KR20110130130A - Multi-component metal oxide catalysts containing a bipo4, preparing method thereof and preparing method of 1,3-butadiene using the same - Google Patents

Abstract

PURPOSE: A bismuth phosphate-containing a multi-component-based metal oxide catalyst, a method for preparing the same, and a method for preparing 1,3-butadiene using the same are provided to improve the yield of the 1,3-butadiene by increasing the selectivity of the catalyst. CONSTITUTION: A method for preparing a bismuth phosphate-containing a multi-component-based metal oxide catalyst includes the following: The catalyst is represented by chemicl formula 1. A bismuth precursor, an iron precursor, and a nickel precursor are dissolved in an aqueous solution, and the dissolved aqueous solution is introduced into a molybdenum precursor dissolved aqueous solution to obtain a first solution. A phosphorus precursor is added into the first solution to obtain a second solution. The pH value of the second solution is adjusted to be in a range between 3.0 and 6.0. A stirring process and a coprecipitating process are implemented to obtain a coprecipitated solution. The coprecipitated solution is filtered to obtain a solid sample. The solid sample is dried at a temperature between 80 and 110 degrees Celsius in order to obtain a dried catalyst. The dried catalyst is thermally treated at a temperature between 400 and 600 degrees Celsius.

Description

Multi-component metal oxide catalysts containing a BiPO4, Preparing method etc. and preparing method of 1,3-Butadiene using the same }

The present invention relates to a multicomponent metal oxide catalyst comprising a BiPO ₄ phase and comprising bismuth, molybdenum, iron, nickel and phosphorus in a specific molar ratio, and a method for preparing the same. A method for producing, 3-butadiene in high yield.

1,3-butadiene is used to prepare synthetic rubbers such as styrene butadiene rubber (SBR), polybutadiene rubber (BR), butadiene homopolymer, or acrylonitrile acrylonitrile, a thermoplastic trimer butadiene styrene (ABS).

Generally, 1,3-butadiene is manufactured by the thermal decomposition method (cracking method) of a saturated hydrocarbon, using naphtha as a raw material normally. Pyrolysis of naphtha results in a mixture of methane, ethane, ethene, acetylene, propane, propene, propene, allene, butene, butadiene, and C ₅ or higher hydrocarbons. Therefore, the production of 1,3-butadiene through the pyrolysis method is also very inefficient as a method for producing 1.3-butadiene because other olefins which are the above by-products are simultaneously synthesized.

Another manufacturing method is a method of manufacturing by direct dehydrogenation, which has a higher yield of 1,3-butadiene than a cracking method, but has a disadvantage in that it is not thermodynamically suitable and requires a high reaction temperature.

Overcoming this drawback is the oxidative dehydrogenation method, which reacts butene with oxygen to produce 1,3-butadiene and water, which is carried out in the presence of steam, The vapor acts as a heat transporter and promotes vaporization of organic deposits on the catalyst, preventing carbonization of the catalyst and increasing the outflow time of the catalyst. Organic deposits are converted to carbon monoxide, carbon dioxide and water, where stable water is produced as a product, which is not only thermodynamically advantageous but also lowers the reaction temperature. In other words, oxidative dehydrogenation is thermodynamically stable and has good selectivity for olefins at low temperatures. In general, in oxidative dehydrogenation reactions, radicals generated at the beginning of the reaction are important reaction intermediates and desorb on the solid surface during the reaction. It is moved to the part to participate in the homogeneous catalysis. Suitable catalysts for oxidative dehydrogenation of butenes to 1,3-butadiene are bismuth molybdenum based oxides [APV Soares, LK Kimitrov, MCA Oliveira, L. Hilaire, MF Portela, RK Grasselli, Appl. Catal., 253, 191 (2003) ( β- Bi ₂ Mo ₂ O ₉ + γ- Bi ₂ MoO ₆ ), P. Boutry, R. Montarnal, J. Wrzyszcz, J. Catal., 13,75 (1969) ( β- Bi ₂ Mo ₂ O ₉ , γ- Bi ₂ MoO ₆ ), Jung, JC, Kim. H., Choi, AS, Chung, YM, Kim, TJ, Lee, SJ, Oh, SH, Song, IK, J. Mol. Catal. A: Chem., 259, 166-170 (2006) ( α- Bi ₂ Mo ₃ O ₁₂ , β- Bi ₂ Mo ₂ O ₉ , γ- Bi ₂ MoO ₆ )] and a zinc ferrite catalyst [Korea Patent No. 10 -0847206], or based on bismuth-molybdenum multi-metal oxide catalyst further comprising iron [US 4,423,281 (Mo ₁₂ BiNi ₈ Pb _0.5 Cr ₃ K _0.2 O _x , Mo ₁₂ Bi _b Ni ₇ Al ₃ Cr _0.5 K _0.5 O _x ), US 4,336,409 (Mo ₁₂ BNi ₆ Cd ₂ Cr ₃ P _0.5 O _x ), DE-A 26 00 128 (Mo ₁₂ BiNi _0.5 Cr ₃ P _0.5 Mg _7.5 K _0.1 O _x + SiO ₂ ), DE -A 24 40 329 (Mo ₁₂ BiCo _4.5 Ni _2.5 Cr ₃ P _0.5 K _0.2 O _x )].

