KR101910091B1 - Ni-based catalyst for SMR reaction coated on metal foam with improved catalyst adhesion and reaction property, and Manufacturing method and Use thereof - Google Patents

Abstract

TECHNICAL FIELD The present invention relates to a porous metal-coated nickel-based catalyst for SMR reaction with improved catalyst adhesion and reaction characteristics, and a method for producing and using the same. Specifically, the present invention provides a method for preparing a nickel-containing composite particle, comprising the steps of: preparing nickel-containing composite particles having a metal support on a ceramic support; A second step of preparing a nickel-based catalyst slurry by mixing the nickel-containing composite particles with an inorganic binder and then milling the mixture; A third step of pretreating the surface of the porous metal body so that the Al ₂ O ₃ oxide film is formed on the surface or formed at a later stage; And a fourth step of preparing a nickel-based catalyst in which the nickel-based catalyst slurry is dip-coated on the pretreated metal porous body, followed by drying and firing, thereby carrying the nickel-containing complex on the porous metal body having the Al ₂ O ₃ oxide film formed on its surface Based catalyst comprising a metal-porous-body-coated nickel-based catalyst. According to the present invention, adhesion and reactivity of the porous metal-oxide-coated catalyst can be maintained even after being used for the steam methane reforming reaction by pretreating the porous metal body.

Description

Technical Field [0001] The present invention relates to a nickel-based catalyst for SMR reaction with improved catalyst adhesion and reaction characteristics,

TECHNICAL FIELD The present invention relates to a porous metal-coated nickel-based catalyst for SMR reaction with improved catalyst adhesion and reaction characteristics, and a method for producing and using the same.

Methane, which is the main component of natural gas, is mainly used as a heat source for power generation and household use, but some of them are used as raw materials for producing liquid fuels and chemicals. The methane conversion reaction for this purpose is mostly a reforming reaction of methane, which is a synthesis gas production process. These syngas are used as raw materials for methanol synthesis, hydrogen production, ammonia production, or synthetic oil production process by Fischer-Tropsch reaction.

Steam Methane Reforming (SMR) of methane during the reforming reaction of methane is a strong endothermic reaction as shown in the following reaction formula. That is, a large amount of heat must be supplied from the outside in order for the methane reforming reaction to take place.

[Reaction Scheme 1]

CH ₄ + H ₂ O? CO + 3 H ₂ ,? H ₂₉₈ = 206.2 kJ / mol

On the other hand, a fuel cell is an energy conversion device that directly converts the chemical energy of a fuel into an electrical energy by an electrochemical reaction. In particular, a solid oxide fuel cell (SOFC) uses a solid oxide as an electrolyte and operates at a high temperature It has two characteristics. As a fuel commonly used for fuel cells, there is hydrogen which is obtained by reacting a hydrocarbon raw material with an oxidizing agent or steam in a fuel reformer. The most commercially used hydrogen production method is to react methane (CH ₄ ) with water vapor in the presence of a catalyst Is steam-methane reforming (SMR) which converts hydrogen (H ₂ ), carbon monoxide (CO), and carbon dioxide (CO ₂ ).

In the SMR process for hydrogen production, relatively inexpensive ceramic supports are used. The steam methane reforming process (SMR) catalyst for hydrogen production is formed by molding a ceramic powder containing active materials such as Ni and Ru into a pellet form. However, the ceramic pellets are easily broken due to their low impact resistance and cause a differential pressure in the reactor. In addition, there is a disadvantage that the energy is insufficient and depend on the activation energy and the catalyst amount of the catalyst.

In order to overcome the disadvantages of conventional ceramic supports, the present invention is intended to apply a metal foam. In this case, the porous body made of metal tends to have poor adhesion to a catalyst made of ceramics, So as to provide a pretreatment step of the porous metal body for increasing the adhesion.

