KR20120077688A - Metal catalyst for dehydrogenation having improved selectivity - Google Patents

Abstract

PURPOSE: A metal catalyst for dehydrogenation is provided to prevent the generation of structural change and the characteristic change of active materials due to heat by increasing the intensity of the catalyst. CONSTITUTION: A metal catalyst for dehydrogenation is used for the dehydrogenation of hydrocarbon. A support for the metal catalyst includes mesopores of 5 to 100nm and macropores of 0.1 to 20um. The active density of platinum in the metal catalyst is in a range between 0.001 and 0.009 weight%/m^2. The catalyst includes 0.05 to 1.5 weight% of platinum, 0.05 to 2.0 weight% of tin, germanium, or gallium, 0.05 to 3.0 weight% of alkali metals or alkali earth metals, 0.1 to 3.0 weight% of a halogen element, and 0.05 to 2.0 weight% of an auxiliary metal based on the total weight of the catalyst. The auxiliary metal is selected form a group including indium, manganese, zirconium, cesium, and cerium. The support is alumina, silica, and the mixture of the same.

Description

Metal catalyst for dehydrogenation having improved selectivity

The present invention relates to a metal catalyst for dehydrogenation reaction, and more particularly, to a metal catalyst for dehydrogenation reaction with improved selectivity of the reaction through the adjustment of the catalyst activity through an auxiliary metal.

The dehydrogenation reaction of the hydrocarbon gas proceeds at a high temperature of 550 ° C. or higher. As the catalytic reaction proceeds at high temperatures, side reactions to it entail pyrolysis and coke formation reactions, the extent of which is a key factor in determining the selectivity and activity of the catalyst. Coke-forming reactions, one of the side reactions, lower the overall reaction conversion rate by covering the active material on the catalyst with coke to block the contact with the reactants.

In the conventionally known dehydrogenation catalyst-related patents, the content of the active ingredient and the type of the carrier of the catalyst is the mainstream, there is no research to increase the selectivity by controlling the catalyst activity using the auxiliary metal. Properly adjusting the activity of the reaction proceeding at high temperature can improve the selectivity of the reaction and at the same time advantageously maintain the catalytic activity.

The present invention has been invented to solve the above problems, the present invention has an object to provide a metal catalyst for the dehydrogenation reaction to improve the selectivity of the reaction by adjusting the catalytic activity through the auxiliary metal.

The metal catalyst for dehydrogenation reaction with improved selectivity according to the present invention has a carrier having mesopores of 5 to 100 nm and macropores of 0.1 to 20 μm, and an active density of platinum is 0.001 to 0.009 wt% / m 2. It is done.

According to another preferred feature of the invention, the catalyst is 0.05 to 1.5% by weight of platinum, 0.05 to 2.0% by weight of tin, germanium or gallium, 0.05 to 3.0% by weight of alkali or alkaline earth metal, 0.1 to halogen based on the total weight of the catalyst 3.0 wt% and 0.05-2.0 wt% auxiliary metal.

According to another preferred feature of the invention, the alkali or alkaline earth metal is selected from the group consisting of calcium, potassium, sodium, magnesium, lithium, strontium, barium, radium and beryllium.

According to another preferred feature of the invention, the halogen component is selected from the group consisting of chlorine, phosphorus and fluorine.

According to another preferred feature of the invention, the auxiliary metal is selected from the group consisting of indium, manganese, zirconium, cesium, cerium.

According to another preferred feature of the invention, the carrier is alumina, silica and mixed components thereof.

The selectivity of the reaction can be improved by controlling the catalytic activity through the auxiliary metal. The dehydrogenation catalyst according to the present invention can improve the selectivity of the catalytic reaction through the auxiliary metal, maintain activity, high activity density of the unit surface area catalyst, easy mass transfer of reactants and products, and coke production The deactivation is delayed, and the coke regeneration is high, there is no change with the initial activity even after regeneration, the strength is strong against external impact, there is no structural change or characteristic change of the active material by heat.

The metal catalyst for dehydrogenation reaction with improved selectivity according to the present invention uses a carrier having mesopores of 5 to 100 nm as a catalyst containing platinum as an active ingredient.

The catalyst of the present invention applies a carrier having mesopores of 0.1-100cc / g to 0.900cc / g with a pore size of 5 to 100nm and macropores of 0.050cc / g to 0.500cc / g of 0.1 to 20㎛, 0.05 to 1.5% by weight of platinum, 0.05 to 2.0% by weight of tin, germanium or gallium, 0.05 to 3.0% by weight of alkali or alkaline earth metal, 0.1 to 3.0% by weight of halogen and 0.05 to 2.0% by weight of auxiliary metal It includes.

