KR20180082682A - Composite catalyst support, dehydrogenation catalysts and preparation method thereof - Google Patents

Abstract

The present invention relates to a composite catalyst carrier in which a carrier having a mesopore of 5 to 50 nm and macropores of 50 nm to 20 μm is doped with a mixture of oxide of magnesium or magnesium tin oxide and components constituting the carrier, to a dehydrogenation catalyst and to a manufacturing method thereof, wherein the dehydrogenation catalyst manufactured by using the composite catalyst carrier of the present invention can be operated under harsh environments, increase the stability and lifetime of a catalyst while improving the efficiency of a dehydrogenation process, and can improve a process basic unit by increasing the selectivity.

Description

TECHNICAL FIELD [0001] The present invention relates to a composite catalyst support, a dehydrogenation catalyst,

The present invention relates to a composite catalyst carrier, a dehydrogenation catalyst, and a production method thereof, and more particularly, to a composite catalyst carrier comprising a composite catalyst carrier capable of operating under harsh conditions and capable of increasing the lifetime of the catalyst while improving process efficiency, Dehydrogenation catalysts and methods for their preparation.

In general, in the case of hydrocarbon gas, especially propane, a process for producing propylene from propane using a noble metal such as platinum or an oxide-based dehydrogenation catalyst such as chromium has been widely practiced industrially. However, since propane dehydrogenation reaction is an endothermic reaction, the reaction temperature of the adiabatic reaction apparatus decreases with the progress of the reaction. Therefore, in order to increase the production amount of propylene, additional reaction heat must be supplied constantly. Also, the propane dehydrogenation reaction is difficult to obtain a high conversion rate because it is an equilibrium reaction by the reversible reaction in which the yield of the maximum propylene is thermodynamically limited.

In the field of catalyst dehydrogenation of hydrocarbons, efforts are being made to develop improved catalysts with high activity and selectivity and high stability during use. The stability of the catalyst means the rate of catalyst deactivation when in use. The rate of deactivation of the catalyst affects the useful life, and in general, the catalyst is required to be highly stable, in order to extend its lifetime and increase the yield of the product under high severity process conditions.

Alumina, silica, zeolite, and the like are used as a carrier of the catalyst used in the dehydrogenation reaction of hydrocarbons. The characteristics required for such a dehydrogenation catalyst should include the content of the active component, the type of promoter, the dispersity of the active component, the type of carrier, the pore characteristics of the carrier, and the acidity of the carrier. However, existing catalysts are inactivated rapidly and there is room for improvement in terms of reaction stability.

In addition, dehydrogenation can improve the yield at a very high temperature, low hydrogen concentration and high pressure. However, since the stability of the catalyst is deteriorated under such a severe condition, development of a catalyst capable of maintaining stability even in harsh conditions is urgently required Is required.

DISCLOSURE Technical Problem The present invention has been made to solve the problems of the prior art as described above, and one object of the present invention is to provide a composite catalyst carrier which can maintain the stability of the catalyst under harsh conditions.

Another object of the present invention is to provide a dehydrogenation catalyst having excellent selectivity and conversion rate which can increase the productivity of products and reduce the unit cost.

It is still another object of the present invention to provide a method for producing a dehydrogenation catalyst.

It is another object of the present invention to provide an improved dehydrogenation process using the dehydrogenation catalyst of the present invention.

Other objects, advantages and novel features of the present invention will become more apparent from the following detailed description and preferred embodiments.

According to an aspect of the present invention,

Characterized in that a mixture of magnesium oxide or magnesium tin oxide and a component constituting the carrier is doped on a carrier having mesopores of 5 to 50 nm and macropores of 50 nm to 20 탆. .

The carrier may be alumina, silica, or a mixture thereof, preferably alumina (Al ₂ O ₃ ) having a crystallinity of 90% or more, and the ratio of the mesopores and macropores is 7: 3 to 8: 2.

According to another aspect of the present invention,

A mixed catalyst carrier doped with a mixture of magnesium oxide (MgO) or a magnesium tin oxide and a component constituting the carrier, on a carrier having mesopores of 5 to 50 nm and macropores of 50 nm to 20 탆; And a dehydrogenation catalyst comprising the transition metal active component supported on the composite catalyst support.

