KR20190071297A - A reforming catalyst on phosphorus-modified alumina support having three dimensional different porous for Producing Hydrogen Gas and Process for Preparation Method thereof - Google Patents

Abstract

The present invention relates to a reforming catalyst alumina support for producing hydrogen, which has 3D heterogeneous pores and is added with phosphorus to solve deactivation of a nickel-based catalyst in a hydrocarbon reforming reaction, and a method of preparing the same. More specifically, mesopores having a size of 50 nm or less and macropores having a size of 200 nm or more are formed by using heterogeneous polymer molds such that the reforming catalyst alumina support has an excellent specific surface area, exhibits an increased loading amount of an activated metal catalyst, and has an substance transferring ability significantly increased by the macropores.

Description

Technical Field [0001] The present invention relates to a process for preparing a catalyst support having a three-dimensional heterogeneous pore structure and a phosphorus-added catalyst support for preventing catalyst deactivation,

The present invention relates to a process for preparing a catalyst support for hydrogen production, which has three-dimensional heterogeneous pores and prevents the catalyst from being deactivated, and more particularly, Mesopore) and macropores of 100 nm or more at the same time, thereby producing a three-dimensional heterogeneous pore of a large specific surface area, and a process for producing the same.

Hydrogen energy is attracting attention as a renewable future energy source to replace conventional fossil fuels with limited available reserves. In particular, the importance of hydrogen fuel cells accelerated from the middle of the 20th century has been acknowledged as a result of research and market expansion.

Generally, hydrogen is produced through a reforming reaction using hydrocarbons and alcohols as main ingredients. Known reforming reactions include steam reforming (partial reforming), partial oxidation Oxidation, and Auto-thermal Reforming.

Among these reforming reactions, the steam reforming reaction has been widely used commercially since it has a relatively high yield of hydrogen production and is capable of stable operation. In addition, the steam reforming reaction is advantageous in the production of hydrogen and synthesis gas for various purposes because the ratio of hydrocarbon and steam used as a reactant and the reaction temperature can be appropriately adjusted to maximize the yield of hydrogen finally obtained.

Especially, methane is used as the main raw material of steam reforming reaction. This methane is mainly composed of Liquefied Natural Gas (LNG), which is vaporized and supplied to the industrial, residential complex, hydrogen station, etc. through the city gas pipeline So that it can be easily supplied.

Rhodium, palladium, ruthenium, platinum, iridium and the like, which are precious metals, and nickel, which is a non-noble metal, have been mainly studied as the active metals of the steam reforming catalyst. The noble metal-based catalyst has the advantage of high reactivity and strong resistance to deactivation, but it is not used in commercial processes because it is disadvantageous from the economical point of view.

On the other hand, typical nickel-based catalysts among non-noble metal-based catalysts exhibit excellent activity comparable to noble metal-based catalysts, and are widely used in hydrogen production processes through hydrocarbon-based steam reforming because they are superior in price competitiveness to noble metal- . However, the nickel-based catalyst is disadvantageous in that the catalyst is inactivated due to carbon deposition, sintering by heat, and poisoning by sulfur in the hydrocarbon-based reforming reaction, which makes stable operation for a long time difficult. Therefore, a series of studies have been carried out to enhance the activity of the nickel-based catalyst and to ensure long-term stability.

However, it has been known that the reaction activity of the nickel-based catalyst is affected not only by the characteristics of the nickel metal itself but also by the physical and chemical properties with the support. Therefore, studies are underway to control physical and chemical properties of alumina, which is mainly used as a support for the production of an efficient nickel-based catalyst. Particularly, studies for increasing the specific surface area through pore formation or adding other materials to the alumina support to improve the physical and chemical properties of the support have been conducted.

