KR20140131861A - Multicomplexes bismuth molybdate catalyst, method of preparing thereof, and method for producing butadiene - Google Patents

Abstract

The present invention relates to a multicomponent bismuth molybdate catalyst, a method for producing the same, and a method for producing butadiene using the same. According to the present invention, when a catalyst is produced, mixing and co-precipitating are simultaneously performed by means of high speed agitation, so that a particular metal componential ratio can be maintained while the co-precipitating is performed. Accordingly, the conversion rates of butane and the selectivity and yield of 1,3-butadiene are improved, so that the stability of the process operation can be also provided.

Description

TECHNICAL FIELD [0001] The present invention relates to a multicomponent bismuth molybdate catalyst, a method for producing the same, and a method for producing butadiene using the catalyst, a method for producing the butadiene,

The present invention relates to a multicomponent bismuth molybdate catalyst, a method for producing the same, and a method for preparing butadiene using the same. More specifically, the present invention relates to a multicomponent bismuth molybdate catalyst, A bismuth molybdate catalyst, and a method for producing the same, and a method for producing 1,3-butadiene and 1,3-butadiene, which can simultaneously provide stability of the process operation while improving the selectivity and yield of 1,3- -Butadiene. ≪ / RTI >

As the intermediates of many petrochemical products in the petrochemical market, the demand and value of which are increasing gradually, there are three methods for producing 1,3-butadiene: naphtha cracking, direct dehydrogenation of n-butene, oxidative dehydration of n-butene There is digestion reaction.

Among them, the oxidative dehydrogenation reaction of n-butene, which produces butadiene via oxidative dehydrogenation (ODH) of n-butene, is an exothermic reaction unlike the direct dehydration reaction, Thus, it is possible to reduce the energy consumption and to remove carbon deposits and carbon deposits by adding an oxidizing agent in the dehydrogenation reaction. Various kinds of metal oxides have been used as catalysts for the oxidation / dehydrogenation reaction of butene, but in particular, bismuth molybdenum-based catalysts, which are complexes of bismuth oxide and molybdenum oxide, are known to exhibit excellent activity.

The bismuth molybdenum-based catalyst includes a pure bismuth molybdate catalyst consisting only of bismuth and molybdenum oxide and a multicomponent bismuth molybdate catalyst to which various metal components are added. The process for producing 1,3-butadiene through the oxidative dehydrogenation reaction of n-butene on a pure bismuth molybdate catalyst is not suitable for the commercialization process due to limitations in increasing the yield of 1,3-butadiene. As an alternative to this, in order to increase the activity of the bismuth molybdate catalyst for the oxidative dehydrogenation reaction of n-butene, the production of multicomponent bismuth molybdate catalyst to which various metal components other than bismuth and molybdate are added actively Research.

A common method used to prepare conventional multicomponent metal oxide catalysts is to mix the two or more metal solutions with controlled coprecipitation pH and to produce the catalyst through the process of precipitation. For example, a metal precursor to be coprecipitated is dissolved in a pH-adjusted solution if necessary, and the coprecipitate is performed by dropping the solution in a solution in which each metal precursor is dissolved. When the coprecipitation is performed as described above, the concentration of the coprecipitation solution is mixed in a composition ratio state that is different from the final target component ratio, and the coprecipitation of the catalyst progresses gradually in the form of approaching the final target concentration as the coprecipitation proceeds. Therefore, unbalance occurs in the ratio of the metal components in the coprecipitation solution, and thus the component ratio of the particles is not constant in the coprecipitation step in which the basic structure is formed, resulting in a phenomenon that the activity is lowered.

It is an object of the present invention to overcome the problems of the prior art as described above, in order to solve the problem of imbalance occurring in the ratio of metal components in the coprecipitation solution, So as to provide a catalyst having a uniform composition ratio.

Another object of the present invention is to provide a process for producing butadiene from a butene mixture using a catalyst having a uniform composition ratio, wherein the butadiene conversion, 1,3-butadiene selectivity and yield are improved, And a method for producing the same.

In order to achieve the above object, a method for producing a multicomponent bismuth molybdate catalyst of the present invention comprises

a) preparing a first precursor aqueous solution comprising a divalent cation metal precursor, a trivalent cation metal precursor, a bismuth precursor, and a first cation metal precursor;

b) preparing a second precursor aqueous solution comprising a molybdenum precursor;

c) co-precipitating the first precursor aqueous solution and the second precursor aqueous solution while continuously mixing and rapidly dispersing the first precursor aqueous solution and the second precursor aqueous solution;

d) drying the coprecipitation solution at 70 to 200 캜 to obtain a solid catalyst; And

and e) heat treating the solid catalyst at 350 to 800 ° C.