According to a first aspect of the present invention, there is provided a process for preparing a nickel-containing composite particle, comprising: a first step of preparing a nickel-containing composite particle on which a metal active component is supported on a ceramic support; A second step of preparing a nickel-based catalyst slurry by mixing the nickel-containing composite particles with an inorganic binder and then milling the mixture; A third step of pretreating the surface of the porous metal body so that the Al ₂ O ₃ oxide film is formed on the surface or formed at a later stage; And a fourth step of preparing a nickel-based catalyst in which the nickel-based catalyst slurry is dip-coated on the pretreated metal porous body, followed by drying and firing, thereby carrying the nickel-containing complex on the porous metal body having the Al ₂ O ₃ oxide film formed on its surface Based catalyst comprising a metal-porous-body-coated nickel-based catalyst. At this time, the order of the first to third steps is not important, and can be partially or totally reversed and concurrently performed.

A second aspect of the present invention is a metal porous body produced by the first aspect, wherein the nickel-containing composite on which the metal active component is supported on the ceramic support is supported on a porous metal body having an Al ₂ O ₃ oxide film formed on its surface, Lt; / RTI >

A third aspect of the present invention provides a method for producing hydrogen comprising the step of performing steam methane reforming using a metal porous body coated nickel-based catalyst according to the second aspect.

Hereinafter, the present invention will be described in detail.

Conventionally, the steam methane reforming process (SMR) catalyst for hydrogen production is formed by molding a ceramic powder containing active materials such as Ni and Ru into pellets. Since the ceramic pellets are easily broken due to their low impact resistance, the present invention provides a porous body made of a metal which can overcome the impact resistance, which is the limit of ceramic, and which has an excellent heat transfer characteristic compared with ceramics and can reduce thermal energy required for the reaction, foam is applied to a ceramic porous substrate on which a catalytically active component is supported.

The metal porous body, which can perform a role as a catalyst, must be coated with a separate catalyst, because the catalyst made of oxide ceramics is coated, so that the adhesion is decreased and the reaction efficiency is lowered.

The present inventors have found that adhesion and reactivity of a ceramic catalyst are improved when a metal foam, which is a porous metal body, is subjected to a heat treatment under high temperature air atmosphere and / or an alumina sol coating, wherein Al ₂ O ₃ oxide layer was formed and the AlCrO ₃ phase was suppressed. The present invention is based on this.

In the present specification, a metal porous body is used in combination with a metal foam. The porous metal body serves as a support for supporting the nickel-containing composite particles carrying the metal active component on the ceramic support.

The term "metal foam coating catalyst" in the present invention means "catalyst coated on a metal foam support".

In the first step, the nickel-containing composite particles are supported on the ceramic support with the metal active component.

The nickel-containing composite particles can be prepared by impregnating a ceramic support with nickel and / or other metal active ingredient-providing precursor (s), followed by drying and calcining.

Non-limiting examples of ceramic supports are MgAl ₂ O ₃ or Al ₂ O ₃ .

The metal active component carried on the ceramic support is nickel alone; Or a metal selected from the group consisting of nickel, titanium, vanadium, chromium, manganese, iron, cobalt, copper, aluminum, magnesium, zirconium, (Zr) and boron (B). Preferably, it may be at least one metal selected from the group consisting of nickel and chromium (Cr), copper (Cu), aluminum (Al), magnesium (Mg) and boron (B).

The metal active ingredient-providing precursor is a water-soluble precursor which is selected from the group consisting of oxides, oxyhydroxides, chloride salts, carbonates, nitrates, nitrates, nitrates and nitrates of metals. Firefighting. Oxalate, carboxylate, sulfate and the like, alkoxy precursors containing hydrocarbons as oil-soluble precursors. Ammonium precursors, and the like.

The drying can be carried out at a temperature of 40 to 70 ° C.

The calcination may be carried out at a temperature of 800 to 900 DEG C under an air atmosphere.

In the second step, the nickel-containing composite particles and the inorganic binder are mixed and then milled to prepare a nickel-based catalyst slurry.

The milling may be ball milling.

The inorganic binder is preferably capable of serving as a dispersing agent capable of highly dispersing the ceramic support on which the metal active component is supported in the catalyst slurry and / or on the surface of the metal porous body. As the inorganic binder, a dispersant having properties suitable for acid can be used, and a non-limiting example thereof is a boehmite-based dispersant.

