WO2017099411A1

WO2017099411A1 - Catalyst for oxidative dehydrogenation reaction and method for producing same

Info

Publication number: WO2017099411A1
Application number: PCT/KR2016/013919
Authority: WO
Inventors: 서명지; 민윤재; 고동현; 차경용; 백세원; 한준규
Original assignee: (주) 엘지화학
Priority date: 2015-12-09
Filing date: 2016-11-30
Publication date: 2017-06-15

Abstract

The present invention relates to a catalyst for an oxidative dehydrogenation reaction and a method for producing the same. The present invention has effects of providing a catalyst for an oxidative dehydrogenation reaction and a method for producing the catalyst, wherein the catalyst has excellent selectivity to a product by easily controlling the heat, which is generated by high-temperature and high-pressure reaction conditions and a side effect, through a porous structure.

Description

Catalyst for oxidative dehydrogenation reaction and preparation method thereof

[Reciprocal citation with application (s)]

This application claims the benefit of priority based on Korean Patent Application No. 10-2015-0174676 of December 09, 2015 and Korean Patent Application No. 10-2015-0179406 of December 15, 2015, All content disclosed in the literature is included as part of this specification.

The present invention relates to a catalyst for an oxidative dehydrogenation reaction and a method for preparing the same, and more particularly, to oxidation of a product having excellent selectivity to a product by easily controlling a high temperature and high pressure reaction conditions and exothermic reactions from side reactions from a porous structure. The present invention relates to a catalyst for the dehydrogenation reaction and a preparation method thereof.

1,3-Butadiene is an intermediate of petrochemical products, and its demand and value are gradually increasing all over the world. The 1,3-butadiene is produced using naphtha cracking, direct dehydrogenation of butene, oxidative dehydrogenation of butene, and the like. However, the naphtha cracking process has a high energy consumption due to the high reaction temperature, and because it is not a sole process for producing 1,3-butadiene alone, there is a problem that other basic oils other than 1,3-butadiene are produced in excess. . In addition, the direct dehydrogenation reaction of normal-butene is not only thermodynamically disadvantageous, but also requires commercialization to produce 1,3-butadiene, requiring high temperature and low pressure conditions to produce high yield of 1,3-butadiene as an endothermic reaction. It is not suitable as a process.

On the other hand, the oxidative dehydrogenation of butene is a reaction of butene and oxygen in the presence of a metal oxide catalyst to produce 1,3-butadiene and water, which has a thermodynamically advantageous advantage because stable water is produced. In addition, unlike direct dehydrogenation of butenes, it is exothermic, so that a higher yield of 1,3-butadiene can be obtained at lower reaction temperatures than direct dehydrogenation, and 1,3-butadiene is not required because no additional heat supply is required. It can be an effective standalone production process that can meet demand. However, in the oxidative dehydrogenation reaction, a high calorific value due to a high temperature reaction condition affects the activity and durability of the metal oxide catalyst, which causes a problem that the selectivity to 1,3-butadiene is lowered. In addition, when a high-pressure reaction condition is applied to facilitate the reaction process system, the calorific value due to side reactions in which COx is generated becomes larger, thereby decreasing the activity of the catalyst and speeding up the performance.

In order to solve this problem, various techniques such as using a zeolite having a pore molecular sieve structure as a support of the catalyst or coating the surface of the catalyst with the zeolite have been reported, but the pore size of the zeolite is very fine, There is a disadvantage in that fever is not alleviated. Therefore, the development of a catalyst that can more effectively alleviate the heat generated by the reaction conditions and side reactions of the high temperature and high pressure is urgently required.

[Prior art document]

[Patent Documents] (Patent Document 1) US5041401 A

The present invention to provide a catalyst for oxidative dehydrogenation reaction having excellent selectivity to the product by easily controlling the heat generated by the reaction conditions and side reactions of high temperature and high pressure from the porous structure from the porous structure. For the purpose of

Another object of the present invention is to provide a method for preparing the catalyst for oxidative dehydrogenation reaction.

The above and other objects of the present invention can be achieved by the present invention described below.

In order to achieve the above object, the present invention provides a catalyst for oxidative dehydrogenation reaction comprising a porous aluminum silicate support and a metal oxide having a composition represented by the following formula (1).

[Formula 1]

A is at least one member selected from the group consisting of divalent cation metals, and B is at least one member selected from the group consisting of trivalent cation metals.

