KR20140082869A - Mixed Phases Manganese Ferrite Honeycomb Type Catalyst, Method of Preparing Thereof and Method of Preparing 1,3-Butadiene Using Thereof - Google Patents

Abstract

The present invention relates to a method for producing a mixed manganese ferrite honeycomb-type catalyst and to a method for producing 1,3-butadiene using the same as a catalyst. In particular, the present invention relates to a method for producing a catalyst by extruding and molding mixed manganese ferrite, which is produced through a co-precipitation technique, in a honeycomb form using a binder and to a method for producing 1,3-butadiene through an oxidative dehydrogenation reaction by directly using normal-butene as a reactant on the produced catalyst. The mixed manganese ferrite honeycomb-type catalyst produced in the present invention can be produced through a simple producing method, and the heating thereof can be easily controlled during an oxidant dehydrogenation reaction, so that 1,3-butadien can be produced from normal-butene at a high yield.

Description

TECHNICAL FIELD The present invention relates to a mixed manganese ferrite honeycomb catalyst, a method for producing the same, and a method for producing 1,3-butadiene using the same. BACKGROUND ART [0002] Mixed Phases Manganese Ferrite Honeycomb Type Catalyst,

 The present invention relates to a mixed manganese ferrite honeycomb catalyst, a process for producing the same, and a process for producing 1,3-butadiene using the same, and more particularly, to a process for producing 1,3-butadiene by a co- Butadiene as a reactant, and a method for producing 1,3-butadiene through an oxidative dehydrogenation reaction using n-butene as a reactant on the catalyst.

Oxidative dehydrogenation of n-butene (1-butene, trans-2-butene, cis-2-butene) to produce 1,3-butadiene, whose demand is increasing in the petrochemical market, And oxygen react with each other to produce 1,3-butadiene and water. As a result, stable water is produced as a product, which is not only thermodynamically favorable but also can lower the reaction temperature.

However, in the oxidative dehydrogenation reaction, since oxygen is used as a reactant, many side reactions such as a complete oxidation reaction are expected. Therefore, it is the most important technology to suppress the side reaction and to develop a catalyst having a high selectivity for 1,3-butadiene .

One of the problems with the oxidative dehydrogenation reaction of n-butene is that the yield of 1,3-butadiene is lowered when a certain amount of n-butane is contained in the reactants [L. Welch, L.J. Croce, H.F. Christmann, Hydrocarbon Processing, p. 131 (1978)]. Therefore, in the above-mentioned prior arts, only the pure n-butene (1-butene or 2-butene) is used as the reactant, and the oxidative dehydrogenation reaction is performed to obviate this problem. In the commercial process using the actual ferrite catalyst The reactant from which normal butane has been removed is used. In the literatures or patents relating to the catalyst and process for producing 1,3-butadiene from n-butene through the oxidative dehydrogenation reaction and the processes based thereon, pure pure n-butene is used as a reactant, An additional separation step of extracting butene from the C4 mixture is required, which inevitably leads to a significant decrease in economy.

As the catalysts used in the oxidative dehydrogenation reaction of n-butene, there are known ferrite catalysts, tin catalysts, and bismuth molybdate catalysts.

Among them, the ferrite catalysts differ in catalytic activity depending on the kind of metal constituting the divalent cation site of the spinel structure. Among them, zinc ferrite, magnesium ferrite and manganese ferrite are excellent for the oxidative dehydrogenation reaction of n-butene. And zinc ferrite has been reported to have higher 1,3-butadiene selectivity than ferrite catalysts of other metals [F.-Y. Qiu, L.-T. Weng, E. Shang, P. Ruiz, B. Delmon, Appl. Catal., 51, 235 (1989)].