According to another aspect of the present invention,

Preparing a carrier having macropores of 5 to 50 nm and macropores of 50 nm to 20 탆;

Mixing an acid solution of a magnesium oxide or magnesium tin oxide precursor with an acid solution of a carrier component on the carrier, heating and heating the resulting gel mixture to obtain a composite catalyst carrier;

Impregnating the resulting composite catalyst carrier with a transition metal active component using an impregnation method, and then calcining the dehydrogenation catalyst.

Another aspect of the present invention is directed to a dehydrogenation process comprising contacting a dehydrogenatable hydrocarbon with a dehydrogenation catalyst comprising a complex catalyst carrier of the present invention under dehydrogenation conditions and obtaining a dehydrogenation product.

According to the dehydrogenation catalyst of the present invention, it is possible to operate under harsh conditions in which process efficiency can be increased, and the production amount can be increased.

Also, according to the present invention, catalyst stability and lifetime can be increased to increase the catalyst reaction-regeneration cycle.

In addition, according to the present invention, it is possible to improve the process unit level and the productivity by increasing the selectivity.

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

One aspect of the present invention is characterized in that a mixture of magnesium oxide or magnesium tin oxide and a component constituting the carrier is doped on a carrier having mesopores of 5 to 50 nm and macropores of 50 nm to 20 탆, Based catalyst support.

The composite catalyst carrier of the present invention is a hydrocarbon dehydrogenation catalyst having improved purity, bimodal pore property and improved selectivity, stability and lifetime by doping magnesium. The composite catalyst carrier of the present invention is composed of MgO, Al ₂ O ₃ and Mg Al ₂ O ₄ coexist.

In the composite catalyst carrier according to the present invention, alumina, silica and a mixed component thereof may be used as the carrier, preferably alumina. The crystallinity of the alumina is a factor for determining the degree of formation of coke, preferably 90% or more. In a preferred embodiment, in the present invention, the crystal form of the carrier may be alumina in which both crystalline forms of theta or shea and gamma coexist. However, when the theta phase is less than 90% and coexists with the alpha crystal phase, it is difficult to maintain the bimodal pore structure.

Mesopores and macropores are pores that act as a channel for reactants and products. The ratio of the mesopores to the macropores is determined in consideration of the dispersibility of the catalyst and the mass transfer rate. The mesopores are preferably larger than the macropores. For example, the ratio of mesopores and macropores is 7: 3 To 8: 2. As the ratio of mesopores increases, the dispersibility improves. As the ratio of macropores increases, mass transfer becomes faster.

The pore size and volume of the carrier are the main factors that determine the mass transfer coefficient of the reactant and the product. When the chemical reaction rate is high, the diffusion resistance of the material determines the overall reaction rate. Therefore, It is advantageous to keep the activity high. Therefore, the use of a carrier having a large pore size becomes insensitive to the accumulation of coke, and the high mass transfer rate results in a high reaction activity even when the liquid hourly space velocity (LHSV) is increased.

On the other hand, when the catalytic reaction is activated and proceeds rapidly, more reactants are supplied from the outside to the catalytic active sites. If the movement of the reactant increases abruptly, the flow will be resisted. This state is called a mass diffusion limited region. In actual catalytic reactors, most of them are used in the same mass transport regime. Therefore, in order to overcome the mass transfer dominant region, it is desirable to adjust meso and macropores in the above-mentioned ratio in the catalyst.

The complex catalyst carrier of the present invention is a substance having a crystal form, and the size distribution, the total volume, the uniform distribution thereof, the mesopore size distribution present in the macropore structure, and the total volume thereof are important in the unit carrier weight. In the present invention, the macropore volume is in the range of 0.05 cc / g to 0.4 cc / g, and the mesopore volume is in the range of 0.2 cc / g to 0.8 cc / g. And has a bimodal distribution with a pore distribution. The application of this macropore carrier shows improved activity and reproducibility in the dehydrogenation reaction after the catalyst is prepared.