In addition, the multicomponent bismuth molybdate catalyst of the present invention is produced according to the above-mentioned method, wherein ME ² MoO ₄ , (ME ² _0.7 ME ³ _0.3 ) MoO ₄ , Bi ₂ Mo ₃ O ₁₂ and ME ¹ _0.13 MoO ₃ The present invention is characterized by having a mixed phase comprising

Also, the multicomponent bismuth molybdate catalyst of the present invention is prepared according to the above-mentioned method, and in the X-ray diffraction analysis, it is 9.84 to 9.96, 13.02 to 13.20, 18.62 to 18.70, 23.18 to 23.26, 25.54 to 25.62, 26.38 to 26.46 , 28.30 to 28.38, 32.00 to 32.08, 33.58 to 33.66, and 45.04 to 45.12.

Further, according to the 1,3-butadiene preparation method of the present invention,

Providing a mixed gas of C4 mixture, oxygen, nitrogen and steam as reactants; And

And an oxidative dehydrogenation reaction step in which the reactant is continuously passed through a catalyst layer on which a multicomponent bismuth molybdate catalyst prepared by the above-described method is immobilized.

The multicomponent bismuth molybdate catalyst according to the present invention can simultaneously improve the stability of the process operation and the energy saving effect while improving the conversion of butene, the selectivity and yield of 1,3-butadiene.

FIG. 1 is a graph showing the effect of the continuous mixing and the fast dispersing step in the coprecipitation step according to the present invention in Example 1 and Comparative Example 1 in which the continuous mixing and the fast dispersing step were not performed in the coprecipitation step according to the prior art, respectively (The abscissa: 2 Theta (Degree), the longitudinal axis: Intensity (AU)) of the component-based bismuth molybdate catalyst, the upper part of the graph corresponds to the catalyst of Example 1 and the lower part corresponds to the catalyst of Comparative Example 1 .
FIG. 2 is a graph showing the results obtained by the method of Example 2 in which the continuous mixing and the fast dispersing step were carried out in the coprecipitation step according to the present invention and the comparative example 2 in which the continuous mixing and the fast dispersing step were not performed in the coprecipitation step according to the prior art (2) Theta (Degree) and the longitudinal axis (Intensity (AU)) were compared with the XRD patterns of the component-based bismuth molybdate catalyst. .

Hereinafter, the present invention will be described in detail.

Specifically, the process for preparing a multicomponent bismuth molybdate catalyst of the present invention comprises the steps of: a) preparing a first precursor aqueous solution comprising a divalent cation metal precursor, a trivalent cation metal precursor, a bismuth precursor, and a first cation metal precursor step; b) preparing a second precursor aqueous solution comprising a molybdenum precursor; c) co-precipitating the first precursor aqueous solution and the second precursor aqueous solution while continuously mixing and rapidly dispersing the first precursor aqueous solution and the second precursor aqueous solution; d) drying the coprecipitation solution at 70 to 200 캜 to obtain a solid catalyst; And e) heat treating the solid catalyst at 350 to 800 ° C.

As used herein, the term " continuous mixing and rapid dispersion " refers to performing the continuous mixing and rapid dispersion processes simultaneously unless otherwise specified.

In the present invention, the liquid-liquid contact between the first precursor aqueous solution and the second precursor aqueous solution is promoted through the continuous mixing and the rapid dispersion step, and the resultant metal component ratio is continuously maintained during co- It is possible to provide a catalyst having a uniform metal composition ratio from the beginning to the end of the coprecipitation reaction.

The continuous mixing and rapid dispersion may be performed at a temperature of 25 to 300 DEG C or 50 to 150 DEG C, 1 to 100 bar, 1 to 50 bar or 1 to 20 bar pressure, 5,000 to 20,000 rpm, or 10,000 to 15,000 rpm Rotation speed condition, and the uniform composition ratio effect of the present invention can be realized within the above range.