Boehemite is γ-AlO (OH), which is a monovalent monoxide having one hydroxyl group (-OH). It is high strength, high acidity, high crystallinity and high growth Al ₂ O ₃ compared to conventional Al ₂ O ₃ . These boehmites are excellent starting materials for gamma / delta / theta / alpha Al ₂ O ₃ as thermal / structural properties. Boehmite has various forms of Al ₂ O ₃ depending on the heat treatment conditions and methods.

The third step is a step of pretreating the surface of the porous metal body such that the Al ₂ O ₃ oxide film is formed on the surface or formed in a later step (for example, the fourth step).

The porous metal body is made of a metal such as Ni, Ti, V, Cr, Mn, Fe, Co, Cu, Mg), zirconium (Zr) and boron (B), and may be an alloy containing two or more metal elements selected from the above metal group. Preferably, at least one selected from the group consisting of Ni, Ti, V, Cr, Mn, Fe, Co, Cu, (Mg), zirconium (Zr), and boron (B). More preferably, it may be a nickel-chromium-aluminum alloy or an iron-chromium-aluminum alloy.

The porous metal body has a porous geometry, thereby maximizing the specific surface area, and having different structural characteristics, hydrodynamic and mechanical properties required for the heterogeneous phase catalysis, which is advantageous as a catalyst support. The porous metal body may have a surface area of 3,000 m ² / m ³ or more.

The porous metal bodies may also have interconnected cavities and interconnected cavities may be useful passages for the gaseous phase flow and allow the reactant gas to be more readily adsorbed to the active sites of the catalyst .

The porous metal body may be a structure having various shapes as illustrated in Fig. The porous metal article has a small heat capacity and excellent heat transfer ability and can be molded into a desired shape. When the catalyst layer is wash coated on the metal foam, a catalyst having good metal dispersion, good surface area and pore volume, light weight and small density can be produced.

In the present invention, adhesion and reactivity of a ceramic catalyst are improved when a metal foam, which is a porous metal body, is heat-treated and / or coated with an alumina sol under a high-temperature air atmosphere, An Al ₂ O ₃ oxide film layer was formed.

The treatment method is not limited as long as the Al ₂ O ₃ oxide film can be formed on the surface or can be formed at a later stage. Non-limiting examples of the pretreatment include heat treatment in an air atmosphere, or alumina sol Coating the metal porous body, or heat treating the porous metal body in an air atmosphere, followed by coating the alumina sol.

At this time, the air atmosphere belongs to the scope of the present invention even if the atmosphere is not an air atmosphere as long as the Al ₂ O ₃ oxide film can be formed on the surface or formed at a later stage. For example, the air atmosphere includes an oxygen-containing atmosphere.

The heat treatment may be performed at, for example, 900 to 1100 DEG C for 10 to 48 hours. Preferably, the heat treatment may be performed at 950 to 1050 DEG C for 10 to 36 hours. If the heat treatment temperature is less than 900 ° C, the effect of improving adhesion and reactivity through heat treatment of the metal foam may be insufficient, and if it exceeds 1100 ° C, economical efficiency may be lowered.

In the fourth step, the nickel-based catalyst slurry is dip-coated on the pretreated porous metal body, followed by drying and firing to produce a nickel-based catalyst having the nickel-containing composite supported on a porous metal body having an Al ₂ O ₃ oxide film formed on its surface . In the fourth step, the inorganic binder can be aluminized by firing.

The nickel-based catalyst slurry may be dried at a temperature of 70 to 90 ° C for 20 minutes to 2 hours to remove moisture of the coated metal porous body or prevent rapid evaporation of water.

The firing may be performed at a temperature of 450 to 650 ° C for 1 hour to 6 hours under air atmosphere.

The fourth step may be repeated until a desired amount of catalyst is carried to improve adhesion of the catalyst.