Hereinafter, the present invention will be described in detail.

The present invention includes the auxiliary metal in the active material of the dehydrogenated composite metal well known by the prior art, by applying a carrier having a macroporous and microporous structure to prepare a catalyst for the dehydrogenation reaction to improve the selectivity of the reaction, Maintaining high activity density of the unit surface area catalyst, easy mass transfer of reactants and products, delayed deactivation due to coke formation, high regeneration of coke, and no change from initial activity after regeneration. It provides a catalyst that is high in external impacts and does not have structural changes due to heat or changes in the properties of active materials.

Saturated hydrocarbons in the present invention are the main target reactants of ethane, propane, butane, isobutane and pentane, olefins having a carbon backbone corresponding to the saturated hydrocarbons used as reactants by dehydrogenation, ie ethylene, propylene, 1 or 2 Converted to butylene, isobutylene, pentene.

Dehydrogenation of these components is an equilibrium reaction in which the maximum olefin yield is limited thermodynamically. Due to the nature of the reaction, endothermic and volume increase reactions, the maximum conversion is limited by chemical equilibrium, so to increase the conversion rate, the reaction temperature should be increased and the reaction pressure should be kept as low as possible.

As the reaction conditions preferred by the catalyst of the present invention, the dehydrogenation reaction temperature is 400 to 900 ° C, specifically 600 to 900 ° C for ethane dehydrogenation, 550 to 700 ° C for propane and 400 to 650 ° C for butane. In case of isobutane, 450 ~ 650 ℃, pentane is 200 ~ 500 ℃, and the reaction pressure is 0.1 ~ 10 absolute air pressure.

In order to continuously or effectively induce the reaction, components added in addition to the saturated hydrocarbons may be a mixture of saturated hydrocarbons and hydrogen or a mixture of the components of the saturated hydrocarbons with hydrogen, or steam or carbon monoxide instead of or together with hydrogen. Is 0-100 mol% of the amount of hydrocarbon influent to be dehydrogenated.

The liquid space velocity of the saturated hydrocarbon and the catalyst flowing (Liquid Hourly Space Velocity) is 0.1?, And 30hr ^-1, particularly 0.1? High availability by use of the catalyst composed according to the present invention in 16 hr ^-1. Industrial catalytic reactor types are applicable to all commercially known reactor types, of which fixed bed or fluidized bed reactors are preferred.

The catalyst should have the function of increasing the rate of dehydrogenation to increase the thermodynamic airfoil attainment rate, suppress the formation of structural isomers, and inhibit the thermal decomposition of hydrocarbons that can occur under the reaction conditions, and maintain stable activity under industrial conditions. Should show.

Stability has the effect of increasing the rate of change of activity and selectivity over the use time and the period of continuous use as a catalyst after a specific time, i.e., increasing the economic life of the catalyst.

Factors that reduce the stability of the catalyst include the generation of carbon deposits, i.e., reduction of the contact efficiency with the reactants on the active surface by caulking and the sintering of the active components between the active components generated for various reasons during the reaction or catalyst regeneration. Of the contact area with the reactants

It is mainly due to the reduction, changes in the conditions of use of the catalyst under industrial conditions, and sometimes caused by loss into the reactants and partial loss of the catalyst components due to crushing of the catalyst and the like.

In order to increase the dehydrogenation performance of the catalyst, selection of appropriate active ingredients and improvement of physical stability of the catalyst itself are also very important. Also, in order to increase the overall activity and to increase the production efficiency of the desired reaction product, that is, the selectivity of pyrolysis and isomerization, etc. The function to reduce side reactions of the polymers should be imposed, and the production and treatment of physicochemical catalysts are required to maintain this performance stably.

According to the conventional published effect, the reaction yield is found to range from 40% to 90% of the theoretical maximum yield (thermodynamic yield) under the conditions under which the comparative test was made.

The dehydrogenation of saturated hydrocarbons of 5 or less carbon atoms is carried out very quickly by the diffusion and reaction of the saturated hydrocarbons, which are reactants, on the catalyst.

