KR101839568B1 - Metal loaded catalyst, preparation method of the same, and preparation method of c4 olefin using the same - Google Patents

Abstract

The present invention relates to a metal supported catalyst which can obtain high-quality olefins at a higher conversion rate and yield from liquefied petroleum gas or hydrocarbon fuel, and can maintain excellent activity after long term reaction; to a preparation method of the same; and a preparation method of C4 olefin using the same.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a metal-supported catalyst, a method for producing the same, and a method for producing olefins having 4 carbon atoms using the same. BACKGROUND ART [0002] METAL LOADED CATALYST, PREPARATION METHOD OF THE SAME, AND PREPARATION METHOD OF C4 OLEFIN USING THE SAME [

The present invention relates to a metal-supported catalyst, a process for producing the same, and a process for producing olefins of 4 carbon atoms using the same, and more particularly, to a process for producing olefins of high quality from a liquefied petroleum gas or a hydrocarbon raw material at a higher conversion rate and yield, And a method for producing olefins of 4 carbon atoms using the same. BACKGROUND ART

Shale gas, which is emerging as a revolutionary resource to replace existing petrochemical raw materials, is being actively developed mainly in the United States and China, and is attracting attention as an alternative energy source. Although supply of ethylene and propylene, which are mainly used in the petrochemical industry, is expected to be smooth due to the production of shale gas and the development of raw materials, the demand for C4 olefins, which can be produced from the decomposition of naphtha, Is expected.

The dehydrogenation process for producing a C4 olefin component containing isobutene, 1-butene, 2-butene and 1,3-butadiene from C4 LPG components is largely divided into a direct dehydrogenation reaction and an oxidative dehydrogenation reaction, The reaction is advantageous in that oxygen is injected together with the reactant to oxidize and remove the coke produced during the dehydrogenation reaction, but the selectivity to the desired C4 olefin component may be lowered due to carbon monoxide and carbon dioxide produced as by-products .

On the other hand, the direct dehydrogenation reaction is capable of producing hydrogen from the reactant and has a high selectivity to the product compared to the oxidative dehydrogenation reaction. However, since the coke produced during the reaction covers the active material of the catalyst, .

More specifically, factors that reduce the stability of the catalyst include reduction of the contact area with the reactants on the active surface due to generation of carbon deposits, that is, coking, and reduction of the contact area between the active components Reduction of the contact area between the active surface and the reactant due to sintering, and the like.

Therefore, there is a need to develop a technique that can solve the sudden deactivation of the catalyst over the reaction time, which is a disadvantage that occurs in the dehydrogenation reaction of n-butane using the dehydrogenation catalyst of the prior art.

The present invention relates to a metal-supported catalyst capable of obtaining high-quality olefins at a higher conversion and yield from liquefied petroleum gas or hydrocarbon raw materials, and capable of maintaining excellent activity even in a long reaction time, a process for producing the same, To provide a process for producing olefins.

The present invention relates to a porous support comprising alloy particles of alumina and at least one member selected from the group consisting of magnesium, oxides thereof, hydroxides thereof and hydrates thereof, and zirconium, oxides thereof and the like dispersed in the inner pores of the porous support A carrier comprising at least one selected from the group consisting of hydrates of alumina and alumina particles; And a catalyst layer fixed on the support and containing at least one of platinum (Pt), nickel (Ni), copper (Cu), zinc (Zn), tin (Sn), lanthanum (La), potassium (K), calcium And at least one metal selected from the group consisting of hydrates thereof.

The present invention also provides a method for producing a zirconium compound, comprising: mixing a zirconium compound and an aluminum compound and sol-gel reaction; Mixing a resultant of the sol-gel reaction, a magnesium compound, and an aluminum compound with a sol-gel to form a carrier; And a method of manufacturing a semiconductor device, comprising the steps of: forming a metal layer on a surface of a substrate; and forming a metal layer on the substrate by depositing platinum (Pt), nickel (Ni), copper (Cu), zinc (Zn), tin (Sn), lanthanum (La), potassium (K) And a step of impregnating at least one metal selected from the group consisting of the above metals.

The present invention can also provide a process for producing an olefin having 4 carbon atoms, which comprises reacting a hydrocarbon compound including normal-butane, hydrogen and water vapor in the presence of a metal supported catalyst.

Hereinafter, a metal supported catalyst according to a specific embodiment of the present invention, a method for producing the same, and a method for producing olefins having 4 carbon atoms using the same will be described in detail.

