KR20190063203A - Metal complex oxide catalysts for production of butadiene, preparation method thereof, and preparation method of butadiene by using the same - Google Patents

Abstract

The present invention relates to a method for producing butadiene from a butene-based multi-component metal such as molybdenum (Mo) - bismuth (Bi) - iron (F) - cobalt (Co) - alkali metal - antimony (Sb) The present invention relates to a composite oxide catalyst, a method for preparing the same, and a method for preparing butadiene using the same, wherein the catalyst of the present invention is improved by appropriate control of the Bi molar ratio and by the use of cesium (Cs) or potassium (K) Butene conversion, and butadiene selectivity and yield.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a metal complex oxide catalyst for use in the production of butadiene, a method for producing the same, and a method for preparing butadiene using the same. BACKGROUND ART [0002] Metals,

The present invention relates to a seven-component multinary compound metal oxide catalyst for producing butadiene from butene at a high yield, a process for producing the same, and a process for producing butadiene using the same.

Butadiene is an important chemical used as a raw material for synthetic rubbers such as automobile tires, and is produced by extracting and isolating butadiene from C4 fractions composed of isobutene, n-butene, butadiene, and the like. The demand for butadiene is steadily increasing, and development of a new butadiene production method is desired.

In the oxidative dehydrogenation reaction of n-butene using the oxidative dehydrogenation catalyst of the prior art, there was a problem of rapid deactivation of the catalyst and a decrease in mechanical strength over the reaction time. In addition, in order to increase 1,3-butadiene production yield, a C4 distillation fraction containing a large amount of 1-butene component is required as a raw material and further a line distillation process is required in order to lower the n-butane content of C4 fraction. This is disadvantageous because it is not economical due to high investment cost and thus it is difficult to apply to commercial process.

A number of documents in this regard disclose improvements in multicomponent bismuth molybdate catalyst activity for the production of butadiene. For example, Korean Patent No. 10-1495478 has improved butadiene conversion, selectivity and yield at low temperatures in relatively small amounts by simultaneously containing Cs and K in an Mo-Bi-Fe-Co based oxidation catalyst Butadiene is produced from the C4 mixture by using the method of producing the bismuth molybdate catalyst according to the present invention, the hot spot (reaction temperature) temperature is lower than the conversion rate when only K is added alone It is too high to drive normally. Korean Patent No. 10-1603820 discloses a butadiene production method of controlling the ratio of Co without adding Ni to a multicomponent bismuth molybdate catalyst. Korean Patent No. 10-1559199 discloses a method of further including a Cs content in a multicomponent bismuth molybdate catalyst. Korean Patent No. 10-1706851 discloses a process for producing 1,3-butadiene using a bismuth molybdate catalyst containing Mo, Bi, Fe, K, Ce and Zr components. However, Is not as high as 66.9%. In addition, U.S. Patent No. 14903813 carried out an oxidative dehydrogenation reaction using a Mo ₁₂ Bi _0.6 Fe ₃ Co ₇ K _0.08 Cr _0.5 Si _1.6 O _x catalyst. The content of n-butene in the reactants was 8% , The conversion of n-butene is 85% or more, but the amount actually converted is small.

The above prior art describes various schemes for preparing multicomponent bismuth-molybdate catalysts for use in the production of 1,3-butadiene. In order to increase the activity of the catalyst and to ensure the stability of the process operation, attempts were made to change the catalyst composition but mainly to change the composition of Cs and K or Co. In this technique, bismuth is fixed on the basis of an oxidation catalyst, and it is difficult to analyze the catalytic activity depending on the bismuth content by preparing a catalyst with the same composition.

On the other hand, Japanese Patent Laid-Open Publication No. 2011-178719 (MITSUI CHEMICALS INC.) Discloses a method for producing a zirconium compound represented by the formula (1): Mo (a) Bi (b) Fe (c) Discloses a catalyst for the production of butadiene, which essentially contains a composite metal oxide (active catalyst) and silica (carrier) represented by the following formula.

As a result, the present inventors have provided a seven-metal complex oxide catalyst having excellent butadiene production activity.

Korean Patent No. 10-1495478 (2015.02.13) Korean Patent No. 10-1603820 (2016.03.09) Korean Patent No. 10-1559199 (2015.10.02) Korean Patent No. 10-1706851 (Feb. U.S. Patent No. 14903813 (Jul. Japanese Laid-Open Patent Publication No. 2011-178719 (September 15, 2011)

It is an object of the present invention to provide a multicomponent bismuth-molybdate metal complex oxide catalyst having an excellent activity as a result of examining an optimal content of a metal component constituting a catalyst.

