KR101340620B1 - Ferrite metal oxide catalysts prepared in the honeycomb, preparing method thereof and preparing method of 1,3-butadiene using the same - Google Patents

Abstract

The present invention relates to a ferrite metal oxide catalyst molded body in a honeycomb structure by spray pyrolysis and a production method thereof and, more specifically, to a catalyst molded body with a carrier or a monolith or a honeycomb coated with metal oxide catalyst powder prepared by spray pyrolysis from a metal oxide precursor containing iron as a main catalyst and magnesium, zinc, or manganese as a cocatalyst; a production method of a molded body which includes: a step of producing a molded body which is directly extruded in a honeycomb; and a method for preparing 1,3-butadiene through oxidative dehydrogenation of n-butene.

Description

Ferrite metal oxide catalysts prepared in the honeycomb, preparing method etc. and preparing method of 1,3-butadiene using the same}

The present invention relates to a molded article having a honeycomb structure of a ferrite metal oxide catalyst using a spray pyrolysis method and a method for manufacturing the same, and more particularly, a metal oxide precursor including iron as a main catalyst and magnesium, zinc or manganese as a cocatalyst. Method of preparing a catalyst compact or a compact in which the metal oxide catalyst powder prepared by the spray pyrolysis method was coated on a carrier or monolith or in a honeycomb form, and through the oxidative dehydrogenation of n -butene using the same. It relates to a method of manufacturing.

1,3-butadiene, the main raw material of tires, which is growing in demand due to the growth of the automobile market every year, is usually produced by naphtha cracking of saturated hydrocarbons. Pyrolysis of naphtha results in a mixture of methane, ethane, ethylene, acetylene, propane, propylene, butane, butene, 1,3-butanediene and higher hydrocarbons of C ₅ or higher. The production of 1,3-butadiene through the above pyrolysis method is responsible for most of the total 1,3-butadiene supply, but other olefins, which are by-products as described above, are also synthesized and the energy cost required for the pyrolysis process is increased. The method of producing 1,3-butadiene is very inefficient.

Another manufacturing method is a method of directly dehydrogenating n -butene. In this method, the yield of 1,3-butadiene is higher than that of naphtha pyrolysis, but because of the endothermic reaction, a large amount of energy is required to maintain a high temperature reaction temperature, and carbon deposits are formed on the surface of the catalyst to activate the catalyst. Its disadvantage is that it requires a lot of energy for catalyst regeneration.

Overcoming this drawback is the oxidative dehydrogenation method of producing 1,3-butadiene by directly reacting n -butene with oxygen. The oxidative dehydrogenation process is carried out in the presence of steam. The added steam acts as a heat transporter and promotes vaporization of organic deposits on the catalyst, thus inhibiting carbonization of the catalyst to prevent deactivation. In addition, n -butene reacts with oxygen to convert 1,3-butadiene and water, and the water produced therein is stable and thermodynamically advantageous, and can lower the reaction temperature. In other words, oxidative dehydrogenation is thermodynamically stable and has good selectivity to olefins at low temperatures. In general, in the oxidative dehydrogenation reaction, radicals generated at the beginning of the reaction are important reaction intermediates, desorb from the surface of the catalyst during the reaction, move to the gas part, and participate in the homogeneous catalytic reaction. However, the oxidative dehydrogenation method in which n -butene and oxygen react to produce 1,3-butadiene is accompanied by side reactions such as partial oxidation and complete oxidation because oxygen is used as a reactant, and thus, these side reactions are suppressed to prevent 1,3 Developing catalysts with high selectivity and yield of butadiene is a key technology. Suitable catalysts for the preparation of 1,3-butadiene in n -butene by the oxidative dehydrogenation method are bismuth-molybdenum based oxides [APV Soares, LK Kimitrov, MCA Oliveira, L. Hilaire, MF Portela, RK Grasselli, Appl. Catal. A: Gem., Vol. 253, 191 (2003); P. Boutry, R. Montarnal, J. Wrzyszcz, J. Catal., Vol. 13, p. 75 (1969) ( β- Bi ₂ Mo ₂ O ₉ , γ- Bi ₂ MoO ₆ ); JC, Jung, H. Kim, AS Choi, Y.-M. Chung, TJ Kim, SJ Lee, S.-H. Oh, IK Song, J. Mol. Catal. A: Chem., Vol. 259, p. 166 (2006) ( α- Bi ₂ Mo ₃ O ₁₂ , β- Bi ₂ Mo ₂ O ₉ , γ- Bi ₂ MoO ₆ ) and ferrite catalyst [HH Kung, B. Kundalkar, MC Kung, WH Cheng, J. Phys. Chem., 84, 382 (1980); JA Toledo-Antonio, N. Nava, M. Martinez, X. Bolhimi, Appl. Catal. A: Gen., vol. 234, p. 137 (2002); H. Lee, JC Jung, H. Kim, Y.-M. Chung, TJ Kim, SJ Lee, S.-H. Oh, YS Kim, IK Song, Catal. Commun., Vol. 9, p. 1137 (2008); H. Lee, JC Jung, H. Kim, Y.-M. Chung, TJ Kim, SJ Lee, S.-H. Oh, YS Kim, IK Song, Catal. Lett., Vol. 122, p. 281 (2008); Korean Patent No. 10-0847206; Korean Patent No. 10-0888143; US Patent Publication No. 2012-0059208 or based on bismuth-molybdenum multiple metal oxide catalyst further comprising iron (US Pat. No. 4,423,281; US Patent No. 4,336,409; US Patent No. 3,110,746.