Korean Patent No. 10-1040657

In order to solve the above problems in the reformed catalyst support for producing hydrogen having 3-dimensional heterogeneous pores of the present invention and the method for producing the same, it has been found that, by using polymer molds of different sizes, And a macropore of 100 nm or more can be formed at the same time. Thus, compared to conventional commercial alumina supports, it has a wide specific surface area, thereby minimizing the loading amount of the active metal, And the catalyst activity can be increased. Further, by adding a non-metallic element having a high electronegativity and a large number of valence electrons to the reforming catalyst support, the carbon in the hydrocarbon reforming reaction We confirmed that the problem of deactivation of catalysts such as deposition and thermal sintering is solved at the same time. It was achieved through the present invention.

The method for preparing the catalyst support according to the present invention is a method for preparing various types of alumina phase having excellent thermal stability through heat treatment at 500 ° C or higher based on the synthesis method of a sol-gel process using a polymer template It can be used as a catalyst support in various fields.

Accordingly, it is an object of the present invention to provide a method for producing high purity hydrogen, which improves the specific surface area and mass transferring ability by forming heterogeneous pores having different sizes and at the same time, adding phosphorus element, phosphorus, to minimize carbon deposition and thermal sintering And to provide a catalyst support for a catalyst and a method for producing the same.

On the other hand,

A method for producing a reforming catalyst support for hydrogen production by methane steam reforming reaction,

i) dissolving a block copolymer, which is a polymeric template for forming mesopores, and an alumina precursor in a solvent in a strong acidic atmosphere;

ii) adding a polystyrene bead, which is a polymeric template for macropore formation, to the solvent;

iii) adding phosphoric acid to the solvent to add phosphorus as a catalyst inactivation preventing component; And

(iv) a step of drying and firing the catalyst support, wherein the catalyst support has a three-dimensional heterogeneous pore structure and phosphoric acid is added to add phosphorus, which is a preventive component for preventing catalyst deactivation.

On the other hand,

In an alumina support of a reforming catalyst for hydrogen production by methane steam reforming reaction,

The support is formed by using a block copolymer and polystyrene beads as polymer molds for forming pores having different mesopores and macropores simultaneously on the alumina support, To provide a support specific to a reforming catalyst for hydrogen production having different sized three-dimensional heterogeneous pores minimizing carbon deposition and deterioration problems in the hydrocarbon reforming reaction.

The support of the reforming catalyst for hydrogen production having different three-dimensional heterogeneous pores according to the present invention has mesopores and macropores simultaneously formed on the alumina support to have a large specific surface area, The reaction gas can be efficiently delivered and the catalytic activity can be increased. In addition, by adding non-metallic phosphoric acid to the support, it is possible to manufacture a reforming catalyst for high-efficiency hydrogen production having long-term stability by minimizing the problem of catalyst deactivation due to carbon deposition and thermal sintering in the hydrocarbon reforming reaction.

In addition, since the process for producing a reforming catalyst support according to the present invention can provide a simple synthesis process of mixing polymer molds for forming heterogeneous pores having different sizes, and drying and firing, the production process is very simple, It is economical in terms of manufacturing cost.

1 is a cross-sectional view of a reforming catalyst support for hydrogen production having three-dimensional heterogeneous pores of different sizes according to an embodiment of the present invention, including a Scanning Electron Microscope (SEM) and a Transmission Electron Microscope (TEM) It is a picture for.
FIG. 2 is a SEM photograph showing a polystyrene bead as a polymer mold for macropore formation of uniform and uniform size according to an embodiment of the present invention.
FIG. 3 is a cross-sectional view of a polymer mold for forming different pores according to an embodiment of the present invention. The block copolymer and polystyrene beads are added to form three-dimensional heterogeneous pores of different sizes. In order to prevent catalyst deactivation, FIG. 7 is a photograph showing the procedure of the production method of the reforming catalyst support for production.
FIG. 4 is a graph showing the hydrogen production activity evaluation results of a reforming catalyst for hydrogen production and a single pore support-based catalyst having phosphorus-added three-dimensional double pores according to an embodiment of the present invention and for preventing catalyst deactivation .