In order to achieve the above object,

As a metal complex oxide catalyst for an oxidative dehydrogenation reaction of a C4 hydrocarbon mixture,

Wherein the catalyst comprises molybdenum (Mo), bismuth (Bi), iron (F), cobalt (Co), alkali metal, antimony (Sb) and silicon (Si).

The present invention also

(a) preparing a solution containing a molybdenum (Mo) compound, a bismuth (Bi) compound, an iron (F) compound, a cobalt (Co) compound and an alkali metal compound;

(b) adding to the solution from the antimony trioxide (Sb ₂ O ₃₎ and silica (SiO ₂₎ to step (a) solution;

(c) evaporating the solution from step (b) to recover the solid product; And

(d) calcining the solid product from step (c) at a temperature of from 300 to 550 占 폚.

Furthermore, the present invention is put into the C4 hydrocarbon mixture under the reaction conditions of the reaction temperature in the metal complex oxide catalyst of the invention 300 to 500 ℃, atmospheric pressure and GHSV (gas hourly space velocity, h -1) 1000 to 5000h ^-1 air And an oxidative dehydrogenation reaction in the presence of steam to produce butadiene.

In the present invention, 1,3-butadiene was produced in high yield from the C4 mixture by controlling the bismuth content in the preparation of the multicomponent bismuth molybdate catalyst. In addition, alkali metal was added to improve 1,3-butadiene selectivity and yield to improve 2-butene conversion, 1,3-butadiene selectivity and yield.

It is an object of the present invention to provide a multicomponent bismuth-molybdate metal complex oxide catalyst having an excellent activity as a result of examining an optimal content of a metal component constituting a catalyst. The optimal Bi molar ratio was investigated by controlling the amount of bismuth used in the multi-component metal complex oxide catalysts.

When the Bi molar ratio was changed, it was confirmed that the conversion of 2-butene and the yield of 1,3-butadiene were increased as the Bi molar ratio was decreased. In particular, when the Bi molar ratio is 0.5, the conversion of 2-butene and the yield of 1,3-butadiene are the highest, and Bi 0.5 is the optimum molar ratio.

In addition, it was confirmed that the alkali metal affects the selectivity of 1,3-butadiene, and alkali metal was added as a method for increasing the conversion of 2-butene, 1,3-butadiene selectivity and yield. High catalytic activity was obtained when Cs was added as alkali metal and high catalytic activity was obtained when K was added in the same amount as Cs. As a result, a bismuth-molybdate metal complex oxide catalyst containing an alkali metal has been developed.

The present invention is described in more detail below.

In one embodiment, the present invention is a metal composite oxide catalyst for oxidative dehydrogenation reaction of a C4 hydrocarbon mixture, wherein the catalyst is selected from the group consisting of molybdenum (Mo), bismuth (Bi), iron (F), cobalt (Sb), and silicon (Si).

In one embodiment,

(a) preparing a solution containing a molybdenum (Mo) compound, a bismuth (Bi) compound, an iron (F) compound, a cobalt (Co) compound and an alkali metal compound;

(b) adding to the solution from the antimony trioxide (Sb ₂ O ₃₎ and silica (SiO ₂₎ to step (a) solution;

(c) evaporating the solution from step (b) to recover the solid product; And

(d) calcining the solid product from step (c) at a temperature of from 300 to 550 占 폚.

In the metal composite oxide catalyst of the present invention, molybdenum (Mo) -bismuth (Bi) -iron (F) -cobalt (Co) -Alkali metal is the main catalyst component showing activity, and silicon (Si) and antimony (See Chemistry and Technology of Fuels and Oils, Vol. 33, No. 3, 1997). In the present invention, silica (SiO ₂ ) as a source of silicon (Si) and antimony trioxide (Sb ₂ O ₃ ) as a source of antimony (Sb) are introduced as a carrier and a promoter, respectively, to complete a final metal complex oxide catalyst It plays a role.

