.

According to the present invention, it is possible to provide a catalyst having a uniform particle size distribution including a metal of iron and a zinc metal, a high reactivity at a low temperature as compared with the prior art, and also a high butadiene yield, Butene, a process for producing the same, and a process for producing butadiene using the same.

1 to 5 are XRD data of the ferrite catalysts prepared in Examples 1-2 and 1-3, respectively.

Hereinafter, the oxidative dehydrogenation reaction catalyst for butene, the process for producing the same, and the process for producing butadiene using the catalyst will be described in detail.

The present inventors have found that when a ferritic catalyst synthesized by a solvent thermo-synthetic method is applied to an oxidative dehydrogenation reaction of butene, a high conversion ratio, butadiene yield and selectivity can be obtained compared with a ferritic catalyst prepared by coprecipitation of the prior art It is confirmed that the catalytic activity is maintained even at a relatively low reaction temperature and that the reactivity does not decrease even if a metal element other than Zn and Fe is added to the catalyst. .

The catalyst for oxidative dehydrogenation of butene of the present invention is characterized by containing a metal oxide represented by the following general formula (1).

[Chemical Formula 1]

A _x Zn _{1 - x} Fe ₂ O ₄

(Wherein A is at least one element selected from the group consisting of Cu, Ra, Ba, Sr, Ca, Be, Fe (II), Mg, Mn, Co, Ni, Al, Cr, Si, V, Ga, In, And x satisfies 0 < x &lt; 1.

The method for preparing an oxidative dehydrogenation catalyst of butane according to the present invention comprises the steps of: i) mixing an Fe (III) precursor, a Zn precursor and an A precursor in a metal-based molar ratio of 2: x-1: x, And the molar concentration of Fe ^{3 +} is 0.05 to 10 mol / L in an organic solvent having a boiling point of 190 to 250 ° C to prepare a reaction solution; Ii) heat-treating the reaction solution at 200 to 300 ° C for 3 to 12 hours; And iii) separating, washing and drying the reaction product after the solvent thermal reaction.

The reaction catalyst may include, for example, 70 to 99.9 wt% of spinel phase (AFe ₂ O ₄ ), 0 to 20 wt% of iron oxide (α-Fe ₂ O ₃ ), and 0 to 10 wt% of zinc oxide And has an excellent catalytic activity within this range.

As another example, the metal oxide includes 80 to 99.9 wt% of spinel phase (AFe ₂ O ₄ ), 0.1 to 11 wt% of iron oxide (α-Fe ₂ O ₃ ), and 0 to 9 wt% of zinc oxide And the butadiene selectivity is high within this range.

As another example, the metal oxide may include 98 to 99.9 wt% of a spinel phase (AFe ₂ O ₄ ), 0.1 to 2 wt% of iron oxide (α-Fe ₂ O ₃ ), and 0 wt% of zinc oxide And has a high degree of butadiene selectivity within this range.

The A is preferably at least one selected from the group consisting of Mn, Ni and Cu, and more preferably Mn. In this case, the conversion ratio, butadiene yield and selectivity of butadiene are excellent.

X is preferably 0 < x &lt; = 1, more preferably 0.01 x 0.5, and most preferably 0.01 x 0.3. Within this range, an effect of substituting zinc and a high catalytic activity have.

In the present description, the x value can be measured by elemental analysis of the metal oxide catalyst or by converting the input amount of the metal precursor with little loss of the metal element.

Hereinafter, the method for preparing the catalyst for oxidative dehydrogenation of butene will be described in detail.

I) reaction liquid preparation step

The Fe (III) precursor may be, for example, oxalate, acetate, acetylacetonate, nitrate, ammonium salt, sulfate and halide ), And it is preferably a nitrate, a halide, or an acetate salt. In this case, the solvent thermal reaction is easily effected.

The Zn precursor may be selected from, for example, oxalate, acetate acetate, acetylacetonate, nitrate, ammonium salt, sulfate and halide. And may be at least one kind of nitrate, halide, or acetate salt. In this case, the solvent thermal reaction is easily effected.

The A precursor may be selected from, for example, oxalate, acetate acetate, acetylacetonate, nitrate, ammonium salt, sulfate and halide. And may be at least one kind of nitrate, halide, or acetate salt. In this case, the solvent thermal reaction is easily effected.