In order to prevent weakening of the strength due to macropores, plastic deformation at a high temperature of 900 ° C to 1,200 ° C for 1 to 24 hours causes a particle crushing strength of 3.0 kgf or more. The surface area of the final catalyst has a nitrogen adsorption specific surface area of 50 m < 2 > / g to 170 mm < 2 > / g or less. If the specific surface area of the support is less than 50 m < 2 > / g, the dispersibility of the metal active component is lowered. If it exceeds 170 m < 2 > / g, the gamma crystallinity of alumina is maintained high,

The alumina having the bimodal pore characteristics of the present invention is determined during the preparation of the carrier material and is commercially available and applicable as a catalyst. Such an alumina support is obtained through a molding process in various organoaluminum slurries, preferably using organoaluminum having 4 to 14 carbon atoms. Alumina is required to be heat treated so as to have an appropriate strength and pore distribution for industrial application. In the present invention, a gas hourly space velocity (GHSV) of 300 to 5,000 hr ^-1 in an oxygen or nitrogen gas atmosphere is 900 to 1,200 hr ^-1 to 0.5 to 20 hr < ^-1 > to process the composite catalyst carrier applied in the present invention.

The composite catalyst carrier having bimodal pore characteristics according to the present invention may be manufactured by controlling the kind and amount of acid used in the production process. The acid component is combined with the aluminum element of the alumina carrier to attenuate the characteristics of the Lewis acid possessed by the alumina itself, thereby facilitating desorption of the product and inhibiting the formation of coke. In addition, the effect of decreasing the acid point inherent in the crystallinity of alumina itself is exhibited by the modification of the property of gamma to the property of theta or alpha.

The dehydrogenation catalyst of another aspect of the present invention is a mixture in which magnesium oxide (MgO) or magnesium tin oxide and a component constituting the carrier are mixed on a carrier having a mesopore of 5 to 50 nm and macropores of 50 nm to 20 탆 Doped composite catalyst carrier and a transition metal active component supported on the composite catalyst carrier.

The dehydrogenation catalyst according to the present invention has a high degree of dispersion when the active ingredient is supported, and the development of mesopores and macropores has an effect of increasing the mass transfer rate. When the size of the pores existing in the catalyst is large, it is insensitive to the reduction of the activity due to the coke generated on the catalyst, and high reaction activity is exhibited even when the liquid space velocity is increased due to the high mass transfer rate.

The catalysts prepared according to the present invention provide improved performance that is different from conventional catalysts, namely, high hydrocarbon conversion and selectivity and performance stability as well as resistance to improved caulking and ease of removal of coke, as the dehydrogenation reaction conditions are severer do. The catalyst of the present invention can be operated under severe process conditions (H2 / C3 ratio = 0 to 1.0, high temperature = 550 to 700 ° C, high pressure = 0.0 to 5.0 kgf / cm ² ) due to increased stability.

In the present invention, the transition metal active component may be at least one selected from the group consisting of platinum (Pt), palladium (Pd), nickel (Ni), cobalt (Co), ruthenium (Ru), rhenium (Re), rhodium (Rh), osmium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), copper (Cu) or zinc (Zn). These may be used singly or in the form of an alloy.

The magnesium-doped dehydrogenation catalyst of the present invention can have many applications. Thus, it can be used, for example, for dehydrogenation of hydrocarbons or other organic compounds, in particular for the dehydrogenation of C2 to C5 linear hydrocarbons. The saturated hydrocarbons in the present invention are mainly reactants of ethane, propane, butane, isobutane, pentane, and olefins having a carbon skeleton corresponding to saturated hydrocarbons used as reactants by dehydrogenation, that is, ethylene, propylene, 1- or 2- -Butylene, isobutylene, and pentene.

The catalysts of the present invention may also be used in a variety of other processes such as hydrosulfuration, hydrodenitrification, desulfurization, hydrodesulfurization, dehydrohalogenation, reforming, steam reforming, cracking, hydrocracking, hydrogenation, dehydrogenation, isomerization, Can be used as catalysts for various reactions such as dismutation, oxychlorination and dehydrocyclization, oxidation and / or reduction reactions, Claus reaction.

Another aspect of the present invention relates to a method for producing a dehydrogenation catalyst, which uses platinum as an active ingredient.

In the method of the present invention, a carrier (for example, alumina) having bimodal pore characteristics having mesopores of 5 to 50 nm and macropores of 50 nm to 20 pm is prepared, and magnesium oxide or magnesium tin oxide The acidic solution of the oxide precursor and the acid solution of alumina are mixed and heated, and the resulting gel-like mixture is doped and fired to obtain a composite catalyst carrier. Subsequently, the obtained composite catalyst carrier may be impregnated with a transition metal active component by impregnation method, and then calcined to prepare a dehydrogenation catalyst.

In the present invention, the acid may be selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, and boric acid.

