KR102052239B1 - Oxidative dehydrogenation catalyst, method for manufacturing catalyst and method for manufacturing propylene - Google Patents

Abstract

The present invention comprises the steps of mixing the aqueous solution containing a surfactant and the aqueous solution of a magnesium oxide precursor to form a magnesium oxide carrier; And adding the magnesium oxide carrier to the vanadium oxide precursor aqueous solution.

Description

OXIDATIVE DEHYDROGENATION CATALYST, METHOD FOR MANUFACTURING CATALYST AND METHOD FOR MANUFACTURING PROPYLENE}

The present specification relates to an oxidative dehydrogenation catalyst, a method for preparing the same, and a method for preparing propylene.

In general, in the case of hydrocarbon gases, in particular, propane, a process for producing propylene from propane using a noble metal type such as platinum or an oxide type dehydrogenation catalyst such as chromium is widely practiced industrially. In addition, the conversion of propane to propylene is of increasing importance as demand for propylene oxide, acrylonitrile, and polypropylene increases.

Since propane dehydrogenation is an endothermic reaction, the reaction temperature in the reaction of the adiabatic reaction apparatus decreases with the progress of the reaction, so that additional heat of reaction must be constantly supplied to increase the yield of propylene. In addition, the propane dehydrogenation reaction was difficult to obtain high conversion because it is an equilibrium reaction by a reversible reaction in which the yield of maximum propylene is limited thermodynamically.

Then, by using the heat generated by the oxidation reaction to selectively oxidize hydrogen generated in the dehydrogenation reaction by adding propane and oxidant simultaneously using an oxidation catalyst, an oxidative dehydrogenation process that can reduce the amount of heat supplied compared to the dehydrogenation reaction Proposed.

Republic of Korea Patent Publication No. 10-1994-0013597

The present specification is to provide a method for preparing an oxidative dehydrogenation catalyst and a method for preparing propylene using an oxidative dehydrogenation catalyst.

One embodiment of the present invention comprises the steps of mixing an aqueous solution containing a surfactant with an aqueous solution of a magnesium oxide precursor to form a magnesium oxide carrier; And it provides a method for producing an oxidative dehydrogenation catalyst comprising the step of adding the magnesium oxide carrier to the aqueous solution of vanadium oxide precursor.

In addition, an exemplary embodiment of the present invention provides an oxide dehydrogenation catalyst including a magnesium oxide carrier and vanadium oxide supported on the magnesium oxide carrier.

Another embodiment of the present invention provides a method for producing propylene, comprising the step of preparing propylene by reacting an oxidative dehydrogenation catalyst, propane gas and oxygen gas.

An oxidative dehydrogenation catalyst having vanadium oxide supported on a magnesium oxide carrier according to one embodiment of the present invention is used as a catalyst for propane oxidative dehydrogenation (PODH) of propane. When the oxidative dehydrogenation reaction of propane is carried out using the oxidative dehydrogenation catalyst, high catalytic activity is exhibited.

When the oxidative dehydrogenation catalyst is manufactured by the method for preparing the oxidative dehydrogenation catalyst according to the exemplary embodiment of the present invention, it is easy to prepare a magnesium oxide carrier at a large capacity because it utilizes a precipitation process.

1 is an X-ray diffraction graph of an oxidative dehydrogenation catalyst according to a preparation example of the present specification.
2 is a nitrogen adsorption-desorption isotherm graph of the oxidative dehydrogenation catalyst according to the preparation example of the present specification.
3 shows a transmission electron microscope (TEM) photograph of an oxidative dehydrogenation catalyst according to a preparation example of the present specification.

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

One embodiment of the present invention comprises the steps of mixing an aqueous solution containing a surfactant with an aqueous solution of a magnesium oxide precursor to form a magnesium oxide carrier; And it provides a method for producing an oxidative dehydrogenation catalyst comprising the step of adding the magnesium oxide carrier to the aqueous solution of vanadium oxide precursor.

In the method for preparing an oxidative dehydrogenation catalyst according to an exemplary embodiment of the present invention, since a magnesium oxide carrier is prepared using a simple precipitation process, it is easy to prepare a large capacity.