In this connection, when the metal complex oxide catalyst of the present invention is compared with the catalyst of Patent Document 6 (Japanese Patent Laid-Open Publication No. 2011-178719) mentioned above, the catalyst of Patent Document 6 is a catalyst in which antimony (Sb) Is added to the production reaction and becomes the active catalyst component constituting the main catalyst of the final metal complex oxide catalyst. On the other hand, silica (carrier) and antimony trioxide (Sb ₂ O ₃ , promoter) are added to the active catalyst (Mo-Bi-F-Co-alkali metal compound) during the production of the metal composite oxide catalyst of the present invention, (Sb ₂ O ₃ ) is a form in which an oxidation structure has already been formed, and acts as a catalyst promoting catalytic activity like silica. Therefore, antimony (Sb) of the catalyst of Patent Document 6 participates in lattice oxygen transfer (redox reaction) as a main component metal, but antimony (Sb) of the metal complex oxide catalyst of the present invention plays a role . That is, the metal complex oxide catalyst of the present invention is a completely different catalyst from the catalyst of Patent Document 6. The inventors of the present invention have found that a finished catalyst obtained by adding antimony trioxide (Sb ₂ O ₃ ) like the catalyst of the present invention to a catalyst prepared using an antimony precursor as in Patent Document 6 is superior in terms of activity, The results of the comparative experiments are shown in Fig.

In one embodiment, the catalyst of the present invention has a molar ratio of Mo: Bi: Fe: Co: alkali metal: Sb: Si of 12: 0.3 to 2: 1 to 3: 5 to 8: 0.01 to 0.3: 0.1 to 2: ~ 4.

In one embodiment, the alkali metal is cesium (Cs) or potassium (K).

In one embodiment, the catalyst of the present invention is used to prepare butadiene from a C4 hydrocarbon mixture.

In one embodiment, the molybdenum (Mo) compound, bismuth compound, iron (F) compound, cobalt (Co) compound, alkali metal compound, antimony trioxide (Sb ₂ O ₃ ) and The molar ratio of silica (SiO ₂ ) is from 12: 0.3 to 2: 1 to 3: 5 to 8: 0.01 to 0.3: 0.1 to 2:

In one embodiment, the alkali metal compound used in the preparation of the catalyst of the present invention is a cesium (Cs) compound or a potassium (K) compound.

In one embodiment, the molybdenum (Mo) compound used in the preparation of the catalyst of the present invention is ammonium molybdate tetrahydrate.

In one embodiment, the bismuth (Bi) compound used in the preparation of the catalyst of the present invention is bismuth nitrate pentahydrate.

In one embodiment, the iron (F) compound used in the preparation of the catalyst of the present invention is iron nitrate nonahydrate.

In one embodiment, the cobalt (Co) compound used in the preparation of the catalyst of the present invention is cobalt nitrate hexahydrate.

In one embodiment, the cesium (Cs) compound used in the preparation of the catalyst of the present invention is cesium nitrate.

In one embodiment, the potassium (K) compound used in the preparation of the catalyst of the present invention is potassium nitrate.

In one embodiment the silica (SiO ₂₎ is colloidal silica (silica Ludox_colloidal) used in the catalyst preparation of the present invention.

In one embodiment, the present invention In the C4 hydrocarbon mixture under the reaction conditions of the reaction temperature in the metal complex oxide catalyst of the invention 300 to 500 ℃, atmospheric pressure and GHSV (gas hourly space velocity, h -1) 1000 to 5000h ^-1 And performing oxidative dehydrogenation reaction in the presence of air and steam to produce butadiene.

In one embodiment, the C4 hydrocarbon mixture has an n-butane content of at least 40 wt% and a 2-butene content of at least 50 wt%.

In one embodiment, the volume ratio of the C4 hydrocarbon mixture: air: steam is 9-11: 55-65: 28-40 under the reaction conditions.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

Preparation of Catalyst

Production Example 1

Bi, Fe, Co, Cs, Sb and Si, and the molar ratio of each component was changed to Mo: Bi: Fe: Co: Cs: Sb: Si = 12: 0.5: 2: 7: 0.05: 0.5: 2.92. As a metal precursor for the preparation of the catalyst, bismuth nitrate pentahydrate as a precursor of bismuth, ammonium molybdate tetrahydrate as a precursor of molybdenum, iron nitrate Cobalt nitrate hexahydrate was used as a precursor of cobalt and cesium nitrate was used as a precursor of cesium. In addition, cobalt nitrate hexahydrate was used as a precursor of cobalt and iron nitrate nonahydrate was used as a precursor of cobalt.