According to an embodiment of the present invention, there is provided a porous support comprising an alloy particle of alumina and at least one member selected from the group consisting of magnesium, an oxide thereof, a hydroxide thereof and a hydrate thereof, and a zirconium compound dispersed in the internal pores of the porous support, A carrier comprising an alloy of alumina and at least one selected from the group consisting of oxides thereof and hydrates thereof; And a catalyst layer fixed on the support and containing at least one of platinum (Pt), nickel (Ni), copper (Cu), zinc (Zn), tin (Sn), lanthanum (La), potassium (K), calcium And a hydrate thereof, may be provided on the surface of the metal supporting catalyst.

DISCLOSURE OF THE INVENTION The present inventors have found that, unlike a conventional carrier, a porous support containing alloy particles of alumina and at least one member selected from the group consisting of magnesium, oxides thereof, hydroxides thereof and hydrates thereof, In the case of a catalyst prepared by using a carrier containing alumina particles of at least one member selected from the group consisting of zirconium, zirconium, oxides thereof and hydrates thereof and alumina, the noble- It has been confirmed through experiments that the olefin component can be synthesized at a high yield and the invention is completed.

Specifically, the metal-supported catalyst of one embodiment includes a porous support containing alloy particles of alumina and at least one member selected from the group consisting of magnesium, oxides thereof, hydroxides thereof and hydrates thereof, and a porous support containing particles dispersed in the inner pores of the porous support , Zirconium, oxides thereof, and hydrates thereof, and an alloy particle of alumina with at least one selected from the group consisting of zirconium, zirconium, oxides thereof, and hydrates thereof.

The magnesium, oxides thereof, hydroxides thereof, hydrates thereof, or a mixture of two or more thereof may form an alloy with alumina, and such an alloy may be used as a support in the metal-supported catalyst. The carrier containing magnesium, oxides thereof, hydroxides thereof, hydrates thereof, or a mixture of two or more thereof and an alloy of alumina can further enhance the activity of the catalyst and efficiently conduct the dehydrogenation reaction of n-butane.

Also, the alumina alloy with at least one selected from the group consisting of zirconium, its oxides and hydrates thereof serves to improve the conversion of n-butane and to maintain the selectivity of the olefin having 4 carbon atoms for a long time during the reaction can do.

On the other hand, in the inner pores of the porous support containing the alloy particles of alumina and at least one selected from the group consisting of magnesium, oxides thereof, hydroxides thereof, and hydrates thereof, and zirconium, oxides thereof and hydrates thereof, Alloy particles of alumina or more can be dispersed.

The magnesium, oxides thereof, hydroxides thereof, hydrates thereof, or a mixture of two or more thereof may form a porous support by aggregation of the alloy particles after forming the alloy particles with alumina. Specifically, the average pore diameter of the porous support is 1 nm to 20 nm, or 8 nm to 14 nm, and the maximum diameter of the porous support is 0.5 mm to 15 mm.

The alloy particles of alumina and at least one selected from the group consisting of zirconium, oxides thereof, and hydrates thereof may have a spherical particle shape, and the maximum diameter may be 0.1 mm to 10 mm. The maximum diameter may mean the longest cross-sectional diameter based on the cross-section of the particles.

As described above, in a single support, a single support contains a compound selected from the group consisting of zirconium, oxides thereof and hydrates thereof in a porous support structure containing alloy particles of alumina and at least one member selected from the group consisting of magnesium, oxides thereof, hydroxides thereof, By dispersing the alloy particles of alumina and alumina particles, it is possible to form a physical bond while maintaining the crystal structure, and it is possible to maintain the acidity appropriately to suppress the side reaction and maintain the conversion rate of the normal-butane for a long time, The specific surface area of the support may be increased to increase the specific surface area of the platinum as the active metal.

Specifically, the weight ratio of magnesium to aluminum contained in the support may be 0.3: 1 to 2: 1, and the weight ratio of zirconium to aluminum contained in the support may be 0.3: 1 to 2: 1. Accordingly, when the carrier is used, it is possible to synthesize a catalyst capable of producing a C4 olefin component at a high yield over a long period of time, thereby improving the economical efficiency.

If the weight ratio of magnesium to aluminum contained in the support is reduced to 0.3 or less, the content of metal may be too small as compared with that of alumina, which may lower the activity of the catalyst. In addition, if the weight ratio of magnesium to aluminum contained in the support is increased to more than 2, the metal may be supersaturated with respect to alumina and may not be uniformly dispersed on the surface of the catalyst.

