KR20200010898A - Catalyst for steam reforming of low-carbon alcohol and apparatus for producing hydrogen gas through steam reforming reaction of low-carbon alcohol comprising the same - Google Patents

Abstract

The present invention provides a catalyst for steam reforming reaction of C1 to C5 low-carbon alcohol, which is in a pellet form, wherein an active material containing at least one member selected from the group consisting of nickel, nickel-lanthanum, and nickel-lanthanum-cerium is carried on an ordered mesoporous silica (OMS) carrier.

Description

Catalyst for steam reforming of low-carbon alcohol and apparatus for producing hydrogen gas through steam reforming reaction of low-carbon alcohol containing the same}

The present invention relates to a catalyst for steam reforming of low carbon alcohol and an apparatus for generating hydrogen gas through steam reforming of low carbon alcohol including the same.

Recently, fuel cells have been developed and are expected to be commercialized as devices for producing electricity in various facilities such as automobiles, buildings, and homes. One of the reasons that fuel cells attract the world's attention is that, unlike conventional electricity production methods, no environmental pollutants are emitted during electricity production. The principle of producing electricity from fuel cells is to produce electricity and water by reacting hydrogen and oxygen in the opposite reaction to water electrolysis. Therefore, the method of producing hydrogen, which is the fuel of a fuel cell, has become more important than ever.

A typical conventional hydrogen production method is to produce naphtha produced by steam reforming of natural gas or crude oil refining process. These methods are well known commercially available hydrogen production methods, but the reactants, either natural gas or naphtha, are fossil fuels and large amounts of carbon dioxide are generated during the steam reforming reaction. Since carbon dioxide generated from the use of fossil fuels is known as a representative greenhouse gas that is a cause of global warming, countries in Europe add expensive carbon taxes to fossil fuels, and have introduced the total amount of carbon emissions and carbon credit trading system. Restrictions on use. Accordingly, countries are making efforts to develop hydrogen for fuel cells from new and renewable energy sources.

On the other hand, low carbon alcohols such as ethanol and glycerol has an advantage that can be easily obtained from renewable resources such as biomass. For example, ethanol can be produced in high concentration from yeast fermentation of starch-based biomass, and glycerol is generated as a by-product in the process of producing biodiesel from vegetable oils such as palm oil, and thus it is possible to secure raw materials at low cost. These low carbon alcohols can be produced in any region, and can be easily stored and transported in the liquid phase, so that high-density hydrogen can be produced therefrom, and distributed generation using a fuel cell or a small gas generator is possible.

Therefore, low carbon alcohols are suitable as a raw material for distributed generation. In order to obtain a high concentration of hydrogen gas from low carbon alcohols, a steam reforming process is required. The steam reforming reaction converts hydrogen and carbon dioxide by catalyzing alcohol and water, but has an advantage of proceeding at atmospheric pressure, but an appropriate catalyst is required to produce high concentration of hydrogen. The high concentration of hydrogen gas produced from steam reforming can produce electricity using a solid acid fuel cell (SOFC) without any post-treatment.

Accordingly, the present inventors have developed a catalyst for steam reforming a low carbon alcohol and a hydrogen gas generating apparatus through a steam reforming reaction of a low carbon alcohol including the same. When hydrogen is generated using this, high concentration of hydrogen can be produced and by-products. The present invention has been found to be able to minimize the occurrence of the present invention and can be applied to a fuel cell without any post-treatment.

Patent Document 1: Republic of Korea Patent No. 10-1052385

It is an object of the present invention to provide a catalyst effective for producing high concentration hydrogen gas from steam reforming of low carbon alcohols such as ethanol and glycerol, and a method for producing the same.

Another object of the present invention is a high-concentration hydrogen gas generating apparatus using a steam reforming reaction of a low carbon alcohol employing a steam reforming reaction that can prevent plugging by a by-product, a method for producing a high concentration hydrogen gas using the same, and the apparatus To provide a fuel cell electricity production system further comprising a fuel cell.

In order to achieve the above object, the present invention

An ordered mesoporous silica (OMS) carrier is supported with an active material comprising at least one member selected from the group consisting of nickel, nickel-lanthanum and nickel-lanthanum-cerium, and is in a pellet form. Provided is a catalyst for the steam reforming reaction of C ₁ to C ₅ low carbon alcohols.

In addition, the present invention

Preparing a ordered mesoporous silica (OMS) carrier;

Spraying a solution containing a metal precursor as an active material onto the prepared regular mesoporous silica carrier to support the active material; And

It provides a method for producing a catalyst for steam reforming reaction of the C ₁ to C ₅ low carbon alcohol comprising the step of forming a regular mesoporous silica carrier carrying the active material into a pellet form.