In addition, the present invention comprises the steps of immersing and coating aluminum silicate in the porous rubber; Firing the porous rubber coated with aluminum silicate; Obtaining a porous aluminum silicate support; Preparing a catalyst slurry including a metal oxide, or a coprecipitation slurry including a precursor of the metal oxide; Coating the porous aluminum silicate support by dipping in the catalyst slurry or the co-precipitate slurry; And calcining the porous aluminum silicate support on which the catalyst slurry or the co-precipitate slurry is coated.

According to the present invention, by easily controlling the exothermic conditions of the reaction conditions and side reactions of the high temperature and high pressure from the porous structure, there is an effect of providing a catalyst for oxidative dehydrogenation reaction excellent in the selectivity to the product and a method for producing the same.

1 is a live-action of a porous rubber, a porous aluminum silicate support and a catalyst for an oxidative dehydrogenation reaction according to the manufacturing process of the present invention.

Hereinafter, the present invention will be described in detail.

The present inventors have continuously studied the catalyst for the oxidative dehydrogenation reaction, and when the catalyst support is prepared by using a porous rubber, the high selectivity to the product by reducing the heat generated by the reaction conditions and side reactions of high temperature and high pressure The present invention was completed based on the fact that it can be maintained.

Looking at the catalyst for the oxidative dehydrogenation reaction according to the present invention in detail.

The oxidative dehydrogenation catalyst is characterized in that it comprises a porous aluminum silicate support and a metal oxide having a composition represented by the following formula (1).

The A may be at least one selected from the group consisting of, for example, a divalent cation metal, specifically, from the group consisting of Cu, Ra, Ba, Sr, Ca, Be, Zn, Mg, Mn, Co, and Fe (II). It may be at least one selected, preferably at least one selected from the group consisting of Zn, Mg, Mn and Co.

The B may be at least one selected from the group consisting of trivalent cationic metal, for example, may be at least one selected from the group consisting of Al, Fe (III), Cr, Ga, In, Ti, La and Ce. , Preferably Al, Fe (III) and Cr may be one or more selected from the group consisting of.

The metal oxide having the composition represented by Chemical Formula 1 may be, for example, a metal oxide having a spinel structure. The spinel structure is composed of eight divalent cations, 16 trivalent cations, and 32 oxygen ions in a unit lattice in an equiaxed system, and the oxygen ions generally form a face-centered cubic lattice, with divalent cations (A ) And trivalent cations (B) can be understood.

For example, the metal oxide may be included in an amount of 1 to 50 wt%, 1 to 30 wt%, 5 to 30 wt%, 2 to 15 wt%, or 5 to 15 wt% with respect to the catalyst for oxidative dehydrogenation reaction. In this range, there is an effect that the oxidative dehydrogenation reaction is initiated.

The porous aluminum silicate support may be, for example, a sponge-type support, and in this case, there is an effect of easily controlling heat generation due to reaction conditions and side reactions of high temperature and high pressure.

The aluminum silicate of the porous aluminum silicate support may be at least one selected from the group consisting of metal oxides, metal carbides, metal nitrides, and aluminum hydride silicates. In another example, the aluminum silicate may be a kaolin mineral, and in particular, kaolinite, dickite, nacrite, halloysite, cordierite , Diatomite, aluminum nitride (AlN), silicon nitride (Si ₃ N ₄ ), silicon carbide (SiC), zirconium carbide (ZrC), tungsten carbide (WC), alumina (Al ₂ O ₃ ), mullite (Mullite) And zirconia (ZrO ₂ ), which may be inert to oxidative dehydrogenation or have a very low catalytic activity, resulting in an uncompetitive physical support for the metal oxide of the catalyst.

The porous aluminum silicate support may have, for example, a pore distribution of 1 to 500 ppi (pores per inch), 1 to 300 ppi, or 1 to 100 ppi, and within this range, high porosity for the product during oxidative dehydrogenation reaction. There is an effect that can maintain the selectivity.

The average particle diameter of the pores of the porous aluminum silicate support may be, for example, 0.2 to 10 mm, 0.5 to 5 mm, 1 to 5 mm, or 0.5 to 3 mm, within the range of the catalyst phase of the gaseous reactants and products. It facilitates the adsorption and desorption of the gas to facilitate the flow of gas.