Several patents and documents have reported utilization of zinc ferrite-based catalysts in the oxidative dehydrogenation reaction of n-butene, and in order to increase utilization and lifetime of the zinc ferrite catalyst for the oxidative dehydrogenation reaction, And 1,3-butadiene can be obtained over a long period of time at higher yields through pre-treatment and post-treatment [F.-Y. Qiu, L.-T. Weng, E. Shang, P. Ruiz, B. Delmon, Appl. Catal., Vol. 51, p. 235 (1989) / L.J. Crose, L. Bajars, M. Gabliks, U.S. Patent No. 3,743,683 (1973) / E.J. Miklas, U.S. Patent No. 3,849,545 (1974) / J.R. Baker, U.S. Pat. No. 3,951,869 (1976)]. In addition to the above zinc ferrite catalysts, the use of manganese ferrite catalysts for the oxidative dehydrogenation reaction of n-butene has also been reported in several patents.

In the case of performing the oxidative dehydrogenation reaction of n-butene, the zinc ferrite catalyst has a low reproducibility such as addition of metal oxide and acid treatment to prevent deactivation, complicated post-treatment is required, In order to exist as a pure spinel phase, it is necessary to maintain a high temperature at the time of coprecipitation, and the yield of 1,3-butadiene is somewhat lower than that of zinc ferrite.

Korean Patent No. 888143 discloses a technique for producing a mixed manganese ferrite catalyst having a simple catalyst production process and high catalytic preparation reproducibility but exhibiting high activity in the oxidative dehydrogenation reaction of n-butene. However, Is not disclosed.

Accordingly, an object of the present invention is to provide a catalyst capable of suppressing side reactions through exothermic control and capable of producing 1,3-butadiene in a high yield, which is excellent in catalytic activity and has a simple process of producing a mixed manganese ferrite honeycomb And a method for producing the catalyst.

Another object of the present invention is to provide a process for producing 1,3-butadiene in a high yield by performing an oxidative dehydrogenation reaction on a catalyst prepared by the above production method directly using a low-cost C4 mixture as a reactant without a separate separation process .

In order to accomplish the object of the present invention, one aspect of the present invention is a method for producing a mixed manganese ferrite honeycomb catalyst,

a) preparing a precursor aqueous solution having a manganese precursor and an iron precursor and mixing them in a basic solution while mixing them; b) washing and filtering the coprecipitated solution to obtain a solid sample and drying; c) drying the dried solid sample, Mixing dough by adjusting the weight ratio of the binder, organic binder, distilled water and acid to 1: 0.05-0.5: 0.01-0.1: 0.1-1.5: 0.005-0.15 and then kneading to obtain a dough; d) Extruding the dough into an extrudate having through-pores having a regular structure; And e) heat treating the extrudate.

According to another aspect of the present invention, there is provided a method for producing 1,3-butadiene, which is characterized in that the through pore cross-section is polygonal or circular and the through pores are pores penetrating through the long axis of the honeycomb- Manganese ferrite honeycomb catalyst.

According to another aspect of the present invention, there is provided a process for preparing 1,3-butadiene comprising the steps of: a) providing a mixture of C4 mixture, air and steam as a reactant; b) an oxidative dehydrogenation reaction step wherein the reactant is passed through a catalyst bed in which the catalyst of the present invention is immobilized; And c) obtaining 1,3-butadiene.

According to another aspect of the present invention, there is provided a process for preparing 1,3-butadiene comprising the steps of: a) providing a mixture of C4 mixture, air and steam as a reactant; b) an oxidative dehydrogenation reaction step wherein the reactant is passed through a fixed catalyst bed prepared according to the production method of the present invention; And c) obtaining 1,3-butadiene.

According to the present invention, when a honeycomb catalyst extruded using a binder is used as the mixed manganese ferrite produced by the coprecipitation method, it is easy to suppress the side reaction through the exothermic control, so that a high yield from the n-butene is obtained through the oxidative dehydrogenation reaction 1,3-butadiene could be prepared.

In addition, it is possible to obtain a hybrid (mixed phase) manganese ferrite honeycomb catalyst having a very simple catalyst composition and a simple synthesis route and excellent reproducibility. When the catalyst prepared according to the present invention is used, It is possible to apply commercial process without the hassle of reactor design such as multi-tubular or radial reactor.