It is known that the chemical reaction at the surface of the catalyst is relatively slow as the microscopic reaction characteristic, and the rate of the entire reaction is controlled by the catalyst surface reaction. In this case, the diffusion rate refers to the structure and the structure of active components or components contained microscopically in the catalyst particles when they come into contact with the catalyst in the gas flow of the hydrocarbon reactant, and to the reaction active sites formed by electrochemical effects. After the surface reaction of, all of the unsaturated hydrocarbons generated after the reaction, ie, the rate of migration of olefins out of the catalyst particles, are included.

However, although the olefin yield by the reaction can be easily obtained by varying the catalyst composition and the content to some extent, it is understood that the closer the thermodynamic equilibrium yield, which is the theoretical limit olefin yield, the better the performance by the catalyst is.

In particular, as the reaction temperature is increased to a high temperature or the mixture molar ratio of hydrocarbon to hydrogen is increased to increase the yield of olefins, the mass transfer rate or diffusion rate is relatively slower than the reaction rate of the catalyst surface, that is, the active material of the reaction system in diffusion resistance. Phenomena that can be interpreted as being accelerated are observed.

Increasing the mass transfer or diffusion resistance in the catalyst before and after the reaction, ie, the increase in the effective residence time of the reaction, delays the reaching of the catalytically active component of the reacted saturated hydrocarbons, resulting in good intrinsic activity but overall improvement in the reaction rate. In addition to the dropping phenomenon, after the reaction, the product is again adsorbed into the catalyst particles, the reaction products are reacted with each other, the skeleton isomers are formed, and the carbon deposition is performed.

It increases the possibility of occurrence of undesirable side reactions such as conversion to water.

In addition, as the reaction proceeds, carbon deposits accumulated in the micropores of the catalyst reduce the function of the transfer and transport passage of reaction-related materials, and thus the main functions of the catalyst, such as catalyst activity, selectivity, and catalyst stability, accelerate the degradation.

In addition to the composition of the catalyst component having a component that exhibits excellent activity, the present invention has a structural structure that facilitates the transfer phenomenon and reduces the diffusion resistance to have a physical structure of the carrier and maximizes such that the improved catalytic activity is sustained. Apply pore.

More specifically, in order to minimize the diffusion resistance, that is, to facilitate mass transfer before and after the reaction, the large pores of the catalyst were imparted to the carrier, and the fine pores and the pore volume were intentionally increased to improve the mass transfer distance between the active ingredient and the catalyst. Pore and surface structure were adjusted to minimize.

The macropores of the present invention have a function as a mass transfer channel that minimizes the mass transfer distance to a set of micropores or minimizes the diffusion resistance.

The expression of the fine pore structure is such that the enlargement of the pores and the reduction of the surface area are close to the active ingredients finely supported on the catalyst, and rather the sintering of the active ingredients can be facilitated, but the change in the structural properties due to the large pores Therefore, it has excellent high temperature resistance and fine dispersibility, leading to an improvement in catalyst performance stability.

The micropores to be classified in the present invention is measured by nitrogen adsorption method (N2 BET) having a size of 500Å or less, mainly 200Å or less, and the macropores which are important in the present invention have a pore size of 1,000Å or more and 10 micron. Below, it can be observed on the cross section or surface at an enlargement ratio of 100 times or more with an electron microscope, and the size distribution of pores can be quantified when the maximum penetration pressure of 15,000 pounds (1b) or more is applied with a mercury (Hg) porosimetry.

The large pores of the present invention may also be expressed as a passage or a void or a hole or cavity. The macropores are not easily measured by nitrogen adsorption because nitrogen gas does not condense in the macropores.

Important considerations in the present invention are the size distribution of total porosity, the total volume, the uniform distribution thereof, the micropore size distribution present in the large pore structure, and the total volume thereof in the unit catalyst weight.

In the present invention, the category which is considered to be effective for dehydrogenation of low molecular weight hydrocarbons having 5 or less carbon atoms has a minimum macropore volume of at least 0.05cc / g and a maximum of 0.5cc / g and a micropore of 5-100 nm and a minimum of 0.10cc. / g and above 0.9cc / g and below are interconnected structures. At this time, the carrier of the preferred catalyst is alumina having fine porosity, and can be easily prepared to have such a structure.

Preferred catalysts in the present invention have a form, and the presence of such macropores and enlargement of micropores may result in poor catalyst strength. When preparing a carrier having macropores in order to enhance the strength, it is subjected to plastic deformation at 900 to 1200 ° C to impart crystallinity. The crystalline form of the carrier formed in the present invention corresponds to alumina in which theta or alpha and two crystalline forms (alpha and theta) coexist.

