KR20140128533A - Catalyst for production from butene mixture to butadiene and method of preparing the same - Google Patents

Abstract

The present invention relates to a multi-component based bismuth molybdate catalyst for manufacturing butadiene. More specifically, in the present invention, the multi-component based bismuth molybdate catalyst includes bismuth, molybdenum and at least one metal component with monovalent, bivalent or trivalent cation and further contains cesium, thereby having effects of improving the conversion rate, the selectivity and the yield of butadiene and securing the stability of process operation by reducing thermal variation rate and the selectivity of by products such CO, COx or the like.

Description

Catalyst for production of butadiene from butane mixture and method for preparing same

The present invention relates to a multicomponent bismuth molybdate catalyst for the production of butadiene from a butene mixture and a process for preparing the same. More particularly, the present invention relates to a multicomponent bismuth molybdate catalyst for bismuth; molybdenum; And at least one metal component having a monovalent, divalent or trivalent cations, wherein the multicomponent bismuth molybdate catalyst further comprises cesium. The multicomponent bismuth molar ratio Ribbed catalyst and a method for producing the same.

The production of 1,3-butadiene, an intermediate of many petrochemical products in the petrochemical market, whose demand and value are gradually increasing, includes 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.

The process for producing 1,3-butadiene using a multicomponent bismuth molybdate catalyst is a process for obtaining 1,3-butadiene with high yield by using 1-butene alone as a reactant having relatively high reaction activity in n-butene, -Butane and n-butene is used as a reactant, a very complicated multicomponent bismuth molybdate catalyst having at least six metal components in any ratio is used. That is, in order to increase catalytic activity, an additional metal component is continuously added, so that the catalyst component is very complicated, so that the synthesis route of the catalyst production is complicated and it is difficult to ensure reproducibility. In addition, the prior arts have found that even if only pure n-butene (1-butene or 2-butene) is used as a reactant or a mixture of n-butane and n-butene is used as a reactant, the content of n-butane is less than 10% C4 mixture is used as a reactant. Therefore, when a C4 mixture having a high content of n-butane is used as a reactant, a C4 mixture is used as a reactant. Therefore, when a C4 mixture having a high n-butane content is used as a reactant, The yield of 3-butadiene is lowered. The C4 mixture, which can be easily obtained in an actual petrochemical process, contains a high content of n-butane. In order to apply the catalyst of the conventional technology to the commercialization process, a further step of separating n-butene is required. Which can not be avoided due to the economical deterioration.

BACKGROUND OF THE INVENTION [0002] Conventional techniques for preparing 1,3-butadiene through oxidative dehydrogenation of n-butene include the use of pure 1-butene and 2-butene as reactants to produce 1,3-butadiene When a C4 mixture containing n-butene is used as a reactant, a multi-component bismuth molybdate catalyst having a very high content of n-butene and a very complicated combination of many metal components for high activity of the catalyst, Is complicated and the reproducibility of catalyst production is poor.

An object of the present invention for solving the problems of the prior art as described above in the manufacture of butadiene from the butene mixture, having a conversion rate, yield and selectivity of the improved butadiene, low for the by-products such as CO or CO ₂ And a method for producing butadiene using the same, which is capable of securing the stability of the process operation by having selectivity.

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

In order to achieve the above object, molybdenum; And at least one metal component or silicon (Si) component having 1 to 3 cations, wherein the multicomponent bismuth molybdate catalyst further comprises cesium. The multicomponent bismuth molybdate for producing butadiene Lt; / RTI >

The present invention provides a process for preparing a bismuth precursor, comprising: a) preparing a first solution by dissolving a bismuth precursor in a solvent; b) preparing a second solution by dissolving 1 to 3 of a cationic metal precursor or a silicon precursor and a cesium precursor in a solvent; c) dissolving the molybdenum precursor in a solvent to prepare a third solution; d) adding and mixing the first solution to the second solution; e) adding a solution mixed with the first solution and the second solution to the third solution and coprecipitating it; And e) drying and calcining the precipitate.

The steps a) to c) may be performed independently and may not be limited to the order.

The present invention also relates to a method for producing a polyamic acid catalyst, comprising the steps of: i) filling a reactor with the multicomponent bismuth molybdate catalyst in a fixed phase; And ii) conducting an oxidative dehydrogenation reaction while continuously passing a C4 mixture containing butene, air and steam into the catalyst bed of the reactor to obtain 1,3-butadiene. 3-butadiene.