If the weight ratio of zirconium to aluminum contained in the support is reduced to 0.3 or less, the content of metal may be too small as compared with that of alumina, which may lower the activity of the catalyst. In addition, if the weight ratio of magnesium to zirconium contained in the support increases to more than 2, the metal may be supersaturated with respect to alumina and may not be uniformly dispersed on the surface of the catalyst, so that the activity of the catalyst may be lowered.

A specific surface area of the support (BET, Brunauer-Emmett-Teller ) may be 100 m ² / g to 150m ² / g, or 120 m ² / g to 140m ² / g. If the specific surface area of the support is too small, the fixed metal may not be evenly distributed, so that the activity of the supported catalyst may be lowered. Also, the carrier may have an average pore diameter of 1 nm to 100 nm, or 15 nm to 20 nm.

The alumina (Al ₂ O ₃ ) may have a crystal structure of? (Alpha),? (Gamma),? (Eta), delta It is preferable to use an alumina carrier having a γ-Al ₂ O ₃ structure. In particular, γ-Al ₂ O ₃ has a relatively large specific surface area as compared with other alumina, so that the metal support is distributed evenly and evenly, and thus is suitable as a support.

The metal-supported catalyst of this embodiment is fixed on the support and is formed of a metal such as platinum Pt, nickel Ni, copper Cu, zinc Zn, tin Sn, lanthanum La, potassium K ), Calcium (Ca), oxides thereof, and hydrates thereof. Thus, the activity of the catalyst can be increased and the selectivity of the olefin component having 4 carbon atoms can be improved.

The order of fixing the metal to the carrier is not limited, and various metals may be fixed at the same time or sequentially.

The metal may be platinum (Pt), nickel (Ni), copper (Cu), zinc (Zn), tin (Sn) , At least one metal compound selected from the group consisting of lanthanum (La), potassium (K), calcium (Ca), oxides thereof, and hydrates thereof.

In order to increase the activity of the metal-supported catalyst and fix the metal to the carrier more efficiently, platinum (Pt), an oxide thereof, or a hydrate thereof in the metal is first fixed on a carrier and nickel It is preferable to fix at least one metal compound selected from copper (Cu), zinc (Zn), tin (Sn), lanthanum (La), potassium (K), calcium (Ca), oxides thereof and hydrates thereof.

It is preferable that the platinum, the oxide thereof, or the hydrate thereof contains 0.1 to 5 wt% of the content of the support.

(Ni), copper (Cu), zinc (Zn), tin (Sn), lanthanum (La), potassium (K), calcium (Ca), oxides thereof, or hydrates thereof in the metal- And can act as an enhancer.

More particularly, the present invention relates to a method for manufacturing a semiconductor device, which comprises the steps of fixing nickel (Ni), copper (Cu), zinc (Zn), tin (Sn), lanthanum (La), potassium (K), calcium (Ca), oxides thereof, The particle size of platinum is kept small so that the dispersion degree of platinum in the carrier is made even and the number of active points involved in the dehydrogenation reaction can be increased. In addition, the stability of the catalyst can be enhanced and the selectivity to olefins having 4 carbon atoms can be improved by suppressing deposition of carbon generated during the reaction. In order to perform such a role, it is preferable to use tin (Sn), an oxide thereof, or a hydrate thereof as a metal.

Wherein said nickel, copper, zinc, tin, lanthanum, potassium, calcium, oxides thereof or hydrates thereof are present in an amount of 0.1 to 5 wt. % Is preferable because the metal can be evenly distributed on the surface of the catalyst and does not interfere with the activity of the platinum. (Ni), copper (Cu), zinc (Zn), tin (Sn), lanthanum (La), potassium (K), calcium (Ca), oxides thereof or hydrates thereof in an amount exceeding 5 wt% A platinum metal in which nickel (Ni), copper (Cu), zinc (Zn), tin (Sn), lanthanum (La), potassium (K), calcium (Ca), oxides thereof, The dehydrogenation effect of the catalyst can be lowered.

More specifically, in 100 parts by weight of the nickel (Ni), copper (Cu), zinc (Zn), tin (Sn), lanthanum (La), potassium (K), calcium (Ca), oxides thereof, The content of the platinum, the oxide thereof, or the hydrate thereof may be 10 parts by weight to 80 parts by weight, or 20 parts by weight to 50 parts by weight.