First, 15 g of ammonium molybdate tetrahydrate (99.0%, SAMCHUN) and 0.03 g of cesium nitrate (99%, Sigma Aldrich) were dissolved in 75 mL of distilled water at 75 캜 and stirred. Then, iron nitrate nonahydrate (98.5% , And 14.4 g of cobalt nitrate hexahydrate (97%, SAMCHUN) were dissolved in 50 mL of distilled water and stirred at room temperature. 1.7 g of bismuth nitrate pentahydrate (97%, SAMCHUN) was difficult to dissolve in distilled water and precipitation occurred easily. 10 mL of 10% nitric acid aqueous solution was prepared, dissolved in acidic conditions and stirred at room temperature.

The stirred bismuth precursor solution was slowly added to the mixed solution of the iron precursor and the cobalt precursor, and then mixed in a stirring solution of the molybdate precursor and the cesium precursor in a heating bath at 75 ° C and stirred.

0.3 g of antimony trioxide (99%, Sigma Aldrich) used as a co-catalyst was added in powder form and 4.14 g of Ludox AS-30 colloidal silica (Sigma Aldrich) was diluted in 25 mL of distilled water The solution was added and mixed evenly. As a result of the acidity measurement of the precursor solution, it was confirmed that the solution was a strong acid solution at a pH of 0 to 0.2. The resulting precursor solution was stirred for 1 hour for complete mixing and then evaporated to dryness to obtain a solid catalyst powder, which was further dried in an oven at 110 DEG C for 24 hours to completely remove water.

The obtained solid catalyst was calcined in a calcining furnace at a temperature of 320 ° C. for 3 hours to remove residual ammonia and nitrogen oxides, and the powder was recovered at room temperature. The recovered catalyst powder was formed into a 2.0 mm size and then calcined at 500 ° C. for 5 hours in the same calcining furnace to prepare a final Mo ₁₂ Bi _0.5 Fe ₂ Co ₇ Cs _0.05 Sb _0.5 Si _2.92 catalyst.

Production Example 2

A catalyst of Mo ₁₂ Bi _0.75 Fe ₂ Co ₇ Cs _0.05 Sb _0.5 Si _2.92 was prepared in the same manner as in Production Example 1 except that the molar ratio of bismuth nitrate pentahydrate (97%, SAMCHUN) was changed to 0.75 in Production Example 1, .

Production Example 3

A Mo ₁₂ Bi ₁ Fe ₂ Co ₇ Cs _0.05 Sb _0.5 Si _2.92 catalyst was prepared in the same manner as in Production Example 1, except that the molar ratio of bismuth nitrate pentahydrate (97%, SAMCHUN) .

Production Example 4

In the same manner as in Production Example 1, except that the molar ratio of bismuth nitrate pentahydrate (97%, SAMCHUN) was changed to 1.25 in Production Example 1, a Mo ₁₂ Bi _1.25 Fe ₂ Co ₇ Cs _0.05 Sb _0.5 Si _2.92 catalyst .

Production Example 5

The procedure of Production Example 1 was repeated except that the molar ratio of bismuth nitrate pentahydrate (97%, SAMCHUN) was changed to 2 in Production Example 1 to prepare a Mo ₁₂ Bi ₂ Fe ₂ Co ₇ Cs _0.05 Sb _0.5 Si _2.92 catalyst .

Production Example 6

The procedure of Production Example 1 was repeated except that 0.03 g of potassium nitrate (99%, Sigma Aldrich) was used instead of Cs in Production Example 1 to prepare a Mo ₁₂ Bi _0.5 Fe ₂ Co ₇ K _0.05 Sb _0.5 Si _2.92 catalyst .

Comparative Example 1

Except that 0.15 g of lanthanum (III) nitrate hexahydrate (99%, Sigma Aldrich) was added instead of Cs in Production Example 1 to prepare Mo ₁₂ Bi _0.5 Fe ₂ Co ₇ La _0.05 Sb _0.5 Si _2.92 catalyst.

Comparative Example 2

(III) acetate [Sb (CH ₃ CO ₂ ) ₃ ] (99%, Sigma Aldrich) was used in place of antimony trioxide (Sb ₂ O ₃ ) powder in Production Example 1 and potassium nitrate (99.0%, SAMCHUN) was prepared by using 0.35 g of the antimony (III) acetate described above in the same manner as in Preparation Example 1 except that 0.03 g of diethylenetriaminepentaacetic acid (99%, Sigma Aldrich) (99%, Sigma Aldrich) in 75 ml of distilled water at 75 ° C and stirred, except that the amount of Mo ₁₂ Bi _0.5 Fe ₂ Co ₇ K _0.05 Sb _0.5 Si _2.92 catalyst.

