KR20160068362A - Metal complex oxide catalyst for manufacturing butadiene and method for preparing the same - Google Patents

Abstract

The present invention relates to a metal complex oxide catalyst, and a manufacturing method thereof. More particularly, the present invention relates to a metal complex oxide catalyst manufactured by mixing a metal complex oxide precursor and metal complex oxide catalyst fine particles, and a manufacturing method thereof. According to the present invention, the metal complex oxide catalyst has increased catalytic strength, thereby having a substantially increased physical stability. The manufacturing method can manufacture the metal complex oxide catalyst at reduced costs without degrading catalytic activity.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a metal complex oxide catalyst and a method for producing the same,

The present invention relates to a metal composite oxide catalyst and a method for producing the same, and more particularly, to a metal complex oxide catalyst and a method for preparing the metal complex oxide catalyst, which are capable of reducing the catalyst production cost without lowering the catalytic activity, Catalyst and a process for producing the same.

1,3-Butadiene is an intermediate in petrochemical products, and its demand and value are increasing worldwide.

Examples of the method for producing 1,3-butadiene include naphtha cracking, direct dehydrogenation reaction of butene, and oxidative dehydrogenation reaction of butene.

Of these, the oxidative dehydrogenation reaction of butene is a reaction in which butene reacts with oxygen in the presence of a metal oxide catalyst to produce 1,3-butadiene and water, which is thermodynamically very advantageous since stable water is produced.

In addition, unlike the direct dehydrogenation reaction of butene, 1,3-butadiene can be obtained in a high yield even at a low reaction temperature as compared with a direct dehydrogenation reaction because of an exothermic reaction.

However, since the metal oxide catalyst has insufficient strength, the amount of the catalyst that can not be used is increased due to the catalyst powder, dust, cracks, or the like generated during the production, and thus there is a problem that the catalyst production unit cost is high.

Korean Patent Laid-Open Publication No. 2014-0119222 (October 10, 2014)

In order to solve the problems of the prior art as described above, the present invention relates to a metal complex oxide catalyst in which the catalyst production cost is reduced without lowering catalytic activity and the physical stability of the catalyst is greatly improved by increasing the catalyst strength, And to provide the above objects.

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 metal complex oxide catalyst characterized in that a metal complex oxide precursor is mixed with a metal complex oxide catalyst fine powder.

The present invention also provides a process for preparing a metal composite oxide catalyst comprising mixing and extruding a metal complex oxide precursor and a metal complex oxide catalyst fine powder.

As described above, according to the present invention, it is possible to provide a catalyst for the production of butadiene and a method for producing the catalyst, wherein the catalyst production cost is reduced without lowering the catalytic activity and the catalyst has a strong physical stability. have.

Hereinafter, the present invention will be described in detail.

The inventors of the present invention have found that when a composite oxide catalyst for the production of butadiene whose strength and activity are improved at the same time is recovered, catalyst powder which is crushed during firing or discarded during a meshing operation, or catalyst powder generated in a subdivision process, In the case of preparing a catalyst by mixing with a certain amount of raw catalyst precursor powder after coprecipitation, the catalyst production cost is greatly reduced but the catalytic activity is not lowered. In particular, the catalyst strength is greatly increased, stability was improved, and the present description was completed on the basis thereof.

The complex oxide catalyst for preparing butadiene according to the present invention is characterized in that a metal complex oxide precursor and a metal complex oxide catalyst fine powder are mixed and produced.

The metal complex oxide precursor may be, for example, a precursor of the metal complex oxide catalyst.

The metal complex oxide precursor may be a powder, and may be a pulverized material. In this case, extrusion molding is easy, and the catalyst strength and catalytic activity are excellent.

The metal complex oxide catalyst fine powder may be, for example, 1 to 30% by weight, 5 to 20% by weight, or 5 to 15% by weight. Within this range, there is an effect of excellent economy, catalyst strength and catalytic activity.

The metal composite oxide catalyst fine powder may have a particle diameter of 2.0 mm or less, 1.0 mm or less, or 0.05 mm or less, for example, and has an excellent workability within this range.

In the present invention, the catalyst particle size or fine particle size can be obtained, for example, by a value corresponding to the hole size of a mesh or a sieve. In a specific example, when the size of the hole of the mesh is 100 μm, The passed particles can be calculated to have a particle size of 100 탆 or less, and the particles that can not pass through the network exceed 100 탆.