However, bismuth molybdenum-based oxide catalysts among the catalysts specified in the above documents and patents are easy to synthesize, but have a low yield of 1,3-butadiene for butene, and very high 1,3-butadiene yield for the multimetal oxide catalyst. Although it can be obtained, there is a problem in commercialization due to the low stability of the catalyst, very difficult synthesis, difficult to secure reproducibility.

Accordingly, the present inventors are oxidative dehydrogenation of butene is a reaction of butene and oxygen to produce a 1,3-butadiene and water through a partial oxidation reaction, at this time, because the oxygen is used as a reactant, a complete oxidation reaction, etc. Because many side reactions are expected, efforts have been made to suppress these side reactions as much as possible and to develop catalysts with high selectivity of 1,3-butadiene. As a result, if iron, nickel and phosphorus (P) were added to the bismuth molybdenum-based oxide catalyst, and the composition ratio between these components was properly adjusted, durability and long-term activity would be superior to those of the bismuth molybdenum-based oxide catalyst for producing 1,3-butadiene. In addition, it was found that the catalyst can be prepared to produce a 1,3-butadiene in a high yield with excellent selectivity to complete the present invention.

Accordingly, an object of the present invention is to provide a multi-component metal oxide catalyst having excellent durability, long-term activity, and selectivity of 1,3-butadiene and a method for preparing the same.

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.

The present invention is characterized by bismuth-molybdenum-iron-nickel-phosphorus multicomponent metal oxide catalyst represented by the following formula (1).

[Formula 1]

BiMoFe _{0 .65} Ni _x P _{0 .8} O _y

In Formula 1, x is 0 <x≤2.0, and y is a real number satisfying the valence of all metal components.

In addition, the present invention is added to the aqueous solution in which the bismuth precursor, iron precursor and nickel precursor dissolved in an aqueous solution in which molybdenum precursor is dissolved, to prepare a first solution containing bismuth, molybdenum, iron and nickel in the molar ratio of the formula (1) First step; A second step of preparing a second solution by dropwise addition of a phosphorus precursor to the first solution to satisfy the molar ratio of Chemical Formula 1; A third step of preparing a coprecipitation solution by adjusting the hydrogen ion index (hereinafter pH) of the second solution to 3.0 to 6.0, followed by stirring and coprecipitation; A fourth step of obtaining a dried catalyst by drying the solid sample obtained by filtering the coprecipitation solution at 80 to 110 ° C; And a fifth step of heat-treating the dried catalyst at 400 to 600 ° C .; and a method for preparing a bismuth-molybdenum-iron-nickel-phosphorus multi-component metal oxide catalyst represented by Chemical Formula 1, comprising: It is done.

In addition, the present invention is characterized by a method for producing 1,3-butadiene by oxidative dehydrogenation of butene under a bismuth-molybdenum-iron-nickel-phosphorus multicomponent metal oxide catalyst represented by Chemical Formula 1.