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

In one embodiment of the present invention, a method for producing a catalyst support for hydrogen production, which has three-dimensional heterogeneous pores and phosphorus added thereto to prevent catalyst deactivation,

A method for producing a reforming catalyst support for hydrogen production by methane steam reforming reaction,

i) dissolving a block copolymer, which is a polymeric template for forming mesopores, and an alumina precursor in a solvent in a strong acidic atmosphere;

ii) adding a polystyrene bead, which is a polymeric template for macropore formation, to the solvent;

iii) adding phosphoric acid to the solvent to add phosphorus as a catalyst inactivation preventing component; And

iv) drying and calcining.

In one embodiment of the invention, the block copolymer is flu in nikgye or Tetronic-base block copolymer _{F108 ((Ethylene Oxide) 132 (} Propylene Oxide) 50 (Ethylene Oxide) 132), F98 ((Ethylene Oxide) 123 ( _{Propylene Oxide) 47 (Ethylene Oxide)} 123), F88 ((Ethylene Oxide) 103 (Propylene Oxide) 39 (Ethylene Oxide) 103), P123 ((Ethylene Oxide) 20 (Propylene Oxide) 70 (Ethylene Oxide) 20), P105 characterized in that at least one member selected from the group consisting of _{((Ethylene Oxide) 37 (Propylene} Oxide) 58 (Ethylene Oxide) 37) , and _{P104 ((Ethylene Oxide) 27 (} Propylene Oxide) 61 (Ethylene Oxide) 57).

The block copolymer, which is a template of the mesopores, can form a circular pore structure on the principle that a self-assembly is formed through arrangement of hydrophilic groups and hydrophobic groups through interaction between molecules.

The block copolymer may be contained in an amount of 25 to 30% by weight based on 100% by weight of the solvent. When the content of the block copolymer satisfies the above range, the block copolymer can form a circular pore structure on the principle that a self-assembly is formed through arrangement of hydrophilic groups and hydrophobic groups through interaction between molecules. However, when the content of the block copolymer does not satisfy the above range, the structure of the pores may be changed by a lamella structure, a 2-d hexagonal P6mm structure, or a cybic Im3m structure depending on the amount and type of the block copolymer.

In one embodiment of the present invention, the alumina precursor is preferably an aluminum alkoxide. Specifically, the alumina precursor is preferably selected from the group consisting of aluminum secondary-butoxide, aluminum ethoxide, aluminum tert- Aluminum tert-butoxide, aluminum isopropoxide, aluminum tri-sec-butoxide and aluminum tri-tert-butoxide, ≪ / RTI >

The alumina precursor may be contained in an amount of 50 to 60% by weight based on 100% by weight of the solvent. If the content of the alumina precursor does not satisfy the above range, a change in the structural form may occur depending on the ratio of the alumina to the template.

In one embodiment of the present invention, the strong acidic atmosphere can be formed in the presence of a strong acid.

Examples of the strong acid include, but are not limited to, hydrochloric acid (HCl), nitric acid (HNO ₃ ), sulfuric acid (H ₂ SO ₄ ), and the like.

The strong acid may be contained in an amount of 6.0 to 6.5% by weight based on 100% by weight of the solvent. The acidity is an important factor in the self-assembling arrangement of the template and the alumina precursor, and the shape may vary depending on the type and amount.

Examples of the solvent include methanol, ethanol, propanol, isopropanol, 1-butanol, and 2-butanol. It is not.

In one embodiment of the present invention, polystyrene (PS) beads, which are macroporous polymeric macromolecules, have expandable nanoparticles, which increase in molecular weight in proportion to the reaction time and can be easily controlled in size . It can be easily removed through heat treatment and is suitable for use as a mold. In the case of the polystyrene beads used in the present invention, styrene and divinyl benzene were used as cross linking agents to make particles of uniform shape and size.

