COMPOSITE OXIDE CATALYST FOR PREPARING BUTADIENE AND METHOD OF PREPARING THE SAME

Abstract

Disclosed are a composite oxide catalyst for preparing butadiene and a method of preparing the same. More particularly, a composite oxide catalyst, for preparing butadiene, including a metal composite oxide and AlPO.sub.4, and a method of preparing the same are disclosed.

According to the present disclosure, a composite oxide catalyst for preparing butadiene, which includes a specific binder material, prevents generation of ingredients with a high boiling point, has superior catalyst strength, catalytic activity and butadiene yield, and a method of preparing the same are provided.

Claims

1. A composite oxide catalyst for preparing butadiene, comprising a metal composite oxide and AlPO.sub.4.

2. A composite oxide catalyst for preparing butadiene, comprising a metal composite oxide and a binder, wherein the binder is AlPO.sub.4.

3. The composite oxide catalyst according to claim 1, wherein the AlPO.sub.4 is comprised in an amount of 5 to 30% by weight based on 100% by weight of the composite oxide catalyst.

4. The composite oxide catalyst according to claim 1, wherein the metal composite oxide is represented by Formula 1 below:
Mo.sub.aBi.sub.bC.sub.cD.sub.dE.sub.eO.sub.f   [Mathematical Equation 3] wherein C is one or more of trivalent cationic metals, D is one or more divalent cationic metals, E is one or more of monovalent cationic metals, and, when a is 12, b is 0.01 to 2, c is 0.001 to 2, d is 5 to 12, e is 0 to 1.5, and f is determined to adjust a valence with other ingredients.

5. The composite oxide catalyst according to claim 4, wherein the trivalent cationic metal is one or more selected from the group consisting of Al, Ga, In, Ti, Fe, La, Cr and Ce.

6. The composite oxide catalyst according to claim 4, wherein the divalent cationic metal is one or more selected from the group consisting of Be, Mg, Ca, Sr, Ba, Ra, Co, Zn and Cu.

7. The composite oxide catalyst according to claim 4, wherein the monovalent cationic metal is one or more selected from the group consisting of Li, Na, K, Rb, Cs, Ag and Fr.

8. The composite oxide catalyst according to claim 4, wherein, in the composite oxide catalyst, a mole ratio of Mo metal to Al metal is 12:0.5 to 3.

9. The composite oxide catalyst according to claim 1, wherein a ratio of acid sites in the composite oxide catalyst is respectively 10 to 30%, 20 to 50%, and 40 to 60% based on ammonia desorption temperatures of 150° C., 580° C., and 720° C.

10. The composite oxide catalyst according to claim 1, wherein the composite oxide catalyst has a strength of 6.0 kgf or more.

11. A method of preparing a metal composite oxide catalyst for preparing butadiene, the method comprising: extrusion molding in a pellet by mixing a metal composite oxide precursor powder and AlPO.sub.4; and firing the pellet.

12. The composite oxide catalyst according to claim 2, wherein the AlPO.sub.4 is comprised in an amount of 5 to 30% by weight based on 100% by weight of the composite oxide catalyst.

13. The composite oxide catalyst according to claim 2, wherein the metal composite oxide is represented by Formula 1 below:
Mo.sub.aBi.sub.bC.sub.cD.sub.dE.sub.eO.sub.f   [Formula 1] wherein C is one or more of trivalent cationic metals, D is one or more divalent cationic metals, E is one or more of monovalent cationic metals, and, when a is 12, b is 0.01 to 2, c is 0.001 to 2, d is 5 to 12, e is 0 to 1.5, and f is determined to adjust a valence with other ingredients.

14. The composite oxide catalyst according to claim 2, wherein a ratio of acid sites in the composite oxide catalyst is respectively 10 to 30%, 20 to 50%, and 40 to 60% based on ammonia desorption temperatures of 150° C., 580° C., and 720° C.

15. The composite oxide catalyst according to claim 2, wherein the composite oxide catalyst has a strength of 6.0 kgf or more.