The C4 mixture may be, for example, a C4 mixture produced in the naphtha cracking process. In another example, it may be a mixture of hydrocarbons having 4 carbon atoms. In another example, it may be a mixture containing butene and normal butane.

As described above, the multicomponent bismuth molybdate catalyst for the production of butadiene from the butene mixture according to the present invention has an excellent butadiene selectivity and an improvement in the yield of butadiene, and the selection of by-products such as CO or CO _x It is possible to secure the stability of the process operation by reducing the degree of heat and thermal fluctuation.

The present invention relates to bismuth; molybdenum; And a metallic component or a silicon component having 1 to 3 cations, wherein the multi-component bismuth molybdate catalyst further comprises cesium. The multi-component bismuth molybdate catalyst for producing a butadiene according to claim 1, Lt; / RTI >

In addition, the present invention provides a multicomponent bismuth molybdate catalyst based on bismuth, molybdenum, tungsten, iron, cobalt, potassium and cesium as metal components.

The cesium component may be contained in an amount of 0.01 to 2 mol, 0.01 to 1 mol, or 0.02 to 0.7 mol based on 1 mol of the bismuth component, and has a high selectivity to yield and a low thermal regression rate within this range.

In addition, the present invention may further include rubidium as a metal component, for example.

The rubidium may be, for example, 0 to 2 mols, 0.01 to 1 mols, 0.05 to 0.5 mols, or 0.05 to 0.15 mols, and the process is more stable with a low thermal fluctuation rate within this range.

The present invention relates to a process for the production of a ferritic stainless steel having a molar ratio of bismuth: molybdenum: tungsten: iron: cobalt: potassium: cesium: rubidium in the range of 0.5 to 3: 11.8: 0.2: 0.5 to 3: 1 to 10: 0 to 1: 0.01 to 2: More preferably from 1 to 2: 11.8: 0.2: 1 to 2: 6 to 9: 0 to 0.1: 0.3 to 0.6: 0 to 0.6 or 1: 2: 6 to 9: 0 to 0.1: 0.01 to 0.15: 0 to 0.15. A low thermal fluctuation ratio within this range has a more stable effect on the process operation.

As a preferred embodiment of the present invention, a process for producing butadiene from a butene raw material by adding Cs to an Mo-Bi-Fe-Co based oxidation catalyst for producing butadiene from butene mixture and further optimizing the amount of Cs added There is provided a multicomponent bismuth molybdate catalyst having improved conversion, yield and selectivity, a method for producing the same, and a method for producing 1,3-butadiene from a C4 mixture containing butene using the same.

In addition, the present invention provides a method for preparing a bismuth precursor solution, comprising the steps of: a) preparing a first solution by dissolving a bismuth precursor in a solvent; b) preparing a second solution by dissolving 1 to 3 of a cationic metal precursor or a silicon precursor and a cesium precursor in a solvent; c) dissolving the molybdenum precursor in a solvent to prepare a third solution; d) adding and mixing the first solution to the second solution; e) adding a solution mixed with the first solution and the second solution to the third solution and coprecipitating it; And e) drying and calcining the precipitate. The present invention also provides a method for producing a multicomponent bismuth molybdate catalyst for producing butadiene.

The first, second and third solutions are, for example, aqueous solutions.

Examples of the metal precursor having 1 to 3 cations include cobalt precursor, zinc precursor, magnesium precursor, manganese precursor, copper precursor, iron precursor, potassium precursor, rubidium precursor, sodium precursor, vanadium precursor, zirconium precursor, And more preferably at least one selected from the group consisting of iron precursors, cobalt precursors, tungsten precursors, potassium precursors and rubidium precursors.

In a preferred embodiment of the present invention, the metal precursor having the 1 to 3 cations is an iron precursor, a cobalt precursor, a tungsten precursor, a potassium precursor and, if necessary, a rubidium precursor, and the bismuth: molybdenum: tungsten: iron: cobalt: potassium The molar ratio of cesium: rubidium is preferably 0.5 to 3: 11.8: 0.2: 0.5 to 3: 1 to 10: 0 to 1: 0.01 to 2: 0 to 2, more preferably 1: 2 to 11.8: 0.2 : 1 to 2: 6 to 9: 0 to 0.1: 0.3 to 0.6: 0 to 0.6 or 1 to 2: 11.8: 0.2: 1 to 2: 6 to 9: 0 to 0.1: 0.01 to 0.15: 0 to 0.15 In this range, the process has a more stable effect with a low thermal fluctuation rate.