A second aspect of the present invention is a metal porous body produced by the first aspect, wherein the nickel-containing composite on which the metal active component is supported on the ceramic support is supported on a porous metal body having an Al ₂ O ₃ oxide film formed on its surface, Lt; / RTI > The metal porous body coated nickel catalyst may be used as a catalyst for steam methane reforming process for hydrogen production.

A third aspect of the present invention provides a method for producing hydrogen comprising the step of performing steam methane reforming using a metal porous body coated nickel-based catalyst according to the second aspect.

The steam reforming reaction of methane is a reaction in which methane is reacted with water vapor, carbon dioxide, or a mixture thereof to produce syngas (CO + H ₂ ). The steam reforming reaction of methane can be carried out at a reaction pressure of 1 to 30 bar and a molar ratio of steam / methane of 1 to 4.

The metal porous body coated nickel based catalyst according to the present invention maintains the adhesion of the catalyst even after aging after the steam methane reforming reaction at 550 to 850 ° C, and deactivation of the catalyst can be remarkably suppressed. The conventional metal foam coating catalysts (Comparative Examples) have a problem in that a large amount of AlCr ₂ O ₃ phase is formed on the metal foam surface after aging, resulting in poor adhesion of the catalyst and inactivation of the catalyst. The metal foam coating catalyst (embodiments) of the present invention can solve this problem by pretreating the metal foam before the catalyst coating and forming the Al ₂ O ₃ oxide layer on the metal foam surface.

According to the present invention, adhesion and reactivity of the metal foam-coated catalyst can be maintained even after the metal foam is used in the steam methane reforming reaction by pretreating the metal foam.

According to the present invention, the impact resistance of the catalyst supported on the ceramic support used in the steam methane reforming process can be improved, and the heat energy required for the reaction can be reduced due to the heat transfer characteristics of the metal.

Fig. 1 schematically shows a manufacturing process of an alloy foam.
FIG. 2 is a graph comparing changes in SMR reaction efficiency depending on whether the alloy foam is pretreated.
Fig. 3 shows the adhesion of the NMA powder (Preparation Example 2), the ceramic foam coated NMA catalyst (Comparative Example 3), the untreated NiCrAl foam coated NMA catalyst (Comparative Example 1) and the untreated FeCrAl foam coated NMA catalyst (Comparative Example 2) And SMR reaction efficiency.
4 shows the SEM-EDS analysis results of the untreated NiCrAl foam-coated catalyst (Comparative Example 1).
5 shows the SEM-EDS analysis results of the Aging untreated NiCrAl foam coating catalyst (Comparative Example 1).
6 shows the SEM-EDS analysis results of the untreated FeCrAl foam coating catalyst (Comparative Example 2).
7 shows the SEM-EDS analysis results of the Aging untreated FeCrAl foam coating catalyst (Comparative Example 2).
8 shows the XRD analysis results of Aging untreated FeCrAl foam coating catalyst (Comparative Example 2) and Aging untreated NiCrAl foam coating catalyst (Comparative Example 1).
9 is a graph showing the results of evaluating the adhesion and reactivity of the metal foam-coated catalysts of Examples 1, 3, 4, and Comparative Examples 1 to 3. FIG.
10 is a SEM-EDS analysis result of the metal foam-coated catalyst of Example 1. Fig.
11 is a SEM-EDS analysis result of the metal foam-coated catalyst of Example 3. Fig.
12 is a SEM-EDS analysis result of the metal foam-coated catalyst of Example 4. Fig.
FIG. 13 shows the XRD analysis results of the catalyst pretreated with NMA + NiCrAl foam for 24 hours aging, alumina sol coating, 24 hours aging and alumina sol coating.

Hereinafter, the present invention will be described in more detail with reference to examples of the present invention. However, these examples are for illustrative purposes only, and the scope of the present invention is not limited to these examples.

Manufacturing example  1: Preparation and Pretreatment of Metal Foam

As shown in FIG. 1, a binder and a chromium alloy powder were put into a pure Ni foam, followed by vacuum firing at 1300 ° C. to prepare an alloy foam (NiCrAl). The alloy foam thus prepared was heat-treated at 1000 ° C for 24 hours under air atmosphere.

