KR100711509B1 - Composite metal supported catalyst used to produce hydrogen from water and ethanol mixture by autothermal reforming reaction, method for preparing the same, and method for producing hydrogen using the catalyst - Google Patents

Abstract

The present invention relates to a catalyst used for producing hydrogen from a mixture of water and ethanol by an auto-thermal reforming reaction, a method for producing the same, and a method for producing hydrogen using the catalyst. In the catalyst used to produce hydrogen by autothermal reforming from and ethanol, the catalyst is at least one selected from the group consisting of Mg, Co, Cu, Zn, Fe, Mo, Cr, Bi, La, Zr and Ce A composite supported catalyst, a method for producing the same, and a method for producing hydrogen using the catalyst, wherein the metal and nickel are supported on alumina as a carrier, and the mixture of water and ethanol using the catalyst of the present invention. When the autothermal reforming reaction is carried out by the autothermal reforming reaction of the ethanol mixture containing water at a relatively low reaction temperature (200 ℃ to 600 ℃) and normal operating conditions Minimize the production of carbon oxides and produce gases rich in hydrogen.

Ethanol, hydrogen, carbon monoxide, autothermal reforming, supported catalyst, complex metal catalyst

Description

HYBRID METAL CATALYST SUPPORTED ON ALUMINA FOR HYDROGEN PRODUCTION FROM THE MIXTURE OF WATER AND ETHANOL, PRODUCTION METHOD THEREOF AND THE PRODUCTION METHOD OF HYDROGEN BY AUTO-THERMAL REFORMING USING SAID CATALYST}

The present invention relates to a method for producing hydrogen by auto-thermal reforming reaction of an ethanol mixture containing water, and more particularly, a catalyst used for producing hydrogen by autothermal reforming reaction from water and ethanol. The catalyst has a structure in which at least one metal and nickel selected from the group consisting of Mg, Co, Cu, Zn, Fe, Mo, Cr, Bi, La, Zr and Ce are supported on alumina as a carrier. The present invention relates to a composite supported catalyst, a method for producing the same, and a method for producing hydrogen using the catalyst.

As hydrogen energy emerges as an alternative energy source for fossil fuels, research on the production, storage and use of hydrogen is being actively conducted. In particular, the process of producing hydrogen from ethanol has the advantages of cleanliness and harmlessness of fuel, ease of storage and use. However, ethanol reforming reactions generally require higher reaction temperatures and lower hydrogen selectivity than methanol reforming reactions. Therefore, the development of a catalyst having high activity in the hydrogen production process by ethanol reforming reaction is a key element technology. In general, the process of producing hydrogen from ethanol is divided into the following depending on the presence of oxygen and water vapor.

Co-ZnO (J. Llorca, N. Homs, J. Sales, J.-LG Fierro, PR de la Piscina, J. Catal) as a catalyst for the ethanol steam reforming reaction represented by the formula (1) , 222, no.2, pp. 470-480, 2004), Rh / Al ₂ O ₃ (S. Freni, N. Momdello, S. Cavallaro, G. Cacciola, VN Parmon, VA Sobyanin, React.Kinet.Catal Lett., Vol. 71, no. 143-152, 2000), Ni / La ₂ O ₃ -Al ₂ O ₃ (AN Fatsikostas, DI Kondarides, XE Verykios, Chem. Commun., Pp. 851-852, 2001) are known to exhibit relatively high activity. However, in the case of steam reforming, the productivity of hydrogen is good, but due to the strong endothermic reaction, appropriate heat must be continuously supplied to the reactor, and additional devices for this are required separately. In addition, Pt / CeO ₂ (LV Mattos, FB Noronha, J. Catal., Vol. 233, No. 453-463, 2005) on the hydrogen production reaction by ethanol partial oxidation represented by the above formula (2), etc. Although the catalyst is reported to be relatively good activity, it is difficult to select the reactor material due to the strong exothermic reaction, the temperature control is not easy and the hydrogen production is lower than the steam reforming reaction or autothermal reforming reaction.