Since the metal oxide having bimodal pore characteristics has different pH characteristics depending on the kind of acid or the degree of modification of the pore characteristics of alumina due to new characteristics depending on the mixed acid, Accordingly, the desired bimodal pore characteristics can be obtained. In addition, pore characteristics can be changed by adjusting the heat treatment temperature 900 to 1200 ° C after the acid treatment. The carrier may be alumina in which a theta crystal phase or a theta crystal phase and a gamma crystal phase coexist. The crystallinity of the alumina is a factor for determining the degree of formation of coke, preferably 90% or more.

In the method of the present invention, the mixture for doping is mixed such that the molar ratio of the carrier component to the magnesium oxide or magnesium tin oxide is in the range of 0.001 to 1.0 mole Al ₂ O ₃ : MgO. The firing after the doping proceeds at 700 ° C to 1200 ° C. When the molar ratio of alumina to magnesium oxide is less than 0.001, the doping effect is insufficient. On the contrary, when the molar ratio of Al ₂ O ₃ : MgO is less than 0.001, MgO itself blocks too much pores and the catalyst itself So that the dispersion degree may decrease.

In the present invention, the transition metal active component refers to a substance capable of electronically, physically, and chemically influencing the dehydrogenation reaction of saturated hydrocarbons, and widely includes a carrier material and finally contains metal fine particles, oxides, chlorides, sulfides, hydrides Form, halogen salt, oxychloride, carrier material, or a combination of the other ingredients.

For example, as a raw material of the platinum component, chloroplatinic acid, ammonium chloroplatinic acid, bromoplatinic acid, platinum chloride hydrate, platinum carbonyl salt or acid, nitroplated platinum salt or acid may be used, preferably chloroplatinic acid (H ₂ PtC ₁₆ ) is supported on the carrier prepared above by a known impregnation method (adsorption method) together with hydrochloric acid.

The impregnation of the composite catalyst carrier with the transition metal active component may be carried out using an incipient wetness method or any other impregnation method. As the precipitation method, a coprecipitation method, a homogeneous precipitation method, or a sequential precipitation method can be used. In the preparation of the catalyst powder by the precipitation method, the active substance and the carrier, which are constituent elements, are simultaneously sedimented to obtain a powdery catalyst, the ratio of the active substance can be freely controlled and the mutual binding force between the active substance and the carrier is strengthened, It is possible to produce this excellent catalyst powder.

On the other hand, the impregnation of the solution containing the transition metal active ingredient is carried out by applying hydrochloric acid at a concentration of 30% of about 1% by weight of the carrier to the aqueous solution after final preparation of the carrier material, Lt; 0 > C for 0.5-60 hours. After drying at 100 to 700 ° C for about 0.5 to 60 hours, it is dried at 500 to 700 ° C for 0.5 to 20 hours under a gas hourly space velocity (GHSV) of 100 to 5,000 hr ^-1 is believed to be advantageous in preventing the coagulation of transition metal active ingredient metal microparticles at high temperatures and removing excess residual chlorine.

Another aspect of the present invention is directed to an improved dehydrogenation process using the dehydrogenation catalyst of the present invention.

The method for producing propylene from propane according to the present invention is characterized in that a mixed gas containing propane, hydrogen and oxygen is reacted at a reaction temperature of 600 to 1000 占 폚, preferably 600 to 800 占 폚, 0.1 to 10 kgf / And the liquid space velocity between the mixed gas and the catalyst is in the range of 0.1 to 30 hr ^-1 , preferably 2 to 20 hr ^{-1 and the} gas phase reaction is carried out by the dehydrogenation reaction Propylene is prepared from propane.

The process for producing propylene from propane according to the present invention is effective for producing propylene even under severe high temperature conditions. When the dehydrogenation catalyst according to the present invention is applied, the production of propylene and the reduction in catalytic activity are low. That is, the propylene production method of the present invention can utilize the heat of reaction generated by the oxidation reaction of oxygen, and exhibits a high propane conversion rate by overcoming the reaction equilibrium. In addition, even when the reaction conditions are severer, the performance of the catalyst is decreased, and even when the deactivation is intensified, the effect is improved in terms of long-term use stability. In addition, the secondary effect of the present invention also has the function of removing the coke on the catalyst during the reaction, thereby improving the activity of the catalyst.

Hereinafter, the present invention will be described in more detail with reference to examples. It should be noted, however, that this is for the purpose of illustrating the present invention and should not be construed as limiting the scope of protection of the present invention.