The particle size of the polystyrene beads is preferably 200 to 400 nm.

The polystyrene beads may be contained in an amount of 10 to 50% by weight based on 100% by weight of the solvent. When the content of the polystyrene beads does not satisfy the above range, the arrangement of the macrostructure of the macropores varies depending on the amount of the polystyrene beads, and when the excessive polystyrene beads are used, ≪ / RTI >

The phosphoric acid to be added for preventing catalyst deactivation may be contained in an amount of 0.1 to 10.0% by weight based on 100% by weight of the solvent. The degree of bonding between the phosphorus component and the support varies depending on the amount of phosphoric acid added. Therefore, the addition of a very small amount of phosphoric acid causes little prevention of carbon deposition, and the excessive addition of phosphoric acid may lower the bonding activity between the supports and reduce the catalytic activity.

The drying can be carried out at 60 to 70 DEG C for 12 to 60 hours. The solvent may be removed through the drying process to produce a powdery catalyst support.

The calcination may be performed at 600 to 1100 캜 for 3 to 4 hours. The method for preparing a reforming catalyst support according to the present invention is characterized in that it has high thermal stability through heat treatment at 500 ° C. or more and that phases of alumina are changed according to firing temperature so that phases can be selectively synthesized according to applications.

Specifically, the alumina support according to the present invention has a high thermal stability at a firing temperature of 500 ° C. or higher, and is formed of an alumina structure having a boehmite structure. The alumina support has an α-alumina - Phase change to alumina is possible.

The firing temperature is preferably 600 to 1000 ° C, more preferably 700 to 1000 ° C.

When the calcination temperature and the calcination time do not satisfy the above range, for example, at a high temperature of 1300 ° C or higher, the alumina phase may be broken and the mesoporous phase may collapse and the catalyst support volume function may be lost.

The present invention relates to a reforming catalyst support for producing hydrogen having phosphorus for preventing catalyst deactivation and having three-dimensional heterogeneous pores of different sizes by the above production method, An alumina support for a hydrogen-reforming catalyst having heterogeneous pores

An alumina support for a hydrogen production reforming catalyst by methane steam reforming reaction,

The support may be prepared by using a block copolymer and polystyrene beads as polymer molds having different pores to form mesopores and macropores simultaneously in the alumina support and adding phosphorus for the purpose of preventing catalyst deactivation to remove carbon in the hydrocarbon reforming reaction Minimizing deposition and deterioration problems.

The present invention also relates to a reforming catalyst for hydrogen production using the modified catalyst alumina support for hydrogen production, which has the above-described three-dimensional heterogeneous pores and has phosphorus added thereto for preventing catalyst inactivation. The alumina support according to one embodiment of the present invention A process for producing a catalyst for producing hydrogen

A method for producing a reforming catalyst for hydrogen production by a methane steam reforming reaction,

i) dissolving a nickel precursor in a solvent in an amount of 5 to 40% by weight based on 100% by weight of the reforming catalyst support; And

ii) washing, filtering, drying and calcining.

In one embodiment of the invention, the nickel precursor is selected from the group consisting of Nickel Nitrate Hexahydrate, Nickel Chloride Hexahydrate, Nickel Acetate Tetrahydrate, Nickel Bromide Hydrate ) And nickel nitrate nonahydrate (nickel nitrate nonahydrate).

The nickel precursor is preferably contained in an amount of 5 to 40 wt%, more preferably 5 to 15 wt%, based on 100 wt% of the catalyst support. When the content of the nickel precursor is excessive, aggregation due to strong interaction between the nickel metals may occur.

The present invention relates to a reforming catalyst for hydrogen production using a phosphoric acid-added alumina support having three-dimensional heterogeneous pores and for preventing catalyst deactivation,

In a reforming catalyst for producing hydrogen by a methane steam reforming reaction,

The reforming catalyst may be prepared by using a block copolymer and polystyrene beads as polymer molds so that mesopores and macropores are formed at the same time and 5 to 40 parts by weight of 100 parts by weight of phosphorus- By weight of nickel is carried.