Furthermore, the present invention

A raw material chamber including a raw material chamber including a C ₁ to C ₅ low carbon alcohol and a first preheater for preheating (first preheating) the raw material; And

An ordered mesoporous silica (OMS) carrier is supported with an active material comprising at least one member selected from the group consisting of nickel, nickel-lanthanum and nickel-lanthanum-cerium, and is in a pellet form. comprises a C ₁ to C ₅ catalyst for steam reforming of a low carbon alcohols, and the reaction unit comprises a reactor for performing steam reforming reaction of the mixture; the steam reforming reaction of the C ₁ to a low-carbon alcohols, C ₅ containing It provides a hydrogen gas generating device through.

In addition, the present invention

Provided is a fuel cell electric production system including a hydrogen gas generating apparatus and a fuel cell through the steam reforming reaction of the C ₁ to C ₅ low carbon alcohol.

Furthermore, the present invention

In the hydrogen gas generating method through the steam reforming reaction of the C1 to C5 low carbon alcohol using the hydrogen gas generating device through the steam reforming reaction of the low carbon alcohol of C ₁ to C ₅ ,

First preheating the raw material comprising C ₁ to C ₅ low carbon alcohol;

Preheating the water to produce water vapor;

Mixing a raw material and water vapor including the C ₁ to C ₅ low carbon alcohol generated above to produce a mixture, and continuously introducing the mixture into a reactor; And

It provides a method for producing hydrogen gas through the steam reforming reaction of C ₁ to C ₅ low carbon alcohol comprising the step of performing a steam reforming reaction of the mixture in the reactor.

The catalyst for steam reforming of the low carbon alcohol according to the present invention is nickel, nickel-lanthanum or nickel on a regular mesoporous silica carrier which has well developed pores and a wide BET specific surface area and maintains a stable structure in a steam reforming reaction environment. By supporting lanthanum-cerium, it is possible to promote the steam reforming reaction to generate high concentration hydrogen gas.

In addition, the hydrogen gas generating apparatus through the steam reforming reaction of the low carbon alcohol according to the present invention can significantly reduce by-products that can occur in the steam reforming reaction to prevent the clogging by the by-products even if the device is operated for a long time, High concentrations of hydrogen can be produced.

Furthermore, the generated hydrogen can be immediately used as fuel of a fuel cell because of its high concentration, and is particularly useful for small-scale fuel cells because the generation of by-products is considerably less.

1 and 2 are schematic diagrams showing a hydrogen gas generating apparatus through a steam reforming reaction;
3 is a schematic diagram schematically showing a method of performing steps 1 and 2 in Examples 1 to 5;
4 and 5 are graphs analyzed through nitrogen adsorption / desorption experiments using the catalysts of Examples 1 to 3 and SBA-15 carriers;
6 is a graph obtained by X-ray diffraction analysis using the catalyst of Examples 1 to 3 and the SBA-15 carrier;
7 is a graph showing the catalytic effect on the steam reforming reaction of ethanol;
8 is a graph showing the total gas generation rate for each catalyst over the operation time of the hydrogen generating device in the steam reforming reaction of ethanol;
9 to 11 are graphs showing the catalytic effect on the steam reforming reaction of glycerol;
12 is a graph showing the effect of the catalyst on the total gas generation rate in the steam reforming reaction of glycerol according to the operating time.

The present invention

An ordered mesoporous silica (OMS) carrier is supported with an active material comprising at least one member selected from the group consisting of nickel, nickel-lanthanum and nickel-lanthanum-cerium, and is in a pellet form. Provided is a catalyst for the steam reforming reaction of C ₁ to C ₅ low carbon alcohols.

Hereinafter, the catalyst for steam reforming of C ₁ to C ₅ low carbon alcohol according to the present invention will be described in detail.

The catalyst provided in one aspect of the present invention is a catalyst for the steam reforming reaction of C ₁ to C ₅ low carbon alcohol, high concentration through the steam reforming reaction in a low carbon alcohol, such as ethanol, glycerol obtained from renewable resources such as biomass Can produce hydrogen.

Specifically, the regular mesoporous silica according to the present invention serves as a carrier in the catalyst for steam reforming of the low carbon alcohol. Mesoporous silica not only has a high surface area, but also has molded mesopores to produce high concentrations of hydrogen, and is useful as a catalyst carrier because it maintains a stable structure in a steam reforming reaction environment.

At this time, the regular mesoporous silica carrier may use SBA (Santa Barbara) series. One specific example may be an SBA-15 carrier.

In addition, the regular mesoporous silica carrier is preferably used having an average pore size of 1 nm to 50 nm, more preferably may be used having an average pore size of 2 nm to 10 nm, 3 nm to 8 nm may be used. If the average pore size of the silica is less than 1 nm, the structural stability of the catalyst is lowered during the reaction, the reaction activity is quickly dropped to the area of the fine pores, and it is difficult to handle in heterogeneous catalyst process, and the average pore size of the silica is If more than 50 nm there is a problem that the activity of the catalyst is reduced because the surface area is small.