According to another embodiment of the present invention, there is provided a method for producing a zirconium compound, comprising: mixing a zirconium compound and an aluminum compound; Mixing a resultant of the sol-gel reaction, a magnesium compound, and an aluminum compound with a sol-gel to form a carrier; And a method of manufacturing a semiconductor device, comprising the steps of: forming a metal layer on a surface of a substrate; and forming a metal layer on the substrate by depositing platinum (Pt), nickel (Ni), copper (Cu), zinc (Zn), tin (Sn), lanthanum (La), potassium (K) The method comprising the steps of: impregnating at least one metal selected from the group consisting of a metal-supported catalyst and a metal-containing catalyst.

The zirconium compound means the zirconium metal itself, an organic salt of zirconium or an inorganic salt of zirconium. This is also true for aluminum compounds and magnesium compounds.

Specifically, the zirconium compound is preferably selected from the group consisting of zirconium (IV) oxynitrate hydrate, zirconium (IV) oxide, zirconium (IV) butoxide, zirconium Zirconium (IV) chloride, zirconium (IV) oxychloride octahydrate, zirconium (IV) silicate, zirconium (IV) acetate may include at least one compound selected from the group consisting of hydroxide, zirconium (IV) hydroxide, zirconium (IV) ethoxide and zirconium (IV) hydrogenphosphate. have.

The magnesium compound may be at least one selected from the group consisting of magnesium sulfate, magnesium oxide, magnesium chloride, magnesium chloride hexahydrate, magnesium phosphate, magnesium nitrate hexahydrate], magnesium nitride, magnesium acetate tetrahydrate, and the like.

The aluminum compound may include at least one compound selected from the group consisting of boehmite, aluminum-tri-sec-butoxide and aluminum nitrate nonahydrate .

The sol-gel reaction is not limited to a specific method. For example, a solution obtained by mixing the zirconium compound, the magnesium compound or the aluminum compound in an aqueous solvent is heated at a temperature of 60 ° C to 100 ° C to form a sol , And adjusting the pH of the sol to 0.5 to 2 to gel.

Meanwhile, the method for preparing a metal supported catalyst according to another embodiment may further include a drying step, if necessary, after mixing the zirconium compound and the aluminum compound and performing sol-gel reaction. In the drying process, a drying method and a drying device commonly known in the art can be used. For example, drying can be performed using a heat source such as a hot air fan, an oven, or a hot plate.

The method of manufacturing a metal supported catalyst according to another embodiment may further include a step of heat treating the resultant of the sol-gel reaction at a temperature of 400 ° C to 600 ° C after mixing the zirconium compound and the aluminum compound and performing a sol-gel reaction. Through this, the impurities can be removed, and the bonding between the metal components of the zirconium compound and the aluminum compound and oxygen can be performed to form a lattice structure.

Further, the method may further include a step of heat-treating the resultant of the sol-gel reaction at a temperature of 400 ° C to 600 ° C after mixing the resultant of the sol-gel reaction, the magnesium compound and the aluminum compound, and performing a sol-gel reaction. Through this, it is possible to remove impurities, to form a bond between the metal components of the magnesium compound and the aluminum compound and oxygen, and to form a lattice structure into which a hydroxide structure is introduced.

If the temperature in the heat treatment step is too low, the metal may not sufficiently bond with the support in the impregnation step, or the activity of the finally produced catalyst may not be sufficiently secured. If the temperature is too high, The reduced or impregnated metal is decomposed and the activity or physical properties of the finally produced catalyst may be greatly deteriorated.

On the other hand, it is preferable that the support is made of platinum (Pt), nickel (Ni), copper (Cu), zinc (Zn), tin (Sn), lanthanum (La), potassium (K), calcium In the step of impregnating at least one metal selected from the group consisting of hydrates, various impregnation methods known in the field of supported catalysts can be applied without limitation. The content of the platinum (Pt), nickel (Ni), copper (Cu), zinc (Zn), tin (Sn), lanthanum (La), potassium (K), calcium (Ca) The above-described contents may be included in the above embodiment.

According to another embodiment of the present invention, there is provided a process for producing an olefin having 4 carbon atoms, which comprises reacting a hydrocarbon compound containing normal-butane, hydrogen and steam in the presence of the metal supported catalyst of the embodiment .