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are for illustrative purpose only and that the scope of the present invention is not limited to these embodiments.

Example 1: Preparation of modified catalytic alumina support for hydrogen production having a three-dimensional porous double structure and phosphoric acid added

3.0 g of a triblock copolymer, Pluronic® P123 (Sigma-Aldrich), a Mesopore polymeric template, and 6.12 g of aluminum isopropoxide as an alumina precursor were dissolved in 60 mL of anhydrous ethanol. Then, 4.5 mL of nitric acid (65 wt%) and 8 wt% of phosphoric acid were added to the melt and stirred. Then, 3.0 g of macropore polymeric polystyrene beads (Polystyrene beads) was added and stirred Respectively.

Then, the catalyst was dried in an oven at a temperature of 60 ° C for 2 days, and then calcined at 700 ° C for 3 hours through a sintering furnace to prepare a reformed catalytic alumina support for hydrogen generation (temperature raising rate: 0.4 / min).

Example 2: Preparation of catalyst for hydrogen production

Nickel hydrate nonahydrate (12 wt%) was dissolved in 150 mL of purified water (D.I. water) based on 100 wt% of the modified catalytic alumina support prepared in Example 1 above. Then, the catalyst was dried in an oven at a temperature of 110 ° C for one day, and then calcined at 700 ° C for 3 hours through a sintering furnace to prepare a catalyst for hydrogen generation (heating rate: 10 / min).

Comparative Example 1: Preparation of a catalyst support for producing hydrogen having a three-dimensional single structure

A support having only a single mesopore free pore was prepared using the same method as that of the catalyst support prepared in Example 1 except that polystyrene beads were not used.

Comparative Example 2: Preparation of catalyst for hydrogen production

A catalyst was prepared in the same manner as in Example 2, except that the catalyst support prepared in Comparative Example 1 was used in place of the catalyst support prepared in Example 1 above.

Experimental Example  1: Evaluation of Physical Properties of Modified Catalytic Alumina Support for Hydrogen Production

The specific surface area and pore size were measured to evaluate the physical properties of the modified catalytic alumina support prepared in Example 1 and Comparative Example 1.

division Example 1 Comparative Example 1 Specific surface area (m ² / g) 261.71 250.16 Mesopore Size (nm) 5.93 5.93 Macro pore size (nm) 300 - Pore volume (cm ³ / g) 0.60 0.60

Referring to Table 1, it was confirmed that the modified catalyst alumina support of Example 1 had a larger specific surface area than that of the catalyst support of Comparative Example 1.

Experimental Example 2: Evaluation of physical properties of a catalyst for producing hydrogen supported on activated metal nickel on a reforming catalytic alumina support for producing hydrogen

The specific surface area and the pore size were measured in order to evaluate the physical properties of the catalyst for hydrogen production according to Example 2 and Comparative Example 2. [

division Example 2 Comparative Example 2 Specific surface area (m ² / g) 238.41 143.87 Mesopore Size (nm) 4.65 2.5 Macro pore size (nm) 290 - Pore volume (cm ³ / g) 0.52 0.21

With reference to Table 2 above, it can be seen that the catalyst having the active metal nickel supported on the alumina support of Example 2 has a higher specific surface area and a larger pore size and volume than the catalyst having the active metal nickel supported on the alumina support of Comparative Example 2 Respectively.

This is because the specific surface area of the small mesopores of the single structure formed in the catalyst of Comparative Example 2 was reduced due to the blocking of the active nickel metal particles and the mesopores and macropores were simultaneously In the case of the dual structure alumina support-based catalyst of Example 2, no such blocking phenomenon occurs, and therefore, there is almost no difference in specific surface area between before and after the active metal nickel deposition.