The catalyst prepared by the present invention has improved performance which is more differentiated than the catalyst by the conventional method, that is, the harsher the dehydrogenation conditions, the higher the hydrocarbon conversion and selectivity and the performance stability, and the improved resistance to coking and the ease of coking removal. . In the known hydrocarbon conversion reaction, there is no knowledge in the art of improving the performance by utilizing a carrier having such a large pore.

In the present invention, the catalyst structure having high performance has a large pore volume of 0.10? 0.40cc / g and a fine pore volume of 0.20-0.80cc / g. Has a double modal distribution. The application of such macroporous carriers shows improved activity and ease of regeneration in the dehydrogenation reaction at the time of reaction with the catalyst.

In order to prevent the weakening of the strength caused by the macropores, plastic deformation at 1 to 24 hours at a high temperature of 900 to 1,200 ° C. results in more than 3.Okgf of particle breaking strength. The surface area of the final catalyst has a nitrogen adsorption specific surface area of 150 mm 2 / g or less. Reducing the surface area also requires microdispersion of platinum with major activity, but can lower the total content of effective platinum.

The preferred alkali group 1 component in the catalyst of the invention is potassium (K). It can be prepared from a compound having potassium (K) in various ways and forms a stable oxide through the final calcining process. Preferred compounds of potassium (K) are aqueous salts, chlorides and nitrates.

Tin can easily prepare tin-containing alumina by mixing with aluminum-containing components which can be converted to alumina in a high temperature oxidizing atmosphere. The raw material of the tin component is tin chloride salt, which is preferably SnCl 2 in the solid phase or SnCl 4 in the liquid phase.

The applied macropore properties of the present invention are determined during the preparation of the carrier material, which can be purchased commercially and applied to the catalyst. Such alumina carriers are obtained through a molding process in various organoaluminum slurries. The preferred carrier in the present invention is organic aluminum having 4 to 14 carbon atoms or less.

The obtained alumina needs heat treatment so as to have a suitable strength and pore distribution for industrial application. In the present invention, the gas hourly space velocity (GHSV) in an oxygen or nitrogen gas atmosphere is 300 to 5,000 hr ^-1 and 900 to 1,200. The carrier to be applied in the present invention is processed by performing a high temperature baking treatment of about 0.5 to 20hr ⁻¹ to hr ⁻¹ .

This carrier is a crystalline material, and the size distribution of the large pore in the unit carrier weight, the uniform distribution of the total volume, the fine pore size distribution in the large pore structure, and the total volume thereof are important.

In the present invention, the category which is considered to be effective for the dehydrogenation of low molecular weight hydrocarbons having 5 or less carbon atoms has a minimum macropore volume of at least 0.05cc / g and a maximum of 0.5cc / g, and the micropores have a distribution of 5-100 nm and a minimum of 0.10. It is interconnected structure of more than cc / g and up to 0.9cc / g.

The crystalline form of the carrier applied in the present invention corresponds to alumina in which theta or alpha and two crystalline forms (alpha and theta) coexist.

In the present invention, the active ingredient refers to a material that can affect the dehydrogenation reaction of saturated hydrocarbons electronically, physically and chemically, and broadly includes a carrier material to finally form metal microparticles, oxides, chlorides, sulfides, hydrides, Halogen salts, oxychlorides, carrier materials or other components in combination.

The raw material of the platinum component in the present invention may be chloroplatinic acid, ammonium chloride platinum salt, bromo platinum acid, platinum chloride hydrate, platinum carbonyl salt or acid, platinum nitrate salt or acid, and the like. PtCl6) is preferably supported on the carrier prepared above by a known impregnation method (adsorption method) together with hydrochloric acid.

On the other hand, the impregnation of the platinum-containing solution is applied to the aqueous solution of 30% concentration hydrochloric acid of about 1% by weight compared to the carrier after the final preparation of the carrier material, and after 0.5 to 4 hours stirring supporting treatment at room temperature, 0.5- at 80-105 ℃ The supporting solution is stirred for 60 hours.

After the drying process and firing process, it is dried for 0.5-60 hours to 100-700 ℃, and 0.5-20 hours isothermal at 500-700 ℃ for gas hourly space velocity (GHSV) 100-5,000hr ^{A value of −1} is considered to be advantageous for preventing the condensation at high temperatures of the platinum metal fine particles and for removing excess residual chlorine.

In order to obtain an effective effect in the present invention, the amount of residual chlorine in the final catalyst should be 0.0-2.0 wt%, preferably 1.5 wt% or less. The chlorine in the catalyst can be vaporized with an aqueous hydrochloric acid solution after preparation of the final catalyst in addition to the platinum support, to adjust the chlorine content in the final catalyst to 0.0 to 2.0% by weight.