The hydrocarbons including the n-butane are the main raw materials which are converted into olefins having 4 carbon atoms through the reaction and may be derived from C4 LPG. The hydrocarbons including n-butane may further contain other components such as iso-butane. Specifically, the hydrocarbons including the n-butane may include 90 wt% to 95 wt% of n-butane, 5 wt% to 10 wt% of iso-butane, and may further include other components.

By mixing the steam with n-butane and introducing it into the reaction gas, the carbon deposit formed on the catalyst can be removed during the reaction, and the activity of the catalyst can be improved. In addition, the catalyst activity is prevented from deteriorating due to the coking phenomenon in which carbon deposits are formed over the reaction time, so that the selectivity of the olefin having 4 carbon atoms can be maintained longer during the reaction time. The water vapor is prepared by heating water to a temperature of 100 ° C or higher, preferably 400 ° C to 600 ° C.

The ratio of the volume of steam to the volume of the hydrocarbon compound having 4 carbon atoms may be 2 to 10 or 4 to 6 and the volume ratio of air to the volume of the hydrocarbon compound having 4 carbon atoms may be 0.1 to 0.8 or 0.4 to 0.6 . The water vapor reduces the time required for the reactants to stay in the catalyst to inhibit the overall reaction due to overaction, removes coke produced during the reaction to maintain the activity of the catalyst for a long time, and controls the heat generation of the dehydrogenation reaction The temperature of the catalyst layer is prevented from rising.

The step of preparing the olefin having 4 carbon atoms can be carried out at 400 ° C to 600 ° C and preferably at 450 ° C to 550 ° C. But the conversion of n-butane and the selectivity of olefins of 4 carbon atoms are both low. When the temperature is higher than 600 ° C., propylene is excessively produced as a byproduct and the conversion of n-butane is excellent. However, The selectivity of the olefin having 4 carbon atoms is lowered, which is not preferable.

In addition, the step of producing the olefin having 4 carbon atoms may be carried out at a GHSV (Gas Hourly Space Velocity) of 0.1 to 10 / Hr and preferably at 1 to 5 / Hr. The gas hourly space velocity (GHSV) represents the velocity of the feed gas relative to the volume of the catalyst used in the dehydrogenation reaction. It can be measured and confirmed by controlling the volume ratio of the catalyst and the flow rate of the feed gas. The GHSV Is higher than 10 / Hr, the conversion and selectivity are both undesirable. When the GHSV is less than 0.1 / Hr, the dehydrogenation efficiency is increased but the amount of the catalyst used is too large It is not desirable.

According to the present invention, there can be provided a metal-supported catalyst capable of obtaining high-quality olefin from a liquefied petroleum gas or a hydrocarbon material at a higher conversion and yield, and capable of maintaining excellent activity even in a long reaction time, a method for producing the same, 4 < / RTI > can be provided.

Fig. 1 shows the XRD structure analysis results of the supports prepared in Preparation Examples 1 and 2.

The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

[Preparation Example 1: Preparation of Pt-Sn / ZrO ₂ -MgAl ₂ (OH) ₈ Preparation of Catalyst]

1. Carrier (ZrO ₂ -MgAl ₂ (OH) ₈ )

(1) Synthesis of ZrO ₂ -Al ₂ O ₃ Powder

16 g of high purity Boehmite Powder (99.999%) was mixed and stirred with 100 ml of distilled water for 30 minutes. Next, 9 g of zirconium (IV) oxynitrate hydrate (99%, Aldrich) was added to the mixed solution of boehmite powder and distilled water. The mixture was heated at 80 ° C. and further stirred for 30 minutes. Hydrochloric acid (36.5 ~ 38.0%, Aldrich) was added to the mixed precursor sol to adjust the pH of the precursor mixture to 0.5 ~ 1. The prepared gel was dried in an oven set at 130 ° C. for 24 hours to completely remove moisture and then calcined at 500 ° C. for 6 hours to prepare ZrO ₂ -Al ₂ O ₃ powder.

(2) Synthesis of ZrO ₂ -MgAl ₂ (OH) ₈ carrier

16 g of high purity Boehmite Powder (99.999%) was mixed and stirred with 100 ml of distilled water for 30 minutes. Next, 38 g of Magnesium nitrate hexahydrate (99.999%, Aldrich) was added to the mixed solution of boehmite powder and distilled water. The mixture was heated at 80 ° C and further stirred for 30 minutes. At this time, the mass ratio of Mg metal to Al metal was 1: 2.