Furthermore, the regular mesoporous silica carrier may be used having a surface area of 100 m ² / g to 1500 m ² / g, may be used 200 m ² / g to 1,000 m ² / g, 600 m ² / g to 900 m ² / g can be used. When the surface area of the silica is less than 100 m ² / g, there is a problem that the catalyst activity is lowered, the catalyst dispersion is lowered, and when the surface area of the silica exceeds 1,500 m ² / g, there is a problem that the structural stability of the catalyst itself is lowered.

In addition, the active material according to the present invention includes at least one of nickel (Ni), nickel-lanthanum (Ni-La) and nickel-lanthanum-cerium (Ni-La-Ce). The catalyst for the steam reforming reaction of the low carbon alcohol according to the present invention may use a single metal nickel as the active material, nickel and lanthanum may be used, and nickel, lanthanum and cerium may be used. Among the low carbon alcohols, the unit reaction between monohydric alcohols such as methanol and ethanol and polyhydric alcohols such as glycerol may be different. At this time, in the present invention, by applying an active material containing at least one of nickel (Ni), nickel-lanthanum (Ni-La) and nickel-lanthanum-cerium (Ni-La-Ce) to each reactant of high concentration Hydrogen can be produced.

The content of nickel (Ni) in the active material is preferably 10 wt% to 30 wt% with respect to the total catalyst, may be 10 wt% to 20 wt%, and may be 10 wt% to 15 wt%. When the content of nickel in the active material is less than 10% by weight, it is difficult to produce high concentration hydrogen, and when it exceeds 30% by weight, the increase in catalytic activity is lowered compared to the supported metal content, which is not preferable because of economic efficiency.

The content of lanthanum (La) in the active material is preferably 5 wt% to 10 wt% with respect to the total catalyst, 5 wt% to 8 wt%, and 5 wt% to 6 wt%.

The content of cerium in the active material is preferably 5 wt% to 10 wt% with respect to the total catalyst, 5 wt% to 8 wt%, and may be 5 wt% to 6 wt%.

Furthermore, the catalyst for steam reforming of the low carbon alcohol according to the present invention is preferably in the form of pellets. Generally, a catalyst in powder form is applied, but the present invention proposes a catalyst in pellet form. By using a catalyst shaped into pellets, it can be applied to a continuous reactor to produce high concentrations of hydrogen.

In addition, the present invention

Preparing a ordered mesoporous silica (OMS) carrier;

Spraying a solution containing a metal precursor as an active material onto the prepared regular mesoporous silica carrier to support the active material; And

It provides a method for producing a catalyst for steam reforming reaction of the C ₁ to C ₅ low carbon alcohol comprising the step of forming a regular mesoporous silica carrier carrying the active material into a pellet form.

Hereinafter, a method for preparing a catalyst for steam reforming of C ₁ to C ₅ low carbon alcohol according to the present invention will be described in detail for each step.

First, a method for preparing a catalyst for steam reforming reaction of C ₁ to C ₅ low carbon alcohol includes preparing a regular mesoporous silica (OMS) carrier.

Specifically, the regular mesoporous silica carrier may be prepared using P-123, which is a Pluronic polymer, and tetraethyl orthosilicate (TEOS) as precursors.

In this case, the regular mesoporous silica carrier prepared above may be SBA (Santa Barbara) series, and as a specific example, may be SBA-15 carrier.

In addition, the regular mesoporous silica carrier is preferably used having an average pore size of 1 nm to 50 nm, more preferably may be used having an average pore size of 2 nm to 10 nm, 3 nm to 8 nm may be used. If the average pore size of the silica is less than 1 nm, the structural stability of the catalyst is lowered during the reaction, the reaction activity is quickly dropped to the area of the fine pores, and it is difficult to handle in heterogeneous catalyst process, and the average pore size of the silica is If more than 50 nm there is a problem that the activity of the catalyst is reduced because the surface area is small.

Furthermore, the regular mesoporous silica carrier may be used having a surface area of 100 m ² / g to 1500 m ² / g, may be used 200 m ² / g to 1,000 m ² / g, 600 m ² / g to 900 m ² / g can be used. When the surface area of the silica is less than 100 m ² / g, there is a problem that the catalyst activity is lowered, the catalyst dispersion is lowered, and when the surface area of the silica exceeds 1,500 m ² / g, there is a problem that the structural stability of the catalyst itself is lowered.

Next, the method for preparing a catalyst for steam reforming of C ₁ to C ₅ low carbon alcohol according to the present invention is to spray a solution containing a metal precursor as the active material to the prepared regular mesoporous silica carrier to support the active material. It comprises the step of.

Various methods exist for supporting the active material on a regular mesoporous silica carrier, but the initial wetting method was used in the present invention. The prepared carrier is sprayed with a solution containing a metal precursor to support the active material.