The metal complex oxide catalyst fine powder may be a catalyst which has been omitted in the calcination or calcination step. Here, the fractionation process is a process of selecting a catalyst of a certain size or larger, and is not limited to the term. For example, the fractionation process includes a selection process and a classification process.

As another example, the metal complex oxide catalyst fine powder may be a waste catalyst that is smaller in size than a conventional shaped catalyst, generated during a firing process or a packing process in a firing process.

When the metal complex oxide precursor and the metal complex oxide catalyst fine powder are mixed, a binder may be further mixed.

The binder may be, for example, 0.1 to 30 parts by weight, or 1 to 15 parts by weight based on 100 parts by weight of the total weight of the metal complex oxide precursor and the metal complex oxide catalyst fine powder, and the balance between the catalyst strength and the catalytic activity It has excellent effect.

The binder is not particularly limited as long as it is a binder commonly used in metal complex oxide catalysts for preparing butadiene, but silica may be a preferred example.

The mixing of the metal complex oxide precursor and the metal complex oxide catalyst fine powder may mean extrusion molding, and may be extrusion molding and firing.

The metal complex oxide may be, for example, a compound represented by the following general formula (1).

[Chemical Formula 1]

Mo _a Bi _b C _c D _e E _e O _f

(Wherein C is at least one of trivalent cation metal components, D is at least one of divalent cation metal components, E is at least one of monovalent cation metal components, and when a is 12, b is from 0.01 to 2, c is from 0.001 to 2, d is from 5 to 12, e is from 0 to 1.5, and f is a value determined to match the valency with other components.

The trivalent cation metal component may be at least one member selected from the group consisting of iron, aluminum, vanadium, zirconium, tungsten, and silicon.

The divalent cation metal component may be at least one member selected from the group consisting of nickel, cobalt, zinc, magnesium, manganese and copper.

The monovalent cationic metal component may be at least one member selected from the group consisting of sodium, potassium, rubidium, and cesium.

As another example, the metal composite oxide may be a molybdate-bismuth complex oxide.

The molybdate-bismuth complex oxide is not particularly limited when it is a molybdate-bismuth complex oxide which can be generally used for oxidative dehydrogenation reaction of butene.

The molybdate-bismuth complex oxide may be, for example, a metal complex oxide including molybdenum, bismuth, and cobalt.

The metal complex oxide catalyst may be, for example, a catalyst used for producing butadiene.

The metal complex oxide catalyst may be, for example, a catalyst used in an oxidative dehydrogenation reaction.

The oxidative dehydrogenation reaction may be, for example, a reaction for producing butadiene by reacting a feed gas containing N-butene and a molecular oxygen-containing gas under a catalyst.

The reactor used for the oxidative dehydrogenation reaction is not particularly limited as long as it is a reactor which can be used in the technical field. For example, 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, for example, a multi-tubular reactor or a plate reactor.

The reactor may be, for example, a reactor that is installed in an electric furnace and maintains a reaction temperature of the catalyst layer constantly, and an oxidative dehydrogenation reaction proceeds while the reactants continuously pass through the catalyst layer.

The metal complex oxide catalyst may have a strength of 3.2 kgf or more, 3.2 to 7.0 kgf, or 3.2 to 5.0 kgf, for example. In this range, the catalytic activity and catalyst strength are all excellent.

The method for producing a metal composite oxide catalyst according to the present invention includes the step of kneading and extruding a metal complex oxide precursor and a metal complex oxide catalyst fine powder.

As another example, The method for preparing a metal composite oxide catalyst according to the present invention comprises the steps of: kneading a metal complex oxide precursor powder and a metal complex oxide catalyst fine powder and extruding them in the form of pellets; And firing the pellet.

As another example, the method for producing a metal composite oxide catalyst of the present invention comprises: kneading a metal complex oxide precursor powder, a metal complex oxide catalyst fine powder and a binder, and extruding the mixture into a pellet; Drying the extruded pellets; And firing the dried pellets.