In addition, the vanadium oxide supported on the magnesium oxide carrier obtained using the surfactant according to one embodiment of the present invention shows higher catalytic activity than the vanadium oxide catalyst supported on the commercial magnesium oxide carrier. This is because the magnesium oxide carrier according to the production method of the present invention has a larger specific surface area and pore volume than commercial magnesium oxide carriers, so that the vanadium oxide catalyst can be uniformly dispersed on the surface or inside of the magnesium oxide carrier.

In one embodiment of the present invention, the surfactant is represented by the following formula (1) or (2).

[Formula 1]

[Formula 2]

In Chemical Formulas 1 and 2,

x1, y1, z1, x2, y2 and z2 are each an integer of 1-150.

In the method for preparing an oxidative dehydrogenation catalyst according to an exemplary embodiment of the present invention, the catalyst may be prepared by changing the type of surfactant to adjust the level of catalyst activity to a desired degree.

In one embodiment, Pluronic® P123 or Pluronic® F127 from BASF may be used as the surfactant.

In the exemplary embodiment of the present specification, the forming of the magnesium oxide carrier may include preparing an aqueous solution containing a surfactant first and then adding an aqueous magnesium oxide precursor solution, or preparing a magnesium oxide precursor aqueous solution first and then adding a surfactant. You can.

In the present specification, the solvent of the "aqueous solution" may be water, or a mixture of water and another solvent may be used.

In the present specification, the concentrations of the "aqueous solution containing surfactant", "aqueous solution of magnesium oxide precursor" and "aqueous solution of vanadium oxide" may be appropriately selected by applying the contents known in the art, and the range thereof is particularly limited. It doesn't work

In one embodiment of the present invention, the step of mixing the aqueous solution containing a surfactant and the aqueous solution of a magnesium oxide precursor to form a magnesium oxide carrier may be carried out under basic conditions. Said "basic condition" means that the pH of the solution is 8 or more.

In one embodiment, the step of mixing the aqueous solution containing the surfactant and the aqueous solution of the magnesium oxide precursor to form a magnesium oxide carrier may be carried out under the conditions of pH 8 to 12. More preferably it may be carried out under the conditions of pH 9 to 11.

In one example, the step of mixing the aqueous solution containing a surfactant and the magnesium oxide precursor solution to form a magnesium oxide carrier is added dropwise to the aqueous ammonium hydroxide solution (NH ₄ OH) while maintaining the pH of the aqueous solution of surfactant at 10 Can be performed. However, the method of adjusting the solution to basic is not limited thereto.

As used herein, the term "precursor" means a substance before a specific substance in a reaction, and means a substance before a specific substance finally obtained in a chemical reaction. For example, in the present specification, the vanadium oxide precursor means a material before becoming vanadium oxide through a reaction, and is not particularly limited. Specifically, the vanadium oxide precursor may use a compound having a vanadium (V) oxidation number of +3 to +5, and may include at least one of NH ₄ VO ₃ , VOSO ₄ , VCl _3, and a hydrate (xH ₂ O). have.

In one embodiment, magnesium nitrate hexahydrate (Mg (NO ₃ ) ₂ 6H ₂ 0) or the like may be used as the magnesium oxide precursor, but is not limited thereto.

In one embodiment, ammonium metavanadate (NH ₄ VO ₃ ) or the like may be used as the vanadium oxide precursor, but is not limited thereto.

In one embodiment of the present specification, the vanadium oxide may include amorphous vanadium oxide. The amorphous vanadium oxide may include at least one of VO ₄ and V ₂ O ₇ .

In one embodiment of the present specification, the vanadium oxide may include no crystalline vanadium oxide or may include an insufficient amount of crystalline vanadium oxide. The crystalline vanadium oxide is represented by V ₂ O _5, if the vanadium oxide crystalline vanadium oxide is V ₂ O ₅ is included above a certain, when lowering the reactivity of the oxide dehydrogenation catalyst used in the propane oxidation dehydrogenation propylene The conversion yield to can be low.