In this case, the metal precursor may be a metal salt containing at least one metal cation among nickel, lanthanum and cerium. The metal salt comprises a metal cation and an anion, the anion is nitrate, hydroxide, acetate, propionate, acetylacetonate, 2,2, 6,6-tetramethyl-3,5-heptanedionate (2,2,6,6-tetramethyl-3,5-heptanedionate), methoxide, secondary-butoxide, 3 Tea-butoxide, n-propoxide, i-propoxide, i-propoxide, ethoxide, phosphate, alkylphosphate, perfer May be at least one of anions such as chlorite, sulfate, alkylsulfonate, phenoxide, bromide, iodide, and chloride; The metal salt may be a hydrate.

The supporting of the active material may be repeatedly performed to support one active material of nickel, nickel-lanthanum and nickel-lanthanum-cerium as the active material. As a specific example, first, nickel may be supported on a silica carrier using a nickel precursor containing a nickel cation to prepare a catalyst on which a nickel metal is supported as an active material, and then nickel may be formed using a lanthanum precursor containing a lanthanum cation. Lanthanum may be supported on the supported silica carrier to prepare a catalyst on which nickel-lanthanum metal is supported as an active material. Then, cerium is deposited on a nickel-lanthanum-supported silica carrier using a cerium precursor containing a cerium cation. It can be supported to prepare a catalyst on which nickel-lanthanum-cerium metal is supported as an active material.

The supporting of the active material may further include spraying a solution containing a metal precursor as an active material on regular mesoporous silica carriers, mixing and drying the carriers. Can be.

The carrier may be mixed such that the injected solution penetrates well into the carrier pores. The drying may be carried out at a temperature range of 80 ℃ to 120 ℃ or a temperature range of 90 ℃ to 110 ℃ at atmospheric pressure.

Further, after performing the step of supporting the active material may include the step of firing at a temperature of 500 ℃ to 700 ℃. The firing may be carried out at a temperature of 550 ℃ to 700 ℃, it may be carried out at a temperature of 600 ℃ to 650 ℃.

In addition, the content of nickel (Ni) in the active material is preferably 10 wt% to 30 wt% with respect to the total catalyst, may be 10 wt% to 20 wt%, may be 10 wt% to 15 wt%. . When the content of nickel in the active material is less than 10% by weight, it is difficult to produce high concentration hydrogen, and when it exceeds 30% by weight, the increase in catalytic activity is lowered compared to the supported metal content, which is not preferable because of economic efficiency.

The content of lanthanum (La) in the active material is preferably 5 wt% to 10 wt% with respect to the total catalyst, 5 wt% to 8 wt%, and 5 wt% to 6 wt%.

The content of cerium in the active material is preferably 5 wt% to 10 wt% with respect to the total catalyst, 5 wt% to 8 wt%, and may be 5 wt% to 6 wt%.

Next, a method for preparing a catalyst for steam reforming reaction of C ₁ to C ₅ low carbon alcohols includes molding a regular mesoporous silica carrier carrying an active substance into pellets.

Through the above steps, a catalyst in powder form is formed. At this time, the method for producing a catalyst for the steam reforming reaction of a low carbon alcohol according to the present invention includes the step of molding the catalyst in powder form into pellets, and finally applying the catalyst shaped into pellets to a continuous reactor in a high concentration of hydrogen Can produce

Specifically, the step of forming the regular mesoporous silica carrier carrying the active material into pellets may be performed by mixing the regular mesoporous silica carrier carrying the active material, the binder, and water, followed by compression molding. have.

The binder may use a mixture of methyl cellulose and ammonium zirconium carbonate.

The mixing may be a mixture of 10% to 15% by weight of methyl cellulose and 18% to 22% by weight of ammonium zirconium carbonate as a binder relative to 1 g of the regular mesoporous silica carrier on which the active material is loaded, and water is 247% by weight. To 337 weight percent. As a specific example, the water is preferably used 337% by weight when the nickel metal is supported by the active material, and 247% by weight when the nickel-lanthanum-cerium metal is supported by the active material. For example, when 10 g of the carrier is used, 1.38 g (13.8 wt%) of methyl cellulose, 2.08 g (20.8 wt%) of ammonium zirconium carbonate and 33.7 g (337 wt%) of water can be used.

Further, after performing the compression molding, it may further comprise the step of firing at a temperature of 500 ℃ to 700 ℃. The firing may be performed in an air atmosphere.

In addition, the present invention

A raw material chamber including a raw material chamber including a C ₁ to C ₅ low carbon alcohol and a first preheater for preheating (first preheating) the raw material; And

An ordered mesoporous silica (OMS) carrier is supported with an active material comprising at least one member selected from the group consisting of nickel, nickel-lanthanum and nickel-lanthanum-cerium, and is in a pellet form. comprises a C ₁ to C ₅ catalyst for steam reforming of a low carbon alcohols, and the reaction unit comprises a reactor for performing steam reforming reaction of the mixture; the steam reforming reaction of the C ₁ to a low-carbon alcohols, C ₅ containing It provides a hydrogen gas generating device through.