The bismuth-molybdenum-iron-nickel-phosphorous multicomponent metal oxide catalyst including the BiPO ₄ phase of the present invention is not only superior in durability and long-term activity but also selectivity than the conventional bismuth molybdenum oxide catalyst for producing 1,3-butadiene. It is excellent in that it can manufacture 1, 3- butadiene with a high yield, and is suitable for the mass production of 1, 3- butadiene. In addition, the bismuth-molybdenum-iron-nickel-phosphorous multicomponent metal oxide catalyst production method of the present invention has a relatively simple synthesis path compared to the conventional multicomponent metal oxide catalyst production method, and is advantageous in securing reproducibility.

1 is an X-ray diffraction pattern of the multi-component complex metal oxide catalyst (BiMoFe _0.65 Ni _x P _0.8 O _y ) prepared in Examples 1 to 5 and Comparative Examples, (a) to (f) in order Results data for catalysts where the molar ratio x of nickel (Ni) at 1 is 0.0, 0.1, 0.3, 0.5, 0.7, and 0.9. ■ is Fe ₂ (MoO ₄ ) ₃ , ● is Bi ₃ FeMo ₂ O ₁₂ , ▼ is BiPO ₄ [low-temp. JCPDS file no. 15-0767], ▲ is BiPO ₄ [high temp. JCPDS file no. 43-0637], ↓ is β- NiMo ₄ .
Figure 2 is a reaction activity results of the catalyst represented by the _{BiMoF 0 .65 Ni x P 0 .8} O y. X stands for X = 0, ● stands for 0.1, ▲ stands for 0.3, ▼ stands for 0.5, ◀ stands for 0.7, and ▶ stands for 0.9.
3 is _{BiMoF 0 .65 Ni x P 0 .8} O y oxidative dehydrogenation results produced 1,3-butadiene (closed indicator) on the catalyst represented by and indicates the selectivity of the carbon dioxide (open display), ( X, Y represent 0.1 (▲, △) 0.3, (▼, ▽) 0.5, (◆, ◇) 0.7, and (◀, ◁) represent 0.9, respectively. .
Figure 4 is a graph showing the changes in reaction activity content of the nickel catalyst represented by the _{BiMoF 0 .65 Ni x P 0 .8} O y.

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

The present invention relates to a bismuth-molybdenum-iron-nickel-phosphorous multicomponent metal oxide catalyst containing bismuth, molybdenum, iron, nickel and phosphorus in a specific molar ratio, and is characterized by the following formula (1).

[Formula 1]

BiMoFe _{0 .65} Ni _x P _{0 .8} O _y

In Formula 1, x is 0 <x≤2.0, and y is a real number satisfying the valence of all metal components.

At this time, when x exceeds 2.0, nickel is present in the catalyst surface excessively, so that complete oxidation of butene occurs and the selectivity of carbon dioxide is increased, so that the number of moles within the range is preferably maintained, and preferably a value of 0.1 ≦ x <1.0. It is good to have.

In addition, the bismuth-molybdenum-iron-nickel-phosphorus multicomponent metal oxide catalyst of the present invention is characterized by having high durability, long life and high reaction activity without a support, and may further include a support according to use. In the case of including the support, the support is not particularly limited, but it is preferable to use one selected from alumina, silica or silica-alumina.

In addition, the present invention relates to a method for preparing a bismuth-molybdenum-iron-nickel-phosphorous multicomponent metal oxide catalyst represented by Chemical Formula 1, to prepare a solution in which bismuth, molybdenum, iron, nickel, and phosphorus are fixed at a specific molar ratio. After that, the mixture is stirred and co-precipitated under a specific pH, and dried and heat-treated to produce bismuth-molybdenum-iron-nickel-phosphorus multicomponent metal oxide catalyst.