In one embodiment of the present specification, the vanadium oxide provided on the surface of the magnesium oxide support may be a layer formed by combining single molecules of vanadium oxide on the magnesium oxide support. In addition, vanadium and magnesium may be formed into magnesium orthovanadate (Mg ₃ V ₂ O ₈ , Magnesium orthovanadate) by the reaction of the oxalate vanadium form and the magnesium oxide carrier produced by the reaction between the oxalic acid dihydrate and the vanadium precursor during the manufacturing process. Magnesium pyrovanadate (Mg ₂ V ₂ O ₇ , Magnesium pyrovanadate) and the like can form a complex crystal phase.

In an exemplary embodiment of the present specification, the adding of the magnesium oxide carrier to the aqueous solution of vanadium oxide precursor includes: adding the magnesium oxide carrier to the aqueous solution of vanadium oxide precursor to provide a vanadium oxide precursor on the surface of the magnesium oxide carrier; And calcining the magnesium oxide carrier having the vanadium oxide precursor on the surface of the magnesium oxide carrier to form vanadium oxide supported on the magnesium oxide carrier.

In an exemplary embodiment of the present specification, after the forming of the vanadium oxide supported on the magnesium oxide carrier, the method may further include drying and calcining the vanadium oxide supported on the magnesium oxide carrier.

In one embodiment, the step of drying and calcining the vanadium oxide supported on the magnesium oxide carrier may use methods known in the art. Specifically, a method of heat treatment for 5 hours or more at a temperature of 550 ° C. or more using a high temperature electric furnace may be used, but is not limited thereto.

One embodiment of the present invention provides an oxidative dehydrogenation catalyst prepared by the above-described preparation method.

Another embodiment of the present invention provides an oxide dehydrogenation catalyst comprising a magnesium oxide carrier and vanadium oxide supported on the magnesium oxide carrier.

In one embodiment of the present specification, the supported amount of vanadium atoms is 1 to 50% by weight based on the total weight of the oxidative dehydrogenation catalyst. In one embodiment of the present specification, the pore volume of the magnesium oxide carrier is 0.5 cm ³ / g or more. In one embodiment, the pore volume of the magnesium oxide carrier is 0.7 cm ³ / g or more.

In one embodiment of the present specification, the specific surface area of the magnesium oxide carrier is 50 m ³ / g or more. In one embodiment, the specific surface area of the magnesium oxide carrier is 100 m ³ / g or more.

The pore volume and specific surface area of the oxidative dehydrogenation catalyst can be measured by nitrogen adsorption-desorption measurement. Equipment for performing the analysis may be used, such as Micromeritics' ASAP 2020, Tristar, etc., but no specific equipment is required.

Prior to performing the nitrogen adsorption and desorption analysis, a glass cell containing 50 to 200 mg of the oxidative dehydrogenation catalyst was treated for about 6 hours using a vacuum pump under 150 ° C heating conditions.

After the glass cell thus pretreated is mounted on the analytical equipment, nitrogen adsorption and desorption isotherms are obtained while adsorbing and desorbing nitrogen in a state in which the glass cell is immersed in a Dewar vessel containing liquid nitrogen.

The nitrogen adsorption and desorption isotherm according to the analysis is obtained in the form of a graph of nitrogen adsorption amount according to the relative pressure, in which the BET (Brunauer-Emmett-Teller) equation is applied by taking a range in which the relative pressure is 0.05 to 0.30. The specific surface area can be calculated by law. In addition, the pore volume and the pore size may be calculated by the BJH method by applying the Barrett-Joyner-Hallender (BJH) equation to the Desorption branch of the graph.

An exemplary embodiment of the present specification provides a method for preparing propylene, including the step of preparing propylene by reacting the above-described oxidative dehydrogenation catalyst, propane gas, and oxygen gas.

The method for producing propylene is not particularly limited as long as the oxidative dehydrogenation catalyst according to the present invention is used for the propane oxidative dehydrogenation reaction, and may be employed from the process of producing propylene by injecting propane and oxygen gas in the art.

In addition, in an exemplary embodiment of the present specification, the description of the above-described oxidative dehydrogenation catalyst and a method for producing the propylene may be cited.