Among these catalysts, the ferrite catalyst has a spinel crystal structure, and the yield of 1,3-butadiene varies greatly in the oxidative dehydrogenation of n -butene depending on the type of divalent cation. In particular, zinc, manganese and magnesium ferrite have been reported to have higher selectivity of 1,3-butadiene than other types of metal ferrites (US Pat. No. 3,334,152; US Patent No. 3,284,536; US Patent No. 3,303,234; US Patent No. 3,849,545; US Patent 4,658,074; US Patent No. 3,937,748; Republic of Korea Patent No. 10-0888143].

In carrying out the oxidative dehydrogenation of n -butene, all of the ferrite catalysts of the above patents are subjected to oxidative dehydrogenation of n -butene using a ferrite catalyst having a spinel structure prepared by a physical mixing and coprecipitation method. Coprecipitation method is a method commonly used in the preparation of a metal oxide catalyst, but the method of preparing 1,3-butadiene, 1) dissolving the precursor of the active metal, 2) alkaline coprecipitation in the solution in which the active metal precursor is dissolved Several steps such as adding a solution, 3) aging after coprecipitation, filtration and washing of the coprecipitated solution, 4) drying the obtained solid, and 5) calcining and activating the dried solid catalyst. There is a problem that wastewater is generated during the filtration and washing process after preparing the catalyst.

In addition, in the case of such a ferrite catalyst is generally applied to the process for producing 1,3-butadiene by producing a catalyst molded body through extrusion or tableting well-known to apply to a commercial process by oxidative dehydrogenation of n -butene, The molding caused problems such as a decrease in the contact area between the reactant and the outer surface of the catalyst and the generation of a differential pressure in the reactor due to the increase in the wear of the catalyst during the long time operation.

1. Republic of Korea Patent No. 10-0847206 2. Republic of Korea Patent No. 10-0888143 3. United States Patent Publication No. 2012-0059208 4. U.S. Patent 4,423,281 5. US Patent No. 4,336,409 6. US Patent No. 3,110,746 7. U.S. Patent No. 3,334,152 8. US Patent No. 3,284,536 9. US Patent No. 3,303,234 10. US Patent No. 3,849,545 11.U.S. Patent 4,658,074 12. US Patent No. 3,937,748

1.A.P.V. Soares, L.K. Kimitrov, M.C.A. Oliveira, L. Hilaire, M.F. Portela, R.K. Grasselli, Appl. Catal. A: Gem., Vol. 253, p. 191 (2003), 2.P. Boutry, R. Montarnal, J. Wrzyszcz, J. Catal., Vol. 13, p. 75 (1969) (β-Bi2Mo2O9, γ-Bi2MoO6) 3. J.C, Jung, H. Kim, A.S. Choi, Y.-M. Chung, T.J. Kim, S.J. Lee, S.-H. Oh, I.K. Song, J. Mol. Catal. A: Chem., Vol. 259, p. 166 (2006) (α-Bi2Mo3O12, β-Bi2Mo2O9, γ-Bi2MoO6) 4. H.H. Kung, B. Kundalkar, M.C. Kung, W.H. Cheng, J. Phys. Chem., 84, 382 (1980), J.A. Toledo-Antonio, N. Nava, M. Martinez, X. Bolhimi, Appl. Catal. A: Gen., vol. 234, p. 137 (2002) 5. H. Lee, J.C. Jung, H. Kim, Y.-M. Chung, T.J. Kim, S.J. Lee, S.-H. Oh, Y.S. Kim, I.K. Song, Catal. Commun., Vol. 9, p. 1137 (2008) 6, H. Lee, J. C. Jung, H. Kim, Y.-M. Chung, T.J. Kim, S.J. Lee, S.-H. Oh, Y.S. Kim, I.K. Song, Catal. Lett., Vol. 122, p. 281 (2008)

In order to overcome the drawbacks of the prior art, the present inventors can manufacture a ferrite catalyst having high activity in the oxidative dehydrogenation of n -butene, which can be prepared without going through several stages of the catalyst preparation process and has a large contact area between the reactants and the catalyst. As a result of the development, the active metal precursor is dissolved in water and spray pyrolysis method without coprecipitation step can produce ferrite catalyst for producing 1,3-butadiene more easily than conventional method, especially ferrite metal oxide catalyst. When the powder is manufactured into a honeycomb molded body by a specific method, the contact area with the reactants is larger than that of the conventional molded body, the wear loss is small, the manufacturing method is simple, and even with a small amount of catalyst, the selectivity is high. It has been found that 1,3-butadiene can be produced in yield to complete the present invention.