As another example, a method for preparing a composite oxide catalyst for preparing butadiene according to the present invention comprises: preparing a pellet by kneading and extruding a metal complex oxide precursor and a metal complex oxide catalyst fine powder; Calcining and separating the pellet produced; And a step of obtaining the metal complex oxide catalyst fine powder which has been eliminated during firing and fractionation to prepare the pellet.

The extrusion molding is not particularly limited in the case of an extrusion molding method, apparatus and conditions used in the production of a metal composite oxide catalyst for producing butadiene.

The drying and calcination are not particularly limited in the case of drying and calcination methods, equipment and conditions used in the production of the metal composite oxide catalyst for the production of butadiene.

The extrusion-molded pellets may be dried at 90 to 200 ° C, or 110 to 150 ° C for 5 to 100 hours, or 10 to 30 hours, for example.

The drying of the dried pellets may be performed at 400 to 600 ° C, 400 to 500 ° C, or 450 to 500 ° C for 1 to 10 hours, or 3 to 7 hours, for example.

The fractionation step is not particularly limited when it is a fractionation method usually used for meshing of the catalyst.

The metal complex oxide is the same as that described in the metal complex oxide catalyst for preparing butadiene as described above.

The metal complex oxide precursor may be prepared in powder form through a coprecipitation step, an aging step and a drying step.

As another example, the metal composite oxide precursor may include: a) a bismuth precursor; A monovalent, divalent or trivalent cationic metal precursor; Potassium precursor; And a cesium precursor; b) preparing a second solution in which the molybdenum precursor is dissolved; c) mixing the first solution and the second solution; d) reacting the mixed solution; And e) drying the product by the reaction.

In the step c), for example, the first solution may be added to the second solution and mixed.

As another example, the metal complex oxide precursor may be prepared by: i) preparing a first solution comprising a monovalent, divalent or trivalent cation metal precursor, a potassium precursor, and a cesium precursor; Ii) preparing a second solution in which the bismuth precursor is dissolved; Iii) preparing a third solution in which the molybdenum precursor is dissolved; Iv) preparing a first mixed solution by mixing a second solution with the first solution; V) preparing a second mixed solution by mixing the first mixed solution and the second solution; Vi) reacting the second mixed solution; And (iii) drying the product by the reaction.

The steps i) to iii) are not limited to the sequence.

The powdery metal complex oxide precursor may be pulverized through a pulverizing step, for example.

The crushing step is a step of mechanically applying a force to make the powder smaller, and is not particularly limited when the crushing method is applied to the production of a metal composite oxide catalyst.

The metal component having a monovalent, divalent or trivalent cation may be at least one member selected from the group consisting of cobalt, zinc, magnesium, manganese, nickel, copper, iron, rubidium, sodium, aluminum, vanadium, zirconium, and tungsten Can be selected.

As another example, the metal component having the monovalent, divalent or trivalent cation may be at least one selected from cobalt, manganese, nickel and iron.

The metal precursor for producing the metal complex oxide precursor is not particularly limited as long as it is conventionally used in the art.

The metal precursor may be, for example, a metal salt containing a corresponding metal component, for example, a nitrate salt or an ammonium salt of the metal component.

As another example, bismuth nitrate (III) as a precursor of bismuth and ammonium molybdate as a precursor of molybdenum can be used.

Since the bismuth nitrate is not well soluble in water, it can be dissolved by adding an acid to water, for example. At this time, the acid is added in such an amount that the bismuth completely melts.

The acid may be, for example, an inorganic acid, and another example may be nitric acid.

The reaction temperature in the reaction step may be, for example, from room temperature to 80 ° C, or from 50 ° C to 70 ° C, and the reaction time may be, for example, from 5 minutes to 24 hours, or from 10 minutes to 4 hours.