X may be, for example, 0 < x < 1, 0.01 x 0.5 or 0.01 x < 0.3.

Such solvents include, for example, ethylene glycol, 1,4-butanediol, benzyl alcohol and

And hexanol. In this case, there is an easy effect for forming a ZnFe ₂ O ₄ structure.

The molar concentration of Fe ^{3 +} in the organic solvent may be, for example, 0.01 to 30 mol / L, 0.05 to 20 mol / L or 0.01 to 10 mol / L, and the effect of facilitating the formation of ZnFe 2 O 4 grains within this range .

The reaction solution may be prepared by charging all the precursors at room temperature, 20 to 25 ° C, or 22 to 23 ° C, stirring at a rate of 50 to 400 rpm, 60 to 300 rpm, or 100 to 200 rpm for 2 to 36 hours , For 3 to 24 hours, or for 5 to 12 hours to completely dissolve the solvent. In this case, the solvent thermal reaction is easily effected.

Ii) Solvent heat  Reaction step

The solvent thermal reaction may be carried out at 100 to 350 ° C, 150 to 320 ° C, or 200 to 300 ° C for 1 to 36 hours, 2 to 24 hours, or 3 to 12 hours, for example, There is an easy effect.

After the solvent thermal reaction is completed, the reaction product is heated at a temperature of 5 to 50 DEG C or 20

The reaction product can be allowed to cool at room temperature without any special treatment. In this case, there is an effect of facilitating the formation of solid particles.

Iii) Post-treatment step (separation, washing and drying step)

The separation may be carried out using a centrifugal separator, for example. In this case, separation efficiency and by-product removal ratio are high.

The washing may be carried out with at least one kind selected from water, ethanol, acetone and isopropyl alcohol, preferably water or ethanol. In this case, the impurities are washed well and the catalyst loss is minimized.

The washing may be performed 1 to 5 times or 2 to 3 times with 100 to 200 parts by weight of the washing solution or 300 to 1000 parts by weight with respect to 100 parts by weight of the solid content. In this range, the impurities are washed away, It is effective.

The drying can be carried out at 70 to 200 ° C for 3 to 24 hours, for example. Within this range, drying efficiency and catalytic activity are excellent.

As another example, the drying can be carried out at 80 to 150 ° C for 10 to 15 hours, and the drying efficiency is excellent within this range.

The method for producing butadiene according to the present invention is characterized in that butadiene is produced by subjecting a raw material containing butene to an oxidative dehydrogenation reaction under a catalyst, wherein the catalyst is an oxidative dehydrogenation reaction catalyst of butene of the present invention.

The oxidative dehydrogenation reaction of butene in the present invention means a reaction in which butene and oxygen react in the presence of a metal oxide catalyst to produce butadiene and water.

The raw material is not particularly limited when it is a raw material containing 50% by volume or more of butene, but it may be raffinate, for example, and it has an economical effect.

The oxidative dehydrogenation reaction can be carried out, for example, by including oxygen, nitrogen and steam. In this case, the conversion, the butadiene yield and the selectivity are excellent, and the reaction apparatus is easy to operate.

The oxygen, nitrogen, and steam may have a volume ratio of 1 to 10: 1 to 10: 1 to 10, or 1 to 5: 1 to 5: 1 to 5, and the conversion, the butadiene yield and the selectivity And it is easy to operate the reaction apparatus.

The oxidative dehydrogenation reaction can be carried out, for example, at 280 to 500 ° C, 290 to 400 ° C, 290 to 360 ° C, 290 to 330 ° C, or 320 to 360 ° C. Within this range, conversion to butadiene is activated Side reaction to COx is minimized and the butene conversion and butadiene selectivity are excellent.

The oxidative dehydrogenation reaction can be, for example, a reaction pressure of 10 bar or less, 5 bar or less, 0.5 to 3 bar, or 1 to 3 bar.

The oxidative dehydrogenation reaction may be performed, for example, in such a manner that the gas space velocity (GHSV) is 20 to 1000 h ^-1 , 50 to 750 h ^-1 , 80 to 650 h ^-1 , or 450 to 650 h ^-1 . &^Lt; / RTI &gt;

In the oxidative dehydrogenation reaction, the butene conversion may be 25% or more, 60% or more, 75% or more, 80% or more, or 85% or more.

In the oxidative dehydrogenation reaction, 1,3-butadiene selectivity can be 80% or more, 85% or more, or 88% or more, for example.