Accordingly, an object of the present invention is to provide a ferrite catalyst molded article having high selectivity and yield of 1,3-butadiene in oxidative dehydrogenation of n -butene.

Another object of the present invention is to provide a method for producing a ferrite catalyst molded article having high selectivity and yield of 1,3-butadiene by a simple process by using a spray pyrolysis method and manufacturing a honeycomb structure.

Another object of the present invention is to provide a method for producing 1,3-butadiene having high selectivity and yield of 1,3-butadiene using the catalyst compact.

In order to solve the above problems, the present invention comprises a first step of preparing a mixed solution containing a precursor of iron and divalent metal; A second step of preparing a ferrite-based metal oxide catalyst in powder form through spray pyrolysis of the mixed solution of the first step; A third step of preparing a catalyst mixture by uniformly mixing the ferrite-based metal oxide catalyst powder obtained in the second step with the organic binder, the inorganic binder and the water; It provides a method for producing a ferrite-based metal oxide catalyst molded body comprising the fourth step of preparing the catalyst mixture prepared in the third step into a honeycomb molded body.

In addition, the present invention is a catalyst composed of a powder form by spray pyrolysis of the mixed solution of the precursor of the bivalent metal and the precursor of iron having a molar ratio of one or more divalent metal and iron selected from magnesium, zinc and manganese 1: 1.8 to 2.2 Provided is a ferrite metal oxide catalyst molded body comprising a catalyst composition in which a powder, an organic binder, an inorganic binder, and water are mixed, and comprising a molded body having a honeycomb structure.

The honeycomb molded body may be formed by coating the catalyst mixture on a honeycomb carrier or monolith, or extruding the catalyst component of the catalyst mixture in a honeycomb form.

In another aspect, the present invention provides a method for producing 1,3-butadiene by oxidative dehydrogenation of n -butene in the presence of a honeycomb-type ferrite metal oxide catalyst molded body.

The catalyst molded body coated with the ferrite-based metal oxide catalyst component of the present invention as described above or directly extruded in the form of a honeycomb has a contact between the reactant and the catalyst as compared to the catalyst molded body prepared in the form of pellets or spheres using conventional extrusion or tableting methods. The area is large, and even when a small amount of catalyst is used, the selectivity of 1,3-butadiene is excellent and a high yield of 1,3-butadiene can be produced, which is suitable for mass production of 1,3-butadiene.

In addition, the catalyst molded body of the present invention can be applied not only to the oxidative dehydrogenation process for producing 1,3-butadiene, but also to the catalyst for the pseudo-oxidation or partial oxidation reaction, so that the economic effect is large.

In addition, since the catalyst prepared by the honeycomb structure is prepared by spray pyrolysis, the catalyst powder can be manufactured by a relatively simple synthetic route compared to the existing coprecipitation method, thereby shortening the manufacturing time and using economic coprecipitation solution. And it is advantageous to ensure reproducibility.

1 is a photograph of a catalyst molded body having a honeycomb structure coated with a zinc-iron ferrite metal oxide catalyst prepared in Example 1 according to the present invention.
2 is a photograph of a zinc-iron ferrite metal oxide honeycomb catalyst molded body prepared in Example 2 of the present invention.
3 is a photograph of a catalyst compact obtained by tableting and extruding the zinc-iron ferrite metal oxide catalysts prepared in Comparative Examples 1 and 2. FIG.
4 is a result of comparing the X-ray diffraction pattern results and the main components of the zinc-iron ferrite metal oxide catalyst prepared in Example 1.

Hereinafter, the present invention will be described in more detail as one embodiment.

The present invention relates to the preparation of a ferrite metal oxide catalyst powder and to the production of a catalyst molded body having a honeycomb structure using the catalyst powder and to the production of 1,3-butadiene using the same.

In the present invention, the ferrite metal oxide catalyst applied to the production of a honeycomb structure is preferably at least one divalent metal and iron precursor selected from magnesium, zinc and manganese dissolved in distilled water in a specific molar ratio, and pyrolysis at high temperature by gas spraying. The ferrite metal oxide catalyst molded body can be manufactured using the catalyst powder prepared by the above method.

In the first step of the process for producing a catalyst compact of the present invention, the divalent water precursor and iron precursor are distilled water such that the molar ratio of at least one divalent metal selected from magnesium, zinc and manganese and iron is 1: 1.8 to 2.2. It is dissolved in to prepare a mixed solution.

The precursor of the divalent metal used in the present invention may be a precursor used in the art, and is not particularly limited, but the iron precursor and the divalent metal precursor are selected from nitrate precursors, sulfate precursors, chloride precursors and carbonate precursors. It is preferable to use 1 or more types. More preferred specific examples of the iron precursor are iron nitrate (Iron (III) nitrate), the zinc precursor is zinc nitrate (Zinc (II) nitrate), the magnesium precursor is magnesium nitrate (Magnesium (II) nitrate), and manganese It is preferable to use manganese nitrate (Manganese (II) nitrate) as the precursor.

In addition, in order to increase the solubility of each precursor used in preparing the mixed solution of the first step, by maintaining the temperature of the solution 10 ~ 80 ℃, preferably 15 ~ 60 ℃, more preferably 25 ~ 40 ℃ It is desirable to allow the precursor to dissolve completely.