Manufacturing example  2: Preparation of catalyst

_{Ni (NO 3) 2 · 6H} 2 O and Mg (NO _{3) 2} · 6H one ₂ O ultrasonic treatment (1 hour) for 1 hour followed by the addition of deionized water (1mol / L) Next, the ceramic support (Al ₂ O ₃ ) at 40 to 70 ° C under 2 step RPM conditions and then dried at 100 ° C for 24 hours. The then calcined at 850 ℃ for 6 hours, after being supported on the ceramic support MgNiAl ₂ O ₄ Catalyst (NMA).

Example  1: Preparation of Metal Foam Coating Catalyst

The MgNiAl ₂ O ₄ catalyst (NMA) prepared in Production Example 2 and the P2 binder (boehmite-based dispersant) were mixed and ball milling (300 RPM) was performed using a 10 mm ball for 12 hours to prepare a catalyst slurry. After a certain period of time, the pH of the slurry was adjusted by using glacial acetic acid, and the particle size and viscosity were analyzed.

An alloy foam (NiCrAl) prepared and pretreated in Preparation Example 1 was immersed in the slurry (dip coating), and the catalyst was evenly dispersed on a NiCrAl foam through a blower. The coated NiCrAl foam was dried in an oven at 80 ° C for 30 minutes to remove moisture and prevent rapid evaporation of water, then heated to 550 ° C in an oven for 2 hours to aluminate the binder, and then maintained for 2 hours.

The amount of catalyst supported on the fired alloy form (NiCrAl) was calculated, and dip coating, drying and firing were repeated 2-4 times, if necessary.

Example  2

Except that an alloy foam (FeCrAl) prepared and pretreated in the same manner as in Production Example 1 was used instead of the alloy foam (NiCrAl) except that an Fe foam was used in place of the Ni foam. .

Example  3

A metal foam-coated catalyst was prepared in the same manner as in Example 1 except that alumina sol was coated on an alloy foam (NiCrAl) instead of heat-treating the alloy foam (NiCrAl) in Production Example 1.

Example  4

A metal foam-coated catalyst was prepared in the same manner as in Example 1, except that alumina foam (NiCrAl) was heat-treated in an air atmosphere and coated with alumina sol in Production Example 1.

Example  5

A metal foam-coated catalyst was prepared in the same manner as in Example 1 except that the alloy foam (NiCrAl) was electrolytically oxidized instead of heat-treated in Production Example 1.

Comparative Example  One

A metal foam-coated catalyst was prepared in the same manner as in Example 1 except that the alloy foam (NiCrAl) was not pretreated in Preparation Example 1.

Comparative Example  2

A metal foam-coated catalyst was prepared in the same manner as in Example 2, except that the alloy foam (FeCrAl) not pretreated in Example 2 was used.

Comparative Example  3

A metal foam-coated catalyst was prepared in the same manner as in Example 1, except that a ceramic foam was used instead of the metal foam.

Experimental Example  1: Catalyst Attachment  And reactivity evaluation

For the metal foam coated catalyst of Example 1 and Comparative Example 1, 0.5 MH ₂ SO ₄ and HNO ₃ The results are shown in Table 1 below. ≪ tb >< TABLE >

Electrochemical evaluation conditions and conditions

- Equipment used: Potentiostat / Galvanostat

- electrolyte _{1: 0.5M CH 3 OH + 0.5MH} 2 SO 4 in DI water

- electrolyte _{2: 0.5M CH 3 OH + 0.5M} HNO 3 in DI water

- Specimen size: 1 * 4 cm ² NiCrAl form

- Voltage: 1.2 V, Holding time: 10,000 sec

Adhesion test H2SO4 HNO3 Example 1
(NMA + NiCrAl (1000 < 0 > C)
92.92% 86.17% 94.70% 88.12% Comparative Example 1
(NMA + NiCrAl Fresh)
94.10% 82.47% 93.92% 83.19%

(The above% value means the weight retention rate of the catalyst in the adhesion test)

As shown in Table 1, it was confirmed that the adhesion of the metal foam-coated catalyst of Example 1 was improved as compared with Comparative Example 1.