Hereinafter, the present specification will be described in more detail with reference to Examples. However, the following examples are intended to illustrate the present invention, and the scope of the present invention is not limited thereto.

Production Example  One : P123 surfactant solution Magnesium oxide Carrier  Produce

First, 1.2 g of P123 ((EO) 20 (PO) 70 (EO) 20, Sigma-Aldrich) surfactant was added to 100 ml of distilled water, and then dissolved by stirring at room temperature for 3 hours. Meanwhile, after dissolving 10.4 g of magnesium nitrate hexahydrate (Mg (NO 3) 26 H 2 O, Sigma-Aldrich) in 30 ml of distilled water, the solution was dissolved in the aqueous surfactant solution by using a syringe pump at 30 ml / h. Was added at a rate of.

At the same time, a magnesium component was precipitated while maintaining a constant pH of the aqueous surfactant solution at 10 while dropwise adding an ammonium hydroxide solution (Nm ₄ OH, Samjeon Chemical) with a disposable pipette. The white slurry obtained was further stirred for 15 hours, and then washed with distilled water while filtering out the solid powder. The obtained solid powder was dried in a convection oven at 100 ° C. for 12 hours, and the dried powder was heat-treated at 550 ° C. for 5 hours using a high temperature electric furnace to finally obtain a magnesium oxide carrier. The carrier was named Mg1.

Production Example  2 : Manufactured Using P123 Aqueous Solution Magnesium oxide On the carrier  Supported Vanadium oxide  Preparation of oxidative dehydrogenation catalyst comprising

First, 0.069 g of ammonium metavanadate (NH ₄ VO ₃ , large purified gold) and 0.149 g of oxalic acid dihydrate (C ₂ H ₂ O ₄ , large purified gold) in 5.3 ml of distilled water After the addition, the mixture was stirred at room temperature for 30 minutes to dissolve. 0.3 g of the Mg1 carrier obtained in Preparation Example 1 was introduced into the solution, and the solvent was evaporated while heating. Thereafter, the obtained solid powder was ground using a pestle, and further dried in a convection oven at 100 ° C. for 12 hours. Thereafter, the dried powder was heat-treated at 550 ° C. for 10 hours using a high temperature electric furnace to obtain an oxidized dehydrogenation catalyst including vanadium oxide finally supported on a magnesium oxide carrier. The catalyst was named VMg1.

Production Example  3 : F127 surfactant solution Magnesium oxide Carrier  Produce

In Preparation Example 1, 2.5 g of F127 ((EO) ₁₀₆ (PO) was added to 100 ml of distilled water instead of 1.2 g of P123 ((EO) ₂₀ (PO) ₇₀ (EO) ₂₀ , Sigma-Aldrich) surfactant. ₇₀ (EO) ₁₀₆ , Sigma-Aldrich) surfactant was added, and the other procedures were carried out in the same manner as in Preparation Example 1 to obtain a magnesium oxide carrier. The carrier was named Mg2.

Production Example  4 : Prepared using aqueous solution of F127 surfactant Magnesium oxide On the carrier  Supported Vanadium oxide  Preparation of oxidative dehydrogenation catalyst comprising

In Preparation Example 2, instead of introducing 0.3 g of the Mg1 carrier, 0.3 g of the Mg2 carrier was introduced, and the other procedures were performed in the same manner as in Preparation Example 2 to obtain an oxidative dehydrogenation catalyst including vanadium oxide supported on a magnesium oxide carrier. Got it. The catalyst was named VMg2.

Production Example  5 : Without surfactant solution Magnesium oxide Carrier  Produce

First dissolve 10.4 g of Magnesium Nitrate Hexahydrate (Mg (NO ₃ ) ₂ 6H ₂ O, Sigma-Aldrich) in 30 ml of distilled water, and then use the syringe pump in 100 ml of distilled water. Was added at a rate of 30 ml / h. At the same time, an aqueous solution of ammonium hydroxide (Ammonium Hydroxide Solution; NH ₄ OH, Samchun) was added dropwise with a disposable pipette to keep the pH of the aqueous solution constant at 10. The white slurry obtained was further stirred for 15 hours, and then washed with distilled water while filtering out the solid powder. The obtained solid powder was dried in a convection oven at 100 ° C. for 12 hours, and the dried powder was heat-treated at 550 ° C. for 5 hours using a high temperature electric furnace to finally obtain a magnesium oxide carrier. The carrier was named Mg3.