Hereinafter, an apparatus for generating hydrogen gas through steam reforming of C ₁ to C ₅ low carbon alcohol according to the present invention will be described in detail with reference to FIGS. 1 and 2.

The hydrogen gas generating device 101 largely includes a raw material supply unit 200 and a reaction unit 500.

First, the raw material supply unit 200 for the steam reforming reaction includes a raw material chamber 220 including a raw material containing C ₁ to C ₅ low carbon alcohol, and a first pump 240 for applying pressure to the raw material from the raw material chamber. ), And a first preheater 260 for preheating the raw material.

In this case, the raw material may include C ₁ to C ₅ low carbon alcohol, may be ethanol, glycerol, etc., the alcohol may be derived from biomass.

In addition, the hydrogen gas generating device 101, a steam supply unit 300 for steam reforming reaction including a water chamber 320 and a second preheater 360 for preheating (second preheating) the water; And a mixing unit 400 for generating a mixture of raw material and water vapor including C ₁ to C ₅ low carbon alcohol through the raw material supply unit 200 and the steam supply unit 300.

The steam reforming reaction steam supply unit 300 may include a water chamber 320, a second pump 340 which applies pressure to water from the water chamber 320, and a preheating water to generate steam. Two preheaters 360.

In this case, the second preheating through the second preheater 360 may be higher than the first preheating through the first preheater 260.

For example, the first preheating may be performed at about 200 ° C to about 500 ° C, and preferably at about 250 ° C to about 300 ° C. If the first preheating is performed at less than 200 ° C., the steam reforming reaction of the low carbon alcohol does not occur smoothly in a subsequent process, so that the amount of hydrogen gas may be lowered. When the temperature is higher than 500 ° C., the carbonization of the low carbon alcohol is performed. This can increase the occurrence of by-products such as tar or char. When the generation of the by-products increases, a process for generating hydrogen gas may not proceed smoothly by causing a blockage of the reactor 520 of the apparatus.

In contrast, the second preheating may be performed at about 600 ° C. to about 800 ° C., and preferably at about 650 ° C. to about 750 ° C. If the second preheating is performed at less than 600 ° C., the steam reforming reaction of the low carbon alcohol does not occur smoothly in a later step, so that the hydrogen gas production rate may be lowered. Carbonization can result in increased by-products such as tar or char. When the generation of the by-products increases, a process for generating hydrogen gas may not proceed smoothly by causing a blockage of the reactor 520 of the apparatus.

The mixing unit 400 generates a mixture of raw material and water vapor containing low carbon alcohol through the steam reforming reaction raw material supply unit 200 and the steam supply unit 300, the mixture is continuously to the reaction unit 500 Supplied. The mixing unit 400 may include a pipe connector 420, and the reaction unit 500 includes a reactor 520 for performing steam reforming of the mixture.

At this time, after preheating and mixing the raw material and the water vapor at different temperatures, and supplying them to the reactor 520, it is possible to minimize the generation of by-products that may occur in the preheating of the raw material. That is, the raw material is first preheated to about 200 ° C to about 500 ° C and then mixed with high temperature water vapor of about 600 ° C or more and immediately put into the reactor by the length of the tube between the mixing unit 400 and the reaction unit 500 By minimizing the amount of by-products before the mixture is introduced into the reaction unit 500 can be significantly reduced. The byproduct is mainly produced by carbonization of the low carbon alcohol raw material, and the higher the temperature, the higher the amount produced. Therefore, the preheating temperature of the organic material raw material is limited to 500 ° C. or less. Thus, the temperature before the mixture is introduced into the reaction unit 500 may be about 250 ℃ to about 500 ℃, but is not limited thereto.

In addition, the pressure before being introduced into the reaction part 500 of the mixture may be atmospheric pressure, but is not limited thereto. When the pressure is higher than the normal pressure, a clogging phenomenon may occur due to byproducts in the reactor 520, and the pressure may be increased.

In this case, the reactor 520 is supported on the ordered mesoporous silica (OMS) carrier active material containing at least one selected from the group consisting of nickel, nickel-lanthanum and nickel-lanthanum-cerium And a catalyst for steam reforming reaction of low carbon alcohol, characterized in that the pellet form. Since the catalyst is as described above, a detailed description thereof will be omitted below.

In addition, the reactor 520 may be a fixed bed reactor or a fluidized bed reactor, but is not limited thereto. However, when the reactor 520 is a fixed bed reactor, generally, clogging of the reactor by by-products occurs more frequently than the fluidized bed reactor. In this case, the by-products are significantly less generated, and thus the blocking by the by-products can be prevented.