In the first step, the first solution is prepared by dropwise adding an aqueous solution in which the bismuth precursor, an iron precursor and a nickel precursor are dissolved in acidified distilled water to an aqueous solution in which molybdenum precursor is dissolved in distilled water, and bismuth, molybdenum, iron and It is prepared to contain nickel in the molar ratio of Chemical Formula 1. When preparing the first solution, the precursor is completely dissolved by maintaining 50 to 70 ° C. Each of the bismuth precursor, molybdenum precursor, iron precursor and nickel precursor may be used in the art, and is not particularly limited, but the bismuth precursor, the iron precursor and the nickel precursor may preferably use a chloride precursor or a nitrate precursor, The molybdenum precursor is preferably used an ammonium precursor. For example, the bismuth precursor is bismuth nitrate, the molybdenum precursor is ammonium molybdate, the iron precursor is iron nitrate, and the nickel precursor is nickel nitrate ( Nickel nitrate) is preferred.

In the second step, a phosphorus precursor is added dropwise to the first solution prepared in the first step to prepare a second solution so that the phosphorus content satisfies the formula (1). The phosphorus precursor may be used in the art, but is not particularly limited, it is preferable to use phosphoric acid (Phosphoric acid) or ammonium phosphate (Ammonium phosphate).

In the third step, a pH adjuster is added to the second solution to adjust pH 3.0 to 6.0, preferably pH 4.8 to 5.2, more preferably pH 4.9 to 5.1, and perform stirring and coprecipitation. If the pH is too low or too high, there may be a problem that the phase of the material participating in the activity is not generated, it is preferable to maintain the acidity in the above range. The pH adjusting agent may be used in the art, and is not particularly limited, for example, a basic solution such as ammonia solution may be used. The solution is sufficiently stirred for 2 to 6 hours in the pH range to obtain a solution in which Bi ₁ Mo ₁ Fe _0.65 Ni _x P _0.8 O _y is co-precipitated.

In the fourth step, the coprecipitation solution is distilled under reduced pressure at 50 ~ 70 ℃ using a reduced pressure evaporator to obtain a solid sample. Next, the solid sample is sufficiently dried at 80 to 110 ° C. for 18 to 24 hours to obtain a dried catalyst.

In the fifth step, the dried catalyst of the fourth step is heat-treated at 400 to 600 ° C. to prepare a bismuth-molybdenum-iron-nickel-phosphorus multi-component metal oxide catalyst including a BiPO ₄ phase represented by Chemical Formula 1 As a process, if the heat treatment temperature is less than 400 ℃ may have a problem that can not obtain the desired crystals, if it exceeds 600 ℃ may have a problem of melting the catalyst to form a high melt, it is preferable to maintain the temperature within the above range .

Hereinafter, a method of preparing 1,3-butadiene using the bismuth-molybdenum-iron-nickel-phosphorus multicomponent metal oxide catalyst of the present invention will be described.

The present invention relates to a method for preparing 1,3-butadiene, wherein the butene is subjected to oxidative dehydrogenation under a bismuth-molybdenum-iron-nickel-phosphorus multicomponent metal oxide catalyst represented by Chemical Formula 1 to 1,3-butadiene. It is characterized by the production of butadiene.

The bismuth-molybdenum-iron-nickel-phosphorus multicomponent metal oxide catalyst may be used after pretreatment at 450 to 600 ° C for oxidative dehydrogenation of butene, preferably 450 to 550 ° C, more preferably 500 to Pretreatment at 520 ° C is recommended. If the pretreatment temperature is too high, there may be a problem that a phase change of the catalyst occurs. On the contrary, if the pretreatment temperature is too low, water and impurities in the air adsorbed on the catalyst may participate in the reaction.

The reactants of the oxidative dehydrogenation of butenes further include a mixture of air and steam in addition to butenes. The mixing ratio is butene: air: steam = 8 to 11% by volume: 30 to 50% by volume: 40 ~ 60% by volume is preferred, more preferably 10% by volume: 35 to 45% by volume: 45 to 55% by volume is preferably used. 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 butene is preferably 1-butene, and when 1-butene is used, the mixing ratio of the reactants is 1-butene: air: steam, and the mixing ratio is 10% by volume: 40% by volume: 50% by volume. It is good. The injection amount (injection amount) of the butene and air may be controlled by a mass flow controller, and the injection amount of steam may be controlled by controlling the injection speed by a microflow pump.