The reactor used in the oxidative dehydrogenation reaction is not particularly limited in the case of a reactor that can be used for the oxidative dehydrogenation reaction. However, for example, when the reaction temperature of the catalyst layer is maintained constant and the reactant passes through the catalyst layer continuously The reactor may be a tubular reactor, a shaping reactor, a fluidized bed reactor, or a fixed bed reactor. The fixed bed reactor may be a multi-tubular reactor or a plate reactor, for example.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention within the scope and spirit of the following claims, Such variations and modifications are intended to be within the scope of the appended claims.

[Example]

Example  One ( ZnFe ₂ O ₄ of Solvent heat  Lt; / RTI &gt;

2.646 g of iron chloride and 0.642 g of zinc chloride were mixed with 60 ml of ethylene glycol and sufficiently stirred. The molar concentration of Fe ^{3 + in the} solution is 0.15 mol / L.

To the solution was added again 11 g of sodium acetate anhydride and completely dissolved by a stirrer at a rotation speed of 500 rpm for 30 minutes. Then, the solution was transferred into a durable container and sealed, followed by stirring at 200 rpm for 12 hours at 300 rpm Lt; / RTI &gt;

After the reaction, the liquid phase was removed by a centrifuge and washed once with distilled water and anhydrous ethyl alcohol. The remaining solid was dried at 80 ° C for 12 hours to obtain ZnFe ₂ O ₄ powder. It was confirmed from the X-ray diffraction pattern that the obtained ZnFe ₂ O ₄ powder had a spinel structure (spinel phase: 98 mol% and iron oxide: 2 mol%) (see FIG.

Example  2 ( MnxZn _{One - x} Fe ₂ O ₄ of Solvent heat  Lt; / RTI &gt;

The procedure of Example 1 was repeated except that 0.12 g of manganese chloride was added as the Mn precursor in Example 1 to prepare a powder of Mn _{1 - x} Zn _x Fe ₂ O ₄ (where x is 0.8) . The obtained Mn _{1 - x} Zn _x Fe ₂ O ₄ powder had a spinel structure (89 mol% of spinel phase and 11 mol% of iron oxide) from the X-ray diffraction pattern (see FIG. 2).

Comparative Example  One ( ZnFe ₂ O ₄ of By co-finishing  Produce)

3.5 g of zinc chloride (ZnCl ₂ , 6H ₂ O) and 14 g of ferric chloride (FeCl ₃ ) were dissolved in 250 ml of distilled water as a first step to prepare 267.6 g of an iron-metal precursor aqueous solution.

At this time, the atomic ratio of the metal components contained in the iron-metal precursor solution was Fe: Zn = 2: 1.

As the second step, the iron-metal precursor aqueous solution was added to a coprecipitation tank filled with 250 ml of water. Then, 5 g of 25% ammonia water was added thereto. After that, a stirring stirrer was used for 1 hour Followed by stirring.

Thereafter, the coprecipitation solution was filtered under reduced pressure using a vacuum filter to discharge the filtrate, and the residue filtrate was washed with water to obtain a slurry of the iron-metal oxide without performing the treatment.

As a third step, the slurry of the iron-metal oxide was dried at 90 ° C. for 16 hours, and the dried co-precipitate was heat-treated at 650 ° C. for 6 hours to obtain ZnFe 2 O 4 powder. It was confirmed from the X-ray diffraction pattern that the obtained ZnFe ₂ O ₄ powder had a spinel structure (spinel phase: 96 mol% and iron oxide: 4 mol%) (see FIG. 3).

Comparative Example  2 ( MnxZn1 - xFe2O4 By co-finishing  Produce)

The procedure of Example 1 was repeated except that 1.1 g of manganese chloride was added as the Mn precursor in Comparative Example 1 to obtain Mn _{1 - x} Zn _x Fe ₂ O ₄ (where x is 0.8) powder . It was confirmed from the X-ray diffraction pattern that the obtained Mn _{1 - x} Zn _x Fe ₂ O ₄ powder had a spinel structure (spinel phase: 76 mol% and iron oxide: 24 mol%) (see FIG.