The porous aluminum silicate support may have, for example, a porosity calculated from the pore volume measured by the liquid impregnation method, from 10 to 99%, 30 to 98%, 70 to 99%, or 70 to 98% of the total volume. Since the heat retention caused by the exothermic reaction is alleviated within the range, the heat generated by the exothermic reaction can be effectively controlled to maintain high selectivity to the product.

The porous aluminum silicate support has, for example, a pore volume calculated from the pore volume measured by liquid impregnation, 0.1 to 120 cm ³ / g, 0.1 to 60 cm ³ / g, 20 to 60 cm ³ / g, 0.1 to 45 cm ³ / g, 5 to 45 cm ³ / g, or 0.1 to 10 cm ³ / g.

The catalyst for the oxidative dehydrogenation reaction may be, for example, a sponge type catalyst, and in this case, there is an effect of easily controlling the exotherm due to reaction conditions and side reactions of high temperature and high pressure.

The oxidative dehydrogenation catalyst may have a pore distribution of, for example, 1 to 500 ppi, 1 to 300 ppi, or 1 to 100 ppi, and has high selectivity for the product during oxidative dehydrogenation within this range. It has a sustainable effect.

The average particle diameter of the pores of the catalyst for the oxidative dehydrogenation reaction may be, for example, 1 to 10 mm, 1 to 5 mm, or 1 to 3 mm, within the range of the catalyst on the gas phase reactants and products It facilitates the adsorption and desorption of the gas to facilitate the flow of gas.

The catalyst for the oxidative dehydrogenation reaction may be, for example, the porosity calculated from the pore volume measured by the liquid impregnation method may be 10 to 99%, 30 to 98%, 70 to 99%, or 70 to 98% of the total volume. In this range, since heat retention caused by exothermic reaction is alleviated within this range, heat generated in the exothermic reaction can be effectively controlled to maintain high selectivity to the product.

The catalyst for the oxidative dehydrogenation reaction, for example, the pore volume calculated from the pore volume measured by the liquid impregnation method, 0.1 to 120 cm ³ / g, 0.1 to 60 cm ³ / g, 20 to 60 cm ³ / g, 0.1 to 45 cm ³ / g, 5 to 45 cm ³ / g, or 0.1 to 10 cm ³ / g.

The oxidative dehydrogenation reaction refers to a reaction in which olefins and oxygen react to generate conjugated diene and water in the presence of a metal oxide, and in particular, butene and oxygen may react to generate 1,3-butadiene and water. have.

The reactor used for the oxidative dehydrogenation reaction is not particularly limited if the reactor can be used for the oxidative dehydrogenation reaction, for example, the reaction temperature of the installed catalyst layer is kept constant, and the reactant is oxidized while continuously passing through the catalyst layer. It may be a reactor in which the dehydrogenation reaction proceeds, and in particular, it may be a tubular reactor, a tank reactor, a fluidized bed reactor or a fixed bed reactor, and the fixed bed reactor may be, for example, a multi-tubular reactor or a plate reactor.

The reactant of the oxidative dehydrogenation reaction may be, for example, oxygen and at least one selected from the group consisting of butan, isobutane, 1-butene, trans-2-butene and cis-2-butene, and additionally nitrogen and May comprise steam.

The oxygen may be, for example, 0.5 to 5 mol, 0.5 to 3 mol, or 0.6 to 1.5 mol based on 1 mol of the reactant, and the nitrogen may be 0 to 30 mol, 2 to 25 mol, based on 1 mol of the reactant, Or it may be 2 to 15 moles, for example, the steam may be 2 to 50 moles, 3 to 30 moles, or 4 to 25 moles, based on 1 mole of the reactants, the catalyst activity is excellent in this range.

In the oxidative dehydrogenation reaction, the gas space velocity (GHSV) may be, for example, 200 to 30,000, 250 to 25,000, or 250 to 20,000 based on the reactant.

In the oxidative dehydrogenation reaction, the reaction temperature (T) may be, for example, 300 to 500 ° C, 320 to 400 ° C, or 320 to 380 ° C.

In the oxidative dehydrogenation reaction, the reaction pressure may be, for example, 0 to 10 bar, 0 to 5 bar, or 0 to 3 bar.

The catalyst for oxidative dehydrogenation may be, for example, 1,3-butadiene selectivity of 80% or more, 85 to 99.9%, 85 to 93%, or 93 to 99.9%.