The continuous mixing and high-speed dispersion can be performed using an in-line homogenizer as a specific example. That is, in an in-line homogenizer, under the condition of a feed amount per hour in which the total amount of the first precursor aqueous solution is injected and the total amount of the second precursor aqueous solution is the same, the first precursor aqueous solution and the second precursor aqueous solution So that the mixing ratio is constant and the high-speed dispersion can be achieved.

The in-line homogenizer may be a continuous or batch type in-line homogenizer.

When the homogenizer is used, the internal temperature, the internal pressure, and the rotational speed conditions are set in accordance with the conditions described above (25 to 300 DEG C or 50 to 150 DEG C, 1 to 100 bar, 1 to 50 bar or 1 to 20 bar , A rotation speed of 5,000 to 20,000 rpm).

When the homogenizer is used, the residence time may be, for example, 0.0001 sec to 5 hr or 0.01 sec to 2 hr.

The divalent cation metal precursor may be, for example, a chloride or nitrate of a metal component selected from one or more of nickel, cobalt, zinc, magnesium, manganese, and copper.

The trivalent cation metal precursor can be, for example, a chloride or nitrate of a metal component selected from one or more of iron, aluminum, vanadium, zirconium, tungsten and silicon.

The bismuth precursor may be, for example, a chloride or nitrate of bismuth.

The monovalent cation metal precursor may be, for example, a chloride or nitrate of a metal component selected from one or more of sodium, potassium, rubidium and cesium.

The molybdenum precursor may be, for example, an ammonium salt of molybdenum.

In another example, the divalent cation metal precursor is cobalt nitrate, the trivalent cation metal precursor is iron nitrate, the primary cation metal precursor is cesium nitrate, the bismuth precursor is Bismuth nitrate, and molybdenum precursor, ammonium molybdate, may be used, respectively.

Since the bismuth nitrate does not dissolve in water, it can be dissolved by adding water to the acid. The acid is added in such an amount that the bismuth completely melts.

The acid may be, for example, inorganic or nitric acid.

The molar ratio of the divalent cation metal precursor, the trivalent cation metal precursor, the bismuth precursor, the monovalent cation metal precursor, and the molybdenum precursor is, for example, 1-12: 0.1-4: 0.1-4: 0.001-2: 12 Can be 3-10: 0.5-3: 0.5-3: 0.01-1: 12 and can be 5-10: 0.8-1.2: 0.8-1.2: 0.3-0.7: 12, or 8: 1 : 1: 0.5: 12, and the conversion, selectivity, and yield of the product are excellent within this range.

And further stirring between step b) and step c), for example, for 15 to 25 hours, or for 20 to 25 hours.

The drying in step d) may be performed at 70 to 200 ° C, or 110 to 150 ° C, for example, for 5 to 50 hours, or 20 to 30 hours.

The heat treatment in step e) may be performed at a temperature ranging from 350 to 800 ° C, for example, at a temperature ranging from 400 to 600 ° C, or from 450 to 500 ° C.

The multicomponent bismuth molybdate catalyst prepared according to the above-mentioned method comprises a mixed phase comprising ME ² MoO ₄ , (ME ² _0.7 ME ³ _0.3 ) MoO ₄ , Bi ₂ Mo ₃ O ₁₂ , and ME ¹ _0.13 MoO ₃ .

Also, the multicomponent bismuth molybdate catalyst prepared by the above-described method had an X-ray diffraction spectrum of 9.84 to 9.96, 13.02 to 13.20, 18.62 to 18.70, 23.18 to 23.26, 25.54 to 25.62, 26.38 to 26.46, , 32.00 to 32.08, 33.58 to 33.66, and 45.04 to 45.12, respectively.

Furthermore, the multicomponent bismuth molybdate catalyst prepared according to the above-mentioned method has, for example, the following general formula.

Mo ₁₂ Bi _a ME ³ _b ME ² _c ME ¹ _d ME ^{1 '} Ox

ME ³ means a trivalent cation metal component, ME ² means a divalent cation metal component, ME ¹ , ME ^{1 '} means a different monovalent cation metal component.

B, 10, 1? C? 20, 0.05? D? 5, 0.01? E? 3, and x is an integer of 1 to 10, Which corresponds to the stoichiometric coefficient considering the valency of the atoms.

A, b, c, d and e are in the range of 0.5? A? 2, 0.5? B? 2, 5? C? 15, 0.1? D? It corresponds to a stoichiometric factor that takes into account the valence of atoms.

As a specific example, the multicomponent bismuth molybdate catalyst has the following general formula.

