KR20160061144A - Multi-component complex metal oxides catalyst, method for preparing thereof and method for preparing 1,3-butadiene using the same - Google Patents

Abstract

The present invention relates to a multi-component bismuth-molybdenum composite metal oxide catalyst, a method for producing the same, and a method for producing 1,3-butadiene by using the same. The multi-component bismuth-molybdenum composite metal oxide catalyst is derived from a composition comprising amorphous composite metal oxide and crystalline composite metal oxide, and exhibits an excellent catalyst activity and excellent mechanical strength, thereby having excellent lifespan properties. The multi-component bismuth-molybdenum composite metal oxide catalyst may have the improved degree of crystallization and thereby have improved mechanical strength. A high catalyst activity is exhibited in a catalyst reaction process using the same, specifically, in an oxidative-dehydrogenation process for producing 1,3-butadiene. Accordingly, excellent crush resistance and wear resistance may be ensured.

Description

TECHNICAL FIELD [0001] The present invention relates to a multi-component metal oxide catalyst, a method for preparing the same, and a method for preparing 1,3-butadiene using the catalyst, a method for preparing the same,

The present invention relates to a multicomponent bismuth-molybdenum composite metal oxide catalyst derived from a composition comprising an amorphous complex metal oxide and a crystalline composite metal oxide, which exhibit excellent catalytic activity and are excellent in mechanical strength and consequently excellent in life characteristics, And a process for producing 1,3-butadiene using the same.

The selective oxidation of olefins is an important reaction in the petrochemical industry as a reaction that can produce intermediate basic materials needed to make various products from olefin raw materials obtained from crude oil. Of these, a process for producing styrene from ethylbenzene, a process for producing 1,3-butadiene from n-butane or n-butene, and the like, have been conducted in recent years due to a rapid increase in the demand for basic materials for producing synthetic rubbers . Particularly, in the case of 1,3-butadiene, there is a rapid increase in demand.

1,3-butadiene is a colorless, odorless, combustible gas which is easily liquefied when it is pressurized and is easily prone to flammability. It is used in various petrochemicals such as styrene-butadiene rubber (SBR), polybutadiene rubber (BR), acrylonitrile -Butadiene-styrene rubber (ABS) and the like.

The process for producing 1,3-butadiene includes naphtha cracking, direct dehydrogenation of n-butene, and oxidative-dehydrogenation of n-butene. Among them, the naphtha cracking process which accounts for more than 90% of 1,3-butadiene supplied to the market, is a method of selectively extracting 1,3-butadiene from the basic oil produced from crackers in the steam cracking process for ethylene production . However, production of 1,3-butadiene by the steam cracking process is mainly performed in the production of other basic fractions other than 1,3-butadiene, such as ethylene, because the production of 1,3-butadiene is an effective process for producing 1,3- And high energy consumption due to high reaction temperature. Thus, the dehydrogenation reaction which extracts all the basic essential oils from the steam cracking process and obtains 1,3-butadiene by removing hydrogen from n-butene in the remaining C4 mixture (C4 raffinate-3) is attracting attention. The dehydrogenation reaction of n-butene has a direct dehydrogenation reaction and an oxidative-dehydrogenation reaction. The direct dehydrogenation reaction of n-butene is a reaction in which 1,3-butadiene is obtained by removing a small amount of n-butene from the n- Endothermic reaction due to endothermic reaction is limited, so that high temperature reaction conditions are required, and even if the temperature is raised and the conversion rate is increased, the side reaction such as the idealization reaction is increased due to the increase in temperature and the yield of 1,3- There is a problem to lose.

On the other hand, the oxidative-dehydrogenation reaction of n-butene, which produces butadiene via oxidative dehydrogenation (ODH) of n-butene, reacts with n-butene to form 1,3-butadiene and water In addition to the direct dehydrogenation reaction, 1,3-butadiene can be obtained at a lower reaction temperature than the direct dehydrogenation reaction due to the exothermic reaction unlike the direct dehydrogenation reaction. . Thus, the process of producing 1,3-butadiene through the oxidative-dehydrogenation reaction of n-butene can be seen as an effective single production process capable of meeting the increasing demand for 1,3-butadiene.

As mentioned above, although the oxidative-dehydrogenation reaction is an effective process for producing 1,3-butadiene alone, there is a disadvantage that many side reactions such as a complete oxidation reaction occur because oxygen is used as a reactant. Therefore, it is necessary to develop a catalyst having a high selectivity for 1,3-butadiene while maintaining high activity through proper oxidation control.

On the other hand, known catalysts for use in the oxidative-dehydrogenation reaction of n-butene include ferrite-based catalysts, tin-based catalysts, and bismuth-molybdenum-based catalysts.

Among them, the bismuth-molybdenum-based catalyst includes a bismuth-molybdenum catalyst composed only of bismuth and molybdenum metal oxide, and a multicomponent bismuth-molybdenum catalyst having various metal components added thereto based on bismuth and molybdenum. In the pure bismuth-molybdenum catalyst, various phases exist depending on the atomic ratios of bismuth and molybdenum, and? -Bismuth molybdenum (Bi ₂ Mo ₃ O ₁₂ ),? -Bismuth molybdenum (Bi ₂ Mo ₂ O ₉ ) and It is known that three phases of γ-bismuth molybdenum (Bi ₂ MoO ₆ ) can be utilized as the catalyst. However, a single phase pure bismuth-molybdenum catalyst is not suitable for commercialization of 1,3-butadiene through the oxidative-dehydrogenation reaction of n-butene due to its low activity.

As an alternative, a multi-component bismuth-molybdenum catalyst having various metal components other than bismuth and molybdenum was added. For example, a composite oxide catalyst composed of nickel, cesium, bismuth and molybdenum, a complex oxide catalyst composed of cobalt, iron, bismuth, magnesium, potassium and molybdenum, a complex oxide catalyst composed of nickel, cobalt, iron, bismuth, phosphorus, .