Example  1: Preparation of dehydrogenation catalyst

Spherical commercial alumina having a gamma crystallinity and an average diameter of 1.65 mm and a packing density of 0.58 g / ml was purchased and thermally deformed at a temperature of 1050 ° C for 6 hours in an air atmosphere Phase. The crystallinity of alumina was measured by X-ray analysis and found to be 90% or higher.

In order to utilize the mesopores of the conventional commercial gamma alumina carrier, it is necessary to proceed with thermal deformation immediately without the acid treatment of the carrier before phase transfer, and to further utilize the macropores, it is necessary to use 1.5% of hydrochloric acid, 0.5% of nitric acid, 1.5 times, stirred for 3 hours, dried at 230 ° C for 5 hours, and thermally deformed at a temperature of 1050 ° C for 2 hours.

Subsequently, magnesium nitrate (Mg (NO ₃ ) ₂ · 6H ₂ O), alumina compared to 0.01M hydrochloric acid (HCl,> 35%) 1.5 % carrier weight ratio, nitric acid (HNO _3, 70%) into 0.5%, to 1.5 times compared to the volume of distilled water carrier substrate weight ratio was stirred for 3 hours The resultant was dried by a rotary evaporator at 80 ° C for 5 hours at 25 rpm and evaporated under reduced pressure. Thereafter, the resultant was heat-treated at 1000 ° C for 2 hours and then dried at 230 ° C for 24 hours to prepare a catalyst carrier having a ratio of the mesopores and macropores of 7: 3 by volume.

15 g of magnesium-doped alumina was loaded in 18.0552 g of distilled water containing 0.3319 g of chloroplatinic acid (H ₂ PtCl ₆ .6H ₂ O), 0.2143 g of hydrochloric acid and 0.0536 g of nitric acid. The supported solution was dried using a rotary evaporator, stirred at 25 rpm for 1.5 hours at room temperature, dried at 80 rpm for 1.5 hours at 25 rpm, dried in a 105 ° C oven for 15 hours, Deg.] C for 3 hours to prepare a dehydrogenation catalyst.

Example  2

The dehydrogenation catalyst was prepared in the same manner as in Example 1, except that the ratio of the mesopores and macropores in Example 1 was 8: 2.

Comparative Example  One

A dehydrogenation catalyst was prepared in the same manner as in Example 1, except that alumina without doping of magnesium oxide was used in Example 1.

Comparative Example  2

A dehydrogenation catalyst was prepared in the same manner as in Example 1 except that a carrier containing only mesopores of 25 nm size was used as the alumina support in Example 1.

Comparative Example  3

A dehydrogenation catalyst was prepared in the same manner as in Example 1 except that a carrier containing only macropores of 100 nm in size was used as the alumina support in Example 1.

Test Example  1: dehydrogenation catalyst Performance test

In order to confirm the performance of the dehydrogenation catalyst according to the present invention, the following experiment was conducted. 1.5 g of the catalyst prepared in Examples 1 to 2 and Comparative Examples 1 to 3 were packed in a quartz reactor having a volume of 7 ml, respectively, and a dehydrogenation reaction was performed by supplying a mixed gas of propane, hydrogen and oxygen. At this time, the ratio of hydrogen to propane was fixed at 1: 1, the ratio of propane and oxygen was fixed at 30: 1, the reaction temperature was maintained at 650 ° C., the pressure was maintained at 1.5 absolute pressure and the liquid space velocity was maintained at 15 hr ^-1 . Respectively. The gas composition after the reaction was analyzed by gas chromatography connected to the reaction apparatus to determine the propane conversion, the propylene selectivity in the product after the reaction, and the propylene yield, and the results are shown in Table 1 below.

Performance (mol%) [Reaction time (1 hr)] Performance (mol%) [Reaction time (7 hr)] Conversion Rate Selectivity yield Conversion Rate Selectivity yield Example 1 39.4% 89.7% 35.3% 36.5% 93.1% 34.0% Example 2 39.1% 88.3% 34.6% 36.5% 92.6% 33.8% Comparative Example 1 35.4% 92.6% 32.8% 28.6% 93.5% 26.7% Comparative Example 2 27.3% 93.6% 25.6% 22.2% 93.0% 20.6%

As shown in Table 1, the catalytic activity of the catalyst according to the present invention was 40.2%, the propylene selectivity was 78.6%, and the propylene yield was 31.6%. It was also confirmed that the catalyst activity was maintained high as the reaction time increased. On the other hand, the catalyst of Comparative Example 1 composed of alumina only had a similar initial activity to that of the catalyst of the present invention (Example 1) under harsh conditions, but the activity rapidly decreased as the reaction time elapsed.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. This will be obvious. Accordingly, the true scope of protection of the present invention should be defined in the appended claims and their equivalents.