Mo ₁₂ Bi _a Fe _b Co _c CS _d Rb _e Ox

If the above formula, a = 1, b = 2 , c = 6, d = 0.3, e = 0.12 , and x is the stoichiometric coefficient, when a = 1, b = 1, c = 7, d = 0.5, e = 0.08 and x can be a stoichiometric coefficient .

Also, in the method for producing 1,3-butadiene according to the present invention,

Providing a mixed gas of C4 mixture, oxygen, nitrogen and steam as reactants; And

And an oxidative dehydrogenation reaction step in which the reactant is continuously passed through a catalyst layer on which a multicomponent bismuth molybdate catalyst prepared according to the above-described method is immobilized.

The C4 mixture includes, for example, 0.01 to 30% by weight of n-butane, 30 to 99.99% by weight of n-butene, and a C4 mixture (trans-2-butene and cis- butene, etc.) is contained in an amount of 0.01 to 10% by weight, and the reactant includes, for example, a molar ratio of n-butene: oxygen: nitrogen: steam of 1: 0.5-2: 2-20: 2-20, Can be a molar ratio of 0.5-1.5: 10-20: 10-20 or a molar ratio of 1: 0.75-1.2: 12-20: 12-20.

According to an embodiment of the present invention, a multicomponent bismuth molybdate catalyst is charged in a reactor for a catalytic reaction, a reactor is installed in an electric furnace to maintain a constant reaction temperature, and the reactant is continuously passed through the catalyst layer in the reactor Let the reaction proceed.

The oxidative dehydrogenation reaction can be carried out at a reaction temperature of 250 to 350 ° C and a gas hourly space velocity (GHSV) of 50 to 5000 ^{-1 on} a n-butene basis.

The reaction temperature may be from 300 to 350 ℃ In one example, the space velocity may be from 100 to 1000h ^-1, or from 100 to 500 h ^-1, for example.

The process for producing 1,3-butadiene according to the present invention comprises filling a fixed phase of a multicomponent bismuth molybdate catalyst for preparing butadiene produced according to the above-described production method into a reactor; A reaction mixture containing C4 mixture containing butene, oxygen, nitrogen and steam is continuously passed through the catalyst layer of the reactor to proceed an oxidative dehydrogenation reaction to obtain a dehydrogenation product mixture, , And 3-butadiene are separated.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention as set forth in the appended claims. Variations and modifications are intended to fall within the scope of the appended claims.

[Example]

Example 1

With cesium precursor cesium nitrate (CeNO _3), rubidium nitrate (RuNO _3), cobalt nitrate hexahydrate _{(Co (NO 3) 2 .6H} 2 O), the iron precursor to the cobalt precursor in the precursor rubidium Iron nitrate hexahydrate (Fe (NO ₃ ) ₃ .9H ₂ O), bismuth nitrate pentahydrate (Bi (NO ₃ ) ₂ .5H ₂ O) as a precursor of bismuth, ammonium molybdate tetra hydrate ((NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O) was used.

Bismuth nitrate in distilled water 274ml was added 32.5g nitrate pentahydrate _{(Bi (NO 3) 2 .5H} 2 O) 104.5g, cesium nitrate (CsNO ₃₎ 12.6g, rubidium nitrate (RuNO ₃₎ 3.8g, cobalt 380.0 g of nitrate hexahydrate (Co (NO ₃ ) ₂ .6H ₂ O) and 174.1 g of iron nitrate 9 hydrate (Fe (N _{O 3} ) ₃ .9H ₂ O) were dissolved and stirred to prepare solution A-1 Respectively.

Separately, 456.4 g of ammonium molybdate tetrahydrate ((NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O) was dissolved in 1,140 ml of distilled water and stirred to prepare separately. This was designated as Solution B-1 .

The total amount of the prepared solution A-1 was 981.5 g, and the total amount of the solution B-1 was 1596.4 g. Supplying the respective solutions in-line (in-line) a solution A- 1 individual inlet of the continuous homogenization device (UTL 25 digital in-line homogenizer, manufactured by IKA) at a rate of 8.18g / min and, at the same time, the B-1 solution Min at a rate of 13.30 g / min. The homogenizer was operated under a rotating condition of 15,000 rpm, a residence time of 1 sec, an internal temperature of 50 캜, and an internal pressure of 1 bar.