The conventional multicomponent bismuth-molybdenum catalyst is prepared by coprecipitating various metal precursors in one step. However, when a multicomponent bismuth-molybdenum catalyst having a complicated component is prepared by one-step co-precipitation, it is difficult to uniformly form a catalyst component, so that the reproducibility of the preparation of the catalyst is deteriorated and the mechanical strength of the catalyst is low The life span is short and the economical efficiency is deteriorated as a result. Therefore, it is necessary to develop a catalyst having improved catalytic activity and high mechanical strength to improve fracture resistance and abrasion resistance.

Under the above background, the inventors of the present invention have been studying a catalyst having excellent catalytic activity, particularly excellent catalytic activity for oxidative-dehydrogenation reaction, and having excellent mechanical strength and excellent fracture resistance and abrasion resistance, Molybdenum composite metal oxide catalyst was prepared by mixing a mixed metal oxide, and the mechanical strength and catalytic activity thereof were measured. As a result, it was confirmed that the catalytic activity was excellent and the mechanical strength could be remarkably improved, thereby completing the present invention.

KR 10-2013-0046214 A

An object of the present invention is to provide a multicomponent bismuth-molybdenum composite metal oxide catalyst derived from a composition comprising an amorphous complex metal oxide and a crystalline metal complex oxide having excellent catalytic activity and excellent mechanical strength and consequently excellent lifetime characteristics .

Another object of the present invention is to provide a process for preparing the multicomponent bismuth-molybdenum composite metal oxide catalyst.

Another object of the present invention is to provide a process for producing 1,3-butadiene using the multicomponent bismuth-molybdenum composite metal oxide catalyst.

In order to solve the above problems, the present invention relates to an amorphous complex metal oxide represented by the following Chemical Formula 1; And a crystalline mixed metal oxide represented by the following formula (2): < EMI ID = 2.0 >

[Chemical Formula 1]

Mo _a Bi _b C _c d _d e _e o _y

(2)

Mo _f Bi _g C _h D _i E _j O _z

In the above Chemical Formulas 1 and 2, C is a trivalent cation metal element, D is a divalent cation metal element, E is a monovalent cation metal element,

a is 0.5 to 15, b is 0.01 to 10, c is 0.01 to 10, d is 0.01 to 10, e is 0.001 to 1, f is 0.5 to 15, g is 0 to 14, h is 0 to 14, 0 to 14, j is 0 to 14, a + f is 1 to 30, g + h + i + j is 0 to 14, and y and z are values determined for matching valences with other components.

The present invention also relates to a method for producing the amorphous complex metal oxide represented by Formula 1 (Step 1); A step (step 2) of producing the crystalline mixed metal oxide represented by Formula 2; And a step (step 3) of preparing a mixture by mixing each of the composite metal oxides of the step 1 and the step 2 and a step (step 3) of preparing the multi-component bismuth-molybdenum composite metal oxide catalyst.

In addition, the present invention relates to a process for preparing a multi-component bismuth-molybdenum composite metal oxide catalyst, comprising the steps of: (a) filling the reactor with the multicomponent bismuth-molybdenum composite metal oxide catalyst in a stationary phase; And a step (B) of conducting an oxidative-dehydrogenation reaction while continuously passing a reactant containing a C4 compound including n-butene to a catalyst bed of a reactor packed with the catalyst (step B) And a manufacturing method thereof.

The multicomponent bismuth-molybdenum composite metal oxide catalyst according to the present invention can be prepared from a composition containing a crystalline composite metal oxide, thereby improving the degree of crystallization of the catalyst. Thus, the catalytic activity of the catalyst is improved, In particular, in the oxidative-dehydrogenation reaction process for producing 1,3-butadiene, it can exhibit high catalytic activity and excellent fracture resistance and abrasion resistance.

Also, the method of manufacturing the catalyst includes a step of mixing and firing a crystalline mixed metal oxide and an amorphous composite metal oxide, so that the crystalline mixed metal oxide acts as a crystal seed during the firing, Can be easily performed.

Therefore, the process for producing 1,3-butadiene using the multicomponent bismuth-molybdenum composite metal oxide catalyst can effectively obtain 1,3-butadiene, and can also prolong the catalyst replacement cycle, thereby increasing the economic efficiency And can be easily applied to a catalytic process, particularly an oxidative-dehydrogenation reaction process.

BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate preferred embodiments of the invention and together with the description of the invention serve to further the understanding of the technical idea of the invention, It should not be construed as limited.
FIG. 1 is a flowchart schematically illustrating a process for preparing a multicomponent bismuth-molybdenum composite metal oxide catalyst according to an embodiment of the present invention.
FIG. 2 is a graph of XRD analysis results for comparative analysis of the crystallinity of a multicomponent bismuth-molybdenum composite metal oxide catalyst according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail in order to facilitate understanding of the present invention.

The terms and words used in the present specification and claims should not be construed in an ordinary or dictionary sense and the inventor can properly define the concept of the term to describe its invention in the best possible way It should be construed as meaning and concept consistent with the technical idea of the present invention.

The present invention provides a multicomponent bismuth-molybdenum composite metal oxide catalyst having excellent catalytic activity and excellent mechanical strength and improved fracture resistance and abrasion resistance.

In general, 1,3-butadiene is produced by a naphtha cracking process, a direct dehydrogenation process of n-butene, and an oxidative-dehydrogenation process of n-butene. Among them, the oxidation of n-butene The red-dehydrogenation process is thermodynamically very advantageous because it produces stable water as a product.