Description

EXAMPLES

Example 1

[0058] [Preparation of Metal Composite Oxide Catalyst Precursor]

[0059] 100 g of iron nitrate 9-hydrate (Fe(NO.sub.3).sub.3.9H.sub.2O), 300 g of cobalt nitrate 6-hydrate (Co(NO.sub.3).sub.2.6H.sub.2O), and 4 g of cesium nitrate (CsNO.sub.3) were dissolved in distilled water and stirred. Separately, 100 g of bismuth nitrate 5-hydrate (Bi(NO.sub.3).sub.2.5H.sub.2O) was added to distilled water including nitric acid and dissolved therein while stirring. After confirming that bismuth was completely dissolved, a bismuth solution was added to a solution including a precursor of cobalt, iron and cesium dissolved therein to prepare an acidic solution including precursors of a precursor of cobalt, iron, cesium and bismuth dissolved therein. In addition, 432 g of ammonium molybdate 4-hydrate ((NH.sub.4).sub.6 (MO.sub.7O.sub.24).4H.sub.2O) was separately dissolved in distilled water and stirred. The prepared acidic solution including the cobalt, iron, cesium, and bismuth precursors dissolved therein was added dropwise to the prepared aqueous molybdate solution. Here, a mole ratio of the metal ingredients was as follows. Mo:Bi:Fe:Co:Cs=12:1:1.2:5:0.1.

[0060] A mixture prepared by mixing as described above was stirred at room temperature for one hour by means of a magnetic stirrer to generate a precipitate. The precipitate was dried for 16 hours or more in a 120° C. convection oven and comminuted. As a result, a powder-type metal composite oxide catalyst precursor with a particle diameter of 355 μm or less was obtained.

[0061] <Extrusion Molding>

[0062] Water and alcohol, which were mixed in equal amount, were added to 90 parts by weight of the obtained metal composite oxide catalyst precursor powder and 10 parts by weight of AlPO.sub.4, followed by kneading until a water content was about 15% by weight. Resultant dough was fed to an extruder constituted of an electric motor, an outer body, a screw-type internal rotor, and a front die. The dough was extruded and, at the same time, cut by a rotating cutter, while being passing through a die having a circular hole with a size of 6 mm. As a result, a pellet-type extrusion molding catalyst having a diameter of 6 mm and a length of 6 mm was prepared.

[0063] <Drying and Firing>

[0064] The prepared extrusion molding catalyst was dried in a 90° C. oven for two to five hours, followed by firing in a 430 to 480° C. electric furnace for five hours while elevating temperature at a rate of 1° C./min. Finally, a metal composite oxide catalyst including Mo and Al in a ratio of 12 to 1 was prepared.

Example 2

[0065] A metal composite oxide catalyst was prepared in the same manner as in Example 1, except that a mole ratio of Fe as a metal ingredient was determined to satisfy the following mole ratio of metal ingredients: Mo:Bi:Fe:Co:Cs=12:1:1.3:5:0.1 (Mo:Al=12:1).

Example 3

[0066] A metal composite oxide catalyst was prepared in the same manner as in Example 1, except that AlPO.sub.4 was added in an amount of 5 parts by weight to satisfy the following mole ratio of metal ingredients: Mo: Bi:Fe:Co:Cs=12:1:1.2:5:0.1.

Example 4

[0067] A metal composite oxide catalyst was prepared in the same manner as in Example 1, except that AlPO.sub.4 was added in an amount of 30 parts by weight to satisfy the following mole ratio of metal ingredients: Mo:Bi:Fe:Co:Cs=12:1:1.2:5:0.1.

Comparative Example 1

[0068] A metal composite oxide catalyst was prepared in the same manner as in Example 1, except that AlPO.sub.4 was not used and silica was added in an amount of 3 parts by weight to satisfy the following ratio: Mo:Si=12:3.

Comparative Example 2

[0069] A metal composite oxide catalyst was prepared in the same manner as in Example 1, except that AlPO.sub.4 was not used.

[0070] Comparative Example 3

[0071] A metal composite oxide catalyst was prepared in the same manner as in Example 1, except that 110 g of iron nitrate 9-hydrate (Fe(NO.sub.3).sub.3.9H.sub.2O) was used such that a mole ratio of metal ingredients included in a mixture was Mo:Bi:Fe:Co:Cs=12:1:1.3:5:0.1, AlPO.sub.4 was not used, and silica was used in an amount of 1 part by weight such that a ratio of Mo to Si was 2:1.

[0072] The strengths of the metal composite oxide catalysts prepared according to Examples 1 to 4 and Comparative Examples 1 to 3 were determined as the highest force when pressure was slowly applied by means of a circular tip with a diameter of 10 mm of a digital force gauge (SLD 50 FGN) manufactured by SPC technology. Results are summarized in Table 1 below.