Claims (15)

Wherein a mixture of magnesium oxide or magnesium tin oxide and a component constituting the carrier is doped on a carrier having a mesopore of 5 to 50 nm and macropores of 50 nm to 20 탆.
The composite catalyst carrier according to claim 1, wherein the carrier is alumina in which a theta crystal phase or a theta crystal phase and a gamma crystal phase coexist, and is alumina (Al ₂ O ₃ ) having a crystallinity of 90% or more.
The method of claim 1, wherein the ratio of the mesopores to the macropores is in the range of 7: 3 to 8: 2 by volume, the macropore volume per unit carrier weight is in the range of 0.05 cc / g to 0.4 cc / g , And the volume of the mesopores is 0.2 cc / g to 0.8 cc / g.
A mixed catalyst carrier doped with a mixture of magnesium oxide (MgO) or a magnesium tin oxide and a component constituting the carrier, on a carrier having mesopores of 5 to 50 nm and macropores of 50 nm to 20 탆; And a transition metal active component supported on the composite catalyst carrier.
The dehydrogenation catalyst according to claim 4, wherein the carrier is alumina in which a theta crystal phase or a crystallite phase and gamma crystal phase coexist, and is alumina (Al ₂ O ₃ ) having a crystallinity of 90% or more.
5. The process according to claim 4, wherein the alumina support has a macropore volume per unit carrier weight of 0.05 cc / g to 0.4 cc / g, and a mesopore volume of 0.2 cc / g to 0.8 cc / g Dehydrogenation catalyst.
5. The method of claim 4, wherein the transition metal active component is selected from the group consisting of platinum (Pt); Or a metal such as palladium (Pd), nickel (Ni), cobalt (Co), ruthenium (Ru), rhenium (Re), rhodium (Rh), osmium (Os), titanium (Ti), vanadium , Manganese (Mn), iron (Fe), copper (Cu), zinc (Zn), or any alloy thereof.
The dehydrogenation catalyst according to claim 4, wherein the hydrocarbon is a C2 to C5 linear hydrocarbon.
Preparing a carrier having macropores of 5 to 50 nm and macropores of 50 nm to 20 탆;
Mixing an acid solution of magnesium oxide or magnesium tin oxide and an acid solution of a carrier component on the carrier, heating and heating the mixture to obtain a composite catalyst carrier;
Impregnating the resulting composite catalyst carrier with a transition metal active component using an impregnation method, and then calcining the catalyst.
The carrier according to claim 9, wherein the support is alumina in which a theta crystal phase or a theta crystal phase and a gamma crystal phase coexist, and alumina (Al ₂ O ₃ ) having a crystallinity of 90% or more is used. Gt;
11. The method of claim 10, wherein the mixture for the doping, the molar ratio of the carrier component and the magnesium or magnesium-tin oxide oxide Al ₂ O _3: characterized in that the mixture so that the molar ratio of MgO (or MgSnO ₃₎ = 0.0001 ~ 1.0 Gt;
10. The method of claim 9, wherein the calcination after the doping is performed at a temperature of 700 deg. C to 1200 deg.
10. The method of claim 9, wherein the acid is selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, and boric acid.
Contacting the dehydrogenatable hydrocarbon with the catalyst according to any one of claims 4 to 8 under dehydrogenation conditions and obtaining the dehydrogenation product.
15. The method of claim 14, wherein the mixed gas containing propane, hydrogen, and oxygen is reacted at a reaction temperature of 600 to 1000 占 폚, 0.1 to 10 kgf / cm < 2 >, using a dehydrogenation catalyst of any one of claims 4 to 8. Wherein the propane is subjected to a gas phase reaction under a condition that the gas pressure and the H2 / C3 ratio are 0 to 1.0 and the liquid space velocity (LHSV) of the mixed gas and the catalyst is 0.1 to 30 hr ^-1 , Way.