The method for preparing a catalyst for the oxidative dehydrogenation reaction according to the present invention comprises the steps of immersing and coating aluminum silicate in a porous rubber; Firing the porous rubber coated with aluminum silicate; Obtaining a porous aluminum silicate support; Preparing a catalyst slurry including a metal oxide, or a coprecipitation slurry including a precursor of the metal oxide; Coating the porous aluminum silicate support by dipping in the catalyst slurry or the co-precipitate slurry; And calcining the porous aluminum silicate support coated with the catalyst slurry or the co-precipitate slurry.

Immersion and coating the aluminum silicate on the porous rubber, for example, preparing an aluminum silicate slurry; Coating the porous rubber by immersing it in the aluminum silicate slurry; And aeration and drying the porous rubber coated with the aluminum silicate slurry.

The aluminum silicate slurry can be prepared, for example, by diluting aluminum silicate with water.

The weight ratio of the aluminum silicate and water may be, for example, 10: 1 to 1:10, 8: 1 to 1: 8, or 5: 1 to 1: 5, in which the aluminum silicate is entirely contained in the porous rubber. It has a coating effect.

The aluminum silicate slurry may include, for example, 0.01 to 10% by weight, 0.01 to 8% by weight, or 0.01 to 5% by weight of a binder for increasing the viscosity. The binder is, for example, polyvinyl alcohol, starch, carboxymethylcellulose, dextrin, wax emulsion, polyethylene glycol, lignosulfonate , Methyl cellulose (methylcellulose), paraffin (paraffin) and polyacrylate (polyacrylate) may be one or more selected from the group consisting of, in this case there is an effect of improving the adhesion of the aluminum silicate to the porous rubber.

Immersion of the porous rubber, for example, may be carried out for a time that the aluminum silicate slurry can contact the entire area of the porous rubber, the time is not particularly limited, 0.1 to 30 minutes, 0.1 to 10 minutes, or 0.1 to It may be one minute.

The aeration means that a gas is blown onto the porous rubber coated with the aluminum silicate slurry so that the aluminum silicate slurry does not block the pores of the porous rubber, and the gas may be, for example, air, nitrogen, helium or argon. The pressure and temperature of the gas are not particularly limited as long as it is within a range in which the effect of the coating is maintained.

Drying of the porous rubber coated with the aluminum silicate slurry is, for example, 0.5 to 24 hours, 0.5 to 16 hours, or 80 to 160 ° C., 90 to 150 ° C., or 100 to 140 ° C. for the porous rubber coated with the aluminum silicate slurry. It can be carried out for 0.5 to 3 hours, there is an effect that all the moisture is removed within this range.

Coating the porous rubber by dipping in the aluminum silicate slurry; And aeration and drying the porous rubber coated with the aluminum silicate slurry may be repeated 1 to 10 times, or 1 to 5 times, respectively.

Firing of the aluminum silica-coated porous rubber may be carried out for 1 to 10 hours, or 1 to 5 hours at 1,000 to 2,000 ℃, 1,200 to 1,800 ℃, or 1,400 to 1,800 ℃, for example, porous within this range Alpha alumina is formed in the aluminum silicate support, thereby improving the strength and durability.

For example, the porous rubber may be burned at a temperature of 300 to 800 ° C., 350 to 700 ° C., or 400 to 660 ° C. upon firing, and in this case, the rubber does not remain in the porous aluminum silicate support.

The porous rubber is not particularly limited as long as it can be used in the form of a foam, but may be, for example, polyurethane. In this case, it is easy to form a large pore structure.

For example, the catalyst slurry may be prepared by diluting a metal oxide having a composition represented by Chemical Formula 1 in water.

[Formula 1]

The weight ratio of the metal oxide and water may be, for example, 10: 1 to 1:10, 8: 1 to 1: 8, or 5: 1 to 1: 5, and the metal oxide may be formed on the porous aluminum silicate support within this range. This has the effect of being coated as a whole.