The coprecipitation solution obtained at the discharge port of the inline continuous homogenizer was stored in a mixed state in a double jacket reactor controlled at 50 ° C. The coprecipitation solution was stirred for 60 minutes using a magnetic stirrer, and the precipitated solution was dried at 120 DEG C for 24 hours to obtain a solid sample.

The solid sample was pulverized and mixed with water and extruded into a cylindrical shape having a diameter of 6 mm and a length of 6 mm. The resultant extrudate was placed in an electric furnace and then heat-treated at a temperature of 450 ° C to obtain Mo ₁₂ Bi ₁ Fe ₂ Co ₆ Cs _0.3 Rb _0.12 Ox was prepared.

As a result of X-ray diffraction analysis, the first catalyst was CoMoO ₄ , (Co _0.7 Fe _0.3 ) MoO ₄ , Bi (Bi ₂ O ₃ ) ₂ Mo ₃ O ₁₂ , and Cs _0.13 MoO ₃ . Detailed analysis results As shown in Fig. 1, it was confirmed that a crystal structure in which cesium and molybdenum are mixed is greatly developed.

From the results of the analysis, it can be seen that the method of producing by using the homogenizing apparatus according to the present invention affects the structure formation in the coprecipitation step of the catalyst and affects the crystal structure of the final catalyst. The elemental component analysis (ICP-AES) confirmed that the desired amount of metal precursor was coprecipitated precisely within the error range of the analysis.

Comparative Example 1

Solution A-1 and Solution B-1 were prepared in the same manner as in Example 1, and then Solution B-1 was added to a double jacket reactor controlled at 50 ° C, and Solution A-1 was mixed in a magnetic stirrer at a rate of 8.18 g, for 120 minutes. The results are shown in Table 1. < tb > < TABLE >

The resulting extrudate was placed in an electric furnace, and then heat-treated at a temperature of 450 ° C to prepare a catalyst having a composition of Mo ₁₂ Bi ₁ Fe ₂ Co ₆ Cs _0.3 Rb _0.12 × 0.

As a result of X-ray diffraction analysis, the first catalyst was CoMoO ₄ , (Co _0.7 Fe _0.3 ) MoO ₄ , Bi (Bi ₂ O ₃ ) ₂ Mo ₃ O ₁₂ , but the crystal structure in which cesium and molybdenum were mixed as in Example 1 could not be confirmed. The elemental component analysis (ICP-AES) confirmed that the desired amount of metal precursor was coprecipitated precisely within the error range of the analysis.

Example 2

Bismuth nitrate in distilled water 270ml was added 32.1g nitrate pentahydrate _{(Bi (NO 3) 2 .5H} 2 O) 103.1g, cesium nitrate (CsNO ₃₎ 20.7g, rubidium nitrate (RuNO ₃₎ 2.5g, cobalt nitrate hexahydrate _{(Co (NO 3) 2 .6H} 2 O) 437.2g and iron nitrate nonahydrate _{(Fe (NO 3) 3 ·} 9H 2 O) and stirred dissolve 85.8g this solution was referred to a solution a-2 Respectively.

Separately, 450.1 g of ammonium molybdate tetrahydrate ((NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O) was dissolved in 1125 ml of distilled water and stirred separately to prepare separately. This solution was designated as solution B-2 .

The total amount of the prepared solution A-2 was 951.4 g and the total amount of the solution B-2 was 1575.1 g. Supplying each solution to solution A-2 is a rate of 7.93g per minute for each injection port of the continuous homogenizing apparatus of the first embodiment and, at the same time, a solution B-2 was supplied at a rate of 13.13g per minute.

The coprecipitation solution discharged from the discharge port of the in-line batch type homogenizer was stored in a mixed state in a double jacket reactor controlled at 50 ° C. The coprecipitation solution was stirred for 60 minutes using a magnetic stirrer, and the precipitated solution was dried at 120 DEG C for 24 hours to obtain a solid sample.