By using the present invention, 1,3-butadiene having a high utilization value in the petrochemical industry can be produced from n-butene having a low utilization value, so that a high added value of C4 oil can be achieved. In addition, it is economical compared to existing processes because it can meet the demand of 1,3-butadiene by securing a single production process capable of producing 1,3-butadiene without installing a cracker.

1 is a schematic view of a mixed manganese ferrite honeycomb catalyst having through-pores of a regular structure.

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

The present invention relates to a process for preparing a mixed manganese ferrite honeycomb catalyst in the oxidative dehydrogenation reaction of n-butene by a coprecipitation process which is preferably carried out at a temperature of 10 to 40 ^° C, more preferably at a temperature of 15 to 30 ^° C To synthesize the mixed manganese ferrite. The honeycomb catalyst is extruded by using a binder, and 1,3-butadiene is produced through an oxidative dehydrogenation reaction of n-butene using the prepared catalyst. ≪ / RTI >

The mixed manganese ferrite honeycomb type catalyst of the present invention for obtaining 1,3-butadiene in a high yield in the oxidative dehydrogenation reaction of n-butene is produced by mixing the active manganese ferrite with an extrudate having through- extrudate to reduce the pressure drop and backmixing while increasing the heat transfer rate in the axial direction while maintaining a large surface area per unit volume and facilitating the exothermic control and the oxidative dehydrogenation reaction of n-butene And exhibit higher activity.

A) preparing a precursor aqueous solution having a manganese precursor and an iron precursor and mixing them in a basic solution while mixing them; b) washing and filtering the coprecipitated solution to obtain a solid sample and drying; c) Adjusting the weight ratio of the dried solid sample, inorganic binder, organic binder, distilled water and acid to 1: 0.05-0.5: 0.01-0.1: 0.1-1.5: 0.005-0.15, mixing and kneading to obtain a dough ) Extruding the dough of step c) into an extrudate having through-pores having a regular structure; And e) subjecting the extrudate to heat treatment. The present invention also relates to a process for preparing a mixed manganese ferrite honeycomb catalyst for the production of 1,3-butadiene.

As the manganese precursor and the iron precursor for synthesizing the mixed manganese ferrite in the step a), it is preferable to use a chloride precursor or a nitrate precursor which is well dissolved in distilled water used as a solvent. Specifically, The iron precursor may be selected from the group consisting of ferrous chloride tetrahydrate, ferrous chloride hexahydrate, ferrous chloride dihydrate, ferric chloride hexahydrate, ferrous nitrate hexahydrate, ferrous nitrate hexahydrate, ferric nitrate Wherein the manganese precursor is selected from the group consisting of manganese chloride, manganese chloride, manganese chloride, manganese chloride, manganese chloride, manganese chloride, manganese chloride, manganese chloride, And manganese nitrate monohydrate, but is not limited thereto.

Preferably, the manganese precursor and the iron precursor are dissolved in distilled water and mixed together by controlling the amounts of the two precursors so that the iron / manganese atom number ratio is 2.0 to 2.5, Outside the range of 2.0 to 2.5, manganese is difficult to enter into the iron lattice or the catalytic activity becomes very low.

On the other hand, in order to coprecipitate the manganese precursor and the iron precursor at room temperature, a basic solution having a concentration of 1.5 to 4 moles, for example, an aqueous solution of sodium hydroxide of 3 moles, is separately prepared. If the concentration of the basic solution is less than 1.5, it is difficult to form a mixed manganese ferrite catalyst structure. If the concentration of the basic solution is higher than 4 mol, the removal of Na ions is difficult in the case of a metal ion bonded with a hydroxyl group, for example sodium hydroxide, . In addition, the molarity of the basic solution is more preferably in terms of formation and post-treatment of the mixed manganese ferrite structure when the concentration is in the range of 2 to 3 moles. Basic solutions used for coprecipitation of manganese precursor and iron precursor may be sodium hydroxide as well as other basic solutions including ammonia water. On the other hand, the pH of the basic solution is 9-14.