Meanwhile, a ferrite catalyst, a tin catalyst, and a bismuth-molybdenum catalyst are currently used for the oxidative-dehydrogenation reaction, and a pure bismuth-molybdenum catalyst of a single phase is used as the bismuth-molybdenum catalyst, There is a difficulty in commercialization due to its activity. As an alternative to this, multicomponent bismuth-molybdenum catalysts with various metal components have been proposed. However, since the conventional multicomponent bismuth-molybdenum catalyst is manufactured by coprecipitation of various metal precursors in one step, it is difficult to uniformly form a large number of metal components in the catalyst, resulting in poor reproducibility of catalyst preparation, poor mechanical strength, There is a high probability of being crushed or abraded at the time of use, resulting in a short life span resulting in poor economical efficiency.

Accordingly, the present invention provides a multicomponent bismuth-molybdenum composite metal oxide catalyst having improved fracture resistance and abrasion resistance by increasing the degree of crystallization of a catalyst prepared by adding a crystalline compound metal oxide as a precursor substance constituting the catalyst, to provide.

The multicomponent bismuth-molybdenum composite metal oxide catalyst according to an embodiment of the present invention includes an amorphous complex metal oxide represented by the following formula (1); And a crystalline complex metal oxide represented by the following formula (2).

[Chemical Formula 1]

Mo _a Bi _b C _c d _d e _e o _y

(2)

Mo _f Bi _g C _h D _i E _j O _z

Wherein D is a divalent cation metal element, E is a monovalent cation metal element, a is 0.5 to 15, b is 0.01 to 10, c is 0.01 F is from 0 to 14, h is from 0 to 14, i is from 0 to 14, j is from 0 to 14, a + f is from 1 to 10, d is from 0.01 to 10, e is from 0.001 to 1, f is from 0.5 to 15, g is from 0 to 14, 1 to 30, g + h + i + j is 0 to 14, and y and z are values determined to match the valency with other components.

The composition may include an amorphous complex metal oxide and a crystalline complex metal oxide in a molar ratio of 1: 99: 99 to 1. When the molar ratio of the crystalline composite metal oxide is less than 1, the effect of improving the crystallinity of the multicomponent bismuth-molybdenum composite metal oxide catalyst is insufficient and consequently the fracture resistance and abrasion resistance of the catalyst may not be improved.

As described above, the amorphous complex metal oxide represented by Formula 1 according to the present invention may have the following composition ratios of the components constituting the amorphous complex metal oxide.

In the formula 1, a is 0.5 to 15, b is 0.01 to 10, c is 0.01 to 10, d is 0.01 to 10, e is 0.001 to 1, and y is a value determined to match the valency with other components B is preferably from 0.5 to 2, c is from 0.5 to 8, d is from 0.5 to 8, and e is from 0.001 to 0.8. That is, the metal components constituting the amorphous complex metal oxide may be Mo: Bi: C: D: E = 12: 0.5 to 2: 0.5 to 8: 0.5 to 8: 0.001 to 0.8. The amorphous complex metal oxide represented by Formula 1 may be a five-component complex metal oxide as shown in the composition ratio described above.

As described above, the crystalline mixed metal oxide represented by Formula 2 according to the present invention may have the following composition ratios of the components constituting the crystalline mixed metal oxide.

G is 0 to 14, h is 0 to 14, i is 0 to 14, j is 0 to 14, g + h + i + j is 0 to 14, and z G, h, i and j may be 0 at the same time, or g, h, i and j may not be 0 at the same time. When f is 12, g may have a composition ratio of 0 to 2, h may be 0 to 8, i may be 0 to 8, and j may be 0 to 0.8.

That is, the crystalline mixed metal oxide represented by Formula 2 may be a binary composite metal oxide, a three-component metal complex oxide, a four-component metal complex oxide, or a five-component metal complex oxide, as shown in the composition ratio described above.

In the above formulas (1) and (2), C means a trivalent cation metal element as described above, and is not particularly limited as long as it is a trivalent cation metal element. And preferably at least one selected from the group consisting of Al, Ga, In, Ti, Fe, La, Cr and Ce. Particularly preferably, C may be Fe.

In the above formulas (1) and (2), D means a divalent cation metal element as described above, and is not particularly limited as long as it is a divalent cation metal element, but preferably Be, Mg, Ca, Sr, Ba, Co, Zn, and Cu. Particularly preferably, D may be Co.

In the above formulas (1) and (2), E represents a monovalent cation metal element as described above, and is not particularly limited as long as it is a monovalent cationic metal element, but Li, Na, K, Rb, Cs, Fr. ≪ / RTI > Particularly preferably, E may be Cs.

According to an embodiment of the present invention, in Formula 1 and Formula 2, C may be Fe, D may be Co, and E may be Cs. In Formula 2, g is not 0, h, Or g, j, i and j may not be 0 at the same time.

The catalyst may be an oxidative-dehydrogenation catalyst, preferably an oxidative-dehydrogenation catalyst for 1,3-butadiene production.

The multicomponent bismuth-molybdenum composite metal oxide catalyst derived from the composition containing the amorphous complex metal oxide and the crystalline compound metal oxide according to the present invention has a crystallinity of 60% to 100% as measured by X-ray diffraction analysis And when the pellet is formed into a pellet having a diameter of 6 mm and a height of 6 mm, the strength is 4 kgf to 10 kgf, and the bulk density of the pellet-shaped catalyst is 1 g / cc to 1.8 g / cc.

The present invention also provides a process for preparing the multicomponent bismuth-molybdenum composite metal oxide catalyst.

The method for preparing a multicomponent bismuth-molybdenum composite metal oxide catalyst according to an embodiment of the present invention includes the steps of: (1) preparing an amorphous complex metal oxide represented by Formula 1; A step (step 2) of producing the crystalline mixed metal oxide represented by Formula 2; And a step (step 3) of mixing the composite metal oxides of steps 1 and 2 to prepare a mixture and firing the mixture.