The autothermal reforming reaction of ethanol represented by Equation (3) above is to inject oxygen and water vapor into the reactants at the same time, which is characterized by a thermodynamically weak exothermic reaction, which is relatively thermally stable and relatively high in hydrogen production. Therefore, many studies on autothermal reforming reactions and processes have been conducted. For example, the hydrogen production process by ethanol steam reforming reaction based on nickel and copper in the presence of oxygen at a reaction temperature of 300 ° C. to 800 ° C. is patented. Reported (International Patent WO 01/00320). It has been reported that the gas containing hydrogen and carbon monoxide thus produced can be mixed with fuel containing gasoline and fed directly to the internal combustion engine to be used to run the engine. In addition, in recent US patent 2005/0244329 A1, autothermal using M _x M ' _(1-x) Al ₂ O ₄ (x = 0-1) catalyst having a spinel structure already reported by French patent (03/08077) A reforming reaction process has been reported. The spinel catalyst contains at least one Group VIII metal (Mg, Cu, Zn, Ni, etc.) and M 'consists of a mixture of non-noble metals with oxides such as alumina, cerium and zirconia. Application of such spinel-structured catalyst to ethanol steam reforming reaction (F. Aupretre, C. Descorme, D. Duprez, D. Casanave, D. Uzio, J. Catal., Vol. 233, pp. 464-477, 2005 ) And cases of steam reforming of general hydrocarbons (Korean Patent 10-2003-7010802, International Patent PCT / US2002 / 04479, 2003) have been reported, but hydrogen production is increased because oxygen causes more side reactions. It is known that other noble metal active ingredients are required for the increase. In addition, catalysts based on nickel supported on alumina (V. Fierro, O. Akdim, H. Provendier, C. Mirodatos, J. Power Sources, Vol. 145, pp. 659-666, 2005) and Cu _{1- x} Ni _x ZnAl and mixed oxide catalysts (S. Velu, K. Suzuki, M. Vijayaraj, S. Barman, CS Gopinath, Appl. Catal. B, Vol. 55, pp. 287-299, 2005) It is also used in. They reported that nickel metal is the most suitable active ingredient in the ethanol reforming reaction among Group VIII metals, but the catalytic performance is improved when alkali and alkaline earth metals are added because they are weak to carbon deposition. In addition, a report on a process for converting bioethanol into hydrogen and electrical energy using a Ni / La ₂ O ₃ catalyst (US Pat. No. 6,605,376B2, 2003) and Cu / Al LDH (Layered Double Hydroxide: (M ²⁺ _{1 -x} M ³⁺ _x (OH) ₂ ) (An ⁻ ) _{x / n} .mH ₂ O) A catalyst system has been used (US Pat. No. 6,668,763 B2, 2003) for a mixed fuel reforming reaction of gasoline and ethanol. However, the method and the catalyst system disclosed in the document had a problem that the amount of carbon monoxide generated.

The present inventors have completed the present invention after solving the above problems and studying a catalyst suitable for producing hydrogen by autothermal reforming reaction from water and ethanol mixture and an efficient process for producing hydrogen using the catalyst.

Therefore, the technical problem of the present invention is to suppress the production of carbon monoxide and produce high hydrogen productivity in the production of hydrogen by autothermal reforming reaction of water and ethanol at a relatively low reaction temperature of 200 to 600 ℃ and normal pressure operation conditions. It is to provide a composite supported catalyst and a method of producing the same.

Another technical problem of the present invention is to provide a method for producing hydrogen by autothermal reforming reaction of water and ethanol mixture using the catalyst.

In order to achieve the above technical problem, the present invention is a catalyst used for producing hydrogen by autothermal reforming reaction from water and ethanol, the catalyst is Mg, Co, Cu, Zn, Fe, Mo, Cr, Bi, La Provided is a composite supported catalyst, characterized in that one or more metals and nickel selected from the group consisting of Zr and Ce have a structure supported on alumina as a carrier.

In addition, the present invention provides a composite supported catalyst, characterized in that the nickel contained in the range of 1 to 30% by weight relative to the alumina carrier.

In addition, the present invention provides a composite supported catalyst, characterized in that the metal is contained in a range of 0.01 to 5% by weight based on the alumina as a carrier.