In order to obtain the mixed manganese ferrite from the manganese precursor and the iron precursor, an aqueous solution in which the manganese precursor and the iron precursor are dissolved at preferably 10 to 40 ^° C is injected into the basic solution, Is stirred for 2 to 12 hours, preferably for 6 to 12 hours.

If coprecipitation is carried out at less than 10 ^° C, coprecipitation is not sufficient and an extremely unstable bond is formed. As a result, a side reaction which is difficult to control when the catalyst is used is caused. When it exceeds 40 ^° C, . The co-precipitation is more preferably in the range of 15 to 30 ^° C, and most preferably in the range of 15 to 25 ^° C.

In the step b), the stirred coprecipitation solution is phase separated for a sufficient time to allow the solid catalyst to precipitate, and after washing, a precipitated solid sample is obtained through a vacuum filter or the like.

The solid sample thus obtained is dried at 70 to 200 ^° C, preferably 120 to 180 ^° C for 24 hours to prepare a mixed manganese ferrite.

In step c), the dried solid sample, the inorganic binder, the organic binder, the distilled water, and the acid are mixed and kneaded to obtain a dough.

At this time, the inorganic binder used to obtain the dough for extrusion-molding the mixed manganese ferrite dried in step b) is preferably alumina or silica having a specific surface area of 10 to 250 m ² / g, but is not limited thereto. As the precursor of alumina or silica, it is preferable to use pseudoboehmite, alumina sol, silicate, silica sol or a mixture thereof, and more preferably, pseudoboehmite is used.

The organic binder may be any of organic binders conventionally added to the inorganic paste for producing the extruded product, but is preferably an ethylcellulose-based, methylcellulose-based, ethylcellulose derivative, methylcellulose derivative or a mixture thereof, more preferably A methylcellulose system is used. The organic binder improves the moldability upon extrusion and mitigates cracking during drying.

In order to obtain the dough for extrusion molding of the completed mixed manganese ferrite, an acid is added to peptize the inorganic binder. The acid used is not limited, but is preferably composed of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, and acetic acid. And nitric acid can be used more preferably.

In step c), the mixed manganese ferrite, the inorganic binder, the organic binder, the distilled water, and the nitric acid may be mixed at a weight ratio of 1: 0.05-0: 0.5-0.01-0.1-0.1: 0.005-0.15. Preferably 1: 0.1 to 0.4: 0.03 to 0.08: 0.5 to 1.0: 0.01 to 0.1, and then kneaded to obtain dough.

In the step (d), the dough of step (c) is extruded into an extrudate having a through-pore having a regular structure.

The inside of the extruder is maintained in a vacuum state at the time of extrusion, and is preferably formed at a molding speed of 300 to 500 mm / min, but is not limited thereto. Both the cylindrical extruder and the piston extruder can be used for the extrusion, but it is preferable to use a cylindrical extruder for the continuous process. The molding speed is a condition in which the honeycomb extruder is not damaged by excessive stress applied at the time of extrusion while increasing the production efficiency at a molding speed optimized for the kneading state.

The viscosity and strength of the dough are optimized by the optimized mixing condition and mixing ratio of the present invention, and the cross-section of the through pores of the regular structure of step d) is polygonal or circular, and pores penetrating through the long axis of the extrudate A honeycomb extruded body having a high specific surface area can be obtained. It is possible to obtain an excellent extruded body having a thickness (wall thickness) between pores having a regular structure and pores of 0.1 to 2 mm through the extrusion.

In the step e), the extrudate is heat-treated.

The extruded mixed manganese ferrite honeycomb catalyst obtained in the step d) is placed in an electric furnace and heat-treated at 100 to 800 ^° C to prepare a 1,3-butadiene-based honeycomb catalyst. In order to prevent cracking due to the heat treatment, a low-temperature heat treatment at 100 to 150 ^° C and a high-temperature heat treatment at 500 to 700 ^° C are more preferable.