TABLE-US-00001 TABLE 1 Comparative Comparative Comparative Classification Example 1 Example 2 Example 3 Example 4 Example 1 Example 2 Example 3 Binder AlPO.sub.4 AlPO.sub.4 AlPO.sub.4 AlPO.sub.4 Silica — Silica Fed Mo:Al = 12:1 Mo:Al = 12:1 Mo:Al = 12:0.5 Mo:Al = 12:3 Mo:Si = 12:3 Mo:Si = 12:0 Mo:Si = 12:1 amount (mol) Catalyst 6.46 6.79 6.12 7.09 5.55 1.89 2.82 strength (kgf)

TEST EXAMPLE

[0073] Butadiene was prepared using the metal composite oxide catalyst prepared according to each of Examples 1 to 4 and Comparative Examples 1 to 3. Results are summarized in Table 2 below.

[0074] 1-Butene and oxygen were used as reactants and, additionally, nitrogen and steam were added thereto together. As a reactor, a metal tubular reactor was used. A ratio of reactants and gas hourly space velocity (GHSV) were set based on 1-butene as summarized in Table 2 below. A fixed bed reactor was filled with the prepared catalyst and the volume of a catalyst layer which the reactants contact was fixed to 20 cc. A reaction apparatus was designed such that water was injected by a vaporizer and vaporized as steam at 150° C. to be mixed along with 1-butene and oxygen and be introduced into the reactor. The amount of butene was controlled by means of a mass flow controller for a liquid, the amounts of oxygen and nitrogen were controlled by means of a mass flow controller for gas, and the amount of steam was controlled by adjusting an injection speed by means of a liquid pump. Reaction temperature was maintained at 320° C. as described in Table 2 below. After reaction, a product was analyzed using gas chromatography. Through the gas chromatography analysis, a transition rate (X), a selectivity (S_BD, S_heavy, S_COx) and a yield (Y) were measured and calculated according to Mathematical Equations 1, 2, and 3 below.

Transition rate (%)=(mol number of reacted 1-butene/mol number of supplied 1-butene)×100   [Mathematical Equation 1]

Selectivity (%)=(mol number of generated 1,3-butadiene(BD), ingredient with high boiling point (heavy), or COx/mol number of reacted 1-butene)×100   [Mathematical Equation 2]

Yield (%)=(mol number of generated 1,3-butadiene/mol number of supplied 1-butene)×100   [Mathematical Equation 3]

TABLE-US-00002 TABLE 2 GHSV Temp (h−1) (° C.) P OBR SBR NBR X S_BD Y S_heavy S_COx Comparative 100 320 12 1 4 12 97.69 93.70 91.53 1.31 1.28 Example 1 Comparative 100 320 12 1 4 12 96.69 94.91 91.77 0.61 0.83 Example 2 120 320 12 1 4 12 94.95 95.32 90.50 0.44 0.71 Example 1 100 320 12 1 4 12 99.30 94.25 93.57 0.62 1.58 120 320 12 1 4 12 98.75 94.72 93.54 0.41 1.48 Comparative 100 320 12 1 4 12 97.16 92.49 89.90 1.06 2.26 Example 3 250 320 12 1 4 12 82.05 95.23 78.1 1.03 1.29 Example 2 100 320 12 1 4 12 98.04 94.19 92.34 0.97 1.90 250 320 12 1 4 12 86.49 95.40 82.42 0.86 1.22 Example 3 100 320 12 1 4 12 97.60 93.49 91.24 1.06 2.31 250 320 12 1 4 12 87.37 94.96 82.97 0.88 1.48 Example 4 100 320 12 1 4 12 98.5 93.47 92.07 1.08 1.92 250 320 12 1 4 12 88.38 94.36 83.39 1.01 1.71

[0075] As shown in Tables 1 and 2, it can be confirmed that the composite oxide catalysts for preparing butadiene according to the present disclosure (Examples 1 to 4) exhibit superior strength, and excellent butene transition rate, butadiene selectivity, and yield, compared to the composite oxide catalysts including silica as a binder (Comparative Example 1 and 3). In addition, it can be confirmed that, in the composite oxide catalysts for preparing butadiene according to the present disclosure (Examples 1 to 4), generation of ingredients with a high boiling point is greatly decreased.

[0076] In addition, it can be confirmed that the composite oxide catalyst for preparing butadiene (Examples 1 to 4) according to the present disclosure exhibit superior butene transition rate and yield, and excellent catalyst strength, compared to the composite oxide catalyst (Comparative Example 2) not including AlPO.sub.4 and a binder.

[0077] Concomitantly, it can be confirmed through the results of Comparative Examples 1 and 3 that, when the amount of silica as a binder is increased, catalyst strength is increased, but butadiene selectivity, and a yield are decreased, and generation of ingredients with a high boiling point is greatly increased.