In the second step in the method for producing a catalyst molded body of the present invention, the ferrite-based metal oxide catalyst is prepared in powder form by spray pyrolysis of the mixed solution of the first step. Preferably, the mixed solution of the first step is gas sprayed. The catalyst powder is prepared by pyrolysis at a high temperature of 600 to 1200 ° C. while spraying into a high temperature reactor using air of 1 to 7 atm in a manner.

The catalyst powder is prepared by a so-called spray pyrolysis method in which the mixed solution of the first stage is introduced into the spray pyrolysis apparatus in the second stage to prepare the catalyst powder by the gas spray method. 1 to 7 atm, more preferably 1.5 to 5 atm, most preferably 2 to 4 atm, and the internal temperature of the spray pyrolysis apparatus is 600 to 1200 ° C, preferably 650 to 1000 ° C, more preferably By maintaining the temperature at 700 to 900 ° C, a ferrite catalyst powder obtained by uniformly dispersing an active metal component composed of a divalent metal and iron can be obtained. If the internal temperature of the spray pyrolysis apparatus is too low, there may be a problem that the desired catalyst crystal structure cannot be obtained. If the temperature is too high, the catalyst may melt to form a high melt, or the crystal structure of the catalyst may change. It is desirable to maintain. At this time, it is better to maintain the pressure in consideration of the correlation with temperature. If the pressure is too low, it is difficult to form a catalyst of desirable physical properties, and if it is too high, the process is difficult and economically disadvantageous, but due to high melt formation or deformation of crystal structure. This can result in lower catalyst performance.

As such, the catalyst is prepared in a powder form in which the mixed solution of the precursor of the divalent metal and the precursor of iron is spray pyrolyzed so that the molar ratio of at least one divalent metal selected from magnesium, zinc and manganese and iron is 1: 1.8 to 2.2. In this case, the catalyst may be prepared from a ferrite metal oxide catalyst powder having a surface area of 20 to 100 m 2 / g and a pore volume of 0.18 to 1 cm 3 / g. At this time, if the surface area and pore volume of the catalyst is too small, the contact area of the n-butene and the catalyst is small, and the conversion rate is low.

Ferrite metal oxide catalyst powder according to the invention as described above is that only its n-1, 3-butadiene as a catalyst for butene from n-a good conversion rate of 75% to 90% of butene, is 84 to 90%, 1, Selectivity of 3-butadiene is 72 to 90%, preferably 80 to 90%.

The ferrite metal oxide catalyst of the present invention has a high durability, long life and high reaction activity without the support of the powdered catalyst itself.

However, the present invention is characterized in that it does not use a powdery ferrite metal oxide catalyst as it is, and is made of a molded body having a honeycomb structure having a specific structure.

In the third step of preparing the catalyst compact of the present invention, the catalyst mixture is prepared by uniformly mixing the ferrite-based metal oxide catalyst powder obtained in the second step with an inorganic binder, an organic binder and water.

The organic binder used in the third step may be used in the art, and is not particularly limited, but it is preferable to use at least one selected from methyl cellulose, ethylene glycol, polyol, food oil or organic fatty acid. For example, it is preferable to use hydroxy methyl cellulose (Hydroxy methyl cellulose) or polyvinyl alcohol (Polyvinyl alcohol) as the organic binder. In addition, the inorganic binder can be used in the art, but is not particularly limited, it is preferable to use at least one selected from solid silica, solid alumina, solid silica-alumina, silica sol, alumina sol, water glass. For example, as an inorganic binder, it is preferable to use fumed silica, silica sol, silica solution, boehmite or alumina sol.

According to the present invention, when the catalyst mixture mixed in the third step is typically coated on a honeycomb structure to prepare a molded body, the mixing ratio of the prepared metal oxide catalyst powder, organic binder, inorganic binder and water is 1.0: 0.01 by weight ratio. 0.1: 0.02 to 0.2: 1.0 to 3.0, preferably 1.0: 0.02 to 0.08: 0.04 to 0.15: 1.3 to 2.5, more preferably 1.0: 0.02 to 0.07: 0.06 to 0.12: 1.5 to 2.2 .

The catalyst mixture prepared in the third step thus prepared is prepared in a honeycomb molded body in the fourth step.

In the present invention, the honeycomb molded body may be prepared by coating the catalyst mixture on a honeycomb carrier or monolith, or by directly extruding the catalyst component of the catalyst mixture in a honeycomb form.

Where the honeycomb carrier or monolith is coated uniformly on a honeycomb having a cell number of 100 to 800, preferably 150 to 700, more preferably 200 to 600 CPSI (Cell per square inch), 100-160 ° C, Preferably it dried at 140 degreeC. If the drying temperature is less than 100 ° C., there may be a problem that the coated solution flows out, resulting in uneven catalyst dispersity on the surface of the honeycomb. After drying the coating solution, a heat treatment was performed at 400 to 650 ° C. using an electric furnace to prepare a honeycomb coated with ferrite-based metal oxides. If the heat treatment temperature is less than 400 ℃ organic binder is not completely removed, if it exceeds 650 ℃ change in the crystal structure of the coated catalyst may be problematic, it is preferable to maintain the temperature within the above range.