One aspect of the present invention provides a mixed manganese ferrite honeycomb catalyst for producing 1,3-butadiene, wherein the through pore cross section is polygonal or circular, and the through pores are pores penetrating through the long axis of the honeycomb catalyst.

According to one embodiment of the present invention, there is provided a mixed manganese ferrite honeycomb catalyst for the production of 1,3-butadiene, wherein the pores of the honeycomb catalyst and the thickness (wall thickness) of the vapor space are 0.1 to 2 mm.

The peaks observed in the X-ray diffraction analysis of the mixed manganese ferrite catalyst for 1,3-butadiene production according to one aspect of the present invention are 18.78 to 18.82, 24.18 to 24.22, 33.2 to 33.24, 35.64 to 35.68, 40.9 to 40.94, The two most prominent peaks have a theta range of 45.26, 49.56 to 49.6, 54.22 to 54.26, 55.24 to 55.28, 57.92 to 57.96, 62.56 to 62.6, 64.04 to 64.08, 66.02 to 66.06, 72.16 to 72.2, and 75.78 to 75.82, ~ 33.24 in the theta range.

One aspect of the present invention is a process for the preparation of 1,3-butadiene, comprising the steps of: a) providing a mixed gas of C4 mixture, air and steam as reactant; b) reacting the mixed manganese ferrite honeycomb- An oxidative dehydrogenation reaction step comprising: And c) obtaining 1,3-butadiene. The present invention also relates to a process for producing 1,3-butadiene using the mixed manganese ferrite honeycomb catalyst.

An aspect of the present invention is a process for the preparation of a catalyst composition comprising the steps of: a) providing a mixture of C4 mixture, air and steam as reactant, b) reacting the catalyst with an oxidative dehydration Digestion reaction step; And c) obtaining 1,3-butadiene. The present invention also relates to a process for producing 1,3-butadiene using the mixed manganese ferrite honeycomb catalyst.

Wherein the C4 mixture is selected from the group consisting of 1-butene, 2-butene, and C4 raffinate-1, 2, 2.5, 3 in the step a).

The present invention provides a method for producing 1,3-butadiene using a C4 mixture which is not subjected to a separate n-butane separation step as a source of n-butene.

According to one embodiment of the present invention, the C4 mixture used in step a) is a mixture of 0.1 to 50% by weight of n-butane, 40 to 99% by weight of n-butene and 0.1 to 50% by weight of n-butane and n- 10% by weight C4 mixture. The C4 mixture excluding n-butane and n-butene includes, for example, isobutane, cyclobutane, methylcyclopropane, isobutene and the like.

In the present invention, the reactant of the oxidative dehydrogenation reaction, n-butene and oxygen, is supplied in the form of a mixed gas. In the n-butene, the C4 mixture serving as the n-butene is supplied by the piston pump, Use a mass flow controller to precisely adjust. To supply steam known to be effective in eliminating the reaction heat of the oxidative dehydrogenation reaction and improving the selectivity of 1,3-butadiene, liquid water is vaporized while being injected using a mass flow controller to allow steam to be fed to the reactor. The temperature of the water inlet is maintained at 300-450 ^° C., preferably at 350-450 ^° C., so that the injected water is immediately vaporized and mixed with the other reactants (n-butene and air) to pass through the catalyst bed.

According to one embodiment of the present invention, a honeycomb type catalyst is fixed to a straight type stainless steel reactor for a catalytic reaction, a reactor is installed in an electric furnace to maintain a reaction temperature of the catalyst layer at a constant level, The reaction can proceed while continuously passing through the catalyst layer in the reactor.