The step 1 is a step for preparing the amorphous complex metal oxide represented by Formula 1, wherein a monovalent cation metal precursor, a divalent cation metal precursor, a trivalent cation metal precursor and a bismuth precursor are mixed to form a first solution Producing step (step a); Dropwise adding the first solution to a molybdenum precursor solution and coprecipitating to prepare a second solution (step b); And drying the second solution (step c).

The step (a) is a step of mixing the monovalent cation metal element, divalent cation metal element, trivalent cation metal element and bismuth metal element constituting the amorphous complex metal oxide represented by the formula (1) Are mixed in a solvent to prepare a first solution. In this case, the first solution may be prepared by dissolving each precursor of each metal element in a solvent to prepare each metal precursor solution and mixing them so that the metal elements are uniformly mixed.

Specifically, a precursor of a trivalent cation metal element represented by C in the above formula (1) is dissolved in a solvent to prepare a solution of a trivalent cation metal precursor, and a solution of the divalent cation metal element represented by D in the above formula The precursor is dissolved in a solvent to prepare a divalent cation metal precursor solution. The precursor of the monovalent cation metal element represented by E in the above formula (1) is dissolved in a solvent to prepare a monovalent cation metal precursor solution. The monovalent cation metal precursor solution, the divalent cation metal precursor solution and the trivalent cation metal precursor solution may be prepared by dissolving the monovalent cation metal precursor solution, the trivalent cation metal precursor solution, and the trivalent cation metal precursor solution in a solvent, An element precursor and a trivalent cation metal element precursor may be dissolved in a solvent at the same time to prepare a precursor solution in a mixed state. The solvent may be distilled water, but is not limited thereto. In addition, an acidic solution may be further added to increase the solubility according to the precursor of each metal element. The acidic solution is not particularly limited, but may be, for example, nitric acid.

The monovalent cationic metal element, the divalent cationic metal element and the trivalent cationic metal element may be as described above.

The precursor of the divalent or trivalent cation metal and the precursor of the monovalent cation metal are not particularly limited and those conventionally used in the art may be used. For example, ammonium, carbonate, Nitrate, acetic acid, oxide, sulfate, chloride, and the like.

The bismuth precursor solution may be prepared by dissolving a precursor of bismuth metal in a solvent, such as a solution of a divalent or trivalent cationic metal precursor and a solution of a monovalent cationic metal precursor, and the solvent may be distilled water, an aqueous nitrate solution, However, it is not particularly limited. When the solvent is distilled water, an acidic solution may be further added to increase the solubility of the bismuth metal precursor. The acidic solution is as described above.

The precursor of the bismuth metal is not particularly limited and those conventionally used in the art may be used. For example, bismuth nitrate may be used.

The first solution can be prepared by mixing the monovalent cation metal precursor solution, the divalent cation metal precursor solution, the trivalent cation metal precursor solution, and the bismuth precursor solution, prepared by the above method, uniformly mixed with each metal element. The mixing is not particularly limited and can be carried out by a method commonly used in the art, but can be carried out, for example, by stirring.

The step b is a step of mixing the first solution and the molybdenum precursor solution to coprecipitate the metal element, adding the first solution to the molybdenum precursor solution, and coprecipitating it to prepare the second solution.

Specifically, the molybdenum precursor solution may be prepared by dissolving a molybdenum metal precursor in a solvent, and the solvent may be distilled water, but is not limited thereto. At this time, an acidic solution may be further added to increase the solubility of the precursor of the molybdenum metal, and the acidic solution is as described above.

The precursor of the molybdenum metal is not particularly limited and may be any of those conventionally used in the art, but may be, for example, ammonium molybdate.

The first solution may be added dropwise to the molybdenum precursor solution prepared by the above method and coprecipitated to prepare the second solution.

The coprecipitation may be performed by slowly dropping (injecting) the first solution into the molybdenum precursor solution at a constant rate while stirring to sufficiently coprecipitate the metal element contained in the second solution.

The step (c) is a step of drying the second solution to obtain the composite metal oxide represented by the formula (1). An aging process may be further performed for sufficient coprecipitation before the drying. At this time, the aging process is not particularly limited and can be carried out by a conventional method known in the art, but can be carried out, for example, by stirring for 30 minutes to 40 hours while maintaining a temperature of 30 ° C to 80 ° C.

The amorphous complex metal oxide is not particularly limited, but may be prepared in the form of powder through pulverization after the drying.

The drying is not particularly limited, but may be carried out, for example, by removing the liquid component from the second solution, followed by heat treatment at a temperature of 100 ° C to 200 ° C for 10 hours to 24 hours. The method for removing the liquid component is not particularly limited, and a method commonly used in the art can be used. For example, the liquid component can be removed by using a vacuum or centrifugal concentrator.

Step 2 is a step for preparing the crystalline mixed metal oxide represented by Formula 2, and may be carried out by the following steps:

Comprising the steps of: i) preparing a precursor solution of at least one of a cationic metal precursor, a divalent cation metal precursor, a trivalent cation metal precursor, and a bismuth precursor;

Step ii) dropwise adding the precursor solution of step i) to the molybdenum precursor solution and coprecipitation to prepare a mixed precursor solution; And

Step iii) drying and calcining the mixed precursor solution.

The step i) may be carried out by mixing at least one metal element selected from the monovalent cation metal element, divalent cation metal element, trivalent cation metal element and bismuth metal element constituting the crystalline mixed metal oxide represented by the formula (2) , The precursor material of each metal element is put into a solvent and mixed to prepare a precursor solution, which can be carried out by a method similar to that shown in step a of the method for producing the amorphous complex metal oxide of step 1 described above .