Catalyst activity test

Experimental Example 1 : Activity test of Bi molar ratio 0.5 catalyst

In the present invention, a fixed-bed catalytic reactor was used, and 1 g of the catalyst Mo ₁₂ Bi _0.5 Fe ₂ Co ₇ Cs _0.05 Sb _0.5 Si _2.92 prepared in Preparation Example 1 was introduced and then oxidized at a normal pressure, a reaction temperature of 350 ° C. and a GHSV of 2200 / Dehydrogenation reaction was carried out.

The reactant used was a C4-raffinate component having a composition of 45 to 50 wt% of n-butane and 50 to 55 wt% of 2-butene, and air and steam were injected together with the reactant. In this case, the ratio of C4: raffinate: air: steam was maintained at 10:58:33. The role of steam was to shorten the residence time of the reactants in the catalyst, So that the activity of the catalyst can be maintained for a long time by removing the generated coke during the reaction. Further, there is an effect that the heat generation of the oxidative dehydrogenation reaction is controlled to prevent the temperature of the catalyst layer from rising sharply.

After 20 hours of reaction, the C4 hydrocarbon mixture was produced as 1,3-butadiene at a conversion of 2-butene of 80%, a selectivity of 1,3-butadiene of 94% and a yield of 1,3-butadiene in the product of 76% It was confirmed that the yield was high without long-term inactivation.

Experimental Example 2 : Activity test of K-containing catalyst

The oxidative dehydrogenation reaction was carried out under the same reaction conditions as in Experimental Example 1 using 1 g of the catalyst Mo ₁₂ Bi _0.5 Fe ₂ Co ₇ K _0.05 Sb _0.5 Si _2.92 produced in Production Example 6.

Experimental Examples 3 to 6 : Bi molar ratio 0.75, 1. 1.25, 2 Catalyst activity test

The oxidative dehydrogenation reaction was carried out under the same reaction conditions as in Experimental Example 1 using the Bi molar ratios 0.75, 1.25, and 1 g of the catalyst prepared in Production Examples 2 to 5, respectively.

Experiment Comparative Example 1 Activation of Mo ₁₂ Bi _0.5 Fe ₂ Co ₇ La _0.05 Sb _0.5 Si _2.92 Catalyst

The oxidation dehydrogenation reaction was carried out under the same reaction conditions as in Experimental Example 1 using 1 g of the catalyst Mo ₁₂ Bi _0.5 Fe ₂ Co ₇ La _0.05 Sb _0.5 Si _2.92 prepared in Comparative Example 1.

Experimental Comparative Example 2 : Activity test of catalyst prepared from antimony (III) acetate

The oxidation dehydrogenation reaction was carried out under the same reaction conditions as in Experimental Example 1 using 1 g of the catalyst Mo ₁₂ Bi _0.5 Fe ₂ Co ₇ K _0.05 Sb _0.5 Si _2.92 produced in Comparative Example 2.

The catalysts obtained in Experimental Examples 1 to 6 and Comparative Experimental Examples 1 and 2 were evaluated for catalytic activity depending on the molar ratio of Bi, activity of the catalyst containing Cs, K or La, antimony (Sb ₂ O ₃ ) III) acetate was shown in Tables 1 and 2 below.

As shown in Table 1, when the Bi molar ratio was changed, it was confirmed that the conversion of 2-butene and the yield of 1,3-butadiene were increased as the Bi molar ratio was decreased. In particular, when the Bi mole ratio was 0.5, the conversion of 2-butene and the yield of 1,3-butadiene were the highest, confirming that the Bi molar ratio 0.5 was the optimum.

As shown in Table 2, alkali metals are related to 1,3-butadiene selectivity. It was confirmed that the conversion of 2-butene and the selectivity and yield of 1,3-butadiene in the product were improved when K was added instead of Cs. On the other hand, it was confirmed that when La, which is not an alkali metal, was added, the conversion of 2-butene and the yield of 1,3-butadiene were lowered, which was ineffective.