The metal foam-coated catalysts of Example 1 and Comparative Example 1 were subjected to an aging test at a high temperature exposure of 1000 ° C for 24 hours and 48 hours after an SMR reaction at 550 to 850 ° C, followed by an SMR reaction at 550 to 850 ° C The efficiency (CH ₄ conversion) was evaluated. The results are shown in FIG. As a result, the metal foam-coated catalyst of Example 1 using the heat-treated alloy foam did not show a significant decrease in SMR reaction efficiency even after aging, compared with the catalyst of Comparative Example 1 using the untreated alloy foam.

From these results, it can be confirmed that the adhesion and the reaction characteristics of the metal foam-coated catalyst are improved through the pretreatment of the metal foam.

Experimental Example  2: Catalyst Attachment  And reactivity evaluation

(Comparative Example 3), uncoated NiCrAl foam-coated NMA catalyst (Comparative Example 1), and untreated FeCrAl foam-coated NMA catalyst (Comparative Example 2). The sex was evaluated. Also, the durability of the catalyst was evaluated by severing it through a high temperature reaction. The results are shown in Fig.

As shown in FIG. 3, the ceramic foam-coated catalyst has good durability but low adhesion. On the other hand, the NiCrAl and FeCrAl foam coating catalysts, which are metal foams, are excellent in adhesion, but the activity of NiCrAl is relatively decreased after aging.

Experimental Example  3: SEM -EDS analysis and XRD  analysis

An SEM-EDS analysis of the untreated NiCrAl foam-coated catalyst (Comparative Example 1) and the FeCrAl foamcoated catalyst (Comparative Example 2) was performed. SEM-EDS analysis of the NiCrAl foam-coated catalyst (Comparative Example 1) and the FeCrAl foam-coated catalyst (Comparative Example 2) was also performed after aging. The results are shown in Fig. 4 to Fig.

As shown in FIGS. 4 and 5, the NiCrAl foam-coated catalysts (Comparative Example 1) exhibited relatively uniform Al and Cr distributions, but showed non-uniform Cr distribution after aging.

Also, as shown in FIGS. 6 and 7, Al and Cr were uniformly distributed in the FeCrAl foam-coated catalyst (Comparative Example 2). However, after aging, an Al wall was formed on the outer wall and a uniform Cr distribution was exhibited.

Therefore, it was confirmed that the NiCrAl foam-coated catalyst (Comparative Example 1) and the FeCrAl foam-coated catalyst (Comparative Example 2), which had not been pretreated, had deteriorated adherence and reactivity due to changes in the physical properties of the catalyst after aging.

XRD analysis of Aging NiCrAl foam coated catalyst and FeCrAl foam coated catalyst was also performed. The results are shown in Fig.

As shown in FIG. 8, it can be seen that the Ag _{1 .98} Cr _{0 .02} O ₃ phase peak intensity of the Aging NiCrAl foam coating catalyst is larger than that of the Aging FeCrAl foam coating catalyst.

Experimental Example  4: Catalyst Attachment  evaluation

(Comparative Example 2), Aged NiCrAl Foam Coating Catalyst (Comparative Example 1), and Aging FeCrAl Foam Coating Catalyst (Comparative Example 2) were prepared in the same manner as in Example 1, except that the untreated NiCrAl foam coating catalyst (Comparative Example 1), the untreated FeCrAl foam coating catalyst , 0.5 MH ₂ SO ₄ and HNO ₃ The results are shown in Table 2 below. ≪ tb >< TABLE >

As shown in Table 2, it can be confirmed that the NiCrAl foam-coated catalyst (Comparative Example 1) has a reduced catalyst adhesion after aging as compared with the FeCrAl foam-coated catalyst (Comparative Example 2).

Experimental Example  5: Catalyst Attachment  And reactivity evaluation

The adhesion and reactivity of the metal foam coating catalysts of Examples 1, 3, 4 and Comparative Examples 1 to 3 were evaluated, and the results are shown in FIG.