Production Example  6 : Manufactured Without Using Aqueous Surfactant Solution Magnesium oxide On the carrier  Supported Vanadium oxide  Preparation of oxidative dehydrogenation catalyst comprising

First, 0.069 g of ammonium metavanadate (NH ₄ VO ₃ , large purified gold) and 0.149 g of oxalic acid dihydrate (C ₂ H ₂ O ₄ , large purified gold) in 5.3 ml of distilled water After the addition, the mixture was stirred at room temperature for 30 minutes to dissolve. 0.3 g of magnesium oxide carrier (Mg 3) obtained in 0.3 g of Preparation Example 5 was introduced into the solution, and the solvent was evaporated while heating. Thereafter, the obtained solid powder was ground using a pestle, and further dried in a convection oven at 100 ° C. for 12 hours. Thereafter, the dried powder was heat-treated at 550 ° C. for 10 hours using a high temperature electric furnace to obtain an oxidized dehydrogenation catalyst including vanadium oxide finally supported on a magnesium oxide carrier. The prepared catalyst was named VMg3.

Production Example  7 Commercial Magnesium oxide On the carrier Supported Vanadium oxide  Preparation of oxidative dehydrogenation catalyst comprising

First, 0.069 g of ammonium metavanadate (NH ₄ VO ₃ , large purified gold) and 0.149 g of oxalic acid dihydrate (C ₂ H ₂ O ₄ , large purified gold) in 5.3 ml of distilled water After the addition, the mixture was stirred at room temperature for 30 minutes to dissolve. 0.3 g of a commercial magnesium oxide carrier (MgO, Sigma-Aldrich) was introduced into the solution, and the solvent was evaporated while heating. Thereafter, the obtained solid powder was ground using a pestle, and further dried in a convection oven at 100 ° C. for 12 hours. Thereafter, the dried powder was heat-treated at 550 ° C. for 10 hours using a high temperature electric furnace to obtain an oxidized dehydrogenation catalyst including vanadium oxide finally supported on a magnesium oxide carrier. The prepared catalyst was named VMg4.

[Crystal Structure Analysis of Prepared Catalyst]

An X-ray diffraction analysis graph of an oxidative dehydrogenation catalyst including vanadium oxide supported on a magnesium oxide carrier is shown in FIG. 1.

X-ray diffraction analysis of an oxidative dehydrogenation catalyst including vanadium oxide supported on a magnesium oxide carrier as shown in FIG. 1 showed that 2 theta = 30-40 ° for the VMg3 catalyst of Preparation Example 6 and the VMg4 catalyst of Preparation Example 7. Finely showed diffraction peaks due to magnesium orthovanadate (Mg ₃ V ₂ O ₈ ) and magnesium pyrovanadate (Mg ₂ V ₂ O ₇ ), while VMg1 and Preparation Example 2 VMg2 catalyst of Preparation Example 4 did not show a diffraction peak by V. This may be determined because V is evenly dispersed on or inside the magnesium oxide in the VMg1 and VMg2 catalysts prepared using the aqueous surfactant solution.

[Analysis of Physical Properties of Prepared Catalysts]

A nitrogen adsorption-desorption graph of an oxidative dehydrogenation catalyst including vanadium oxide is shown in FIG. 2.

As a result of performing nitrogen adsorption-desorption analysis (Nitrogen adsorption-desorption) of the oxidative dehydrogenation catalyst containing vanadium oxide supported on the magnesium oxide carrier as shown in FIG. 2, the oxidative dehydrogenation catalyst containing vanadium oxide supported on the commercial magnesium oxide carrier ( It can be seen that the remaining three catalysts showed higher nitrogen adsorption compared to VMg 4; In particular, the VMg1 and VMg2 catalysts using surfactants show higher nitrogen adsorption than the VMg3 catalysts without surfactants, indicating that they have more advanced medium pores.