The reaction temperature for carrying out the oxidative dehydrogenation reaction was maintained at 300 to 600 ^° C, preferably 350 to 500 ^° C, more preferably 400 ^° C. The amount of the reactant to be injected was maintained at a space velocity (WHSV: Weight Hourly Space Velocity) is 0.1 ~ 1.5hr ^-1, preferably from 0.5 ~ 1h ^-1, more preferably to set the amount of catalyst to be 0.75h ^-1. The molar ratio of n-butene to air and steam is set to 1: 0.5 to 10: 1 to 30, preferably 1: 2 to 4: 10 to 30 as a reactant. If the composition ratio of the mixed gas exceeds or falls below the above range, a desired degree of butadiene yield can not be obtained, or a problem may occur due to rapid heat generation during operation of the reactor.

Hereinafter, the method of the present invention, the catalyst prepared by the method of the present invention, and the method for producing 1,3-butadiene will be described in detail with reference to the accompanying drawings and examples. The following drawings and embodiments are provided as examples so that those skilled in the art can fully understand the spirit of the present invention. Therefore, the present invention may be embodied in other forms without being limited to the following drawings and embodiments.

[Example 1]

Preparation of mixed manganese ferrite

For the preparation of mixed manganese ferrite, manganese chloride tetrahydrate (MnCl ₂ .4H ₂ O) was used as a precursor of manganese and iron chloride hexahydrate (FeCl ₃ .6H ₂ O) was used as a precursor of iron. Both precursors were well dissolved in distilled water 198 g of manganese chloride tetrahydrate and 541 g of iron chloride hexahydrate were dissolved in distilled water (1000 ml) and mixed. After sufficient agitation, it was confirmed that the precursor was completely dissolved. At 20 ^° C, the precursor aqueous solution was added dropwise to a 3 molar aqueous sodium hydroxide solution (6000 ml) at a constant rate. The mixed solution was agitated at room temperature for 12 hours using a stirrer so that sufficient stirring was performed, and then left for 12 hours at room temperature for phase separation. The precipitated solution was washed with a sufficient amount of distilled water, filtered through a vacuum filter, and the solid sample was dried at 120 ^° C for 24 hours. Hybrid manganese ferrite was prepared by heat treatment in an electric furnace of air atmosphere at 650 ^o C for 3 hours. The phases of the prepared catalysts were confirmed by X-ray diffraction analysis under the following conditions, and the results are shown in Table 1. As shown in Table 1, it was confirmed that the catalyst prepared at room temperature was a mixed manganese ferrite including iron oxide (α-Fe ₂ O ₃ ) and manganese iron oxide (MnFeO ₃ ).

≪ X-ray diffraction analysis condition >

X-ray generator: 3 kW, Cu-K? Line (? = 1.54056 Å)

Tube voltage: 40kV

Tube current: 40mA

2 Theta measurement range: 5deg to 90deg

Sampling width: 0.02 deg

Scanning speed: 2deg / min at 5deg

Diverging slit: 1deg

Scattering slit: 1deg

Receiving slit: 0.15mm

[Table 1] X-ray diffraction analysis results of mixed manganese ferrite

[Example 2]

3.6 mm Mixed manganese ferrite having a pitch of Honeycomb type  Preparation of Catalyst

In Example 1, before the heat treatment step, 80 g of dried mixed manganese ferrite, 20 g of shudo boehmite (SASOL), 4.8 g of methyl cellulose, 65.5 g of distilled water and 6.7 g of nitric acid (60%) were mixed at room temperature, To prepare a dough. The kneaded product was put into a cylindrical extruder, the extruder was kept in a vacuum state, and the extruded product was produced at a molding speed of 400 mm / min at a cylinder rotation speed of 50 rpm. The extruded body manufactured using a furnace was heat-treated at 120 ^° C for 2 hours and then heat-treated at 650 ^° C for 3 hours to have a shape as shown in FIG. 1 and having a pitch of 3.6 mm A honeycomb type catalyst for the production of 1,3-butadiene was prepared. The physical shapes of the produced 1,3-butadiene-producing honeycomb catalysts are summarized in Table 2 on the basis of the reference numerals shown in FIG.