At this time, the temperature of the mixture discharged from the reactor 520 may be about 500 ℃ to about 750 ℃, but is not limited thereto. The temperature rise of the mixture after the reaction in the reactor 520 may be, but is not limited thereto, as the temperature is increased by the steam reforming reaction.

The hydrogen gas generating device is for a fuel cell, and the hydrogen generated by the device can be used as a fuel of a fuel cell.

The hydrogen gas generating device 101 may further include a cooling unit 600 and a separation unit 700 after the reaction unit 500, but is not limited thereto.

In this case, the cooling unit 600 may be connected to the reaction unit 500 and may include a cooler 620. The cooler 620 may cool the hot product discharged through the reactor 520 of the reaction part 500.

For example, the cooler 620 may cool the temperature of the product to less than about 20 ℃, but is not limited thereto.

In addition, the separator 700 may be connected to the cooling unit 600, and the separator 700 may include a separator 720 and a flow meter 740. The separator 720 is for phase separation of the product material discharged through the cooling unit 600, the phase separation may be a liquid-phase separation. In this case, when the phase separation is liquid-gas separation, the gaseous substance (gas) may pass through the flow meter 740 to measure the amount of gas generated per hour.

Furthermore, the present invention

Provided is a fuel cell electric production system including a hydrogen gas generating apparatus and a fuel cell through the steam reforming reaction of the C ₁ to C ₅ low carbon alcohol.

Hereinafter, the fuel cell electric system according to the present invention will be described in detail.

Specifically, fuel cells are electrochemical devices that directly convert the chemical energy of a fuel into electrical energy, potentially providing a clean and very efficient source of electrical vehicle power. The fuel cell may be a solid oxide fuel cell, but is not limited thereto.

The fuel cell produces electricity and water by reacting hydrogen and oxygen as a counter reaction to water electrolysis. Therefore, it is important to produce a high concentration of hydrogen for use as fuel in the fuel cell.

Therefore, in the present invention, by connecting the hydrogen gas generating device and the fuel cell through the steam reforming reaction, the hydrogen generated in the device can be immediately supplied as fuel to the fuel cell. In this case, the reaction unit 500 may be directly supplied to the fuel cell without passing through the cooling unit 600, and since the hydrogen generated in the apparatus is high in concentration, a more efficient fuel cell electric system may be configured.

Furthermore, the present invention

As the C ₁ to the hydrogen gas generation method using the hydrogen gas generator through the steam reforming reaction of the low-carbon alcohols, C ₅ through the steam reforming reaction of the low-carbon alcohols, C ₁ to C _5,

First preheating the raw material comprising C ₁ to C ₅ low carbon alcohol;

Preheating the water to produce water vapor;

Mixing a raw material and water vapor including the C ₁ to C ₅ low carbon alcohol generated above to produce a mixture, and continuously introducing the mixture into a reactor; And

It provides a method for producing hydrogen gas through the steam reforming reaction of C ₁ to C ₅ low carbon alcohol comprising the step of performing a steam reforming reaction of the mixture in the reactor.

First, the C ₁ to the hydrogen gas generated through a steam reforming method of the low carbon alcohols, C ₅ according to the invention comprises a first pre-heating the raw material including a low-carbon alcohols, C ₁ to C _5.

In this step, the steam reforming reaction may be easily proceeded by preheating the raw material including the low carbon alcohol.

Specifically, the raw material may include low carbon alcohol of C ₁ to C ₅ , may be ethanol, glycerol, and the like, and the alcohol may be derived from biomass.

Next, the hydrogen gas production method through the steam reforming reaction of the C ₁ to C ₅ low carbon alcohol according to the present invention includes the step of preheating the water to produce steam.

In this step, water is steamed by preheating the second water, and the steam reforming reaction can be easily performed through the preheating.

In this case, the second preheating may be performed through a second preheater, and the second preheating may be hotter than the first preheating through the first preheater.

For example, the first preheating may be performed at about 200 ° C to about 500 ° C, and preferably at about 250 ° C to about 300 ° C. If the first preheating is performed at less than 200 ° C., the steam reforming reaction of the raw material containing the low carbon alcohol may not occur smoothly in a subsequent process, so that the amount of hydrogen gas may be reduced. Carbonization of can lead to increased generation of by-products such as tar or char. When the generation of by-products increases, a process for generating hydrogen gas may not proceed smoothly by causing a blockage of the reactor.

In contrast, the second preheating may be performed at about 600 ° C. to about 800 ° C., and preferably at about 650 ° C. to about 750 ° C. If the second preheating is performed at less than 600 ° C., the steam reforming reaction of the raw material containing the low carbon alcohol may not occur smoothly in a later step, so that the hydrogen gas production amount may be lowered. The carbonization of the raw material can cause an increase in by-products such as tar or char. When the generation of by-products increases, a process for generating hydrogen gas may not proceed smoothly by causing a blockage of the reactor.