If the number of cells of the honeycomb structure is less than 100 CPSI, the contact area of the catalyst is too low to lower the reaction activity, and if it is larger than 800 CPSI, there is a problem that the reaction pressure increases during the oxidative dehydrogenation of n -butene.

According to the invention, the catalyst mixture comprises extrusion molding the honeycomb structure directly.

In order to directly extrude the ferrite-based metal oxide catalyst mixture into a honeycomb structure, the ratio of the metal oxide catalyst powder, the organic binder, the inorganic binder, and the water is in a weight ratio of 1.0: 0.01 to 0.1: 0.02 to 0.2: 0.02 to 0.2, preferably 1.0: 0.01 to 0.06: 0.03 to 0.1: 0.03 to 0.1, more preferably 1.0: 0.02 to 0.04: 0.04 to 0.07: 0.04 to 0.06 is preferably mixed. The catalyst mixture may be extruded in honeycomb form using an extruder equipped with a honeycomb extrusion mold. Extruded honeycomb molded body is subjected to a drying process, the drying is naturally dried for 24 hours at 10 ~ 40 ℃, preferably 15 ~ 35 ℃, more preferably 20 ~ 25 ℃, preferably at 110 ℃ 24 After further drying for an additional time, the honeycomb molded body coated with ferrite-based metal oxide may be manufactured by heat-treating at 400 to 650 ° C. in an electric furnace. If the heat treatment temperature is less than 400 ℃ organic binder is not completely removed, if it exceeds 650 ℃ change in the crystal structure of the coated catalyst may be problematic, it is preferable to maintain the temperature within the above range.

The present invention is a honeycomb-structured catalyst molded body prepared as described above, wherein a mixture of the precursor of iron and the precursor of the divalent metal having a molar ratio of at least one divalent metal selected from magnesium, zinc and manganese is from 1: 1.8 to 2.2 The solution includes a catalyst powder composed of powder by spray pyrolysis and a catalyst mixture in which an organic binder, an inorganic binder, and water are mixed, and a ferrite metal oxide catalyst molded body, characterized in that it is formed of a honeycomb molded body.

Here, the honeycomb molded body may be formed by coating the catalyst mixture on a carrier or monolith of the honeycomb structure, or extruding the catalyst mixture in a honeycomb form. In this case, the honeycomb molded body has a cell number of 50 to 950, preferably 200 to 600 200 CPSI (Cell per square inch).

On the other hand, the above-described ferrite metal oxide catalyst molded body prepared according to the present invention is used as a catalyst for the production of 1,3-butadiene, the present invention is n -butene in the presence of the ferrite metal oxide catalyst molded body of the honeycomb structure as described above. Oxidative dehydrogenation to produce 1,3-butadiene.

The reactant for the reaction in the oxidative dehydrogenation of n -butene used in the method for producing 1,3-butadiene using the catalyst molded body of the present invention is a mixture of air and steam in addition to n -butene. N -butene is preferably used in a C ₄ mixture having a content of 50 to 75% by weight. Herein, the C ₄ mixture may include 0.5 to 25% by weight of n -butane and include 0.5 to 10% by weight of impurities except n -butene and n -butane. The mixing ratio of the reactants is n -butene: air: steam = 4 to 12% by volume: 15 to 45% by volume: 45 to 80% by volume is more preferable, more preferably 5 to 9% by volume: 16 to 30% by volume: 60 It is recommended to use the volume ratio of ~ 78% by volume. The air refers to general air containing 79% by volume of nitrogen and 21% by volume of oxygen. When the mixing ratio of the reactants is outside the above range, the reaction activity may decrease or the by-products may increase. The injection amount of n -butene and air may be controlled by a mass flow controller, and the injection amount of steam may be controlled by a microflow pump.

The injection amount of the reactant may be injected at a space velocity of 150 to 700 h ⁻¹ based on n -butene (GHSV, Gas Hourly Space Velocity), preferably at a space velocity of 175 to 600 h ⁻¹ , and more preferably. Preferably it is injected at a space velocity of 200 ~ 500 h ^-1 . If the space velocity is less than 150 h ^-1, the amount of the product per unit time may be low, and there may be a problem in profitability. If the space velocity exceeds 700 h ^{- 1} , the time for n -butene to react with the catalyst is short, resulting in an increase in unreacted product. The yield of 1,3-butadiene can be lowered.

And the oxidative dehydrogenation reaction is preferably performed under the temperature range of 300 ~ 500 ℃, preferably 330 ~ 470 ℃, more preferably 350 ~ 450 ℃ temperature range, when the reaction temperature is less than 350 ℃ If the temperature is too low to perform, and the catalyst may be that not active and not become a problem, the partial oxidation reaction well, reaction at temperatures in excess of 500 ℃ C ₁ Maintaining temperature in the above range is preferable because there may be a problem of decomposition products or complete oxidation of C ₃ .