The injection amount (injection amount) of the reactant is 300 to 700 h ⁻¹ gas velocity space velocity (GHSV) based on butene, preferably at a space velocity of 600 to 650 h ⁻¹ , and more preferably. Preferably it is injected at a space velocity of 620 ~ 640 h ^-1 . If the space velocity is less than 300 h ^-1 , there may be a problem in profitability due to the small amount of product per unit time. If the space velocity exceeds 700 h ^-1 , butene may react with the catalyst shortly, resulting in an increase in unreacted substances. -Butadiene yield can be lowered.

And, the oxidative dehydrogenation reaction is preferably carried out under a temperature range of 350 ~ 550 ℃, preferably 350 ~ 450 ℃, more preferably 400 ~ 420 ℃ temperature, when the reaction temperature is less than 350 ℃ If the reaction temperature is too low, there may be a problem that the partial oxidation reaction does not occur well because the catalyst is not activated, and when the reaction is performed at a temperature exceeding 550 ° C., cracking products or complete oxidation of C ₁ to C ₃ may occur. It is good to maintain the temperature in the above range because there may be.

Bismuth-molybdenum-iron-nickel-phosphorous multi-component metal oxide catalyst including BiPO ₄ phase of the present invention has higher durability, long-term activity, and selectivity than conventional bismuth molybdenum-based oxide catalyst for producing 1,3-butadiene, thus providing high yield. 1,3-butadiene can be produced, and the bismuth-molybdenum-iron-nickel-phosphorous multicomponent metal oxide catalyst of the present invention is relatively simple compared with the conventional multicomponent metal oxide catalyst production method. It has a path and is advantageous for ensuring reproducibility.

Hereinafter, the present invention will be described in more detail based on examples. However, the scope of the present invention is not limited by the following examples.

[Example]

Example 1 Preparation of Bismuth-molybdenum-iron-nickel-phosphorus multicomponent metal oxide catalyst

12.4 g of bismuth nitrate pentahydrate (Bi (NO ₃ ) ₃ ㆍ 5H ₂ O, Aldrich, 98%) and 6.7 g of iron nitrate hexahydrate (Fe (NO ₃ ) ₃ ㆍ 9H ₂ O, Junsei, 98%), 0.7 g of nickel nitrate hexahydrate (Ni (NO ₃ ) ₂ .6H ₂ O, SAMCHUN, 98%) was added to distilled water (85 ml) to which nitric acid was added, followed by stirring. Bi: Fe: Ni = 1: 0.65: A bismuth-iron-nickel aqueous solution containing 0.1 molar ratio was prepared. Since bismuth nitrate pentahydrate is well dissolved in a strong acid solution, nitric acid solution was added to distilled water to dissolve bismuth nitrate pentahydrate. Since iron nitrate hexahydrate and nickel nitrate hexahydrate were well dissolved in distilled water, the salt was added to the acid solution in which bismuth nitrate pentahydrate was dissolved. Separately, 4.5 g of ammonium molybdate tetrahydrate ((NH ₄ ) ₆ Mo ₇ O ₂₄ 4H ₂ O, Wako Pure Chemical, 98%) was added to distilled water (74 ml) and stirred to dissolve the molybdenum precursor solution. Was prepared. The temperature of the distilled water was adjusted to 60 ℃ for the dissolution of ammonium molybdate. Then, the bismuth-iron-nickel aqueous solution is added dropwise to the molybdenum aqueous solution, and the bismuth, molybdenum, iron, and nickel are contained in a molar ratio of Bi: Mo: Fe: Ni = 1: 1: 0.65: 0.1 by adjusting the temperature of the aqueous solution to 60 ° C. To prepare a first solution.

Next, 2.3 g of a phosphoric acid solution (H ₃ PO ₄ , SAMCHUN) at a concentration of 85% was added dropwise to the first solution as a precursor of phosphorus to the first solution to prepare a second solution, followed by aqueous ammonia solution (NH 4 OH, SAMCHUN, 28). %) Was adjusted to pH 5.0 and stirred for 3 hours at 60 ℃ using a magnetic stirrer to prepare a coprecipitation solution.