The metal oxide may be in the form of a powder, for example, and may be prepared through a coprecipitation step, a filtration step, a drying step, and a firing step. As a specific example, the metal oxide may include (1) preparing a catalyst precursor solution including a divalent and trivalent cation metal precursor; (2) adding the catalyst precursor solution dropwise to an aqueous ammonia solution (pH 7 to 10) at 10 to 50 ° C .; (3) maintaining the pH of the aqueous ammonia solution in which the catalyst precursor solution is added dropwise, and coprecipitation by stirring for 30 minutes to 24 hours; (4) filtering the co-precipitate under reduced pressure to obtain a co-precipitate; (5) drying the obtained coprecipitate at 60 to 150 ° C. for 6 to 30 hours; And (6) heating to 400 to 800 ° C. at a heating rate of 0.5 to 10 ° C./min, and then holding and baking for 2 to 16 hours.

The metal precursor of step (1) is not particularly limited as long as it is conventionally used, but may be, for example, a metal salt including a divalent or trivalent cationic metal component, and specific examples of nitrate, ammonium salt, sulfate or chloride of the metal component. Can be. Maintaining the pH of step (3) may be carried out by, for example, dropwise addition of an additional aqueous ammonia solution simultaneously with the dropwise addition of the aqueous catalyst precursor solution.

The co-precipitated slurry including the precursor of the metal oxide may be prepared by coprecipitating a catalyst precursor having the same stoichiometric ratio as the metal oxide having the composition represented by Chemical Formula 1, for example.

The coprecipitation slurry is prepared by preparing a catalyst precursor solution including, for example, (1 ′) divalent and trivalent cationic metal precursors; (2 ') adding the catalyst precursor solution dropwise to an aqueous ammonia solution (pH 7 to 10) at 10 to 50 ° C; (3 ') maintaining the pH of the aqueous ammonia solution in which the catalyst precursor solution is added dropwise, and coprecipitation by stirring for 30 minutes to 24 hours; The coprecipitation solution (4 ′) may be prepared by filtration under reduced pressure to adjust the concentration of the coprecipitation slurry.

The metal precursor of step (1 ′) is not particularly limited as long as it is conventionally used, but may be, for example, a metal salt including a divalent or trivalent cationic metal component, and specific examples include nitrates, ammonium salts, sulfates, or the like. Chloride. The concentration of the catalyst precursor solution may be, for example, 1 to 70% by weight, 2 to 50% by weight, or 3 to 30% by weight, and when the coprecipitation is fired within this range, the effect of having a composition represented by Chemical Formula 1 may be obtained. have. Maintaining the pH of the step (3 ′) may be performed by, for example, adding an additional aqueous ammonia solution dropwise simultaneously with the dropwise addition of the catalyst precursor solution. The concentration of the coprecipitate slurry in step (4 ′) may be, for example, 10: 1 to 1:10, 8: 1 to 1: 8, or 5: 1 to 1: 5 based on the weight ratio of the coprecipitate and water, Within this range, the co-precipitate is coated on the porous aluminum silicate support as a whole.

The coprecipitation slurry may include, for example, 0.01 to 10% by weight, 0.01 to 8% by weight, or 0.01 to 5% by weight of a binder for increasing the viscosity. The binder is, for example, polyvinyl alcohol, starch, carboxymethylcellulose, dextrin, wax emulsion, polyethylene glycol, lignosulfonate , Methyl cellulose (methylcellulose), paraffin (paraffin) and polyacrylate (polyacrylate) may be one or more selected from the group consisting of, in this case there is an effect of improving the adhesion to the porous aluminum silicate support of the coprecipitation.

Coating the porous aluminum silicate support by immersing the catalyst slurry or the co-precipitate slurry may include, for example, immersing the porous aluminum silicate support in the catalyst slurry or the co-precipitate slurry. And aeration and drying the porous aluminum silicate support coated with the catalyst slurry or the co-precipitate slurry.

Immersion of the porous aluminum silicate support may be performed, for example, for a time when the catalyst slurry or the co-precipitate slurry can contact the entire area of the porous aluminum silicate support, and the time is not particularly limited, but is 0.1 to 30 minutes. , 0.1 to 10 minutes, or 0.1 to 1 minutes.

The aeration means that a gas is blown onto the porous aluminum silicate support coated with the catalyst slurry or the coprecipitation slurry so that the catalyst slurry or the coprecipitation slurry does not block the pores of the porous rubber. The gas may be, for example, air, nitrogen, Helium or argon. The pressure and temperature of the gas are not particularly limited as long as it is within a range in which the effect of the coating is maintained.

Drying of the porous aluminum silicate support coated with the catalyst slurry or the coprecipitation slurry is, for example, 0.5 to 24 hours, 0.5 to 16 hours, or 0.5 to 3 at 80 to 160 ° C, 90 to 150 ° C, or 100 to 140 ° C. It can be carried out for a time, and there is an effect that all moisture is removed within this range.