The solid sample was pulverized and mixed with water and extruded into a cylinder having a diameter of 6 mm and a length of 6 mm. The resultant extrudate was placed in an electric furnace and then heat-treated at a temperature of 450 ° C. to obtain a Mo ₁₂ Bi ₁ Fe ₁ Co ₇ Cs _0.5 Rb _0.08 × 0 ≪ / RTI >

As a result of X-ray diffraction analysis, the first catalyst was CoMoO ₄ , (Co _0.7 Fe _0.3 ) MoO ₄ , Bi (Bi ₂ O ₃ ) ₂ Mo ₃ O ₁₂ , and Cs _0.13 MoO ₃ . Detailed analysis results As shown in Fig. 2, it was confirmed that the crystal structure in which cesium and molybdenum are mixed is greatly developed. From the results of the analysis, it can be seen that the method using the homogenizer affects the structure formation in the catalyst coprecipitation step and also affects the crystal structure of the final catalyst. The elemental component analysis (ICP-AES) confirmed that the desired amount of metal precursor was coprecipitated precisely within the error range of the analysis.

Comparative Example 2

The solution A-2 and the solution B-2 were prepared in the same manner as in Example 2, and then the solution B-2 was introduced into a double jacket reactor controlled at 50 ° C. Using the magnetic stirrer, the solution A- g, for 120 minutes.

The resultant extrudate was placed in an electric furnace and then heat treated at a temperature of 450 ° C. to prepare a catalyst having a composition of Mo ₁₂ Bi ₁ Fe ₁ Co ₇ Cs _0.5 Rb _0.08 × 0.

As a result of X-ray diffraction analysis, the first catalyst was CoMoO ₄ , (Co _0.7 Fe _0.3 ) MoO ₄ , Bi (Bi ₂ O ₃ ) ₂ Mo ₃ O ₁₂ , and a crystal structure in which cesium and molybdenum were mixed as in Example 2 could not be confirmed. The elemental component analysis (ICP-AES) confirmed that the desired amount of metal precursor was coprecipitated precisely within the error range of the analysis.

[Test Example]

1 - butene and oxygen were used as reactants, and nitrogen and steam were added together. As the reactor, a metal tubular reactor was used. The ratio of reactants and the gas hourly space velocity (GHSV) were set on the basis of 1-butene.

The molar ratio of butane: oxygen: nitrogen: steam was set to 1: 0.75: 10: 6 and the GHSV was 50 or 75 h ^-1 based on 1-butene. The bismuth molybdate catalyst prepared in Example 1-2 and Comparative Example 1-2 was charged in a fixed bed reactor and the volume of the catalyst bed in contact with the reactants was fixed at 200 cc.

The content of 1 - butene was controlled by using a mass flow controller for liquid, oxygen and nitrogen were controlled by using mass flow controller for gas, and the feed rate was controlled by using liquid pump. Steam was injected in the form of water as a vaporizer, vaporized at 340 ° C, and mixed with other reactants, 2-butene and oxygen, to flow into the reactor. The reaction products were analyzed by gas chromatography.

In addition to the targeted 1,3-butadiene, the product also contained carbon dioxide, C4 by-products, unreacted trans-2-butene, and cis-2-butene. The conversion (X) of 2-butene, the selectivity (S_BD) of 1,3-butadiene and the yield (Y) were calculated by the following formulas 1, 2 and 3, respectively.

[Equation 1]

[Equation 2]

[Equation 3]

The conversion of butene, the degree of selectivity of butadiene, and the yield of butadiene prepared in Examples 1 to 2 and Comparative Examples 1 and 2 were measured by the above-mentioned method, and the results are shown in Table 1 below.

Temperature
(° C) GHSV (h ^-1 ) SBR
(Steam Butene Ratio) OBR
(Oxygen Butene Ratio) NBR
(Nitrogen Butene Ratio) X (%) S_BD (%) Y (%) Example 1 320 75 One 5.3 16 99.7 89.8 89.5 310 100 One 5.3 16 99.4 92.2 91.7 310 100 0.75 4 12 99.3 91.2 98.5 310 125 One 4 12 99.5 90.3 89.9 Comparative Example 1 320 100 One 4 12 82.4 91.6 75.5 320 75 One 4 12 89.9 91.5 82.2 320 75 One 3 10 90.0 90.1 81.1 340 75 One 4 12 92.6 91.7 84.3 Example 2 320 75 One 4 12 96.4 93.0 89.7 Comparative Example 2 320 75 One 4 12 91.6 92.6 84.8

As shown in Table 1, in Examples 1 and 2 in which 1,3-butadiene was produced by using a multicomponent bismuth molybdate catalyst comprising a continuous mixing and a high-speed dispersion process according to the present invention, Comparative Examples 1 and 2, in which 1,3-butadiene was produced using a multicomponent bismuth molybdate catalyst prepared without containing a high-speed dispersion process, were improved in terms of conversion of butene, selectivity and yield of butadiene Respectively.