[Table 2]

[Example 3]

1.96 mm  Mixed manganese ferrite with pitch Honeycomb type  Preparation of Catalyst

A 1,3-butadiene-producing honeycomb catalyst having a pitch of 1.96 mm was produced under the same conditions as in the extrusion and heat treatment of Example 2. [ The physical shapes of the produced 1,3-butadiene-producing honeycomb-type catalysts are summarized in Table 3 based on the reference numerals shown in Fig.

[Table 3]

[Comparative Example 1]

Tableting Molded  About 1 mm Preparation of mixed manganese ferrite particulate catalyst

The mixed manganese ferrite prepared in Example 1 was prepared in the form of a pellet through a pelletizing process and pulverized into a size of 0.9 to 1.2 mm.

[Comparative Example 2]

Hybrid manganese ferrite without inorganic binder Honeycomb type  Preparation of Catalyst

The dough was produced in the same manner as in Example 2, except for chondroboemite and nitric acid, and extruded under the same conditions. As a result of Comparative Example 2, an amorphous extrudate which had lost its shape due to a decrease in the strength of the catalyst was obtained and could not be extruded into a honeycomb shape.

[Example 4]

Mixed manganese ferrite Honeycomb type  Lt; RTI ID = 0.0 > n-hexane < / RTI & Buten Oxidative  Dehydrogenation reaction

The oxidative dehydrogenation reaction of n-butene was carried out by using the mixed manganese ferrite honeycomb type and granular catalyst according to Examples 2 and 3 and Comparative Example 1, and specific experimental conditions were as follows.

The reactants used in the oxidative dehydrogenation reaction of n-butene are C4 mixture and the composition thereof is shown in Table 4 below. The reactant C4 mixture was injected in the form of mixed gas with air and steam, and a stainless steel fixed bed reactor was used as the reactor.

The composition ratio of the reactants was set on the basis of n-butene in the C4 mixture, and the molar ratio of n-butene: air: steam was set to 1: 2.75: 10. Steam was vaporized at 350 ^° C and mixed with other reactants, C4 mixture and air, and then introduced into the reactor. The amount of C4 mixture was controlled by using a piston pump. The amount of air and steam was controlled through a mass flow controller Respectively.

The feed rate of the reactants was determined by setting the amount of catalyst such that the space velocity (WHSV) was 0.75 hr ^-1 based on n-butene in the C4 mixture, and the reaction temperature was adjusted so that the catalyst bed inlet temperature of the fixed bed reactor was 400 ^° C Respectively. The product after the reaction includes not only the target 1,3-butadiene in the product, but also carbon dioxide which is a by-product of complete oxidation, by-product by cracking, by-product by isomerization reaction and n-butane contained in the reactant. And analyzed using gas chromatography. The conversion, 1,3-butadiene selectivity and yield of n-butene through the mixed manganese ferrite honeycomb type and the granular catalyst with respect to the oxidative dehydrogenation reaction of n-butene were calculated by the following equations 1, 2 and 3 Respectively.

[Table 4] Composition of C4 mixture used as reactant

The catalysts prepared by the production methods of Examples 2 and 3 and Comparative Example 1 were applied to the oxidative dehydrogenation reaction of the C4 mixture by the reaction method of Example 4, and the results are shown in Table 5.

The mixed manganese ferrite honeycomb catalyst showed remarkable activity and exothermic control compared to the granular catalyst. In the case of the mixed manganese ferrite honeycomb catalyst having a pitch of 1.96 mm, the conversion of n-butene was 74 wt%, the selectivity of 1,3-butadiene 94 wt%, and the yield of 1,3-butadiene was 70 wt%.

[Table 5] Evaluation results of catalytic activity

As shown in Table 5, it is considered that the mixed manganese ferrite honeycomb catalyst has a smaller surface area per unit volume than the granular catalyst, but mass transfer and heat transfer in the axial direction are easy.

Although the present invention has been described in detail with reference to specific embodiments thereof and specific examples thereof, it is to be understood that the same is by way of illustration and example only and is not to be taken by way of limitation, It is to be understood that the invention is not limited thereto and that various modifications and changes may be made thereto by those skilled in the art.