Immersing the porous aluminum silicate support in the catalyst slurry or the co-precipitate slurry; And aeration and drying the porous aluminum silicate support coated with the catalyst slurry or the co-precipitate slurry may be repeated 1 to 10 times or 1 to 5 times, respectively.

Firing of the porous aluminum silicate support coated with the catalyst slurry or the co-precipitate slurry is not particularly limited in the case of the firing method used when preparing the catalyst for the oxidative dehydrogenation reaction, for example, 0.5 to 10 ° C./min, 0.5 to 5 After heating up to 400 to 800 ° C, or 450 to 750 ° C at a temperature increase rate of 0.5 ° C to 3 ° C / min, it may be a method of baking for 2 to 16 hours or 3 to 9 hours.

Hereinafter, preferred examples are provided to aid in understanding the present invention, but the following examples are merely for exemplifying the present invention, and various changes and modifications within the scope and spirit of the present invention are apparent to those skilled in the art. It is natural that such variations and modifications fall within the scope of the appended claims.

EXAMPLE

Example 1

A slurry of kaolinite (Al ₂ Si ₂ O ₅ (OH) ₄ ) and maltodextrin was mixed in a 1: 1 weight ratio. The slurry was immersed in a 15 ppi (pores per inch) porous rubber of a polyurethane foam (foam), coated, and aerated so as not to block the pores and dried at 120 ℃ for at least 1 hour. The dried polyurethane foam was again immersed in the slurry, the process of aeration and drying was repeated four times, and then calcined at 1,600 ° C. for 2 hours to prepare a porous aluminum silicate support.

12 g of zinc chloride (ZnCl ₂ ) and 48 g of ferric chloride (FeCl ₃ ) were dissolved in distilled water to prepare a metal precursor solution. At this time, the molar ratio of the metal components included in the metal precursor solution was Zn: Fe = 1: 2. To the aqueous ammonia solution of pH 9 at room temperature, the prepared metal precursor solution and the aqueous ammonia solution to maintain pH 9 were simultaneously added dropwise, and stirred for 1 hour to coprecipitate. Thereafter, the coprecipitate was filtered under reduced pressure to obtain a coprecipitate, which was dried at 90 ° C. for 16 hours, and then heated up to 650 ° C. at 80 ° C. at a temperature increase rate of 1 ° C./min under an air atmosphere for 6 hours. The zinc-iron oxide (ZnFe ₂ O ₄ ) powder having a spinel structure was prepared, and the prepared metal oxide powder was pulverized to 250 μm or less and diluted in water at a weight ratio of 1: 1 to prepare a catalyst slurry.

The prepared porous aluminum silicate support was immersed in the prepared catalyst slurry, aerated, and dried at 120 ° C. for 1 hour. Thereafter, the dried porous aluminum silicate support was again immersed in the catalyst slurry, aerated and dried three times. The catalyst thus obtained was dried at 120 ° C. for 16 hours, heated to 80 ° C. at a temperature increase rate of 1 ° C./min at 80 ° C. under an air atmosphere, and then maintained for 4 hours to oxidative dehydrogenation reaction having a porous structure. Catalyst was prepared.

Example 2

When preparing the porous aluminum silicate support of Example 1, the same method as in Example 1 except for using a polyurethane foam of 10 ppi porous rubber instead of a polyurethane foam of 15 ppi (pores per inch) porous rubber Was carried out.

Example 3

When preparing the porous aluminum silicate support of Example 1, the same method as in Example 1 except for using a polyurethane foam of 45 ppi porous rubber instead of a polyurethane foam of 15 ppi (pores per inch) porous rubber Was carried out.

Example 4

In preparing the metal oxide of Example 1, 12 g of zinc chloride (ZnCl ₂ ) and 48 g of ferric chloride (FeCl ₃ ), 12 g of zinc chloride (ZnCl ₂ ), 42 g of iron nitrate (FeNO ₃ ), and aluminum chloride ( 6 g of AlCl ₃ ) was dissolved in distilled water, and a metal precursor solution was prepared in the same manner as in Example 1. At this time, the molar ratio of the metal components included in the metal precursor solution was Zn: Fe: Al = 1: 1.75: 0.25.