1.4 g of the ZrO ₂ -Al ₂ O ₃ powder prepared in the previous step was added to the mixed solution of the mixed precursor, followed by stirring. Hydrochloric acid (36.5 ~ 38.0%, Aldrich) was added to the mixed solution to adjust the pH of the mixed solution of the precursor to 0.5 ~ 1. The prepared gel was dried in an oven set at 130 ° C for 24 hours to completely remove water and then calcined at 500 ° C for 6 hours to prepare a ZrO ₂ -MgAl ₂ (OH) ₈ carrier.

The XRD structure analysis results for the ZrO ₂ -MgAl ₂ (OH) ₈ carrier are shown in FIG. The ZrO ₂ -MgAl ₂ (OH) ₈ carriers include MgAl ₂ (OH) is measured, a separate peak ZrO _2, which are clearly separated from the carrier _8, to check that the MgAl ₂ (OH) ZrO ₂ particles dispersed structure in carrier ₈ have.

2. Impregnation step of Pt

A precursor solution prepared by dissolving 0.06 g of chloroplatinic acid hexahydrate (37.5% Pt basis, Aldrich) in 5 ml of distilled water was impregnated into 5 g of the carrier prepared above using an initial wet impregnation method, followed by drying in an evaporator. The carrier, which had been dried and impregnated with platinum, was calcined at 550 ° C for 6 hours.

3. Impregnation of Sn and preparation of catalyst

The catalyst prepared in the above step 2 was impregnated with Sn, which serves as an enhancing agent, to prepare a catalyst. 0.2 g of Sn metal was impregnated in the same manner as the Pt metal impregnation in the second step except that Tin (II) acetylacetonate (99.9%, Aldrich) was dissolved in methanol, and the catalyst was dried by an evaporator. The dried catalyst for 6 hours to prepare a 1.5% Sn-0.5% Pt / ZrO 2 -MgAl 2 (OH) 8 to the final catalyst by calcining at 550.

[Preparation Example 2: Preparation of Pt-Sn / MgAl ₂ (OH) ₈ Preparation of Catalyst]

MgAl ₂ (OH) ₈ carrier was prepared by proceeding in the same manner as in Production Example 1, except that ZrO ₂ -Al ₂ O ₃ Powder was not used, and then the same Pt and Sn impregnation steps as in Production Example 1 were carried out 1.5% Sn-0.5% Pt / MgAl ₂ (OH) ₈ .

The XRD structure analysis results for the MgAl ₂ (OH) ₈ carrier are shown in FIG.

[Preparation Example 3: Preparation of Pt-Sn / ZrO ₂ -MgAl ₂ O ₄ Preparation of Catalyst]

A MgAl ₂ O ₄ carrier was prepared in the same manner as in Preparation Example 1, except that the calcination temperature was changed to 900 ° C in the synthesis of the carrier. Then, the MgAl ₂ O ₄ carrier was subjected to the same Pt and Sn impregnation steps as in Preparation Example 1, 0.5% Pt / MgAl ₂ O ₄ was prepared.

[Preparation Example 4: Preparation of Pt-Sn / ZrAl ₂ O ₄ Preparation of Catalyst]

First, 16 g of high purity Boehmite Powder (99.999%) was mixed with 100 ml of distilled water for 30 minutes to prepare a ZrAl 2 O 4 carrier. Next, 9.1 g of zirconium (IV) oxynitrate hydrate (99%, Aldrich) was added to the mixed solution of boehmite powder and distilled water. The mixture was heated at 80 ° C and further stirred for 30 minutes.

Hydrogelic acid (36.5 ~ 38.0%, Aldrich) was added to the mixed precursor mixture solution to adjust the pH of the precursor mixture solution to 0.5 ~ 1 to complete the sol-gel.

The prepared gel was dried in an oven set at 130 ° C. for 24 hours to completely remove water and then calcined at 500 ° C. for 6 hours to prepare a final ZrAl ₂ O ₄ carrier. At this time, the mass ratio of Zr metal to Al metal was 1: 2.

A precursor solution prepared by dissolving 0.06 g of chloroplatinic acid hexahydrate (37.5% Pt basis, Aldrich) in 5 ml of distilled water was impregnated into 5 g of the prepared carrier using an initial wet impregnation method, followed by drying with an evaporator. The carrier, which was dried and impregnated with platinum, was calcined at 550 ° C. for 6 hours to prepare a 0.5% Pt-ZrAl ₂ O ₄ carrier.