Experimental Example 3: Evaluation of hydrogen production effect of catalyst for hydrogen production

The hydrogen production reaction experiment was performed by the steam reforming reaction of liquefied natural gas (LNG) composed of a mixed gas of methane and ethane using the reforming catalyst for hydrogen production produced by the method of Example 2 and Comparative Example 2.

The reforming catalyst was filled in the reactor for the steam reforming reaction, and the reforming catalyst was reduced with a mixed gas of nitrogen (30 ml) and hydrogen (3 ml) at 800 ° C. for 3 hours before the reaction, and the reactants methane and ethane The reforming reaction was allowed to proceed while the mixed gas was continuously passed through the catalyst bed in the reactor. The space velocity of the reactants was maintained at 30,180 ml / h · g-catalyst, and the volume ratio of reactant steam / liquefied natural gas (LNG) was maintained at 1.5. The steam reforming reaction of liquefied natural gas was carried out at 650 ° C. The conversion of liquefied natural gas and the composition of hydrogen in the dry gas are calculated by the following formulas 1 and 2, respectively, and the values are shown in Table 3.

[Formula 1]

[Formula 2]

division Example 2 Comparative Example 2 Conversion Rate (%) 92.7 - Hydrogen composition in dry gas (%) 76.4 -

Table 3 shows average values of hydrogen production evaluation results of the catalysts of Example 2 and Comparative Example 2 (see Fig. 4).

Referring to Table 3, when the conversion of methane through the hydrocarbon reforming reaction for 12 hours and the hydrogen composition in the dry gas were averaged, the conversion rate was 92.7% in the case of Example 2, 76.4%, indicating that the catalytic activity of hydrogen production is greatly improved. However, the catalyst of Comparative Example 2 was inactivated completely after 6 hours of catalytic reaction at a methane conversion of about 50% at the initial stage of the reaction.

Therefore, the reforming catalyst for hydrogen production according to the present invention can improve the specific surface area by macropores and mesopores and improve the mass transfer capability through macropores, It was confirmed that hydrogen production ability and deactivation were greatly improved by the effect of reducing carbon deposition on the catalyst surface by acting as an electron donor.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention. Do. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Accordingly, the actual scope of the invention is defined by the appended claims and their equivalents.

Claims (11)