When the molar ratio of cesium and rubidium is 0.01 to 2: 0 to 2, the sum (x + y) of molar ratios of cesium (x) and rubidium (y) may be 0.6, Process operation is more stable.

The sum (x + y) of the molar ratio of cesium (x) and rubidium (y) may be 0.15, for example, in the case where the mole ratio of cesium and rubidium is 0.01 to 0.15: 0 to 0.15. Process operation is more stable.

The metal precursor for preparing the multicomponent bismuth molybdate catalyst may be any metal conventionally used in the art. In the present invention, bismuth nitrate is used as a precursor of bismuth, and ammonium bismuth nitrate is used as a precursor of molybdenum. Ammonium molybdate is used.

The first solution may further include an acid, for example.

The acid may be, for example, an inorganic acid or nitric acid, and may be contained in an amount such that the bismuth precursor can be dissolved.

The drying of the e) may be performed at 100 to 200 ° C, 100 to 150 ° C, or 110 to 130 ° C, for example.

The calcination of e) is carried out at a temperature of 300 to 600 ° C, preferably at a temperature of 350 to 550 ° C, more preferably 400 to 500 ° C, It is effective.

In addition, the process for producing 1,3-butadiene according to the present invention comprises the steps of: a) charging the reactor with the multicomponent bismuth molybdate catalyst for producing the butadiene in a fixed phase; And b) conducting an oxidative dehydrogenation reaction while continuously passing a reactant containing a C4 mixture containing butene, air and steam into the catalyst bed of the reactor to obtain 1,3-butadiene.

The oxidative dehydrogenation reaction is preferably carried out at a reaction temperature of 250 to 350 ° C and a contact time of 50 to 5000 grams of catalyst per hour of moles of butene mole.

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 present invention. Such variations and modifications are intended to be within the scope of the appended claims.

[Example]

Example  One

As a precursor of bismuth, bismuth nitrate pentahydrate was used. As a precursor of molybdenum, ammonium molybdate tetra hydrate ((NH ₄ ) ₆ (Mo ₇ O ₂₄ ) .4 (H ₂ O)) and tungsten precursor is ammonium tungstate para-pentahydrate _{(10 (NH 4) W 12} O 41 · 5 (H 2 O)), as the iron precursor is iron nitrate _{(Fe (NO 3) 3 ·} 9 (H 2 O)) 9 As a precursor of hydrate and cobalt, cobalt nitrate hexahydrate (Co (NO ₃ ) ₂ .6 (H ₂ O)), potassium nitrate (KNO ₃ ) as a precursor of potassium and rubidium nitrate RbNO ₃ ), and cesium nitrate (CsNO ₃ ) was used as a precursor of cesium. Other metal precursors dissolve well in distilled water, but since bismuth nitrate pentahydrate is well soluble in strong acidic solutions, nitric acid solution is added to distilled water to dissolve bismuth nitrate pentahydrate separately.

Thereafter, the bismuth precursor aqueous solution was mixed with a metal precursor aqueous solution having 1 to 3 cations, and this mixed aqueous solution was mixed with an aqueous solution of a molybdenum precursor and coprecipitated. Subsequently, the co-precipitated precipitate was dried in an oven at 120 ° C. for one day and then calcined at 400 to 500 ° C. for 5 hours to prepare a multicomponent bismuth molybdate catalyst. In this case, the respective molar ratios were Mo: W: Bi: Fe: Co: Cs: Rb: K = 11.8: 0.2: 1: 1: 4.4: 0.6: 0: 0.06.

Example  2

Example 1 was carried out in the same manner as in Example 1 except that the catalyst was prepared by increasing the molar ratio of Co to 5.70 and reducing the molar ratio of Cs to 0.3 and the molar ratio of Rb to 0.3 in Example 1.

Example  3

The procedure of Example 1 was repeated except that the molar ratio of Co was increased to 7.0, the molar ratio of Cs was reduced to 0.3, and the molar ratio of Rb was 0.3 to prepare a catalyst.