Example 5

In preparing the metal oxide of Example 1, instead of 12 g of zinc chloride (ZnCl ₂ ) and 48 g of ferric chloride (FeCl ₃ ), 18 g of magnesium nitrate (MgNO ₃ ) and 48 g of ferric chloride (FeCl ₃ ) were dissolved in distilled water. It was carried out in the same manner as in Example 1 except that the metal precursor solution was prepared. At this time, the molar ratio of the metal components included in the metal precursor solution was Mg: Fe = 1: 2.

Example 6

Dissolving the first embodiment in the manufacture of a metal oxide, zinc chloride (ZnCl ₂₎ 12 g and ferric chloride (FeCl ₃₎ 48 g instead of the manganese nitrate (MnNO ₃₎ 18 g, and ferric chloride (FeCl ₃₎ 48 g of distilled water It was carried out in the same manner as in Example 1 except that the metal precursor solution was prepared. At this time, the molar ratio of the metal components included in the metal precursor solution was Mn: Fe = 1: 2.

Example 7

In preparing the metal oxide and the catalyst slurry in Example 1, the coprecipitation liquid was filtered under reduced pressure to obtain a coprecipitated slurry, and the prepared porous aluminum silicate support was prepared in the prepared coprecipitated slurry when the catalyst for oxidative dehydrogenation reaction was prepared. The same procedure as in Example 1 was carried out except for immersion in.

Comparative Example 1

The same metal oxide as in Example 1 was prepared, but the coprecipitation solution was filtered under reduced pressure to obtain a coprecipitate, which was dried at 90 ° C. for 16 hours, and then the dried coprecipitate was pulverized to form a powder. After mixing and kneading maltodextrin, it is extruded using a screw-type rotor, cut to a size of 5 mm and dried to prepare a catalyst having a cylindrical pellet (cylindrical pellet) form, under an air atmosphere, The catalyst was heated to 80 ° C. at a temperature increase rate of 1 ° C./min to 650 ° C., and then maintained for 6 hours and calcined to prepare a catalyst in pellet form.

[Test Example]

Butadiene was prepared by the following method using the catalyst for oxidative dehydrogenation reaction prepared in Examples 1 to 7 and Comparative Example 1, and the results are shown in Table 1 below.

Butadiene manufacturing

As a reaction, a mixture of 1-butene, trans-2-butene and cis-2-butene and oxygen were used, and additionally nitrogen and steam were introduced together. As the reactor, a metal tubular fixed bed reactor was used. The proportion of reactants and gas hourly space velocity (GHSV) were set based on the butene mixture as described in Table 1 below. 10 cc of the catalysts prepared in Examples and Comparative Examples were charged to a fixed bed reactor, and steam was injected in the form of water, and vaporized at 150 ° C. using a vaporizer to be mixed with reactant butene mixture and oxygen to react with the reactor. It was allowed to flow into. After the reaction, the product was analyzed by gas chromatography (GC), and the conversion (X_butene), selectivity (S_1,3-butadiene, S_CO _x ) and yield of the butene mixture were measured by gas chromatography. Through, it was calculated according to the following formulas (1) to (3).

As shown in Table 1, in Examples 1 to 7 using the catalyst having a porous structure prepared according to the present invention, it was confirmed that the butene conversion, butadiene selectivity and yield are all excellent.

On the other hand, in the case of Comparative Example 1 using a pellet-type catalyst using a metal oxide of the same composition as in Example 1, butene conversion, butadiene selectivity and yield were all poor compared to Example 1.

[Reference Example]

When preparing butadiene of the test example, using the catalyst for the oxidative dehydrogenation reaction prepared in Example 1, the molar ratio of O ₂ , steam and N _{2 in} the reaction temperature (T) 360 ℃ 1: 1 with respect to 1 mol of butene, respectively. The reaction was performed at 4:12, and the results were 56.56 for X_butene, 90.55 for S_1,3-butadiene, 51.22 for Yield, and 7.46 for S_CO _x , respectively. From this, it was confirmed that the higher the content of steam compared to the butene mixture, the better the catalytic activity.

From this, the present inventors confirmed that when the porous catalyst was prepared using the porous rubber, high selectivity to the product could be maintained by alleviating the heat generated by reaction conditions and side reactions at high temperature and high pressure.

Claims

A catalyst for oxidative dehydrogenation reaction comprising a porous aluminum silicate support and a metal oxide having a composition represented by the following formula (1).