A process for preparing a reforming catalytic alumina support for hydrogen production by methane steam reforming reaction,
i) dissolving a block copolymer, which is a polymeric template for forming mesopores, and an alumina precursor in a solvent in a strong acidic atmosphere;
ii) adding a polystyrene bead, which is a polymeric template for macropore formation, to the solvent;
iii) adding phosphoric acid to the solvent to add phosphorus as a catalyst inactivation preventing component; And
and iv) drying and calcining the catalyst support, wherein the catalyst support has a three-dimensional heterogeneous pore, and the catalyst is deactivated. The method of claim 1 wherein the block copolymer is flu in nikgye or Tetronic-base block copolymer _{F108 ((Ethylene Oxide) 132 (} Propylene Oxide) 50 (Ethylene Oxide) 132), F98 ((Ethylene Oxide) 123 (Propylene Oxide _{) 47 (Ethylene Oxide) 123)} , F88 ((Ethylene Oxide) 103 (Propylene Oxide) 39 (Ethylene Oxide) 103), P123 ((Ethylene Oxide) 20 (Propylene Oxide) 70 (Ethylene Oxide) 20), P105 (( _{Ethylene Oxide) 37 (Propylene Oxide)} 58 (Ethylene Oxide) 37) , and _{P104 ((Ethylene Oxide) 27 (} Propylene Oxide) 61 (Ethylene Oxide) 57) 3 -dimensional two kinds of pores, characterized in that at least one member selected from the group consisting of And a phosphorus-added catalyst support for preventing the deactivation of the catalyst. [3] The method of claim 1, wherein the alumina precursor is aluminum alkoxide. The aluminum precursor is preferably aluminum alkoxide, aluminum tert-butoxide, aluminum ethoxide, aluminum tert-butoxide ) Selected from the group consisting of aluminum tri-tert-butoxide, aluminum isopropoxide, aluminum tri-sec-butoxide and aluminum tri-tert-butoxide. Wherein the catalyst support has a three-dimensional heterogeneous pore structure. The method of claim 1, wherein the calcination is performed at a temperature of 700 to 1000 ° C for 3 to 4 hours. A reforming catalytic alumina support for the production of hydrogen by methane steam reforming reaction,
The alumina support has three-dimensional heterogeneous pores in which mesopores and macropores are simultaneously formed on the alumina support by using a block copolymer and polystyrene beads as polymer molds, and phosphorus added to prevent catalyst deactivation Wherein the alumina support has a three-dimensional heterogeneous pore structure and is doped with phosphorus to prevent catalyst deactivation. The method of claim 5, wherein the block copolymer is flu in nikgye or Tetronic-base block copolymer _{F108 ((Ethylene Oxide) 132 (} Propylene Oxide) 50 (Ethylene Oxide) 132), F98 ((Ethylene Oxide) 123 (Propylene Oxide _{) 47 (Ethylene Oxide) 123)} , F88 ((Ethylene Oxide) 103 (Propylene Oxide) 39 (Ethylene Oxide) 103), P123 ((Ethylene Oxide) 20 (Propylene Oxide) 70 (Ethylene Oxide) 20), P105 (( _{Ethylene Oxide) 37 (Propylene Oxide)} 58 (Ethylene Oxide) 37) , and _{P104 ((Ethylene Oxide) 27 (} Propylene Oxide) 61 (Ethylene Oxide) 57) 3 -dimensional two kinds of pores, characterized in that at least one member selected from the group consisting of And a phosphorus-added reforming catalyst alumina support for hydrogen production to prevent catalyst deactivation. [7] The method of claim 5, wherein the alumina precursor is aluminum alkoxide. The aluminum precursor is preferably aluminum alkoxide, aluminum tert-butoxide, aluminum ethoxide, aluminum tert-butoxide ) Selected from the group consisting of aluminum tri-tert-butoxide, aluminum isopropoxide, aluminum tri-sec-butoxide and aluminum tri-tert-butoxide. Wherein the alumina support has a three-dimensional heterogeneous pore structure and is phosphorus-added to prevent catalyst deactivation. The method of claim 5, further comprising: adding a phosphorus having a high electronegativity and a high number of valence electrons to reduce carbon deposition and thermal sintering due to the high temperature reaction in the reforming reaction. A reformed catalyst alumina support for the production of hydrogen added with phosphorus to prevent catalyst deactivation. A method for producing a reforming catalyst for hydrogen production by a methane steam reforming reaction,
i) dissolving a nickel precursor in a solvent in an amount of 5 to 40% by weight based on 100% by weight of the modified catalyst alumina support; And
and ii) drying and calcining the alumina support, wherein the alumina support has a three-dimensional heterogeneous pores and is doped with phosphorus to prevent catalyst deactivation. The method of claim 9, wherein the nickel precursor is selected from the group consisting of Nickel Nitrate Hexahydrate, Nickel Chloride Hexahydrate, Nickel Acetate Tetrahydrate, Nickel Bromide Hydrate, Wherein the alumina support has three-dimensional heterogeneous pores and at least one member selected from the group consisting of nickel nitrate nonahydrate and nickel nitrate nonahydrate. In a reforming catalyst for producing hydrogen by a methane steam reforming reaction,
The reforming catalyst is characterized in that 5 to 40% by weight of nickel is supported on 100% by weight of an alumina support on which a mesopore and macropore are simultaneously formed using a block copolymer and polystyrene beads as a polymer mold A reforming catalyst for hydrogen production using an alumina support having phosphorus added thereto to prevent catalyst deactivation.

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