Next, after evaporating the water of the coprecipitation solution using a reduced pressure distillation to obtain a solid catalyst, the solid catalyst was dried at 100 ° C. for 24 hours, then placed in an electric furnace and heat treated at 550 ° C. for 2 hours to prepare a BiPO ₄ phase. A bismuth-molybdenum-iron-nickel-phosphorous multicomponent metal oxide catalyst was prepared.

Examples 2 to 5: Preparation of Bismuth-molybdenum-iron-nickel-phosphorous multicomponent metal oxide catalyst

A multicomponent metal oxide catalyst was prepared in the same manner as in Example 1 except that bismuth-molybdenum-iron-nickel-different molar ratio of nickel was adjusted by adjusting the amount of nickel nitrate hexahydrate. The composition ratio is shown in Table 1 below.

Comparative Example: Preparation of Bismuth-molybdenum-iron-phosphorus Multicomponent Metal Oxide Catalyst

In the same manner as in Example 1, a bismuth-molybdenum-iron-phosphorus multicomponent metal oxide catalyst was prepared, which did not use nickel nitrate hexahydrate.

division Mole ratio Bi Mo Fe Ni P Comparative example 1.00 1.00 0.65 0.00 0.80 Example 1 1.00 1.00 0.65 0.10 0.80 Example 2 1.00 1.00 0.65 0.30 0.80 Example 3 1.00 1.00 0.65 0.50 0.80 Example 4 1.00 1.00 0.65 0.70 0.80 Example 5 1.00 1.00 0.65 0.90 0.80

Test Example  1: manufactured Multicomponent system  X-ray of metal oxide catalyst Diffraction analysis ( XRD ) exam

The prepared catalyst was analyzed using an X-ray diffractometer (Siemens D-5005, CuKα = 1.5418 Hz) using Ni-filter at 40 kV and 40 mA. The analysis results are shown in FIG. 1 and Table 2 below. Same as

division Manufacture catalyst Mole ratio X-ray Diffraction Bi Mo Fe Ni P Comparative example _{BiMoFe 0 .65 P 0 .8 O 7} .475 1.00 1.00 0.65 0.00 0.80 BiPO ₄ [JCPDS file no. 43-0637], BiPO ₄ [JCPDS file no. 15-0767], Fe ₂ (MoO ₄ ) ₃ , Bi ₃ FeMo ₂ O ₁₂ Example 1 _{BiMoFe 0 .65 Ni 0 .1 P 0} .8 O 7 .575 1.00 1.00 0.65 0.10 0.80 BiPO ₄ [JCPDS file no. 43-0637], BiPO ₄ [JCPDS file no. 15-0767], Fe ₂ (MoO ₄ ) ₃ , Bi ₃ FeMo ₂ O _12, β -NiMo ₄ Example 2 _{BiMoFe 0 .65 Ni 0 .3 P 0} .8 O 7 .775 1.00 1.00 0.65 0.30 0.80 BiPO ₄ [JCPDS file no. 43-0637], BiPO ₄ [JCPDS file no. 15-0767], Fe ₂ (MoO ₄ ) ₃ , Bi ₃ FeMo ₂ O _12, β -NiMo ₄ Example 3 _{BiMoFe 0 .65 Ni 0 .5 P 0} .8 O 7 .975 1.00 1.00 0.65 0.50 0.80 BiPO ₄ [JCPDS file no. 43-0637], BiPO ₄ [JCPDS file no. 15-0767], Fe ₂ (MoO ₄ ) ₃ , Bi ₃ FeMo ₂ O _12, β -NiMo ₄ Example 4 _{BiMoFe 0 .65 Ni 0 .7 P 0} .8 O 8 .175 1.00 1.00 0.65 0.70 0.80 BiPO ₄ [JCPDS file no. 43-0637], BiPO ₄ [JCPDS file no. 15-0767], Fe ₂ (MoO ₄ ) ₃ , Bi ₃ FeMo ₂ O _12, β -NiMo ₄ Example 5 _{BiMoFe 0 .65 Ni 0 .9 P 0} .8 O 8 .375 1.00 1.00 0.65 0.90 0.80 BiPO ₄ [JCPDS file no. 43-0637], BiPO ₄ [JCPDS file no. 15-0767], Fe ₂ (MoO ₄ ) ₃ , Bi ₃ FeMo ₂ O _12, β -NiMo ₄

As shown in Figure 1 and Table 2, it can be seen that the catalytic properties of various components are formed, in particular β -NiMo ₄ according to the addition of nickel It can be seen that the catalyst phase has formed.