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 1

≪ Preparation of metal complex oxide catalyst precursor >

Cesium nitrate (CsNO ₃ ) was used as a precursor of cesium and cobalt nitrate hexahydrate (Co (NO ₃ ) ₂ .6H ₂ O) was used as a precursor of cobalt. Iron precursor was iron nitrate 9 (Fe (NO ₃ ) ₃ .9H ₂ O), bismuth nitrate pentahydrate (Bi (NO ₃ ) ₂ .5H ₂ O) as a precursor of bismuth and ammonium molybdate tetra hydrate as a precursor of molybdenum NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O) was used. Other metal precursors dissolve well in distilled water, but since bismuth nitrate pentahydrate dissolves well in strong acidic solutions, nitric acid is added to distilled water to dissolve bismuth nitrate pentahydrate separately. 18.0 g of cesium nitrate (CsNO ₃ ) as a precursor of cesium, 320.8 g of cobalt nitrate hexahydrate (Co (NO ₃ ) ₂ .6H ₂ O) and iron nitrate 9 hydrate (Fe (NO ₃ ) ₃ .9H ₂ O ) Was dissolved in 250 ml of distilled water and stirred. Separately, 75.6 g of bismuth nitrate pentahydrate (Bi (NO ₃ ) ₂ .5H ₂ O) was dissolved in 75 ml of distilled water to which 22.7 g of nitric acid had been added. After confirming that the bismuth was completely dissolved, the bismuth solution was added to the solution containing the precursor of cesium, cobalt and iron to prepare an acid solution in which the precursors of cesium, cobalt, iron and bismuth were dissolved. Further, 326.9 g of ammonium molybdate tetrahydrate ((NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O) was dissolved in 1300 ml of distilled water and stirred to prepare separately. An acidic solution in which the prepared nickel, iron, and bismuth precursors had been dissolved was dropped one by one into the molybdate solution. The resulting mixed solution was stirred at room temperature for 1 hour using a magnetic stirrer, and the precipitated solution was dried in an oven at 120 ° C for 24 hours to prepare a powdery metal complex oxide catalyst precursor.

≪ Crushing step of metal complex oxide catalyst precursor >

250 g of the prepared metal complex oxide catalyst precursor powder was introduced into a pulverizer and pulverized. Then, the powder was passed through a mesh having a size of 350 μm to obtain a metal complex oxide catalyst precursor pulverized product having a size of 350 μm or less.

<Extrusion molding step>

250 g of the metal complex oxide catalyst precursor pulverization product obtained and Mo ₁₂ Bi ₁ Fe ₂ Co ₇ Cs _0.6 O _x having a size of 350 μm or less (x is a value determined by other components to match the valence) 12.5 g and 2.7 g, respectively, were fed into an extruder and extrusion-molded to prepare a pellet-shaped extrusion catalyst.

<Drying and firing step>

The extrusion-molded catalyst was dried at 90 ° C for 4 hours and then calcined at 450 ° C for 5 hours to finally prepare a metal composite oxide catalyst.

Example 2

A metal complex oxide catalyst was prepared in the same manner as in Example 1 except that 37.5 g of the catalyst fine powder was added in the above Example 1.

Comparative Example 1

A metal complex oxide catalyst was prepared in the same manner as in Example 1, except that the catalyst fine powder was not added in Example 1.

[Test Example]

The metal complex oxide catalysts prepared in Examples 1 and 2 and Comparative Example 1 and their reaction characteristics were measured by the following methods. The results are shown in Table 1 below.

* Catalyst strength (kgf): Measured using a digital force gauge.

Reaction characteristics: 1-butene and oxygen were used as reactants, and nitrogen and steam were added together. As the reactor, a metal tubular reactor was used. The ratio of the reactants and the gas hourly space velocity (GHSV) were set on the basis of 1-butene as shown in Table 1 below. The prepared catalyst was packed in a fixed bed reactor, and the volume of the catalyst layer contacting the reactants was fixed at 200 cc. Steam was injected in the form of water as a vaporizer, vaporized by steam at 340 ° C, mixed with reactant 1-butene and oxygen, and introduced into the reactor. The amount of butenes was controlled using a mass flow rate controller for liquids, oxygen and nitrogen were controlled using mass flow controllers for gases, and the amount of steam was controlled using a liquid pump. The conversion rate (X), selectivity (S_BD, S_heavy, S_COx) and yield (Y) were determined by gas chromatography using a gas chromatograph The results obtained by the chromatography were calculated according to the following equations (1), (2) and (3).