Nitrogen adsorption-desorption results of the oxidative dehydrogenation catalyst including vanadium oxide supported on a magnesium oxide carrier are summarized in Table 1 below. The VMg4 catalyst (Preparation Example 7) showed a lower specific surface area and pore volume than other catalysts prepared by the precipitation method. Considering these low physical properties, the pore size of 23.2 nm is thought to be due to the textural porosity caused by the interstitial space rather than the framework porosity. VMg1 and VMg2 catalysts with surfactants showed improved specific surface area, pore volume, and pore size compared to VMg3 catalysts without surfactants, which would predict that the same loading of vanadium in VMg1 and VMg2 catalysts would be smoother. Can be. In addition, the VMg2 catalyst using F127 showed a higher specific surface area and pore volume than the VMg1 catalyst using P123, and from this, the VMg2 catalyst showed higher activity in Propane Oxidative Dehydrogenation (PODH). It was predicted. The pore size is smaller than that of the VMg1 catalyst, but it is difficult to determine that the molecular size of the reactant propane and oxygen is very limited compared to the pore size.

Physical properties data of VMg1 (Preparation Example 2), VMg2 (Preparation Example 4), VMg3 (Preparation Example 6) and VMg4 (Preparation Example 7) catalysts were compared and shown in Table 1 below.

The specific surface area and pore volume of the oxidative dehydrogenation catalyst in the following data were measured using the above-described measuring method.

catalyst VMg1
(Manufacture example 2) VMg2
(Manufacture example 4) VMg3
(Manufacture example 6) VMg4
(Manufacture example 7) Specific surface area
(m ² / g) 112 153 82 12 Pore volume
(cm ³ / g) 0.74 0.78 0.27 0.06 Pore size
(nm) 27.3 16.9 10.6 23.2

[Shape analysis of the prepared catalyst]

An oxide dehydrogenation catalyst including vanadium oxide supported on a magnesium oxide carrier was confirmed by transmission electron microscopy.

As a result of analyzing the oxidative dehydrogenation catalyst containing vanadium oxide supported on the magnesium oxide carrier as shown in FIG. 3 by Transmission Electron Microscopy, the VMg1 (Preparation Example 2) and VMg2 (Preparation Example 4) catalysts were used in the aqueous surfactant solution. Oxide dehydrogenation catalyst (VMg3; Preparation Example 6) containing vanadium oxide supported on a magnesium oxide carrier prepared without using the above, and Oxidation dehydrogenation catalyst (VMg4; Preparation Example 7) containing vanadium oxide supported on a commercial magnesium oxide carrier It can be seen that compared to the developed porosity. That is, the porosity of the oxidative dehydrogenation catalyst including vanadium oxide supported on the magnesium oxide carrier can be improved through the use of a surfactant. Particularly, the VMg2 catalyst using the F127 (Preparation Example 4) is VMg1 using the P123 (Preparation Example 2). It can be seen that the pore structure is more evenly dispersed than the catalyst.

Example  One : Magnesium oxide On the carrier Supported Vanadium oxide  Of propane using an oxidative dehydrogenation catalyst Oxidative  Propylene Production by Dehydrogenation

Propylene by Propane Oxidative Dehydrogenation (PODH) using VMg1, VMg2, VMg3 and VMg4 catalysts prepared by Preparation Examples 2, 4, 6 and 7 The production process was carried out. In this embodiment, the catalytic reaction was performed using a high-throughput system (HTS). First, 0.1 g of each catalyst was charged to a glass reactor (Pyrex material), and then the reactor was mounted in an HTS apparatus. The temperature of the reactor was raised to 550 ° C. while flowing nitrogen (96 ml / min) and oxygen (12 ml / min) gas, and the temperature increase rate was set to 10 ° C./min. Thereafter, the mixture was maintained for 30 minutes under the same conditions, and a catalytic reaction was performed by flowing propane gas at a flow rate of 12 ml / min. At this time, the total flow rate value relative to the catalyst mass was maintained at 72,000 ml / h · g-catalyst. The gas exiting the reaction apparatus was quantified by Gas Chromatography (GC) analysis. Propane Conversion, Propylene Selectivity, and Propylene Yield in the present Example were calculated by Equations 1 to 3, respectively.