Another aspect of the present invention is a method for producing a catalyst used for producing hydrogen by autothermal reforming reaction from water and ethanol, the method for producing a catalyst, i) dissolving a nickel precursor in a solvent to prepare a solution state ; Ii) dissolving at least one metal precursor selected from the group consisting of Mg, Co, Cu, Zn, Fe, Mo, Cr, Bi, La, Zr and Ce in a solvent to prepare a solution; Iii) mixing the nickel solution alone or the nickel solution / metal precursor mixed solution with alumina as a carrier to support nickel or nickel / metal; Iii) drying the supported carrier; Iii) optionally, supporting the metal and drying the supported catalyst by mixing the metal precursor solution and the nickel-supported carrier when the nickel precursor solution alone is supported in the supporting step; Iii) calcining the carrier on which the nickel / metal is supported while flowing air at 500 to 800 ° C. for 7 to 10 hours, and then reducing the catalyst while flowing a mixed gas of hydrogen and nitrogen at 500 to 800 ° C. for 2 to 5 hours. It provides a composite supported catalyst manufacturing method comprising the step of.

In order to achieve another technical problem of the present invention, the present invention is a reaction temperature of 200 ℃ ~ 600 ℃, space velocity 1000 ~ 50000h ^-1 , reactant water / ethanol molar ratio of 1 to 5, oxygen / ethanol molar ratio of 0.1 to 2 conditions And at least one metal and nickel selected from the group consisting of Mg, Co, Cu, Zn, Fe, Mo, Cr, Bi, La, Zr and Ce in the presence of a composite supported catalyst having a structure supported on alumina as a carrier. Provided is a method for producing hydrogen by autothermal reforming reaction of water and ethanol mixture.

In addition, the present invention provides a method for producing hydrogen by autothermal reforming reaction of water and ethanol, characterized in that the metal and nickel are contained in the range of 0.01 to 5% by weight and 1 to 30% by weight relative to the alumina as a carrier, respectively. to provide.

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

The complex supported catalyst of the present invention is a catalyst used to produce hydrogen by autothermal reforming reaction from water and ethanol. As described above, there have been many studies for obtaining hydrogen from water and ethanol by the autothermal reforming reaction, but there is a problem that the amount of carbon monoxide is generated and the economic efficiency is low, and the catalyst efficiency is also lowered. The composite supported catalyst of the present invention can solve the above problems and reduce the concentration of carbon monoxide in the product by at least 15% to 80% or more with high conversion.

The composite supported catalyst of the present invention has a structure in which at least one metal and nickel selected from the group consisting of Mg, Co, Cu, Zn, Fe, Mo, Cr, Bi, La, Zr and Ce are supported on alumina as a carrier. It features. The at least one metal and nickel selected from the group consisting of Mg, Co, Cu, Zn, Fe, Mo, Cr, Bi, La, Zr and Ce are in the range of 0.01 to 5% by weight and 1 to 30, respectively, for the alumina as a carrier. It is preferably contained in the weight% range.

The composite supported catalyst of the present invention comprises the steps of i) dissolving a nickel precursor in a solvent to prepare a solution; Ii) dissolving at least one metal precursor selected from the group consisting of Mg, Co, Cu, Zn, Fe, Mo, Cr, Bi, La, Zr and Ce in a solvent to prepare a solution; Iii) mixing the nickel precursor solution alone or the nickel precursor solution / metal precursor mixed solution with alumina as a carrier to support nickel or nickel / metal; Iii) drying the supported carrier; Iii) optionally, supporting the metal and drying the supported catalyst by mixing the metal precursor solution with a nickel-supported carrier when the nickel precursor solution alone is supported in the supporting step; Iii) calcining the carrier on which the nickel / metal is supported while flowing air at 500 to 800 ° C. for 7 to 10 hours, and then reducing the catalyst while flowing a mixed gas of hydrogen and nitrogen at 500 to 800 ° C. for 2 to 5 hours. It includes a step. The composite supported catalyst is prepared by using alumina as a carrier to make a nickel precursor and a precursor of the metal component into an aqueous solution, and then impregnating them together or sequentially impregnating the alumina. The catalyst thus prepared is dried for 5 to 10 hours while flowing air at 80 to 120 ° C., and then calcined for 7 to 10 hours while flowing air at 500 to 800 ° C., and then hydrogen and nitrogen at 500 to 800 ° C. for 2 to 5 hours. A catalyst for reforming reaction is prepared by reducing the catalyst while flowing a mixed gas (hydrogen: nitrogen = 1: 1 (molar ratio)).