Accordingly, the spirit of the present invention should not be construed as being limited to the embodiments described, and all of the equivalents or equivalents of the claims, as well as the following claims, belong to the scope of the present invention .

a is the length, b is the width, c is the opening, d is the wall thickness, and pitch is c + d.

Claims (15)

a) preparing an aqueous solution of a precursor having a manganese precursor and an iron precursor, and co-
b) washing and filtering the coprecipitated solution to obtain a solid sample and drying
c) The weight ratio of the dried solid sample, the inorganic binder, the organic binder, the distilled water and the acid is adjusted to 1: 0.05-0.5: 0.01-0.1: 0.1-1.5: 0.005-0.15, then kneaded, Steps to Obtain
d) extruding the dough of step c) into an extrudate having through-pores having a regular structure; And
and e) subjecting the extrudate to a heat treatment. The method of claim 1, wherein the heat treatment in step (e) is performed at 100 to 800 ^° C. The method according to claim 1, wherein the heat treatment in step (e) is a two-step heat treatment in which a high temperature heat treatment at 500 to 700 ^° C is performed after a low temperature heat treatment at 100 to 150 ^° C. A method for producing a honeycomb type catalyst. [4] The method according to claim 1, wherein the through pores in step d) are polygonal or circular in cross section, and are pores passing through the long axis of the extrudate. The method of claim 1, wherein the thickness (wall thickness) between the pores and the pores in step d) is 0.1 to 2 mm. The method according to claim 1, wherein the inorganic binder is alumina or silica having a specific surface area of 10 to 250 m ² / g. [7] The method according to claim 6, wherein the alumina is a precursor of chondroobromite or alumina sol. [7] The method according to claim 6, wherein the silica is a silicate or silica sol as a precursor, wherein the silica is a precursor of 1,3-butadiene. The method according to claim 1, wherein the organic binder is a methylcellulose-based mixed catalyst for producing 1,3-butadiene. Wherein the through-pore cross-section is polygonal or circular, and the through pores are pores passing through the long axis of the honeycomb-type catalyst. The mixed manganese ferrite honeycomb type catalyst for producing 1,3-butadiene according to claim 10, wherein the pore of the honeycomb catalyst and the thickness (wall thickness) of the vapor space are 0.1 to 2 mm. The mixed manganese ferrite honeycomb catalyst according to claim 10 or 11, wherein X-ray diffraction spectrum of the mixed manganese ferrite honeycomb catalyst is 18.78 to 18.82, 24.18 to 24.22, 33.2 to 33.24, 35.64 to 35.68, 40.9 to 40.94, 45.22 to 45.26, 49.56 to 49.6, Butadiene having a peak in the two theta range of from 54.22 to 54.26, 55.24 to 55.28, 57.92 to 57.96, 62.56 to 62.6, 64.04 to 64.08, 66.02 to 66.06, 72.16 to 72.2, and 75.78 to 75.82 Hybrid manganese ferrite honeycomb catalysts. a) providing a mixed gas of C4 mixture, air and steam as reactants
b) an oxidative dehydrogenation reaction step in which the reactant is passed through a catalyst bed in which the catalyst according to any one of claims 10 to 12 is fixed; And
c) obtaining 1,3-butadiene. The process for producing 1,3-butadiene using a hybrid manganese ferrite honeycomb catalyst. a) providing a mixed gas of C4 mixture, air and steam as reactants
b) an oxidative dehydrogenation reaction step in which the reactant is passed through a catalyst bed fixed according to any one of claims 1 to 9; And
c) obtaining 1,3-butadiene. The process for producing 1,3-butadiene using a hybrid manganese ferrite honeycomb catalyst. The mixed manganese ferrite honeycomb catalyst according to claim 13 or 14, wherein the C4 mixture is selected from the group consisting of 1-butene, 2-butene, and C4 raffinate-1, 2, 2.5, , 3-butadiene.

Images