<Equation 1>

% Propane conversion = [moles of propane reacted] / [moles of propane fed] * 100

<Equation 2>

Propylene Selectivity (%) = [moles of propylene produced] / [moles of propane reacted] * 100

<Equation 3>

Propylene Yield (%) = [moles of propylene produced] / [moles of propane fed] * 100

[Propane using manufactured catalyst Oxidative  Dehydrogenation result]

Experimental results of the oxidative dehydrogenation reaction of propane on the catalyst prepared by the preparation example are shown in Table 2 below.

As shown in Table 2, the VMg1 of Preparation Example 2 and the VMg2 catalyst of Preparation Example 4 showed a relatively high propylene yield (Propylene Yield) compared to the VMg3 of Preparation Example 6 and the VMg4 catalyst of Preparation Example 7. This is believed to be due to a phenomenon in which the properties of magnesium oxide (MgO) are improved by the use of a surfactant, thereby enhancing the dispersion and surface exposure of vanadium oxide (VOx). In addition, higher catalytic activity was obtained in the VMg2 catalyst using the F127 surfactant than the VMg1 catalyst using the P123 surfactant, which means that the catalytic activity of vanadium oxide can be controlled according to the type of the surfactant.

catalyst VMg1
(Manufacture example 2) VMg2
(Manufacture example 4) VMg3
(Manufacture example 6) VMg4
(Manufacture example 7) Propane conversion rate
(%) 39.3 43.2 35.4 24.6 Propylene selectivity
(%) 40.5 41.3 37.0 36.7 Propylene yield
(%) 15.9 17.8 13.1 9.0

Claims (10)

Mixing an aqueous solution containing a surfactant with an aqueous solution of a magnesium oxide precursor to form a magnesium oxide carrier; And
A method for preparing an oxidative dehydrogenation catalyst comprising adding the magnesium oxide carrier to an aqueous solution of a vanadium oxide precursor,
The magnesium oxide precursor aqueous solution includes magnesium nitrate hexahydrate (Mg (NO ₃ ) ₂ 6H ₂ 0),
Forming the magnesium oxide carrier is carried out under basic conditions,
The pore volume of the magnesium oxide carrier is 0.5 cm ³ / g or more,
The vanadium oxide precursor solution containing oxalic acid dihydrate
Method for producing an oxidative dehydrogenation catalyst. The method of claim 1, wherein the surfactant is represented by the following Chemical Formula 1 or Chemical Formula 2:
[Formula 1]

[Formula 2]

In Chemical Formulas 1 and 2,
a, b, c, x, y and z are each an integer from 1 to 150. delete The method of claim 1, wherein the adding of the magnesium oxide carrier to the aqueous solution of vanadium oxide precursor,
Adding the magnesium oxide carrier to the aqueous solution of vanadium oxide precursor to provide a vanadium oxide precursor on the surface of the magnesium oxide carrier; And
Calcining the magnesium oxide carrier having the vanadium oxide precursor provided on its surface to form vanadium oxide supported on the magnesium oxide carrier. delete Magnesium oxide carriers; And
Vanadium oxide supported on the magnesium oxide carrier,
As an oxidative dehydrogenation catalyst produced by the manufacturing method of claim 1,
The pore volume of the oxidative dehydrogenation catalyst is 0.5 cm ³ / g or more,
The specific surface area of the oxidative dehydrogenation catalyst is 100 m ³ / g or more. The oxidative dehydrogenation catalyst according to claim 6, wherein the supported amount of vanadium atoms is 1 to 50% by weight based on the total weight of the oxidative dehydrogenation catalyst. delete delete A process for producing propylene comprising the step of reacting an oxidative dehydrogenation catalyst, propane gas and oxygen gas according to claim 6 or 7 to produce propylene.

Images