The catalyst of the present invention may also be suitable for the reduction operation to express the performance in the dehydrogenation reaction of the saturated hydrocarbon, which may be used in the actual process, or may be used through a reduction process in advance. The catalyst of this process flows hydrogen with a purity of 99.0% or more to 1.0-100 GHSV, and when sufficient 0.1-48 hours are reduced at 400-600 degreeC, sufficient activity can be expressed.

On the other hand, the catalyst of the present invention may regenerate the deactivated catalyst after the reaction by removing the periodic carbon deposits for long-term use or using steam to improve the activity.

Carbon deposits may be removed by combustion in a nitrogen atmosphere mixed with controlled oxygen, or may gently degass the carbon product in a controlled atmosphere of steam, nitrogen and air. In order to maintain the same activity after the coke component is removed, effective chlorine is supplemented by the vapor phase adsorption method to restore performance.

The density of platinum acting as an active point is preferably 0.001 wt.% / M ² to 0.009 wt.% / M ² . When the density of platinum is less than 0.001 wt.% / M ^{2, the} active conversion point is insufficient due to insufficient activity point, and when it is more than 0.009 wt.% / M ^2, the dispersion degree of platinum is lowered to increase the amount of coke produced and increase side reaction. Reaction selectivity is lowered.

Meanwhile, the catalyst according to the present invention is 0.05 to 1.5% by weight of platinum, 0.05 to 2.0% by weight of tin, germanium or gallium, 0.05 to 3.0% by weight of alkali metal or alkaline earth metal, 0.1 to 3.0% by weight of halogen component and auxiliary 0.05-2.0 wt% of the metal.

Platinum is contained 0.05 ~ 1.5% by weight based on the total weight of the catalyst, in the case of platinum is 0.05% or less, the lower the proportion of the active ingredient, the lower the reaction activity, and if more than 1.5% the dispersion is low because the reaction activity is low You lose.

The component of any one of tin, germanium or gallium is included at 0.05 to 2.0 wt% based on the total weight of the catalyst. If the content is less than 0.05% by weight, the side reactivity is increased to decrease the selectivity of the reaction. If the content is more than 2.0% by weight, the platinum-metal alloy is increased due to the excessive amount of the metal component, thereby decreasing the activity.

Alkali metal or alkaline earth metal contains 0.05 to 3.0% by weight relative to the total weight of the catalyst, if less than 0.05% by weight of the acid side of the catalyst has a problem of increasing the side reactions, if exceeding 3.0% by weight of the active point is lowered activity is reduced there is a problem.

The halogen component contains 0.1 to 3.0% by weight based on the total weight of the catalyst. If the content is less than 0.1% by weight, the formation of coke on the catalyst is rapidly increased, the coke regeneration of the catalyst is lowered, and the platinum dispersity is lowered during catalyst regeneration. When the percentage is exceeded, the catalyst activity is lowered due to poisoning of the noble metal by the halogen component. The halogen component in the present invention is selected from the group consisting of chlorine, phosphorus and fluorine, preferably chlorine.

Auxiliary metals contain 0.05 to 2.0 weight percent based on the total weight of the catalyst. If less than 0.05% by weight there is a problem that the performance of the auxiliary metal is not properly expressed, if more than 3.0% by weight there is a problem that the activity point of the platinum component is lowered, the activity is lowered. The auxiliary metal in the present invention is selected from the group consisting of indium, manganese, zirconium, cesium, cerium, preferably indium.

Alumina having spherical gamma crystallinity prepared according to US Pat. No. 4,542,113 was purchased from Sasol, Germany, and 1100 on air flow 300ml / min using a tubular electric furnace (Korea Electric Furnace). It was thermally deformed for 6 hours at a temperature of < RTI ID = 0.0 >