In addition, the present invention provides a reformed gas rich in hydrogen and low in carbon monoxide by autothermal reforming reaction of water and ethanol mixture by using a complex supported catalyst in which other metal components as cocatalysts are supported on alumina together with nickel as the main catalyst. It provides a method of manufacturing. More specifically, the present invention is to prepare a catalyst on which a metal is supported on alumina, but using nickel as a metal component exhibiting main activity, and other metals, more preferably magnesium (Mg), cobalt (Co), copper A supported catalyst was prepared by adding (Cu), iron (Fe), zinc (Zn), chromium (Cr), bismuth (Bi), lanthanum (La), zirconium (Zr) or cerium (Ce) as a promoter. After the final heat treatment of the catalyst, and then reduced to hydrogen to produce a metal catalyst having a variety of active sites, by applying these catalysts to the autothermal reforming reaction of water and ethanol mixture provides a method for producing a hydrogen-rich reformed gas do.

In the present invention, the supported catalyst prepared as described above was applied to the autothermal reforming reaction of the water and the ethanol mixture. For the reforming reaction, a solid supported catalyst was installed in a continuous flow quartz reactor, the reaction temperature was 200 ° C. to 600 ° C., the space velocity was 1000 to 50000 h ⁻¹ , and the reactant water / ethanol molar ratio was 1 to 5 and oxygen / The reaction was carried out by maintaining the molar ratio of ethanol at 0.1 to 2 and introducing the reaction mixture into the reactor using nitrogen as a carrier gas.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments of the present invention. However, the following examples are merely to help the understanding of the present invention, the scope of the present invention is not limited only to the following examples.

(Produce) Comparative example  1 (alumina Supported  Preparation of nickel catalyst)

A non-reactive rod, dropping a solution of nickel nitrate (Ni (NO ₃ ) ₂ 6H ₂ O), a nickel precursor, in distilled water within 0.5 ml, dropwise to 1 gram of alumina (manufactured by Degussa), a carrier. Mix using. In this case, the amount of the nickel precursor added was adjusted to carry 5%, 10%, and 20% nickel metal in a weight ratio with respect to the amount of alumina when converted into the amount of nickel metal. The content of water was adjusted so that the alumina powder was not completely wetted, and then the nickel particles were uniformly dispersed, and then dried in an oven at 100 ° C. for 8 hours. The dried sample was ground finely using a mortar and then placed in a crucible, the temperature was raised to 800 ° C. at a rate of 5 ° C. per minute, calcined at 800 ° C. for 8 hours, and then slowly cooled.

(Produce) Example  1-1 (at the same time alumina Supported  Preparation of Binary Metal Catalysts)

Distilled water within 0.5 ml of nickel nitrate (Ni (NO ₃ ) ₂ 6H ₂ O), which is a precursor of nickel as the main catalyst, and magnesium nitrate (Mg (NO ₃ ) ₂ 6H ₂ O), which is a precursor of magnesium as the promoter Dissolved in. The mixed solution was added dropwise to 1 gram of cod alumina and mixed using an inactive rod. At this time, the amount of the added metal precursor was adjusted to be 10% by weight and 3% by weight of nickel and cocatalyst metal, respectively, based on the amount of alumina to support the metal component. The water content was adjusted so that the alumina powder was not completely wetted, and the metal particles were evenly dispersed so as to be uniformly dispersed and dried in an oven at 100 ° C. for 8 hours. The dried sample was ground finely using a mortar and then placed in a crucible, the temperature was raised to 800 ° C. at a rate of 5 ° C. per minute, calcined at 800 ° C. for 8 hours, and then slowly cooled.

(Produce) Example  1-2 (at the same time alumina Supported  Preparation of Binary Metal Catalysts)

A catalyst was prepared in the same manner as in (Production) Example 1-1, except that corporate nitride (Cu (NO ₃ ) ₂ 6H ₂ O) was used as the metal precursor of the cocatalyst.

(Produce) Example  1-3 (at the same time alumina Supported  Preparation of Binary Metal Catalysts)

A catalyst was prepared in the same manner as in Example 1-1, except that cobalt nitrate (Co (NO ₃ ) ₂ 6H ₂ O) was used as the metal precursor of the cocatalyst.