Thereafter, a precursor solution obtained by dissolving 0.2 g of Tin (II) acetylacetonate (99.9%, Aldrich) in 4 ml of methanol as a step of impregnating tin metal as an active enhancing substance was subjected to initial wet impregnation to prepare 0.5% Pt-ZrAl ₂ O ₄ catalyst, followed by drying with an evaporator. After completion of the drying, the tin-impregnated catalyst was calcined at 550 ° C for 6 hours to prepare 1.5% Sn-0.5% Pt / ZrAl ₂ O ₄ as a final catalyst.

[Preparation Example 5: Preparation of Pt-Sn / ZnAl ₂ O ₄ Preparation of Catalyst]

A carrier was synthesized by adding 16.4 g of Zinc nitrate hexahydrate (98%, Aldrich) instead of zirconium (IV) oxynitrate hydrate (99%, Aldrich) precursor. The mass ratio of Zn metal to Al metal was 1: 2 , 1.5% Sn-0.5% Pt / ZnAl ₂ O ₄ was prepared in the same manner as in Production Example 4. [

[Example 1: Preparation and analysis of C4 olefin component]

1 g of the catalyst prepared in Preparation Example 1 was charged into a fixed-bed catalytic reactor, and the catalyst was reduced with 5% H ₂ -N ₂ gas at 500 ° C. Thereafter, a hydrocarbon mixture having 4 carbon atoms (92 wt% of normal-butane and 8 wt% of iso-butane), steam and hydrogen were supplied at a molar ratio of 1: 5: 0.4, (Isobutene, 1-butene, 2-butene and 1,3-butadiene) were synthesized by dehydrogenation reaction while keeping the gas hourly space velocity.

Upon completion of the dehydrogenation reaction, the gas was directly collected and analyzed by Gas Chromatography to calculate the conversion of n-butane.

[Comparative Example 1]

Butene and 1,3-butadiene) were synthesized in the same manner as in Example 1, except that the catalyst prepared in Preparation Example 2 was used, and the conversion of n-butane Respectively.

[Comparative Example 2]

Butene and 1,3-butadiene) were synthesized in the same manner as in Example 1, except that the catalyst prepared in Preparation Example 3 was used, and the conversion of n-butane Respectively.

[Comparative Example 3]

Except that the catalyst prepared in Preparation Example 4 was used, C4 olefin components (isobutene, 1-butene, 2-butene and 1,3-butadiene) were synthesized in the same manner as in Example 1, Respectively.

[Comparative Example 4]

C4 olefin components (isobutene, 1-butene, 2-butene and 1,3-butadiene) were synthesized in the same manner as in Example 1 except that the catalyst prepared in Preparation Example 5 was used, Respectively.

Comparison of Dehydrogenation Performance of Catalysts division  [Reaction time (2Hr)] [Reaction time (6Hr)] [Reaction time (12Hr)] [Reaction time (15Hr)] Conversion Rate Conversion Rate Conversion Rate Conversion Rate Example 1 67.44 65.32 63.21 61.67 Comparative Example 1 47.40 43.53 40.59 39.62 Comparative Example 2 52.95 47.09 44.56 45.51 Comparative Example 3 39.31 31.05 27.33 25.53 Comparative Example 4 23.56 19.44 18.15 17.56

Conversion rate: The ratio of conversion of normal-butane to other materials (for example, isobutene, 1-butene, 2-butene and 1,3-butadiene)

As shown in Table 1, the dehydrogenation catalyst in the initial stage of the reaction (2 hours) of the above example exhibited a very high catalytic activity as 67.44%. Also, it was confirmed that the catalytic activity was maintained because the lowering of the conversion rate was not so large as the reaction progressed.

On the other hand, it was confirmed that the catalysts (Comparative Examples 1 to 4) using different carriers instead of ZrO ₂ -MgAl ₂ (OH) ₈ as the carrier were not significantly better than those of Example 1. More specifically, in the catalysts of Comparative Examples 1 to 4, the conversion rate at the initial stage of the reaction (2 hours) was lower than that of Example 1, and the conversion rate was sharply decreased according to the reaction time.

That is, the use of ZrO ₂ -MgAl ₂ (OH) ₈ carrier in the n-butane dehydrogenation reaction of the catalyst of Example 1 maintains the conversion rate of the n-butane at the initial stage as well as during the reaction, And exhibits high catalytic activity.