Next, the hydrogen gas generation method through the steam reforming reaction of the C ₁ to C ₅ low carbon alcohol according to the present invention by mixing the raw material and water containing the C ₁ to C ₅ low carbon alcohol produced in the above step to prepare a mixture Producing and continuously introducing the mixture into the reactor.

Specifically, by preheating and mixing the raw material and the water vapor containing the low-carbon alcohol, respectively, at a different temperature, it is possible to minimize the generation of by-products that may occur in the preheating of the raw material by supplying to the reactor. That is, the raw material is first preheated to about 200 ° C to about 500 ° C and then mixed with high temperature water vapor of about 600 ° C or more and immediately introduced into the reactor to minimize the length of the tube between the mixing part and the reaction part to the mixture. The generation of by-products can be significantly reduced before entering the reaction section. The by-product is mainly produced by carbonization of the raw material, and the higher the temperature, the higher the amount produced. Therefore, the preheating temperature of the said raw material is restrict | limited to 500 degrees C or less. Thus, the temperature before the mixture is introduced into the reactor may be about 250 ℃ to about 500 ℃, but is not limited thereto.

In addition, the pressure before being introduced into the reaction part 500 of the mixture may be atmospheric pressure, but is not limited thereto. When the pressure is higher than the normal pressure, a clogging phenomenon may occur due to byproducts in the reactor 520, and the pressure may be increased.

Next, the hydrogen gas generation method through the steam reforming reaction of the C ₁ to C ₅ low carbon alcohol according to the present invention is a step of performing a steam reforming reaction of the mixture in the reactor.

Specifically, the reactor is loaded with an active material comprising at least one selected from the group consisting of nickel, nickel-lanthanum and nickel-lanthanum-cement on a regular mesoporous silica (OMS) carrier, and pellets And a catalyst for steam reforming reaction of low carbon alcohol, characterized in that form. The catalyst may be reduced in a hydrogen atmosphere for at least 6 hours, preferably at least 8 hours, 8 hours to 24 hours at a temperature of 600 ° C to 700 ° C immediately after hydrogen generation after the reactor.

In addition, the reactor may be a fixed bed reactor or a fluidized bed reactor, but is not limited thereto. However, when the reactor is a fixed bed reactor, generally, clogging of the reactor by the by-products occurs more frequently than the fluidized bed reactor. In this case, by-product generation is significantly less, and thus the clogging by the by-products can be prevented.

At this time, the temperature of the mixture discharged from the reactor may be about 500 ℃ to about 750 ℃, but is not limited thereto. The temperature rise of the mixture after the reaction in the reactor may be, but is not limited thereto, as the temperature is increased by the steam reforming reaction.

The hydrogen gas generated through the above steps may be used as fuel of the fuel cell.

In addition, the hydrogen gas generation method through the steam reforming reaction of the low carbon alcohol, the step of performing the steam reforming reaction, the step of cooling the resulting material through the steam reforming reaction of the mixture and the step, It may further comprise the step of separating the product.

Specifically, by performing the steam reforming reaction, a high temperature, high pressure product may be produced. The product may be introduced into a cooler to cool the temperature of the product to less than about 20 ° C., but is not limited thereto.

Subsequently, the product cooled by the cooling step may include two or more phases, and may be introduced into a separator to cause phase separation of the product. In this case, the phase separation may be a liquid-phase separation, in which case the liquid material may be discharged to the bottom of the separator and the gas phase material (gas) may be discharged to the top of the separator. In this case, the gaseous substance may include hydrogen.

Hereinafter, it will be described in more detail through Examples and Experimental Examples of the present invention.

However, the following Examples and Experimental Examples are only illustrative of the present invention, and the content of the present invention is not limited by the following Examples and Experimental Examples.

< Example  1> SBA -15 On the carrier  Nickel Supported  Preparation of the catalyst

Step 1: The precursor P123 is mixed with distilled water at a temperature of 40 ° C., dissolved by adding a small amount of dilute hydrochloric acid, mixed for 24 hours with the addition of TEOS, and then dried for 48 hours at a temperature of 100 ° C. to evaporate moisture. . The solid obtained by drying was calcined at a temperature of 500 ° C. for 6 hours to prepare SBA-15 carrier as a regular mesoporous silica carrier.

Step 2: Ni (NO ₃ ) ₂ .6H ₂ O as a Ni precursor was dissolved in distilled water to prepare a Ni precursor solution, and then evenly sprayed onto the SBA-15 carrier prepared in powder form, and the carriers were mixed well for 20 to 30 minutes Allow the sprayed solution to penetrate inside the support pores. This process was continued until the Ni precursor solution was consumed completely. Thereafter, the mixture was completely dried at a temperature of 100 ° C. and atmospheric pressure, and finally calcined for 6 hours at a temperature of 650 ° C. and an air atmosphere to support nickel on the SBA-15 carrier. At this time, the nickel was supported 10 wt%, the manufacturing process of the step 1 and step 2 is shown in FIG.