Specifically, a precursor of a trivalent cation metal element represented by C, a divalent cation metal element represented by D, a monovalent cation metallic element represented by E, and a bismuth metal element represented by C in the above formula (2) To prepare a precursor solution. At this time, the precursor solution may be prepared by dissolving the precursors of the respective metal elements constituting the crystalline mixed metal oxide represented by Formula 2 simultaneously in a solvent to prepare a mixed precursor solution, Dissolving them in separate solvents to prepare precursor solutions, and then mixing the precursor solutions. The solvent may be distilled water, but is not limited thereto. In addition, an acidic solution may be further added to increase the solubility according to the precursor of each metal element. The acidic solution is not particularly limited, but may be, for example, nitric acid.

The monovalent cationic metal element, the divalent cationic metal element, and the trivalent cationic metal element may be as described above, and the precursors and the bismuth precursors of the respective metal elements may be as described above.

The mixing is not particularly limited and can be carried out by a method commonly used in the art, but can be carried out, for example, by stirring.

In the step ii), the precursor solution is added dropwise to the molybdenum precursor solution to coprecipitate the metal element by mixing the precursor solution and the molybdenum precursor solution, and coprecipitated to prepare a mixed precursor solution.

Specifically, the molybdenum precursor solution can be prepared by the method as described above.

The precursor solution may be added dropwise to the molybdenum precursor solution prepared by the above method and coprecipitated to prepare a mixed precursor solution.

The coprecipitation can be performed by gradually dropping (injecting) the precursor solution into the molybdenum precursor solution at a constant rate while stirring to sufficiently coprecipitate the metal element contained in the mixed precursor solution.

The step iii) is a step of drying and firing the mixed precursor solution to obtain the crystalline mixed metal oxide represented by the formula (2). An aging process may be further performed for sufficient coprecipitation before the drying, and the aging process may be performed by the method as described above.

The crystalline mixed metal oxide is not particularly limited, but may be prepared in the form of powder through pulverization after the drying. The drying can be carried out by the method as described above.

The calcination in the step iii) is not particularly limited, but can be carried out, for example, by heat treatment at a temperature of 300 ° C to 500 ° C for 5 hours to 40 hours.

The step 3 is a step of mixing and mixing the respective composite metal oxides of the step 1 and the step 2 to obtain a multicomponent bismuth-molybdenum composite metal oxide catalyst having a high degree of crystallinity.

The composite metal oxides may be mixed in a powder state.

And kneading and molding the mixture before the firing. In this case, the dough may be performed using a liquid binder, and the liquid binder is not particularly limited and those conventionally used in the art may be used, and examples thereof include distilled water, ethylene glycol, glycerin, propionic acid, benzyl alcohol, , Polyvinyl alcohol, phenol and the like, nitric acid, silica sol and the like can be used.

If necessary, additives such as a molding aid, a reinforcing agent, and a pore-forming agent may be further added to the kneading composition. Examples of the additives include stearic acid, maleic acid, ammonium nitrate, ammonium carbonate, graphite, starch, cellulose, , Glass fiber, silicon carbide, silicon nitride, and the like, but is not limited thereto.

The shaping is performed so that the catalyst to be produced has a certain shape, and the shaping shape is not particularly limited, but may be spherical or pellet shape (cylindrical shape). Preferably, it may be molded into a pellet having a diameter of 4 mm to 8 mm and a height of 4 mm to 8 mm.

The firing in the step 3 is not particularly limited, but can be carried out, for example, by heat treatment at a temperature of 300 to 500 캜 for 5 to 40 hours.

The process according to the present invention can increase the degree of crystallization of the catalyst prepared by adding the crystalline composite metal oxide, thereby increasing the strength of the catalyst and improving the fracture resistance and abrasion resistance. As a result, There is an economic advantage.

In addition, the present invention provides a process for producing 1,3-butadiene using the multicomponent bismuth-molybdenum composite metal oxide catalyst.

The method for producing 1,3-butadiene according to an embodiment of the present invention includes the following steps.

Filling the multicomponent bismuth-molybdenum composite metal oxide catalyst with a fixed bed in the reactor (step A); And

(Step B) wherein the reactant containing the C4 compound including n-butene is continuously passed through the catalyst layer of the packed-bed reactor while the catalyst is passed through the oxidizing-dehydrogenation reaction.

The oxidative-dehydrogenation reaction may be carried out at a reaction temperature of 250 ° C to 380 ° C and a space velocity of 50 h ^-1 to 2000 h ^-1 based on the n-butene.

Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. However, the following examples and experimental examples are provided for illustrating the present invention, and the scope of the present invention is not limited thereto.

Example  One

1) Preparation of crystalline mixed metal oxide

Bismuth nitrate pentahydrate (Bi (NO ₃ ) ₂ .5H ₂ O) was added to an aqueous nitric acid solution at room temperature and stirred to prepare a bismuth nitrate aqueous solution. Separately, the ammonium molybdate tetrahydrate ((NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O) was dissolved in distilled water while maintaining the constant temperature at 40 ° C., and the aqueous solution of bismuth nitrate was added thereto while being stirred to coprecipitate Followed by stirring at 40 DEG C for 1 hour to prepare a coprecipitation solution. The prepared coprecipitation solution was dried in an oven at 120 ° C. for 18 hours, and the obtained powder was pulverized and then calcined at 450 ° C. for 7 hours to obtain a crystalline composite metal oxide powder [Mo ₃ Bi ₂ O ₁₂ ].