The honeycomb molded body of the ferrite metal oxide catalyst prepared by the spray pyrolysis method of the present invention has a simpler manufacturing method than the existing ferrite oxide catalyst for producing 1,3-butadiene, which is advantageous in securing reproducibility, and has excellent reaction activity and selectivity. 1,3-butadiene can be produced in high yield.

In the manufacture of 1,3-butadiene by using the ferrite metal oxide catalyst molded article prepared by the above spray pyrolysis method, n - in the oxidative dehydrogenation reaction of n-butene is n - butene in addition to a mixed gas of air and steam (Steam) In addition, n -butene is used in a C ₄ mixture having a content of 50 to 75% by weight. The C ₄ mixture contains 0.5-25 wt% of n -butane and contains 0.5-10 wt% of impurities except n -butene and n -butane. The mixing ratio of the reactants is n -butene: air: steam = 4 to 12% by volume: 15 to 45% by volume: 45 to 80% by volume is preferred, more preferably 5 to 9% by volume: 16 to 30% by volume: 60 It is recommended to use the volume ratio of ~ 78% by volume. The air refers to general air containing 79% by volume of nitrogen and 21% by volume of oxygen. When the mixing ratio of the reactants is outside the above range, the reaction activity may decrease or the by-products may increase. The injection amount of n -butene and air can be controlled by a mass flow controller, and the injection amount of steam is controlled by a microflow pump.

The injection amount of the reactant may be injected at a space velocity of 150 to 700 h ⁻¹ based on n -butene (GHSV, Gas Hourly Space Velocity), preferably at a space velocity of 175 to 600 h ⁻¹ , and more preferably. Preferably it is injected at a space velocity of 200 ~ 500 h ^-1 . If the space velocity is less than 150 h ^-1 , there may be a problem in profitability due to the small amount of product per unit time, and if it exceeds 700 h ^-1 , the time for n -butene to react with the catalyst is short, resulting in an increase in unreacted substances. The yield of, 3-butadiene may be lowered.

And the oxidative dehydrogenation reaction is preferably performed under the temperature range of 300 ~ 500 ℃, preferably 330 ~ 470 ℃, more preferably 350 ~ 450 ℃ temperature range, when the reaction temperature is less than 350 ℃ If the temperature is too low to perform, and the catalyst may be that not active and not become a problem, the partial oxidation reaction well, reaction at temperatures in excess of 500 ℃ C ₁ Maintaining the temperature in the above range may be a problem because decomposition products or complete oxidation of C ₃ may occur.

The honeycomb structured ferrite metal oxide catalyst molded body according to the present invention has a simpler manufacturing method than the existing ferrite oxide catalyst for producing 1,3-butadiene, which is advantageous for securing reproducibility, and the reaction activity and selection due to the structural characteristics and the superiority of the catalyst component. It is excellent in the degree and can produce 1, 3- butadiene in a high yield.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.

Example 1 Honeycomb Coating of Zinc-iron Metal Oxide Catalysts

3213.3 g of iron nitrate (Fe (NO ₃ ) ₃ · 9H ₂ O, SAMCHUN, 98%) and 1152.6 g of zinc nitrate (Zn (NO ₃ ) ₂ · 6H ₂ O, SAMCHUN, 98%) were added to 4,500 g of distilled water. The mixture was sufficiently stirred for 2 hours at 25 ° C. to prepare a mixed solution containing zinc / iron at a 1.0 / 2.0 molar ratio. Thereafter, the prepared mixed solution was thermally decomposed by spraying into the reactor of the spray pyrolysis apparatus using air as a transport gas at 0.75 L per hour. At this time, the spray pyrolysis conditions were the zinc-iron ferrite metal oxide catalyst was prepared by operating the air pressure of 3 atm, reactor temperature of 750 ℃. 1,000 g of the zinc-iron catalyst prepared, 93.7 g of boehmite (AlOOH, SASOL), 2,000 g of water, and 31.3 g of acetic acid (SAMCHUN, 98%) were uniformly mixed at room temperature, followed by 600 CPSI (Cell per square inch). The honeycomb with the cell number was uniformly coated and dried at 140 ° C. After drying the coating solution, a heat treatment was performed at 550 ° C. for 4 hours using an electric furnace to prepare a honeycomb molded body coated with a ferritic metal oxide.

1 is a photograph of a honeycomb catalyst coated with a zinc-iron ferrite metal oxide catalyst prepared in Example 1. FIG.

Example 2 Honeycomb Extrusion of Zinc-iron Metal Oxide Catalysts

1,000 g of the zinc-iron catalyst prepared in Example 1, hydroxy methyl cellulose (Hydroxymethyl cellulose, MC-40H, Samsung Fine Chemical) 22.6 g, silica sol, Dupont, AS-40, 40 wt% 131.57 g and 45.2 g of water were uniformly mixed and then the honeycomb having a cell count of 200 CPSI was extruded using a single-screw extruder equipped with a honeycomb type nozzle. After drying for 24 hours at 25 ℃, dried for 24 hours at 110 ℃, and heat treatment for 4 hours at 550 ℃ using an electric furnace to prepare a honeycomb molded body.