(Produce) Example  1-4 (at the same time alumina Supported  Preparation of Binary Metal Catalysts)

A catalyst was prepared in the same manner as in Example 1-1, except that iron (III) nitrate (Fe (NO ₃ ) ₂ 6H ₂ O)) was used as the metal precursor of the cocatalyst.

(Produce) Example  2-1 (sequential to alumina Supported  Preparation of Binary Metal Catalysts)

Nickel nitrate (Ni (NO ₃ ) ₂ 6H ₂ O), a precursor of nickel as the main catalyst, was dissolved in distilled water within 0.3 ml, and mixed by using a non-reactive rod while dropping dropwise to 1 gram of a cod alumina. The sample thus prepared was placed in an oven at 100 ° C. for 3 hours to remove moisture to carry nickel on the alumina. After dissolving magnesium nitrate (Mg (NO ₃ ) ₂ 6H ₂ O), a metal precursor of the cocatalyst, in distilled water within 0.3 ml, the solution was dropped dropwise onto the nickel sample loaded on the alumina prepared as described above. Mix using a non-reactive rod. The amount of the metal precursor to be added was adjusted so that the nickel and the promoter metal were 10% by weight and 3% by weight, respectively, based on the amount of metal, to support the metal component. The water content was adjusted so that the alumina powder was not completely wetted, and the metal particles were evenly dispersed so as to be uniformly dispersed and dried in an oven at 100 ° C. for 8 hours. The dried sample was ground finely using a mortar and then placed in a crucible, the temperature was raised to 800 ° C. at a rate of 5 ° C. per minute, calcined at 800 ° C. for 8 hours, and then slowly cooled.

(Produce) Example  2-2 (at the same time alumina Supported  Preparation of Binary Metal Catalysts)

A catalyst was prepared in the same manner as in (Preparation) Example 2-1, except that corporate nitride (Cu (NO ₃ ) ₂ 6H ₂ O) was used as the metal precursor of the cocatalyst.

(Produce) Example  2-3 (at the same time alumina Supported  Preparation of Binary Metal Catalysts)

A catalyst was prepared in the same manner as in (Production) Example 2-1, except that cobalt nitrate (Co (NO ₃ ) ₂ 6H ₂ O) was used as the metal precursor of the cocatalyst.

(Produce) Example  2-4 (at the same time to alumina Supported  Preparation of Binary Metal Catalysts)

A catalyst was prepared in the same manner as in Example 2-1, except that iron (III) nitrate (Fe (NO ₃ ) ₂ 6H ₂ O)) was used as the metal precursor of the cocatalyst.

(Use) Comparative Example 1 (Characteristics of Autothermal Reforming of Water and Ethanol Mixture by Nickel Catalyst Supported in Alumina)

Hydrogen production was carried out by autothermal reforming reaction of water and ethanol mixture using the supported catalyst prepared in Comparative Example 1. (Preparation) Charge 0.05 gram of the supported catalyst prepared by the method of Comparative Example 1 to the catalyst bed of a fixed bed reactor supported by quartz cotton and then flow nitrogen gas containing 50% of hydrogen at 700 ° C. at 40 ml / min for 4 hours. The catalyst was reduced. Thereafter, a sample for the reaction was injected while maintaining the temperature of the reactor at 500 ° C. Water and ethanol mixtures (molar ratio of water / ethanol = 2) were injected at a rate of 4 ml per hour using a syringe pump. Nitrogen, a carrier gas, was flowed together at a rate of 20 ml per minute to supply the reactants smoothly. The nitrogen mixture was allowed to enter the reactor in a sufficiently vaporized state while passing through a preheater maintained at 150 ° C. before reaching the reactor. Another reactant, oxygen, was introduced into the reactor at a rate of 8 ml per minute using a mass flow controller. Analysis of the product was done using gas chromatography equipped with a thermal conductivity detector. The reaction test results are summarized in Table 1 below. As shown in Table 1, as the nickel content supported on the alumina increases, the ethanol conversion and the hydrogen production amount increase while the carbon monoxide contents are similar to each other. This shows that the nickel metal component is an active metal suitable for the autothermal reforming reaction of water and ethanol mixture and the catalytic activity is proportional to the amount.