As shown in FIG. 9, the catalysts of Examples 1, 3 and 4 exhibited much less decrease in reaction efficiency after aging than those of Comparative Example 1 (NMA + NiCrAl) and Comparative Example 2 (NMA + FeCrAl) .

Experimental Example  6: SEM -EDS analysis and XRD  analysis

SEM-EDS analysis was performed to evaluate the adhesion and durability of the metal foam coated catalysts of Examples 1, 3 and 4. The results are shown in FIG. 10 to FIG.

As shown in FIGS. 10 and 12, Al ₂ O ₃ layers were formed on the surfaces of the metal foams of Examples 1 and 4.

Also, as shown in FIG. 11, an Al layer was formed on the surface of the metal foam of Example 3.

XRD analysis was also performed on the metal foam coated catalysts of Examples 1, 3 and 4. The results are shown in Fig.

As shown in FIG. 13, NiO and MgAl ₂ O ₄ peaks were confirmed by XRD analysis of NMA + NiCrAl foam pretreated with aging, alumina sol coating, 24 hour aging and alumina sol coating for 24 hours. No peak was detected.

From these results, it can be seen that the deactivation phenomenon of the catalyst can be remarkably suppressed by forming the Al ₂ O ₃ oxide layer on the surface layer of the metal foam through the pretreatment of the metal foam.

Experimental Example  7: Catalyst Attachment

The adhesion tests were carried out on the metal foam-coated catalysts of Examples 1, 3 and ₄ by electro-oxidation using 0.5 MH ₂ SO ₄ and HNO ₃ solutions, and the results are shown in Table 3 below.

As shown in Table 3, the adhesion of the catalysts of Examples 1, 3 and 4, which were pretreated with the metal foam, compared to the untreated NiCrAl foam-coated catalyst (Comparative Example 1) Respectively.

Claims (9)

A first step of preparing a nickel-containing composite particle on which a metal active component is supported on a ceramic support;
A second step of preparing a nickel-based catalyst slurry by mixing the nickel-containing composite particles with an inorganic binder capable of aluminizing by firing and then milling the mixture;
A third step of pretreating the surface of the porous metal body so that the Al ₂ O ₃ oxide film is formed on the surface or formed at a later stage; And
The nickel-based catalyst slurry is dip-coated on the pretreated porous metal body, followed by drying and firing to alumina the inorganic binder, and a nickel-based catalyst carrying the nickel-containing complex on the porous metal body having the Al ₂ O ₃ oxide film formed thereon And a fourth step of manufacturing
Wherein the pretreatment in the third step is a heat treatment of the porous metal body in an air atmosphere, followed by coating with an alumina sol. The method of claim 1, wherein the metal active component carried on the ceramic support is nickel alone; Or a metal selected from the group consisting of nickel, titanium, vanadium, chromium, manganese, iron, cobalt, copper, aluminum, magnesium, zirconium, (Zr) and boron (B). ≪ / RTI > The process of claim 1, wherein the ceramic support is MgAl ₂ O ₃ or Al ₂ O ₃ . The metal porous body according to claim 1, wherein the porous metal body is at least one selected from the group consisting of Ni, Ti, V, Cr, Mn, Fe, Co, Cu, Is a metal element selected from the group consisting of aluminum (Al), magnesium (Mg), zirconium (Zr) and boron (B). The method according to claim 1, wherein the porous metal body is a nickel-chromium-aluminum alloy or an iron-chromium-aluminum alloy. The method for producing a metal porous body-coated nickel-based catalyst according to claim 1, wherein the porous metal body has a surface area of 3,000 m ² / m ³ or more. The method of manufacturing a metal porous body coated nickel catalyst according to claim 1, wherein the porous metal body has mutually connected cavities. The method according to claim 1, wherein the drying in the fourth step is carried out at a temperature of 70 to 90 캜 for 20 minutes to 2 hours. The method for producing a metal porous body-coated nickel-based catalyst according to claim 1, wherein the calcination in the fourth step is carried out in an air atmosphere at a temperature of 450 to 650 ° C for 1 to 6 hours.

Images