As shown in Table 3, compared with the catalyst prepared by adding the antimony precursor (Sb (CH ₃ CO ₂ ) ₃ ) in the case of the catalyst prepared by adding the antimony trioxide (Sb ₂ O ₃ ) It was confirmed that the catalytic activity was high. If in the same way as the addition of antimony precursors with other metal precursors to prepare the catalyst are included in the main catalyst metal component of the catalyst, this catalyst and 2-butene conversion than the catalyst used in antimony trioxide (Sb ₂ O ₃₎ This crude catalyst It was also confirmed that the yield of 1,3-butadiene was low.

In summary, according to the present invention, it is possible to provide improved 2-butene conversion, 1,3-butadiene selectivity and yield by controlling the Bi molar ratio of the multicomponent bismuth molybdate catalyst to an optimum range. In addition, it was confirmed that the relationship between the selectivity of alkali metal and 1,3-butadiene can be grasped and Cs used in the multicomponent bismuth molybdate catalyst can be substituted with K. Further, it was confirmed that the conversion of 2-butene and the yield of 1,3-butadiene were higher than that of the catalyst containing antimony as a main catalyst metal component by using antimony trioxide (Sb ₂ O ₃ ) as a cocatalyst. The present invention provides multicomponent bismuth molybdate catalysts of a composition not previously disclosed and unpredictable.

While the present invention has been particularly shown and described with reference to specific embodiments thereof, those skilled in the art will appreciate that such specific embodiments are merely preferred embodiments and that the scope of the present invention is not limited thereby. something to do. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.

Claims (11)

As a metal complex oxide catalyst for an oxidative dehydrogenation reaction of a C4 hydrocarbon mixture,
Wherein the catalyst comprises molybdenum (Mo), bismuth (Bi), iron (F), cobalt (Co), alkali metal, antimony (Sb) and silicon (Si). The method of claim 1, wherein the metal composite oxide catalyst has a molar ratio of Mo: Bi: Fe: Co: alkali metal: Sb: Si of 12: 0.3-2: 1: 3: 5: 8: 0.01-0.3: : ≪ / RTI > 1-4. The metal composite oxide catalyst according to claim 1, wherein the alkali metal is cesium (Cs) or potassium (K). The metal composite oxide catalyst according to claim 1, wherein the catalyst is used for producing butadiene from a C4 hydrocarbon mixture. (a) preparing a solution containing a molybdenum (Mo) compound, a bismuth (Bi) compound, an iron (F) compound, a cobalt (Co) compound and an alkali metal compound;
(b) adding to the solution from the antimony trioxide (Sb ₂ O ₃₎ and silica (SiO ₂₎ to step (a) solution;
(c) evaporating the solution from step (b) to recover the solid product; And
(d) calcining the solid product from step (c) at a temperature of from 300 to 550 占 폚. The method of claim 5, wherein the molybdenum (Mo) compounds, bismuth (Bi) compound, the iron (F) compound, a cobalt (Co) compound, alkali metal compound, antimony trioxide (Sb ₂ O ₃₎ and silica (SiO ₂₎ Wherein the molar ratio of the metal complex oxide is 12: 0.3 to 2: 1 to 3: 5 to 8: 0.01 to 0.3: 0.1 to 2: 1 to 4. The method for producing a metal composite oxide catalyst according to claim 5, wherein the alkali metal compound is a cesium (Cs) compound or a potassium (K) compound. 6. The method of claim 5, wherein the molybdenum (Mo) compound is ammonium molybdate tetrahydrate,
The bismuth (Bi) compound is bismuth nitrate pentahydrate,
The iron (F) compound is iron nitrate nonahydrate,
The cobalt (Co) compound is cobalt nitrate hexahydrate,
The cesium (Cs) compound is cesium nitrate,
The potassium (K) compound is potassium nitrate,
The silica (SiO ₂₎ is a method of producing a colloidal silica (silica Ludox_colloidal) would a metal mixed oxide catalyst. Any one of claims 1 to 4 C4 hydrocarbon mixture on any one of a metal mixed oxide catalyst to the reaction temperature of 300 to 500 ℃ described in, atmospheric pressure and GHSV the reaction conditions ^{(gas hourly space velocity, h -1} ) 1000 to 5000h ^-1 in the anti- And then subjecting the mixture to oxidative dehydrogenation reaction in the presence of air and steam to produce butadiene. 10. The method of claim 9, wherein the C4 hydrocarbon mixture has an n-butane content of at least 40 wt% and a 2-butene content of at least 50 wt%. The method of claim 9, wherein the volume ratio of the C4 hydrocarbon mixture: air: steam is 9-11: 55-65: 28-40 under the reaction conditions.