catalyst Ethanol Conversion Rate (%) Hydrogen content in the product (%) Carbon monoxide content in the product (%) 5 wt% Ni / Al ₂ O ₃ 82.4 23.1 30.4 10 wt% Ni / Al ₂ O ₃ 85.4 42.5 32.9 20 wt% Ni / Al ₂ O ₃ 94.1 50.7 29.2

Example 1 (Characteristics of Autothermal Reforming of Water and Ethanol Mixture by Binary Metal Catalyst Supported Simultaneously on Alumina)

Hydrogen production was carried out by autothermal reforming reaction of water and ethanol mixture using the supported catalysts prepared in Examples 1-1 to 1-4. (Preparation) Charge 0.05 gram of each of the supported catalysts prepared by the method of Examples 1-1 to 1-4 into the catalyst bed of a fixed bed reactor supported by quartz cotton, and then nitrogen gas containing 50% of hydrogen at 700 ° C. The catalyst was reduced for 4 hours while flowing at 40 ml per minute. Thereafter, a sample for the reaction was injected while maintaining the temperature of the reactor at 500 ° C. Water and ethanol mixtures (molar ratio of water / ethanol = 2) were injected at a rate of 4 ml per hour using a syringe pump. Nitrogen, a carrier gas, was flowed together at a rate of 20 ml per minute to supply the reactants smoothly. The nitrogen mixture was allowed to enter the reactor in a sufficiently vaporized state while passing through a preheater maintained at 150 ° C. before reaching the reactor. Another reactant, oxygen, was introduced into the reactor at a rate of 8 ml per minute using a mass flow controller. Analysis of the product was done using gas chromatography equipped with a thermal conductivity detector. The reaction test results are summarized in Table 2 below. As shown in Table 2, when a small amount of copper, cobalt and magnesium were added as cocatalysts, ethanol conversion was remarkably increased than when nickel metal was used (Comparative Example 1). It is believed that this is because these metals are used as promoters to cause synergy between nickel and promoters. Among the cocatalyst metals, in particular copper and cobalt have been shown to increase hydrogen production and at the same time significantly reduce carbon monoxide production.

catalyst Ethanol Conversion Rate (%) Hydrogen content in the product (%) Carbon monoxide content in the product (%) 10% by weight Ni / Al ₂ O ₃ [(Manufacturing) Comparative Example 1] 85.4 42.5 32.9 10% by weight Ni-3% by weight Cu / Al ₂ O ₃ 94.7 49.9 18.0 10 wt% Ni-3 wt% Co / Al ₂ O ₃ 88.7 46.2 12.1 10% by weight Ni-3% by weight Fe / Al ₂ O ₃ 81.3 41.7 28.2 10 wt% Ni-3 wt% Mg / Al ₂ O ₃ 89.5 40.1 11.6

(Use) Example 2 (Characteristics of Autothermal Reforming of Water and Ethanol Mixture by Binary Metal Catalysts sequentially Supported on Alumina)

Hydrogen production was carried out by autothermal reforming reaction of water and ethanol mixture using the supported catalysts prepared in Examples 2-1 to 2-4. 0.05 gram of each of the supported catalysts prepared by the methods of Preparation Examples 2-1 to 2-4 was charged to a catalyst bed of a fixed bed reactor supported by quartz cotton, and then nitrogen gas containing 50% of hydrogen at 700 ° C. was added to 40 ml / min. The catalyst was reduced for 4 hours while flowing. Thereafter, a sample for the reaction was injected while maintaining the temperature of the reactor at 500 ° C. Water and ethanol mixtures (molar ratio of water / ethanol = 2) were injected at a rate of 4 ml per hour using a syringe pump. Nitrogen, a carrier gas, was flowed together at a rate of 20 ml per minute to supply the reactants smoothly. The nitrogen mixture was allowed to enter the reactor in a sufficiently vaporized state while passing through a preheater maintained at 150 ° C. before reaching the reactor. Another reactant, oxygen, was introduced into the reactor at a rate of 8 ml per minute using a mass flow controller. Analysis of the product was done using gas chromatography equipped with a thermal conductivity detector. The reaction test results are summarized in Table 3 below.