Figure 2 is a photograph of the zinc-iron ferrite metal oxide honeycomb catalyst molded body prepared in Example 2.

Comparative Example 1 Preparation of Extruded Zinc-iron Metal Oxide Catalysts

500 g of zinc-iron catalyst prepared in Example 1, 11.3 g of hydroxy methylcellulose, 65.8 g of silica sol, and 32.25 g of water were uniformly mixed at room temperature, and then a twin screw form having a diameter of 3 mm. The extruder was used to extrude cylindrical pellets 3 mm in diameter and 3 to 5 mm in height. The extruded zinc-iron catalyst is naturally dried at room temperature for 24 hours and then dried at 110 ° C. for 24 hours, and then put in an electric furnace and calcined at 550 ° C. for 4 hours to extruded zinc-like catalyst as shown in FIG. 3 (Comparative Example 1). Iron pellet shaped bodies were prepared.

Comparative Example 2 Preparation of Tableted Zinc-Iron Metal Oxide Catalyst

500 g of zinc-iron metal oxide catalyst prepared in Example 1 and 10.2 g of stearic acid (Stearic acid, SAMCHUN, 95%) were uniformly mixed, and then, using a tablet molding machine, a cylindrical pellet having a diameter of 3 mm and a height of 3 mm was used. Tableting. The compressed zinc-iron catalyst was put into an electric furnace and calcined at 550 ° C. for 4 hours to prepare a compressed zinc-iron pellet molded body as shown in FIG. 3 (Comparative Example 2).

The amount of catalyst powder used and the contact area with the reactants of the catalyst compacts prepared in Examples 1 and 2 and Comparative Examples 1 and 2, respectively, were calculated and shown in Table 1 below.

division Catalyst Powder Usage
(g / L) ^* Per 1 liter of catalyst compact
Contact area (cm ² / L) ^** Relative value ^*** Example 1 120 27,413 196 Example 2 700 18,600 133 Comparative Example 1 1,500 13,975 100 Comparative Example 2 2,100 13,975 100

^* Catalyst Powder Usage (g) / Catalyst Molded Body Volume (L)

^** Catalyst molded body exposed surface area (cm ² ) / catalyst molded body volume (L)

^*** Comparative comparison of the contact area per liter of catalyst of Comparative Example 1 to 100

Test Example: X-ray diffraction analysis (XRD) test of the prepared ferrite metal oxide catalyst

In order to confirm the crystal structure of the prepared catalyst was analyzed by X-ray diffractometer (Siemens D-5005, Cukα = 1.5418 Å) using Ni-filter at 40 kV and 40 mA conditions, the analysis results are shown in FIG. . The zinc-iron ferrite catalyst prepared by spray pyrolysis in Example 1 shown in FIG. 4 was mostly a spinel structure [ZnFe ₂ O ₄ , JCPDS Card # 65-3111], and the crystal structure of α- Fe ₂ O ₃ [JCPDS Card # 33-0664] were mixed.

Experimental Example: n -butene oxidative dehydrogenation experiment

The catalyst prepared in Examples and Comparative Examples was charged to a space velocity (GHSV) of 250 h ⁻¹ in a stainless steel reactor, and activated at 370 ° C. while flowing air. Using a mass flow controller at 370 ° C., 1,3-butadiene was subjected to an oxidative dehydrogenation reaction using a mixed gas having a mixing ratio of n -butene: air: steam at 10% by volume: 40% by volume: 50% by volume. Was prepared. The reactor was designed to supply steam to the reactants using an initial micro-quantitative pump but to set the preheating section and vaporize it with steam before being injected into the fixed bed reactor. The n -butene used a C ₄ mixture as shown in Table 2 below.

The catalyst activity was analyzed by sending the product of the oxidative dehydrogenation reaction to a gas chromatograph equipped with a thermal conductivity detector and a flame ion detector from 10 minutes after the reactants passed through the catalyst bed. The conversion of n -butene, 1,3-butadiene selectivity, and 1,3-butadiene yield are shown in Table 3. n -butene conversion, 1,3-butadiene selectivity, and 1,3-butadiene yield were calculated using Equations 1 to 3, respectively.

Equation 1: n -butene conversion

Equation 2: 1,3-butadiene selectivity

Equation 3: 1,3-butadiene yield

The composition of the C ₄ mixture used as a reactant is shown in Table 2 below.