Comparative Example  3 ( ZnFe ₂ O ₄ of By solvent thermo-synthesis  Produce)

ZnFe ₂ O ₄ powder was obtained in the same manner as in Example 1 except that 0.88 g of zinc nitrate and 2.4 g of iron nitrate were used as the precursors of Zn and Fe in Example 1. It was confirmed from the X-ray diffraction pattern that the obtained ZnFe ₂ O ₄ powder had a spinel structure (spinel phase: 91 mol%, zinc oxide: 7 mol% and iron oxide: 1.8 mol%) (see FIG.

[Test Example 1]

The composition, structure, and raw consumption of the ferrite catalysts prepared in Examples 1-2 and 1-3 were measured by the following methods, and the results are shown in FIGS. 1 to 5 and Table 1, respectively.

* Catalyst structure: X-ray diffraction analysis (XRD) was performed to compare the structural characteristics of the catalyst prepared in the above Examples and Comparative Examples, and X-ray diffraction analysis was performed using a Bruker AXS D4 E ndeavor XRD (voltage 40 kV, Using the FDS 0.5, the 2 theta 5 to 80 degree region was scanned every 0.02 degree every second using a 40 mA current, Cu-target tube, wavelength 1.5418 angstroms, and Lynx Eye position sensor detector (3.7 deg slit) Respectively.

Unit: mol% ZnFe ₂ O ₄ α-Fe ₂ O ₃ ZnO Example 1 98 2 0 Example 2 89 11 0 Comparative Example 1 96 4 0 Comparative Example 2 76 24 0 Comparative Example 3 91 1.8 7

As shown in Table 1, the ferrite catalysts (Examples 1 and 2) prepared by the solvent thermosynthetic method according to the present invention were synthesized in comparison with the ferrite catalysts prepared by the conventional coprecipitation method (Comparative Examples 1 and 2) It was confirmed that the loss of heavy metal ions was small and the content ratio of the spinel phase structure was high.

In addition, it was confirmed that ZnO content was greatly increased in the ferritic catalyst prepared by the solvent thermo-synthesis method but containing no manganese, that is, the third metal (Comparative Example 3).

[Test Example 2]

Butadiene was produced through the following oxidative dehydrogenation reaction using the ferrite catalyst synthesized by the solvent thermo-synthetic method in Examples 1 and 2 and the ferrite catalyst synthesized by coprecipitation in Comparative Examples 1 and 2, The results are shown in Table 2 below.

As the reactor, the catalyst prepared in Example or Comparative Example was fixed to a metal tubular reactor having a diameter of 1.8 cm at a catalyst bed volume of 30 cc and 40 wt% of cis-2-butene and 60 wt% of trans- Mixture and oxygen were used and nitrogen and steam were introduced. The reactant ratios were set at a molar ratio of oxygen / butene 0.75, steam / butene 12 and nitrogen / butene 3, and the steam was introduced into the reactor together with the reactants by vaporizing water at 340 ° C vaporizer.

The amount of butene mixture was controlled at 0.625 cc / min using a mass flow controller for liquids. The oxygen and nitrogen were controlled using a mass flow controller for gas, and the feed rate was controlled using a liquid pump. The gas hourly space velocity (GHSV) of the reactor was set to 500 h ^-1 and reacted under the conditions of normal pressure (pressure gauge 0) and the temperature shown in Table 2.

Were analyzed after the reaction product by gas chromatography (GC), a mixture cabinet butene conversion (X), selected 1, 3-butadiene is also (S-BD), 1,3-butadiene yield (Y), CO ₂ selectivity of the (S_CO ₂ ), and CO selectivity (S_CO) were calculated according to the following expressions (1) to (5).

[Equation 1]

Conversion rate (%) = (number of moles of butene reacted / number of moles of butene fed) x 100

&Quot; (2) &quot;

Butadiene selectivity (%) = (moles of produced 1,3-butadiene / moles of reacted butene) x 100

&Quot; (3) &quot;

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

&Quot; (4) &quot;

CO ₂ selectivity (%) = (moles of produced CO ₂ / moles of reacted butene) x 100

&Quot; (5) &quot;