Example  4

The catalyst was prepared in the same manner as in Example 3, except that a catalyst having a Cs molar ratio reduced to 0.15 in Example 3 was prepared.

Example  5

The procedure of Example 3 was repeated, except that the catalyst was prepared by reducing the molar ratio of Cs to 0.07 and reducing the molar ratio of Rb to 0.08 in Example 3 above.

Example  6

Example 3 was carried out in the same manner as in Example 3 except that the catalyst was prepared by reducing the molar ratio of Cs to 0.03 and reducing the molar ratio of Rb to 0.12 in Example 3.

Comparative Example  One

The procedure of Example 1 was repeated except that Cs was not added.

Comparative Example  2

Except that Cs, Rb, and K were not added.

[Test Example]

The conversion, the selectivity of butadiene, the yield of butadiene, the selectivity of Co _x and the thermal fluctuation rate of the bismuth molybdate catalyst prepared in Examples 1 to 6 and Comparative Examples 1 and 2 were measured by the following method, Are shown in Table 1 below.

As reactants, trans-2-butene, cis-2-butene and oxygen were used and nitrogen and steam were added together. As the reactor, a metal tubular reactor was used. The ratio of the reactants and the gas hourly space velocity (GHSV) were set on the basis of 2-butene. The ratio of butane: oxygen: steam: nitrogen was set to 1: 0.75: 6: 10, and the GHSV was adjusted to 50 and 75h ^{- 1} on the basis of butene. The volume of the catalyst layer contacting the reactants was fixed at 200 cc. The steam was injected in the form of water as a vaporizer, vaporized at 340 ° C by steam, mixed with other reactants, 2-butene and oxygen, Respectively. The amount of butenes was controlled by using a mass flow controller for liquids. The oxygen and nitrogen were controlled using a mass flow controller for gas, and the amount of steam was controlled using a liquid pump. The reaction temperature was maintained at 300 ℃, 320 ℃ and 340 ℃, and 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 the 2-butene, the selectivity (S_BD) and the yield (Y_BD) of 1,3-butadiene were calculated by the following equations (1), (2) and (3), respectively.

[Equation 1]

&Quot; (2) "

&Quot; (3) "

Metrics Co (moles) K (moles) Cs (moles) Rb (mol) X (%) S_BD (%) Y_BD (%) Thermal fluctuation rate? T (占 폚) Comparative Example 1 4.40 0.06 0.00 0.00 80.35 87.72 70.47 66.6 Comparative Example 2 7.00 0.00 0.00 0.00 94.22 41.72 39.32 133.0 Example 1 4.40 0.06 0.60 0.00 66.91 93.39 62.49 26.9 Example 2 5.70 0.06 0.30 0.30 75.73 91.48 69.28 43.7 Example 3 7.00 0.06 0.30 0.30 76.72 92.34 70.84 46.2 Example 4 7.00 0.06 0.15 0.00 79.16 93.89 75.53 35.0 Example 5 7.00 0.06 0.07 0.08 79.12 92.16 72.92 31.8 Example 6 7.00 0.06 0.03 0.12 81.79 90.03 73.64 32.8

As shown in Table 1, Comparative Examples 1 and 2 show high ΔT and low selectivity. To solve the problems, Examples 1 to 6 in which Cs was added show low conversion and yield of 1,3-butadiene , But the selectivity is improved and 隆 T is lowered. In order to obtain reduced conversion and yield in Example 1, the molar ratios of Co were increased to 5.7 and 7.0, the molar ratio of Cs was reduced to 0.3, and the molar ratio of Rb was increased to 0.3 as in Examples 2 and 3, respectively Comparing Example 1 with Examples 2 and 3, the higher the content of Co, the lower the selectivity, but the higher the conversion and yield and the higher the value of T, the influential of Co can be confirmed . In the case of Comparative Example 2, it was confirmed that δT reached 133 ° C. as a result of proceeding at a level corresponding to 80% of the flow rate of 2-butene under the experimental conditions specified in the present invention. The conversion was found to be as high as 94% due to the influence of Co, but the selectivity was extremely lowered due to the absence of Cs. As a result, yields of 60% of those of Examples 3 to 6 were obtained. These comparative examples and embodiments show that the selectivity increases when Cs and optionally Rb are included. It can be confirmed that Examples 3 to 6 have a higher selectivity and yield than Comparative Example 1 and significantly lower δT.