Ethanol Conversion Rate (%) Hydrogen content in the product (%) Carbon monoxide content in the product (%) 10% by weight Ni / Al ₂ O ₃ [(Manufacturing) Comparative Example 1] 85.4 42.5 32.9 10% by weight Ni-3% by weight Cu / Al ₂ O ₃ 98.6 43.3 25.6 10 wt% Ni-3 wt% Co / Al ₂ O ₃ 92.8 43.7 28.7 10% by weight Ni-3% by weight Fe / Al ₂ O ₃ 82.2 38.5 8.5 10 wt% Ni-3 wt% Mg / Al ₂ O ₃ 84.1 39.2 4.5

Comparing the results of Table 3 with the results of Table 2, it can be seen that the activity changes according to the order in which the metal catalyst is supported. In the case of supporting the promoter sequentially (Preparation Examples 2-1 to 2-4), the hydrogen productivity was slightly reduced compared to the case of supporting the promoter at the same time (Preparation Examples 1-1 to 1-4). This may be because the supported promoter was not evenly dispersed or because the combination of the two metal catalysts did not work efficiently. However, the addition of magnesium or iron significantly reduced the amount of carbon monoxide in the product, suggesting that these two components have a weak side reaction control function but are effective in suppressing carbon monoxide production. As a result, it was found that the method of simultaneously supporting nickel as the main catalyst and the metal as the promoter is more efficient for producing hydrogen by autothermal reforming reaction of water and ethanol mixture.

As described above, in preparing an efficient catalyst for producing hydrogen by autothermal reforming reaction of water and ethanol mixture, when the nickel as main catalyst and the metal as cocatalyst are supported on alumina, When the promoter is simultaneously supported on alumina, hydrogen productivity is increased and carbon monoxide production is reduced.

The embodiments of the present invention described above should not be construed as limiting the technical idea of the present invention. The protection scope of the present invention is limited only by the matters described in the claims, and those skilled in the art can change and change the technical idea of the present invention in various forms. Therefore, such improvements and modifications will fall within the protection scope of the present invention, as will be apparent to those skilled in the art.

Claims (6)

In the catalyst used to produce hydrogen by autothermal reforming reaction from water and ethanol, The catalyst is a composite supported catalyst comprising a structure in which at least one metal and nickel selected from the group consisting of Co, Cu, Zn, Fe, Mo, Cr, Bi, La, Zr and Ce are supported on alumina as a carrier. . The method of claim 1, The nickel is complex supported catalyst, characterized in that contained in the range of 1 to 30% by weight relative to the alumina carrier The method of claim 1, The supported catalyst, characterized in that the metal is contained in a range of 0.01 to 5% by weight relative to the alumina carrier. In the production method of the catalyst used to produce hydrogen by autothermal reforming reaction from water and ethanol, The catalyst manufacturing method, Iii) dissolving the nickel precursor in a solvent to prepare a solution; Ii) dissolving at least one metal precursor selected from the group consisting of Mg, Co, Cu, Zn, Fe, Mo, Cr, Bi, La, Zr and Ce in a solvent to prepare a solution; Iii) The nickel precursor solution is mixed with alumina as a carrier to support and dry nickel, and then the nickel-supported carrier is mixed with the metal precursor solution to support nickel / metal or the nickel precursor solution / metal precursor mixed solution. Mixing nickel / metal with alumina as a carrier; Iii) drying the supported carrier; Iii) calcining the carrier on which the nickel / metal is supported while flowing air at 500 to 800 ° C. for 7 to 10 hours, and then reducing the catalyst while flowing a mixed gas of hydrogen and nitrogen at 500 to 800 ° C. for 2 to 5 hours. Composite supported catalyst manufacturing method comprising the step of. Reaction temperature 200 to 600 ℃, space velocity 1000 to 50000h ^-1 , reactant water / ethanol molar ratio 1 to 5, oxygen / ethanol molar ratio 0.1 to 2 conditions and Mg, Co, Cu, Zn, Fe, Mo, Cr, Bi A method for producing hydrogen by autothermal reforming of a mixture of water and ethanol in the presence of a composite supported catalyst having a structure in which at least one metal and nickel selected from the group consisting of La, Zr and Ce are supported on alumina as a carrier. The method of claim 5, The metal and nickel, respectively, in the range of 0.01 to 5% by weight and 1 to 30% by weight with respect to alumina as a carrier, characterized in that the hydrogen production method by the autothermal reforming reaction of water and ethanol mixture.