Furtherance weight % C ₁ to C ₃ 0.4 iso -butane 1.2 n -butane 23.3 1-butene 40.9 trans -2-butene 23.3 cis -2-butene 10.9 Sum 100

As shown in Table 3 below, when the n -butene oxidative dehydrogenation reaction was carried out using the prepared catalyst molded body, a conversion rate of 71.5%, 1, The 3-butadiene selectivity is 88.4%, which shows high activity due to the large contact area with the reactants even when using a small amount of catalyst compared to pellet-type extrusion or compressed moldings, thereby stably producing 1,3-butadiene. It is expected that a single process can be secured.

division Conversion Rate
(%) 1,3-butadiene selectivity
(%) 1,3-butadiene yield
(%) Example 1 71.5 88.4 66.3 Example 2 75.0 85.0 63.8 Comparative Example 1 65.5 76.0 49.8 Comparative Example 2 70.0 77.5 54.3 [ n -butene oxidative dehydrogenation reaction condition]
Reaction temperature: 370 ℃
Response time: 7 h
Space Speed: 250 h ^-1
Reactant content (% by volume): n -butene / air / steam-10/40/50

Through the above examples, comparative examples, test examples and experimental examples, the catalyst molded body of the honeycomb structure manufactured using the ferrite metal oxide catalyst powder prepared by the spray pyrolysis method of the present invention is a catalyst prepared by the conventional coprecipitation method or other It was confirmed that it is an excellent catalyst having a high 1,3-butadiene selectivity and yield compared to the tablet press of the form.

In addition, when the metal oxide catalyst powder prepared by the spray pyrolysis method of the present invention is prepared with a honeycomb catalyst formed body, the production method is simpler than the conventional coprecipitation method, and there is no additional treatment process, so it is economical and easy to secure catalyst reproducibility. It is expected to secure a single process that can stably produce 1,3-butadiene.

The honeycomb structured ferrite metal oxide catalyst molded body produced according to the present invention is used as a catalyst in the oxidative dehydrogenation process for producing 1,3-butadiene, and more specifically for producing 1,3-butadiene.

In addition, the catalyst molded body of the present invention can be applied as a catalyst for pseudo oxidation or partial oxidation reaction.

Claims (14)

A first step of preparing a mixed solution containing a precursor of iron and divalent metal;
A second step of preparing a ferrite-based metal oxide catalyst in powder form through spray pyrolysis of the mixed solution of the first step;
A third step of preparing a catalyst mixture by uniformly mixing the ferrite-based metal oxide catalyst powder obtained in the second step with the organic binder, the inorganic binder and the water;
Comprising a fourth step of preparing the catalyst mixture prepared in the third step in a honeycomb molded body,
The honeycomb molded body in the fourth stage is a catalyst mixture of the third stage, and the ratio of the metal oxide catalyst powder, the organic binder, the inorganic binder, and the water obtained in the second stage is 1.0: 0.01 to 0.1: 0.02 to 0.2: 1.0 to 3.0. The catalyst mixture obtained by mixing at a weight ratio of was coated on a honeycomb carrier or monolith, or the ratio of the metal oxide catalyst powder, organic binder, inorganic binder and water obtained in the second step was 1.0 as the catalyst mixture of the third step. A method for producing a ferrite metal oxide catalyst shaped article, characterized in that it is produced by extrusion molding using a catalyst mixture obtained by mixing at a weight ratio of 0.01 to 0.1: 0.02 to 0.2: 0.02 to 0.2.
The method of claim 1, wherein the precursor of the divalent metal and the precursor of iron are each one or more selected from nitrate precursors, sulfate precursors, chloride precursors, and carbonate precursors. .
The method of claim 1, wherein the divalent metal is at least one selected from magnesium, zinc, and manganese.
The method of claim 1, wherein the molar ratio of divalent metal and iron in the mixed solution is 1: 1.8 to 2.2 molar ratio.
The method of claim 1, wherein the temperature of the solution is maintained at 15 to 60 ° C. when the mixed solution is prepared in the first step.
delete delete delete A mixed solution of the precursor of the bivalent metal and the precursor of iron, prepared according to claim 1 and having a molar ratio of one or more divalent metals selected from magnesium, zinc, and manganese 1: 1.8 to 2.2, is spray pyrolyzed into powder form. The catalyst powder comprises an organic binder, an inorganic binder, and a catalyst mixture in which water is mixed. The catalyst powder is composed of a honeycomb molded body, and the ratio of the catalyst powder, the organic binder, the inorganic binder, and water is 1.0: 0.01 to 0.1: 0.02. The catalyst mixture obtained by mixing at a weight ratio of 0.2 to 1.0 to 3.0 is coated on a honeycomb carrier or monolith, or the ratio of the catalyst powder, organic binder, inorganic binder and water is 1.0: 0.01 to 0.1: 0.02 to 0.2: 0.02. A ferrite metal oxide catalyst formed body, characterized in that the catalyst mixture obtained by mixing at a weight ratio of ˜0.2 is extruded.
delete A method for producing 1,3-butadiene prepared by oxidative dehydrogenation of n -butene in the presence of a ferrite metal oxide catalyst shaped body according to claim 9.
The reactant of the oxidative dehydrogenation reaction comprises n -butene, air and steam, and the mixing ratio of the reactants is n -butene: air: steam = 4-12 vol%: 15-45 Volume%: 1,3-butadiene production method characterized in that 45 to 80% by volume.
The method for preparing 1,3-butadiene according to claim 12, wherein in the oxidative dehydrogenation reaction, the reactant is injected at a space velocity of 150 to 700 h ⁻¹ based on n -butene.
The method of claim 12, wherein the oxidative dehydrogenation reaction is performed at a temperature in a range of 300 to 500 ° C. 13.

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