2) Preparation of amorphous complex metal oxide

Nitrate, bismuth pentahydrate _{(Bi (NO 3) 3 ·} 5H 2 O), ferric nitrate nonahydrate _{(Fe (NO 3) 3 ·} 9H 2 O), cobalt nitrate hexahydrate _{(Co (NO 3) 2 ·} 6H 2 O) , Cesium nitrate (CsNO ₃ ) were dissolved in distilled water to prepare a mixed solution of bismuth, iron, cobalt and cesium precursors. Separately, the precursor mixture solution was slowly added dropwise to a molybdenum precursor solution prepared by dissolving ammonium molybdenum tetrahydrate ((NH ₄ ) ₆ (Mo ₇ O ₂₄ ) .4H ₂ O) in distilled water, coprecipitated and stirred to prepare a coprecipitation solution . The prepared solution was then dried in a co-precipitation of 120 ℃ oven for 18 hours and milled to obtain an amorphous composite metal oxide powder _{[Mo 12 Bi 1 Fe 2 Co} 5 Cs 0 .1 0 65].

3) Preparation of multicomponent bismuth-molybdenum composite metal oxide catalyst

The amorphous complex metal oxide powder prepared in 2) was mixed with the crystalline mixed metal oxide powder prepared in 1) so as to have a molar ratio of 90:10 to prepare a mixed powder, and distilled water and alcohol were added to the mixed powder Kneaded, extruded into pellets having a size of 6 mm × 6 mm (diameter × height), and then subjected to calcination in an electric furnace at 450 ° C. for 7 hours to obtain a multicomponent bismuth-molybdenum composite metal oxide catalyst.

Example  2

The same procedure as in Example 1 was carried out except that the amorphous complex metal oxide powder and the crystalline phase complex coarse powder were mixed at a molar ratio of 50:50 instead of 90:10 A multi-component bismuth-molybdenum composite metal oxide catalyst was obtained.

Example  3

Except that the amorphous complex metal oxide powder and the crystalline mixed metal oxide powder were mixed in a molar ratio of 1:99 instead of 90:10 in Example 1-3. Component bismuth-molybdenum composite metal oxide catalyst.

Example  4

1) Preparation of crystalline mixed metal oxide

Nitrate, bismuth nitrate aqueous solution at room temperature pentahydrate _{(Bi (NO 3) 2 ·} 5H 2 O), ferric nitrate nonahydrate _{(Fe (NO 3) 3 ·} 9H 2 O), cobalt nitrate hexahydrate (Co (NO _{3) 2} 6H ₂ O) and cesium nitrate (CsNO ₃ ) were added and stirred to prepare an aqueous nitrate solution containing bismuth, iron, cobalt and cesium. Separately, ammonium molybdate tetrahydrate ((NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O) was dissolved in distilled water in a double-jacketed reactor while maintaining the temperature at 40 ° C., Lt; 0 > C for 1 hour to prepare a coprecipitation solution. The prepared coprecipitation solution was dried in an oven at 120 ° C. for 18 hours, and the obtained powder was pulverized and then calcined at 450 ° C. for 7 hours to obtain a crystalline composite metal oxide powder [Mo ₁₂ Bi ₁ Fe ₂ Co ₅ Cs _0.1 O ₆₅ ] .

2) Preparation of amorphous complex metal oxide

Nitrate, bismuth pentahydrate _{(Bi (NO 3) 3 ·} 5H 2 O), ferric nitrate nonahydrate _{(Fe (NO 3) 3 ·} 9H 2 O), cobalt nitrate hexahydrate _{(Co (NO 3) 2 ·} 6H 2 O) , Cesium nitrate (CsNO ₃ ) were dissolved in distilled water to prepare a mixed solution of bismuth, iron, cobalt and cesium precursors. Separately, the precursor mixture solution was slowly added dropwise to a molybdenum precursor solution prepared by dissolving ammonium molybdenum tetrahydrate ((NH ₄ ) ₆ (Mo ₇ O ₂₄ ) .4H ₂ O) in distilled water, coprecipitated and stirred to prepare a coprecipitation solution . The prepared solution was then dried in a co-precipitation of 120 ℃ oven for 18 hours and milled to obtain an amorphous composite metal oxide powder _{[Mo 12 Bi 1 Fe 2 Co} 5 Cs 0 .1 0 65].

3) Preparation of multicomponent bismuth-molybdenum composite metal oxide catalyst

The amorphous complex metal oxide powder prepared in 2) was mixed with the crystalline mixed metal oxide powder prepared in 1) so as to have a molar ratio of 90:10 to prepare a mixed powder, and distilled water and alcohol were added to the mixed powder Kneaded, extruded into pellets having a size of 6 mm × 6 mm (diameter × height), and then subjected to calcination in an electric furnace at 450 ° C. for 7 hours to obtain a multicomponent bismuth-molybdenum composite metal oxide catalyst.

Example  5

Except that amorphous complex metal oxide powder and crystalline mixed metal oxide powder were mixed at a molar ratio of 50:50 instead of 90:10 in Example 4-3) Component bismuth-molybdenum composite metal oxide catalyst.

Example  6

Except that the amorphous complex metal oxide powder and the crystalline mixed metal oxide powder were mixed in a molar ratio of 1:99 instead of 90:10 in Example 4-3) Component bismuth-molybdenum composite metal oxide catalyst.

Comparative Example  One

Bismuth nitrate pentahydrate (Bi (NO ₃ ) ₂ .5H ₂ O) was added to an aqueous nitric acid solution at room temperature and stirred to prepare a bismuth nitrate aqueous solution. Separately, the ammonium molybdate tetrahydrate ((NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O) was dissolved in distilled water while maintaining the constant temperature at 40 ° C., and the aqueous solution of bismuth nitrate was added thereto while being stirred to coprecipitate Followed by stirring at 40 DEG C for 1 hour to prepare a coprecipitation solution. The prepared coprecipitation solution was dried in an oven at 120 ° C. for 18 hours. Distilled water and alcohol were added to the obtained powder, kneaded and extruded into pellets having a size of 6 mm × 6 mm (diameter × height) For 7 hours to obtain a multicomponent bismuth-molybdenum composite metal oxide catalyst [Mo ₃ Bi ₂ O ₁₂ ].