[Equation 1]

Conversion rate (%) = (moles of reacted 1-butene / moles of fed 1-butene) x 100

&Quot; (2) &quot;

Selectivity (%) = (number of moles of 1,3-butadiene (BD) produced, heavy or COx / mole of reacted 1-butene) x 100

&Quot; (3) &quot;

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

Waste Catalyst Use Rate Conversion Rate (%) Selectivity (%) yield(%) Strength (kgf) Example 1 5% 94.0 93.6 88.0 3.7 Example 2 15% 94 2 93 8 88 3 4.0 Comparative Example 1 0% 94.5 94.0 88.8 3.1

As shown in Table 1 above, the composite oxide catalyst for the production of butadiene (Examples 1 and 2) according to the present invention reuses the spent catalyst, so that the production cost is greatly reduced, and the conversion and selectivity of the conventional butadiene- , Yield, etc., and the catalyst strength was rather increased.

Claims (19)

Wherein the metal complex oxide precursor and the metal complex oxide catalyst fine powder are mixed
Metal complex oxide catalyst. The method according to claim 1,
Wherein the metal complex oxide precursor is a precursor of the metal complex oxide catalyst
Metal complex oxide catalyst. The method according to claim 1,
And the metal complex oxide catalyst fine powder is contained in an amount of 1 to 30 wt%
Metal complex oxide catalyst. The method according to claim 1,
Wherein the metal composite oxide catalyst fine powder has a particle diameter of 2.0 mm or less
Metal complex oxide catalyst. The method according to claim 1,
Characterized in that a binder is added during the mixing
Metal complex oxide catalyst. 6. The method of claim 5,
Characterized in that the binder is silica
Metal complex oxide catalyst. The method according to claim 1,
Wherein the metal complex oxide is represented by the following Chemical Formula 1
[Chemical Formula 1]
Mo _a Bi _b C _c D _e E _e O _f
(Wherein C is at least one of trivalent cation metal components, D is at least one of divalent cation metal components, E is at least one of monovalent cation metal components, and when a is 12, b is from 0.01 to 2, c is from 0.001 to 2, d is from 5 to 12, e is from 0 to 1.5, and f is a value determined to match the valency with other components Characterized by
Metal complex oxide catalyst. 8. The method of claim 7,
Wherein the trivalent cationic metal component is at least one selected from the group consisting of iron, aluminum, vanadium, zirconium, tungsten, and silicon
Metal complex oxide catalyst. 8. The method of claim 7,
Wherein the divalent cation metal component is at least one selected from the group consisting of nickel, cobalt, zinc, magnesium, manganese, and copper
Metal complex oxide catalyst. 8. The method of claim 7,
Wherein the monovalent cationic metal component is at least one selected from the group consisting of sodium, potassium, rubidium and cesium
Metal complex oxide catalyst. The method according to claim 1,
Wherein the metal composite oxide catalyst has a strength of 3.2 kgf or more
Metal complex oxide catalyst. 12. The method according to any one of claims 1 to 11,
Wherein the metal complex oxide catalyst is a catalyst used for preparing butadiene
Metal complex oxide catalyst. 12. The method according to any one of claims 1 to 11,
Wherein the metal composite oxide catalyst is a catalyst used in an oxidative dehydrogenation reaction
Metal complex oxide catalyst. And mixing and extruding the metal complex oxide precursor and the metal complex oxide catalyst fine powder
Metal complex oxide catalyst. 15. The method of claim 14,
Wherein the metal complex oxide precursor is a precursor of the metal complex oxide catalyst
Metal complex oxide catalyst. 15. The method of claim 14,
And the metal composite oxide catalyst fine powder is mixed in an amount of 1 to 30 wt%
Metal complex oxide catalyst. 15. The method of claim 14,
Wherein the metal complex oxide catalyst fine powder is removed in the calcination or firing step.
Metal complex oxide catalyst. 15. The method of claim 14,
Wherein the metal complex oxide is represented by the following Chemical Formula 1
[Chemical Formula 1]
Mo _a Bi _b C _c D _e E _e O _f
(Wherein C is at least one of trivalent cation metal components, D is at least one of divalent cation metal components, E is at least one of monovalent cation metal components, and when a is 12, b is from 0.01 to 2, c is from 0.001 to 2, d is from 5 to 12, e is from 0 to 1.5, and f is a value determined to match the valency with other components Characterized by
Metal complex oxide catalyst. Preparing a pellet by kneading and extruding a metal complex oxide precursor and a metal complex oxide catalyst fine powder; Calcining and separating the pellet produced; And a step of obtaining the metal complex oxide catalyst fine powder which has been removed by firing and fractionation to prepare the pellet
Metal complex oxide catalyst.