Test Example 2: Test for Determination of Activity of Catalyst

Each of the catalysts prepared in Examples 1 to 5 and Comparative Example was fixed in the stainless steel (SUS) reactor with the heat treated catalyst, and the reactor was installed in an electric furnace and pretreated at 500 ° C. for 2 hours in a nitrogen atmosphere. After the reaction temperature of the pretreated catalyst bed was kept constant, the reaction was allowed to run for 14 hours while continuously passing the reactants through the catalyst bed.

The reaction temperature for the oxidative dehydrogenation reaction was maintained at 420 ° C., and the injection amount of the reactant was adjusted to a space velocity (GHSV) of 632 h ⁻¹ based on 1-butene, and the amount of catalyst was set at 0.5 g. . In addition, as a reactant, a product containing 1.3-butadiene was subjected to an oxidative dehydrogenation reaction using a mixed gas having a mixing ratio of 1-butene: air: steam at 10% by volume: 40% by volume: 50% by volume. Prepared. The air is general air containing 79% nitrogen and 21% oxygen.

The reaction device was designed such that steam of the reactants was initially injected into the water, but before the injection into the fixed bed reactor by setting a preheating section, the steam was vaporized at 190 ° C. and injected into the reactor together with the other reactants. In addition, the amount of 1-butene and air was controlled through a mass flow controller, and the amount of steam was controlled by adjusting the injection rate of the microfluidic pump.

The catalytic activity was measured by sending each of the products of the oxidative dehydrogenation reaction to a gas chromatograph (Varian CP3800) equipped with a thermal conductivity detector and a flame ion detector, using a PORAPAK Q packed column maintained at 60 ° C. Hydrocarbons were analyzed by Al ₂ O ₃ capillary column. The conversion rate of 1-butene with time is shown in FIG. 2, and the selectivity of 1,3-butadiene and carbon dioxide with time is shown in FIG. 3, and the conversion rate of 1-butene after 14 hours of oxidative dehydrogenation reaction, 1,3- The yield and selectivity of butadiene and the yield of carbon dioxide are shown in Table 3 and FIG. 4. Conversion of 1-butene, selectivity of 1,3-butadiene, and yield of 1,3-butadiene were calculated using the following Equations 1 to 3, respectively.

 Equation 1: conversion rate of 1-butene

Equation 2: Selectivity of 1,3-butadiene

Equation 3: yield of 1,3-butadiene

division BiFe _{0 .65} Ni _x MoP _{0 .8}
Nickel content 1-butene
% Conversion 1,3-butadiene
Selectivity (%) 1,3-butadiene
yield(%) CO ₂ of
yield(%) Comparative example 0.0 47.6 87.0 41.4 5.0 Example 1 0.1 52.4 74.6 39.1 12.1 Example 2 0.3 62.9 85.9 54.0 8.1 Example 3 0.5 84.1 86.1 72.4 10.7 Example 4 0.7 86.8 85.9 74.6 11.1 Example 5 0.9 69.6 78.9 54.9 14.6

After 14 hours of oxidative dehydrogenation, the product contains not only 1,3-butadiene but also carbon dioxide produced by complete oxidation and by-products of C ₁ to C ₃ such as methane and ethane by cracking. As shown in Table 3, the bismuth-molybdenum-iron-nickel-phosphorus multicomponent metal oxide catalyst of the present invention showed a difference in reactivity according to the content of nickel (Ni), in particular BiMoFe _{0 . 65} Ni _{0 .7} yield of the conversion and the 1,3-butadiene after 14 hours the reaction of P _{0 .8} butene was the highest to 87%, 75%, respectively. Nickel-free bismuth-iron-molybdenum-based multi-component metal oxide catalysts have a high selectivity for 1,3-butadiene and low carbon dioxide yields as shown in Table 3 and FIGS. 3 and 4. However, the conversion was lower than the catalyst of the present invention.