As a result, it has been confirmed that the continuous mixing and the high-speed dispersion process are performed during the preparation of the catalyst, so that it is possible not only to maintain a constant composition ratio from the beginning of the coprecipitation process to the end of the coprecipitation process, but also to provide safety of operation.

Claims (16)

a) preparing a first precursor aqueous solution comprising a divalent cation metal precursor, a trivalent cation metal precursor, a bismuth precursor, and a first cation metal precursor;
b) preparing a second precursor aqueous solution comprising a molybdenum precursor;
c) co-precipitating the first precursor aqueous solution and the second precursor aqueous solution while continuously mixing and rapidly dispersing the first precursor aqueous solution and the second precursor aqueous solution;
d) drying the coprecipitation solution at 70 to 200 캜 to obtain a solid catalyst; And
and e) heat treating the solid catalyst at 350 to 800 ° C.
The method according to claim 1,
Wherein the continuous mixing and the rapid dispersion are carried out in the step c) at a temperature of 25 to 300 DEG C, a pressure of 1 to 100 bar, and a rotation speed of 5,000 to 20,000 rpm. Way.
The method according to claim 1,
Wherein the continuous mixing and the high-speed dispersion are carried out using an in-line homogenizer of continuous or batch type in the step c).
The method according to claim 1,
Wherein the divalent cation metal precursor is a chloride or nitrate of a metal component selected from the group consisting of nickel, cobalt, zinc, magnesium, manganese and copper.
The method according to claim 1,
Wherein the trivalent cation metal precursor is a chloride or nitrate of a metal component selected from at least one of iron, aluminum, vanadium, zirconium, tungsten, and silicon.
The method according to claim 1,
Wherein the bismuth precursor is a chloride or a nitrate of bismuth.
The method according to claim 1,
Wherein the monovalent cation metal precursor is a chloride or nitrate of a metal component selected from at least one of sodium, potassium, rubidium and cesium.
The method according to claim 1,
Wherein the molybdenum precursor is an ammonium salt of molybdenum.
The method according to claim 1,
Wherein the divalent cation metal precursor, the trivalent cation metal precursor, the bismuth precursor, the monovalent cation metal precursor, and the molybdenum precursor have a molar ratio of 1-12: 0.1-4: 0.1-4: 0.001-2: 12 Wherein the bismuth molybdate catalyst is a bismuth molybdate catalyst.
The method according to claim 1,
And stirring the mixture for 15 to 25 hours between the steps b) and c).
The catalyst prepared according to the process of any one of claims 1 to 10 comprises ME ² MoO ₄ , (ME ² _0.7 ME ³ _0.3 ) MoO ₄ , Bi ₂ Mo ₃ O ₁₂ , and ME ¹ _0.13 MoO ₃ Characterized in that it has a mixed phase
Multicomponent bismuth molybdate catalyst.
The catalyst prepared according to the process of any one of claims 1 to 10 has an X-ray diffraction spectrum of at least one of 9.84 to 9.96, 13.02 to 13.20, 18.62 to 18.70, 23.18 to 23.26, 25.54 to 25.62, 26.38 to 26.46, 28.38, 32.00 to 32.08, 33.58 to 33.66, and 45.04 to 45.12 in the range of 2 theta.
Providing a mixed gas of C4 mixture, oxygen, nitrogen and steam as reactants; And
And an oxidative dehydrogenation reaction step in which the reactant is continuously passed through a catalyst layer on which a multicomponent bismuth molybdate catalyst prepared according to the method of any one of claims 1 to 10 is fixed By weight of 1,3-butadiene.
14. The method of claim 13,
Wherein the C4 mixture comprises 0.01 to 30% by weight of n-butane, 30 to 99.99% by weight of n-butene and 0.01 to 10% by weight of a C4 mixture excluding n-butane and n-butene. 3-butadiene.
14. The method of claim 13,
Wherein the reactant comprises n-butene: oxygen: nitrogen: steam in a molar ratio of 1: 0.5-2: 2-20: 2-20.
14. The method of claim 13,
Wherein the oxidative dehydrogenation reaction is carried out at a reaction temperature of 250 to 350 占 폚 and a space velocity (GHSV) of 50 to 5000 ^{-1 on} a n-butene basis.

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