In addition, it can be confirmed that the multicomponent bismuth molybdate catalyst for producing butadiene according to Examples 1 to 6 has a lower thermal fluctuation rate than Comparative Examples 1 and 2, thereby ensuring the stability of the process operation.

Claims (14)

Bismuth; molybdenum; And at least one metal component or a silicon component having 1 to 3 cations, wherein the cerium compound further comprises cesium, and from the mixture containing butene, 1,3-butadiene Component bismuth molybdate catalyst for the production of butadiene. The method according to claim 1,
Wherein the metal component having 1 to 3 cations is cobalt, zinc, magnesium, manganese, copper, iron, potassium, sodium, aluminum, rubidium, vanadium, zirconium and tungsten. . 3. The method of claim 2,
Component bismuth molybdate catalyst for the production of butadiene characterized in that the metal component having the 1 to 3 cations is iron, cobalt tungsten, potassium and rubidium. The method of claim 3,
Wherein the molar ratio of bismuth: molybdenum: tungsten: iron: cobalt: potassium: cesium: rubidium is 0.5-3: 11.8: 0.2: 0.5-3: 1 - 10: 0-1: 2: 0 to 2. 2. The multicomponent bismuth molybdate catalyst for producing butadiene according to claim 1, a) preparing a first solution by dissolving a bismuth precursor in a solvent;
b) preparing a second solution by dissolving 1 to 3 of a cationic metal precursor or a silicon precursor and a cesium precursor in a solvent;
c) dissolving the molybdenum precursor in a solvent to prepare a third solution;
d) adding and mixing the first solution to the second solution;
e) adding a solution mixed with the first solution and the second solution to the third solution and coprecipitating it; And
and e) drying and calcining the precipitate. The method for producing a multicomponent bismuth molybdate catalyst for producing butadiene according to claim 1, 6. The method of claim 5,
The 1 to 3 valent cation metal precursors include a cobalt precursor, a zinc precursor, a magnesium precursor, a manganese precursor, a copper precursor, a iron precursor, a potassium precursor, a sodium precursor, a rubidium precursor, an aluminum precursor, a vanadium precursor, a zirconium precursor and a tungsten precursor Wherein at least one kind of the bismuth molybdate catalyst is selected from the group consisting of a bismuth molybdate catalyst and a bismuth molybdate catalyst. The method according to claim 6,
The molar ratio of bismuth: molybdenum: tungsten: iron: cobalt: potassium: cesium: rubidium is 0.5 to 3: 11.8: 0.2 Component bismuth molybdate catalyst for producing butadiene, wherein the molar ratio of bismuth molybdate catalyst is 0.5 to 3: 1 to 10: 0 to 1: 0.01 to 2: 0.00 to 2. 6. The method of claim 5,
Wherein the bismuth precursor is bismuth nitrate. The method of claim 1, wherein the bismuth precursor is bismuth nitrate. 6. The method of claim 5,
Wherein the molybdenum precursor is ammonium molybdate. ≪ RTI ID = 0.0 > 11. < / RTI > 6. The method of claim 5,
Wherein the first solution comprises an acid. ≪ RTI ID = 0.0 > 11. < / RTI > 6. The method of claim 5,
Wherein the drying is carried out at a temperature of from 100 to 200 ° C. 2. The method for producing a multicomponent bismuth molybdate catalyst for producing butadiene according to claim 1, 6. The method of claim 5,
Wherein the calcination is carried out at a temperature ranging from 300 to 600 ° C. 2. The method for producing a multicomponent bismuth molybdate catalyst for producing butadiene according to claim 1, I) filling the reactor with a fixed bed of the multicomponent bismuth molybdate catalyst for preparing the butadiene of claim 1; And
Ii) 1,3-butadiene is obtained by conducting an oxidative dehydrogenation reaction while continuously passing a C4 mixture containing butene, air and steam into the catalyst bed of the reactor. -Butadiene. 14. The method of claim 13,
Wherein the oxidative dehydrogenation reaction is carried out at a reaction temperature of 250 to 350 ° C and a contact time of 50 to 5000 grams of catalyst per hour of moles of butene mole.