Through the above examples and test examples, the bismuth-molybdenum-iron-nickel-phosphorus multicomponent metal oxide catalyst of the present invention has a high butene conversion and selectivity of 1,3-butadiene, and is an excellent catalyst capable of maintaining long-term activity. Confirmed. In addition, the production method of the bismuth-molybdenum-iron-nickel-phosphorous multi-component metal oxide catalyst of the present invention can be reproduced by a relatively simple catalyst synthesis process, thereby securing a single process capable of stably producing 1,3-butadiene. In addition, it is expected to be able to cope effectively with the demand of 1,3-butadiene in the era of high oil prices.

Claims (8)

Bismuth-molybdenum-iron-nickel-phosphorus multicomponent metal oxide catalysts represented by the following Chemical Formula 1;
[Formula 1]
_{BiMoFe 0 .65 Ni x P 0 .8} O y
In Formula 1, x is 0 <x≤2.0, and y is a real number satisfying the valence of all metal components.
A first step of preparing a first solution containing bismuth, molybdenum, iron, and nickel in a molar ratio of Formula 1 by adding an aqueous solution in which a bismuth precursor, an iron precursor, and a nickel precursor are dissolved into an aqueous solution in which a molybdenum precursor is dissolved;
A second step of preparing a second solution by dropwise addition of a phosphorus precursor to the first solution to satisfy a molar ratio of Formula 1;
A third step of preparing a coprecipitation solution by adjusting the pH of the second solution to 3.0 to 6.0, followed by stirring and coprecipitation;
A fourth step of obtaining a dried catalyst by drying the solid sample obtained by filtering the coprecipitation solution at 80 to 110 ° C; And
A fifth step of heat-treating the dried catalyst at 400 to 600 ° C;
Method for producing a bismuth- molybdenum- iron- nickel- phosphorus multi-component metal oxide catalyst represented by the formula (1) comprising a;
[Formula 1]
_{BiMoFe 0 .65 Ni x P 0 .8} O y
In Formula 1, x is 0 <x≤2.0, and y is a real number satisfying the valence of all metal components.
According to claim 2, wherein the bismuth precursor is bismuth nitrate (Bismuth nitrate), the molybdenum precursor is ammonium molybdate, the iron precursor is iron nitrate (Iron nitrate), the precursor of nickel is nickel nitrate ( Nickel nitrate) bismuth-molybdenum-iron-nickel-phosphorous multicomponent metal oxide catalyst.
The method of claim 2, wherein the phosphorus precursor is phosphoric acid (Phosphoric acid) or ammonium phosphate (Ammonium phosphate), characterized in that the bismuth- molybdenum- iron- nickel- phosphorus multi-component metal oxide catalyst production method.
A method for preparing 1,3-butadiene by oxidative dehydrogenation of butenes under a bismuth-molybdenum-iron-nickel-phosphorus multicomponent metal oxide catalyst represented by Formula 1;
[Formula 1]
_{BiMoFe 0 .65 Ni x P 0 .8} O y
In Formula 1, x is 0 <x≤2.0, and y is a real number satisfying the valence of all metal components.
The reaction product of claim 5, wherein the reactant of the oxidative dehydrogenation of butene comprises butene, air (79% by volume of N ₂ and 21% by volume of O ₂ ) and steam, wherein the butene: air: steam = 8 to 11% by volume: 30 to 50% by volume: a method for producing 1,3-butadiene, characterized in that it comprises a ratio of 40 to 60% by volume.
The method of claim 5, wherein the oxidative dehydrogenation reaction is carried out at a temperature of 350 ~ 550 ℃, the reaction is carried out by supplying the reaction to 300 ~ 700 h ^{- 1} based on the butenes to prepare a 1,3-butadiene How to.
8. The method of claim 1, wherein the butene is 1-butene. 9.

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