Claims (20)

A porous support containing alloy particles of alumina and at least one member selected from the group consisting of magnesium, oxides thereof, hydroxides thereof, and hydrates thereof, and
A support comprising alloy particles of alumina and at least one member selected from the group consisting of zirconium, oxides thereof and hydrates thereof dispersed in the internal pores of the porous support; And
At least one metal compound fixed on the carrier and selected from the group consisting of platinum (Pt), oxides thereof, and hydrates thereof; And at least one selected from the group consisting of nickel (Ni), copper (Cu), zinc (Zn), tin (Sn), lanthanum (La), potassium (K), calcium (Ca), oxides thereof, A metal compound,
The porous support is formed of a set of alloy particles of alumina and at least one member selected from the group consisting of magnesium, oxides thereof, hydroxides thereof and hydrates thereof,
The alloy particles of alumina and at least one selected from the group consisting of zirconium, oxides thereof and hydrates thereof have a spherical particle shape with a maximum diameter of 0.1 mm to 10 mm,
Wherein the maximum diameter of the porous support is 0.5 mm to 15 mm.
The method according to claim 1,
Wherein the support has a specific surface area of 100 m 2 / g to 150 m 2 / g.
The method according to claim 1,
Wherein the carrier has an average pore diameter of 1 nm to 100 nm.
The method according to claim 1,
Wherein the porous support has an average pore diameter of 1 nm to 20 nm.
delete delete The method according to claim 1,
Wherein the weight ratio of magnesium to aluminum contained in the carrier is 0.3: 1 to 2: 1.
The method according to claim 1,
Wherein the weight ratio of zirconium to aluminum contained in the carrier is 0.3: 1 to 2: 1.
delete The method according to claim 1,
The metal-supported catalyst may comprise at least one metal compound selected from the group consisting of platinum (Pt), oxides thereof, and hydrates thereof, in the presence of 0.1 to 5% by weight of a dehydrogenation Supported metal catalyst.
The method according to claim 1,
Wherein at least one selected from the group consisting of nickel (Ni), copper (Cu), zinc (Zn), tin (Sn), lanthanum (La), potassium (K), calcium (Ca), oxides thereof, The dehydrogenation reaction of the hydrocarbon compound having 4 carbon atoms, which is 10 to 80 parts by weight, based on 100 parts by weight of the metal compound, of the at least one metal compound selected from the group consisting of platinum (Pt), an oxide thereof, Supported catalyst.
Mixing the zirconium compound and the aluminum compound and sol-gel reaction;
Mixing a resultant of the sol-gel reaction, a magnesium compound, and an aluminum compound with a sol-gel to form a carrier; And
At least one metal compound selected from the group consisting of platinum (Pt), oxides thereof, and hydrates thereof; And at least one selected from the group consisting of nickel (Ni), copper (Cu), zinc (Zn), tin (Sn), lanthanum (La), potassium (K), calcium (Ca), oxides thereof, Impregnating a metal compound,
Wherein the sol-gel reaction is carried out by heating at a temperature of 60 ° C to 100 ° C to form a sol and adjusting the pH of the sol to from 0.5 to 2, Gt;
13. The method of claim 12,
Further comprising the step of heat-treating the resultant sol-gel reaction at a temperature of 400 ° C to 600 ° C after mixing the zirconium compound and the aluminum compound and performing a sol-gel reaction.
13. The method of claim 12,
A step of heat-treating the resultant sol-gel reaction at a temperature of 400 ° C to 600 ° C after mixing the resultant of the sol-gel reaction, the magnesium compound and the aluminum compound, and performing a sol-gel reaction.
A process for producing an olefin having 4 carbon atoms, which comprises reacting a hydrocarbon compound containing normal-butane, hydrogen and water vapor in the presence of the metal supported catalyst of claim 1.
16. The method of claim 15,
Wherein the hydrocarbon compound comprises 90 wt% to 95 wt% of n-butane.
16. The method of claim 15,
Wherein the volume ratio of water vapor to the volume of hydrocarbon compound having 4 carbon atoms is 2 to 10.
16. The method of claim 15,
Wherein the volume ratio of water vapor to the volume of the hydrocarbon compound having the number of carbon atoms of 4 is 0.1 to 0.8.
16. The method of claim 15,
Wherein the step of reacting the hydrocarbons including normal-butane, hydrogen and water vapor is carried out at a temperature of 400 ° C to 600 ° C.
16. The method of claim 15,
Wherein the step of reacting the hydrocarbons including normal-butane, hydrogen and steam includes the step of operating at a gas hourly space velocity (GHSV) of from 0.1 / Hr to 10 / Hr.

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