Comparative Example  2

Nitrate, bismuth pentahydrate _{(Bi (NO 3) 3 ·} 5H 2 O), ferric nitrate nonahydrate _{(Fe (NO 3) 3 ·} 9H 2 O), cobalt nitrate hexahydrate _{(Co (NO 3) 2 ·} 6H 2 O) , Cesium nitrate (CsNO ₃ ) were dissolved in distilled water to prepare a mixed solution of bismuth, iron, cobalt and cesium precursors. Separately, the precursor mixture solution was slowly added dropwise to a molybdenum precursor solution prepared by dissolving ammonium molybdenum tetrahydrate ((NH ₄ ) ₆ (Mo ₇ O ₂₄ ) .4H ₂ O) in distilled water, coprecipitated and stirred to prepare a coprecipitation solution . The prepared coprecipitation solution was dried in an oven at 120 ° C. for 18 hours and pulverized to obtain a powder. Distilled water and alcohol were added to the obtained powder, kneaded and extruded into pellets having a size of 6 mm × 6 mm (diameter × height) , And then calcined in an electric furnace at 450 ° C. for 7 hours to obtain a multicomponent bismuth-molybdenum composite metal oxide catalyst [Mo ₁₂ Bi ₁ Fe ₂ Co ₅ Cs _{0 . 1} O ₆₅ ].

Experimental Example  One

In order to compare and analyze the degree of crystallization of each of the multicomponent bismuth-molybdenum composite metal oxide catalysts prepared in Examples 1 to 6 and Comparative Example 2, XRD analysis of each catalyst was carried out. The results are shown in Fig.

X-ray diffraction (XRD) was performed using an X-ray diffractometer (Bruker D4 Endeavor) equipped with a monochromatic CuKa radiation (wavelength (ν) = 1.54 A) operating at 40 kV and 30 mA. Germany) at room temperature. The diffraction pattern was measured in steps of 0.02 degrees in the 2 &thetas; scan mode and in an angular range from 10 degrees to 50 degrees at a speed of 0.1 s / step.

As shown in FIG. 2, the multicomponent bismuth-molybdenum composite oxide catalyst of Examples 1 to 6 according to the present invention showed higher crystallinity than the multicomponent bismuth-molybdenum composite oxide catalyst of Comparative Example 2. This is because the multicomponent bismuth-molybdenum composite oxide catalyst according to the present invention is produced from a composition containing a certain proportion of the crystalline compound metal oxide so that the crystalline compound metal oxide acts as a crystalline seed to facilitate crystallization and structure formation This is a result that means that it has played a catalytic role to make it happen.

Experimental Example  2

In order to comparatively analyze the activity of each of the catalysts prepared in Examples 1 to 6 and Comparative Examples 1 and 2, the conversion of 1-butene, the selectivity of 1,3-butadiene, the catalyst strength before and after the reaction, Were measured. The results are shown in Table 1 below.

1) Conversion of 1-butene and 1,3-butadiene selectivity

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 reactants and the gas space velocity (GHSV) were described on the basis of 1-butene. The ratio of 1 - butene: oxygen: steam: nitrogen was set to 1: 1: 3: 10 and the gas space velocity was constantly controlled to 250 h ^{- 1} . The volume of the contacting catalytic layer contacting the reactants was fixed at 200 cc. The steam was injected in the form of water as a vaporizer, vaporized at 320 ° C. by steam, mixed with other reactants, 1-butene and oxygen, The device was designed. The amount of 1-butene was controlled using a mass flow controller for liquids, oxygen and nitrogen were controlled using a mass flow controller for gases, and the amount of steam was controlled using a liquid pump. The reaction proceeded at 320 psig at 12 psig pressure. The reaction products were analyzed by gas chromatography. Conversion of 1-butene The following formula 1 was calculated, respectively.

[Equation 1]

2) Catalyst strength and density

The catalyst strength was measured at the maximum force when the pressure was slowly applied to a 10 mm diameter round tip of digital force guage (SLD 50 FGN) manufactured by SPC technology.

The catalyst density was calculated by weighing the catalyst filling the measuring cylinder to 200 cc and dividing this value by the volume of 200 cc.

division 1-butene
Conversion Rate (%) Selectivity of 1,3-butadiene (%) Catalyst density before reaction (g / cc) Catalyst strength before reaction (kgf) Catalyst strength after reaction (kgf) Example 1 64.1 75.9 1.02 4.2 3.1 Example 2 75.6 74.8 1.29 5.6 4.2 Example 3 82.8 70.9 1.58 6.9 6.1 Example 4 52.1 94.8 1.18 4.8 4.1 Example 5 81.8 92.1 1.44 6.2 5.0 Example 6 56.4 95.1 1.74 9.7 9.2 Comparative Example 1 12.1 87.9 1.02 3.1 2.3 Comparative Example 2 83.6 94.0 1.05 4.6 3.5

As shown in Table 1, the multicomponent bismuth-molybdenum composite metal oxide catalysts of Examples 1 to 6 according to the present invention were compared with the multicomponent bismuth-molybdenum composite metal oxide catalysts of Comparative Example 1 and Comparative Example 2 Butene conversion and 1,3-butadiene selectivity, the catalyst strength was remarkably increased.

Accordingly, the multicomponent bismuth-molybdenum composite metal oxide catalyst according to the present invention can exhibit excellent crushing resistance and abrasion resistance while exhibiting excellent catalytic activity, and thus the catalyst life can be increased and the economical efficiency of the catalyst process using the catalyst can be improved .