CO selectivity (%) = (moles of produced CO / moles of reacted butene) x 100

catalyst T (占 폚) Conversion (%) Selectivity_BD (%) Yield (%) Selectivity_CO2 (%) Selectivity_CO (%) Example 1 300 27.04 86.91 23.50 4.44 0.37 325 64.25 88.81 57.06 6.75 0.75 350 79.57 85.55 68.07 8.24 0.88 Example 2 300 28.32 88.00 24.92 4.63 0.54 325 67.49 90.60 61.15 5.97 0.56 350 85.64 87.42 74.87 7.66 0.60 Comparative Example 1 300 18.63 81.63 15.20 3.87 0.00 325 58.73 91.80 53.91 5.18 0.37 350 90.19 90.26 81.41 6.45 0.47 Comparative Example 2 300 9.06 49.61 4.49 11.64 1.42 325 40.41 75.56 30.54 12.71 1.13 350 74.06 82.66 61.22 9.63 0.74

As shown in Table 1, in the case of producing butadiene using the ferrite catalyst prepared by the thermal reaction of the solvent according to the present invention (Examples 1 and 2), the ferrite catalyst prepared by the conventional coprecipitation method 1 and 2), it was confirmed that the conversion of butane, butadiene selectivity and yield were remarkably excellent, and that the catalyst had high catalytic activity and reactivity even at low temperatures.

Claims (14)

And a metal oxide represented by the following formula (1)
Oxidative Dehydrogenation of Butene.
[Chemical Formula 1]
A _x Zn _{1 - x} Fe ₂ O ₄
(Wherein A is at least one element selected from the group consisting of Cu, Ra, Ba, Sr, Ca, Be, Fe (II), Mg, Mn, Co, Ni, Al, Cr, Si, V, Ga, In, And x satisfies 0 < x &lt; 1.
The method according to claim 1,
Wherein the metal oxide comprises 70 to 99.9% by weight of a spinel phase (AFe ₂ O ₄ ) and 0.1 to 10% by weight of zinc oxide (ZnO)
Catalyst for Oxidative Dehydrogenation Reaction.
Ⅰ) Fe (Ⅲ) precursor, Zn precursor and A the molar ratio of precursor: x-1:. In the x (where x is 0 <x <satisfies 1) to Fe ³ in an organic solvent of a boiling point of 190 to 250 ℃ ⁺ &Lt; / RTI &gt; molar concentration of 0.05 to 10 mol / L to prepare a reaction solution;
Ii) heat-treating the reaction solution at 200 to 300 ° C for 3 to 12 hours; And
And iii) separating, washing and drying the reaction product after the solvent thermal reaction.
A process for preparing an oxidative dehydrogenation catalyst of butene.
The method of claim 3,
The Fe (III) precursor can be prepared from oxalate, acetate, acetylacetonate, nitrate, ammonium salt, sulfate, and halide. And at least one selected from the group consisting of
A process for preparing an oxidative dehydrogenation catalyst of butene.
The method of claim 3,
The Zn precursor may be one selected from the group consisting of oxalate, acetate, acetylacetonate, nitrate, ammonium salt, sulfate, and halide. Or more
A process for preparing an oxidative dehydrogenation catalyst of butene.
The method of claim 3,
The A precursor is selected from the group consisting of oxalate, acetate, acetylacetonate, nitrate, ammonium salt, sulfate and halide. Or more
A process for preparing an oxidative dehydrogenation catalyst of butene.
The method of claim 3,
Wherein the solvent is at least one selected from ethylene glycol, 1,4-butanediol, benzyl alcohol and hexanol
A process for preparing an oxidative dehydrogenation catalyst of butene.
The method of claim 3,
Characterized in that the separation is carried out using a centrifugal separator
A process for preparing an oxidative dehydrogenation catalyst of butene.
The method of claim 3,
The washing is carried out with at least one selected from water, ethanol, acetone and isopropyl alcohol.
A process for preparing an oxidative dehydrogenation catalyst of butene. The method of claim 3,
Wherein the drying is carried out at 70 to 200 DEG C for 3 to 24 hours
A process for preparing an oxidative dehydrogenation catalyst of butene.
Butene is oxidatively dehydrogenated in the presence of a catalyst to produce butadiene, wherein the catalyst is an oxidative dehydrogenation catalyst according to claim 1 or 2.
Butadiene.
12. The method of claim 11,
Characterized in that the raw material is raffinate
Butadiene.
12. The method of claim 11,
Characterized in that the oxidative dehydrogenation reaction is carried out with oxygen, nitrogen and steam.
Butadiene.
12. The method of claim 11,
Characterized in that the oxidative dehydrogenation reaction is carried out at 280 to 500 &lt; RTI ID = 0.0 &gt;
Butadiene.

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