[Formula 1]

(A is at least one selected from the group consisting of divalent cation metals, and B is at least one selected from the group consisting of trivalent cation metals.)
The method of claim 1,

A is a catalyst for oxidative dehydrogenation reaction, characterized in that at least one selected from the group consisting of Cu, Ra, Ba, Sr, Ca, Be, Zn, Mg, Mn, Co and Fe (II).
The method of claim 1,

B is a catalyst for oxidative dehydrogenation reaction, characterized in that at least one selected from the group consisting of Al, Fe (III), Cr, Ga, In, Ti, La and Ce.
The method of claim 1,

Aluminum silicate of the porous aluminum silicate support is a catalyst for oxidative dehydrogenation reaction, characterized in that at least one selected from the group consisting of metal oxides, metal carbides, metal nitrides and aluminum hydride silicate.
The method of claim 1,

Catalyst for oxidative dehydrogenation reaction, characterized in that the aluminum silicate of the porous aluminum silicate support is a kaolin mineral.
The method of claim 1,

The porous aluminum silicate support is a catalyst for oxidative dehydrogenation, characterized in that it has a pore distribution of 1 to 500 ppi (pores per inch).
The method of claim 1,

The metal oxide is an oxidative dehydrogenation catalyst, characterized in that contained in 1 to 50% by weight relative to the oxidative dehydrogenation catalyst.
The method of claim 1,

The catalyst for oxidative dehydrogenation is oxidative dehydrogenation catalyst, characterized in that 1,3-butadiene selectivity is 80% or more.
Immersing and coating aluminum silicate in the porous rubber;

Firing the porous rubber coated with aluminum silicate;

Obtaining a porous aluminum silicate support;

Preparing a catalyst slurry including a metal oxide, or a coprecipitation slurry including a precursor of the metal oxide;

Coating the porous aluminum silicate support by dipping in the catalyst slurry or the co-precipitate slurry; And

A method for preparing a catalyst for oxidative dehydrogenation reaction, comprising calcining the porous aluminum silicate support coated with the catalyst slurry or the co-precipitate slurry.
The method of claim 9,

The dipping and coating the aluminum silicate on the porous rubber may include preparing an aluminum silicate slurry; Coating the porous rubber by immersing it in the aluminum silicate slurry; And aeration and drying the porous rubber coated with the aluminum silicate slurry, wherein the catalyst is prepared for oxidative dehydrogenation.
The method of claim 9,

Firing of the aluminum silica-coated porous rubber is a catalyst for producing an oxidative dehydrogenation reaction, characterized in that carried out for 1 to 4 hours at 1,200 to 2,000 ℃.
The method of claim 9,

The porous rubber is a method for producing a catalyst for the oxidative dehydrogenation reaction, characterized in that when firing at a temperature of 300 to 800 ℃.
The method of claim 9,

The porous rubber is a method for producing a catalyst for oxidative dehydrogenation reaction, characterized in that the polyurethane.
The method of claim 9,

The catalyst slurry is prepared by diluting a metal oxide having a composition represented by the following formula (1) in water.

[Formula 1]

(A is at least one selected from the group consisting of divalent cation metals, and B is at least one selected from the group consisting of trivalent cation metals.)
The method of claim 14,

The weight ratio of the metal oxide and water is 10: 1 to 1:10, characterized in that the catalyst for oxidative dehydrogenation reaction method.
The method of claim 9,

Immersing and coating the porous aluminum silicate support in the catalyst slurry or the co-precipitate slurry comprises immersing the porous aluminum silicate support in the catalyst slurry or the co-precipitate slurry; And aeration and drying the porous aluminum silicate support coated with the catalyst slurry or the co-precipitate slurry.
The method of claim 16,

Drying of the catalyst slurry or the porous aluminum silicate support coated with the co-precipitate slurry is carried out at 80 to 160 ℃ for 0.5 to 24 hours, characterized in that the catalyst for oxidative dehydrogenation reaction.
The method of claim 9,

The calcining of the porous aluminum silicate support coated with the catalyst slurry or the co-precipitate slurry is carried out by raising the temperature to 400 to 800 ° C. at a temperature increase rate of 0.5 to 10 ° C./min, and then maintaining the mixture for 2 to 16 hours. Method for producing catalyst for dehydrogenation reaction.