Claims (23)

An amorphous complex metal oxide represented by the following formula (1); And bismuth-molybdenum composite metal oxide catalysts derived from a composition comprising a crystalline composite metal oxide represented by the following formula (2)
[Chemical Formula 1]
Mo _a Bi _b C _c d _d e _e o _y
(2)
Mo _f Bi _g C _h D _i E _j O _z
In the above formulas (1) and (2)
C is a trivalent cation metal element,
D is a divalent cation metal element,
E is a monovalent cation metal element,
a is 0.5 to 15, b is 0.01 to 10, c is 0.01 to 10, d is 0.01 to 10, e is 0.001 to 1, f is 0.5 to 15, g is 0 to 14, h is 0 to 14, 0 to 14, j is 0 to 14,
a + f is 1 to 30, g + h + i + j is 0 to 14,
y and z are values determined to match the valences by different components.

The method according to claim 1,
Wherein when a is 12, b is 0.5 to 2, c is 0.5 to 8, d is 0.5 to 8, and e is 0.001 to 0.8.
The method according to claim 1,
Wherein when f is 12, g is 0 to 2, h is 0 to 8, i is 0 to 8, and j is 0 to 0.8.
The method according to claim 1,
Wherein the trivalent cation metal element is at least one element selected from the group consisting of Al, Ga, In, Ti, Fe, La, Cr and Ce.
The method according to claim 1,
Wherein the divalent cation metal element is at least one selected from the group consisting of Be, Mg, Ca, Sr, Ba, Ra, Co, Zn and Cu.
The method according to claim 1,
Wherein the monovalent cation metallic element is at least one selected from the group consisting of Li, Na, K, Rb, Cs, Ag and Fr.
The method according to claim 1,
C is Fe, D is Co, E is Cs,
Wherein g is not 0, and h, i and j are 0 at the same time.
The method according to claim 1,
C is Fe, D is Co, E is Cs,
Wherein the g, h, i and j are not 0 at the same time.
The method according to claim 1,
Wherein the composition comprises an amorphous complex metal oxide and a crystalline composite metal oxide in a molar ratio of 1: 99: 99 to 1: 1.
The method according to claim 1,
Wherein the catalyst has a crystallinity of 60% to 100%.
The method of claim 10,
Wherein the catalyst has a strength of 4 kgf to 10 kgf and a bulk density of 1 g / cc to 1.8 g / cc when molded into a pellet having a diameter of 6 mm and a length of 6 mm. Metal oxide catalyst.
1) preparing an amorphous complex metal oxide represented by the following Chemical Formula 1;
2) preparing a crystalline complex metal oxide represented by the following Chemical Formula 2; And
3) A method for producing a multicomponent bismuth-molybdenum composite metal oxide catalyst comprising the steps of: mixing the composite metal oxides of step 1) and step 2)
[Chemical Formula 1]
Mo _a Bi _b C _c d _d e _e o _y
(2)
Mo _f Bi _g C _h D _i E _j O _z
In the above formulas (1) and (2)
C is a trivalent cation metal element,
D is a divalent cation metal element,
E is a monovalent cation metal element,
a is 0.5 to 15, b is 0.01 to 10, c is 0.01 to 10, d is 0.01 to 10, e is 0.001 to 1, f is 0.5 to 15, g is 0 to 14, h is 0 to 14, 0 to 14, j is 0 to 14,
a + f is 1 to 30, g + h + i + j is 0 to 14,
y and z are values determined to match the valences by different components.
The method of claim 12,
The amorphous complex metal oxide of step 1)
a) preparing a first solution by mixing a monovalent cation metal precursor, a divalent cation metal precursor, a trivalent cation metal precursor, and a bismuth precursor;
b) dropwise adding the first solution to the molybdenum precursor solution and coprecipitation to produce a second solution; And
and c) drying the second solution. < Desc / Clms Page number 20 >
The method of claim 12,
The crystalline composite metal oxide of step 2)
i) preparing a precursor solution of at least one of a monovalent cation metal precursor, a divalent cation metal precursor, a trivalent cation metal precursor, and a bismuth precursor;
ii) dropwise adding the precursor solution of step i) to the molybdenum precursor solution and coprecipitating it to prepare a mixed precursor solution; And
and iii) drying and calcining the mixed precursor solution. The method for producing a multicomponent bismuth-molybdenum composite metal oxide catalyst according to claim 1,
15. The method of claim 14,
Wherein the calcination in step iii) is a heat treatment in a temperature range of 300 ° C to 500 ° C for 5 hours to 40 hours.
The method of claim 12,
Further comprising kneading and molding the mixture prior to firing the step 3). ≪ RTI ID = 0.0 > 11. < / RTI >
The method of claim 12,
Wherein the trivalent cation metal element is at least one element selected from the group consisting of Al, Ga, In, Ti, Fe, La, Cr and Ce.
The method of claim 12,
Wherein the divalent cation metal element is at least one selected from the group consisting of Be, Mg, Ca, Sr, Ba, Ra, Co, Zn and Cu.
The method of claim 12,
Wherein the monovalent cationic metal element is at least one selected from the group consisting of Li, Na, K, Rb, Cs, Ag and Fr.
The method of claim 12,
C is Fe, D is Co, E is Cs,
Wherein g is not 0, and h, i and j are 0 at the same time.
The method of claim 12,
C is Fe, D is Co, E is Cs,
Wherein the g, h, i and j are not 0 at the same time.
Filling the multi-component bismuth-molybdenum composite metal oxide catalyst of claim 1 into a reactor in a stationary phase; And
Comprising the steps of: continuously passing a reactant containing a C4 compound containing n-butene to a catalyst bed of a reactor packed with said catalyst to proceed an oxidative-dehydrogenation reaction.
23. The method of claim 22,
Wherein the oxidative-dehydrogenation reaction is carried out at a reaction temperature of 250 ° C to 380 ° C and a space velocity of from 50 h ^-1 to 2000 h ^-1 based on the n-butene. Way.

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