The catalyst was prepared by a room temperature / temperature adsorption support method using a heat-modified alumina carrier. Indium chloride (InCl3) was added to distilled water to dissolve it, and then heat-modified alumina was loaded to carry it. The supporting solution was dried using a rotary evaporator, and stirred at 25 rpm for 1.5 hours at room temperature, and then dried by rotating at 25 rpm for 1.5 hours at 80 ° C under reduced pressure. For complete drying it was dried for 15 hours in a 105 ℃ oven and heat-treated for 2 hours in a 700 ℃ heating furnace. Thereafter, the indium-supported alumina was loaded in distilled water in which tin chloride (SnCl 2), hydrochloric acid (HCl), and nitric acid (HNO 3) were dissolved. The supporting solution was dried using a rotary evaporator, and stirred at 25 rpm for 1.5 hours at room temperature, and then dried by rotating at 25 rpm for 1.5 hours at 80 ° C under reduced pressure. For complete drying it was dried for 15 hours in a 105 ℃ oven and heat-treated for 2 hours in a 700 ℃ heating furnace. Thereafter, indium and tin-supported alumina were loaded in distilled water in which platinum acid (H 2 PtCl 6), hydrochloric acid, and nitric acid were dissolved. The supporting solution was dried and heat treated in the same manner as above. Subsequently, indium, tin and platinum-supported alumina were loaded in distilled water in which potassium nitrate (KNO 3) and hydrochloric acid were dissolved. The supporting solution was dried and heat treated in the same manner as above to prepare a dehydrogenation catalyst A.

The heat-modified alumina used in Example 1 was used as a carrier for catalytic synthesis.

The catalyst was prepared by a room temperature / temperature adsorption support method using a heat-modified alumina carrier. Manganese chloride (MnCl 2) was added to distilled water to dissolve it, and then heat-modified alumina was loaded to carry it. Thereafter, drying and heat treatment were performed in the same manner as in Example 1, and tin and platinum and potassium were sequentially supported and heat treated to prepare a dehydrogenation catalyst B.

Comparative Example 1 Catalyst C was prepared by carrying out the same heat treatment and active ingredient as in Example 1, except that indium was not supported in Example 1.

Experimental Example: Performance Experiment of Dehydrogenation Catalyst

In order to confirm the performance of the dehydrogenation catalyst according to the present invention, the following experiment was performed.

2.4 ml of catalysts A, B and C prepared in Examples 1 and 2 and Comparative Example 1 were respectively filled in a 7 ml quartz reactor, and then a mixed gas of propane and hydrogen was supplied to dehydrogenation, respectively. At this time, the ratio of hydrogen and propane was fixed at 1: 1, and the dehydrogenation reaction was carried out while maintaining the reaction temperature at 620 ° C., the absolute pressure at 1.5 atm, and the liquid space velocity at 15 hr −1 under adiabatic conditions. The gas composition after the reaction was analyzed by gas chromatography connected with the reaction apparatus to determine the propane conversion and the propylene selectivity in the product after the reaction.

The conversion, selectivity, and yield at 5 hours after the start of the reaction are shown in the table.

Conversion rate (% by weight) Selectivity (wt%) Yield (wt%) Catalyst A 26.9 96.8 26.0 Catalyst B 25.9 93.7 24.2 Catalyst C 25.3 87.5 22.1

As shown in the table, catalyst A of the present invention has very good reaction selectivity due to the influence of indium. Propane conversion was maintained at a similar level as compared to Comparative Example C. In addition, the 5 hour average coke production amount of the catalysts A, B and C were 0.13% / hr, 0.41% / hr and 0.45% / hr, respectively, and it was found that the coke production amount decreased when indium was used as an auxiliary metal.

Claims (6)

In the metal catalyst for dehydrogenation reaction used in the hydrocarbon dehydrogenation process,
The metal catalyst for the dehydrogenation reaction with improved selectivity, characterized in that the carrier has meso pores of 5 to 100 nm and macro pores of 0.1 to 20 μm, and the active density of platinum is 0.001 to 0.009 wt% / m 2. According to claim 1, wherein the catalyst is 0.05 to 1.5% by weight of platinum, 0.05 to 2.0% by weight of tin, germanium or gallium, 0.05 to 3.0% by weight of alkali metal or alkaline earth metal, 0.1 to 3.0% by weight of halogen component And 0.05 to 2.0 wt% of an auxiliary metal. 3. The metal catalyst for dehydrogenation of claim 2, wherein the alkali metal or alkaline earth metal is selected from the group consisting of calcium, potassium, sodium, magnesium, lithium, strontium, barium, radium and beryllium. 3. The metal catalyst for dehydrogenation of claim 2, wherein the halogen component is selected from the group consisting of chlorine, phosphorus and fluorine. The metal catalyst for dehydrogenation of claim 2, wherein the auxiliary metal is selected from the group consisting of indium, manganese, zirconium, cesium, and cerium. The metal catalyst for dehydrogenation of claim 1, wherein the carrier is alumina, silica, or a mixed component thereof.