Step 3: The catalyst in which the nickel was supported on the SBA-15 carrier prepared in step 2 was molded into pellets because it was difficult to use it in a continuous reactor in powder form. First, a powdered catalyst, a binder, and distilled water are mixed to form a dough. The mixing ratio of catalyst, binder, and water was 13.8 wt% of methyl cellulose binder, 20.8 wt% of ammonium zironium (IV) carbonnate solution binder, and 337 wt% of water. The dough was placed in a compression molding apparatus or extrudator, compressed and molded into pellets of a predetermined size, dried at 105 ° C., and then calcined again at 650 ° C. in an air atmosphere to finally prepare a catalyst for steam reforming reaction of low carbon alcohol.

The catalyst was maintained at the maximum activity by reducing treatment in a hydrogen atmosphere at a temperature of 650 ° C. for at least 8 hours while being charged to the reactor immediately before the steam reforming experiment.

< Example  2> SBA -15 On the carrier  Nickel-lanthanum Supported  Preparation of the catalyst

Step 1: The precursor P123 is mixed with distilled water at a temperature of 40 ° C., dissolved by adding a small amount of dilute hydrochloric acid, mixed for 24 hours with the addition of TEOS, and then dried for 48 hours at a temperature of 100 ° C. to evaporate moisture. . The solid obtained by drying was calcined at a temperature of 500 ° C. for 6 hours to prepare SBA-15 carrier as a regular mesoporous silica carrier.

Step 2: Ni (NO ₃ ) ₂ .6H ₂ O as a Ni precursor was dissolved in distilled water to prepare a Ni precursor solution, and then evenly sprayed onto the SBA-15 carrier prepared in powder form, and the carriers were mixed well for 20 to 30 minutes Allow the sprayed solution to penetrate inside the support pores. This process was continued until the Ni precursor solution was consumed completely. Subsequently, completely dried at a temperature of 100 ° C. and atmospheric pressure, La (NO ₃ ) ₂ .6H ₂ O was dissolved in distilled water with La precursor to prepare a La precursor solution, and then evenly sprayed on the carrier. Mix well and allow the sprayed solution to penetrate inside the support pores. This process was continued until the La precursor solution was consumed completely. Thereafter, the mixture was completely dried at a temperature of 105 ° C. and atmospheric pressure, and finally calcined for 6 hours at a temperature of 650 ° C. and an air atmosphere to support nickel-lanthanum on the SBA-15 carrier. At this time, the nickel was supported by 10 wt%, lanthanum was supported by 5 wt%.

Step 3: The catalyst in which nickel-lanthanum was supported on the SBA-15 carrier prepared in step 2 was molded into pellets because it was difficult to use a continuous reactor in powder form. First, a powdered catalyst, a binder, and distilled water are mixed to form a dough. The mixing ratio of catalyst, binder, and water was 13.8 wt% of methyl cellulose binder, 20.8 wt% of ammonium zironium (IV) carbonnate solution binder, and 315 wt% of water. The dough was placed in a compression molding apparatus or extrudator, compressed and molded into pellets of a predetermined size, dried at 105 ° C., and then calcined again at 650 ° C. in an air atmosphere to finally prepare a catalyst for steam reforming reaction of low carbon alcohol.

The catalyst was maintained at the maximum activity by reducing treatment in a hydrogen atmosphere at a temperature of 650 ° C. for at least 8 hours while being charged to the reactor immediately before the steam reforming experiment.

< Example  3> SBA -15 On the carrier  Nickel-lanthanum-cerium Supported  Preparation of the catalyst

Step 1: The precursor P123 is mixed with distilled water at a temperature of 40 ° C., dissolved by adding a small amount of dilute hydrochloric acid, mixed for 24 hours with the addition of TEOS, and then dried for 48 hours at a temperature of 100 ° C. to evaporate moisture. . The solid obtained by drying was calcined at a temperature of 500 ° C. for 6 hours to prepare SBA-15 carrier as a regular mesoporous silica carrier.

Step 2: Ni (NO ₃ ) ₂ .6H ₂ O as a Ni precursor was dissolved in distilled water to prepare a Ni precursor solution, and then evenly sprayed onto the SBA-15 carrier prepared in powder form, and the carriers were mixed well for 20 to 30 minutes Allow the sprayed solution to penetrate inside the support pores. This process was continued until the Ni precursor solution was consumed completely. Subsequently, completely dried at a temperature of 100 ° C. and atmospheric pressure, La (NO ₃ ) ₂ .6H ₂ O was dissolved in distilled water with La precursor to prepare a La precursor solution, and then evenly sprayed on the carrier. Mix well and allow the sprayed solution to penetrate inside the support pores. This process was continued until the La precursor solution was consumed completely. Then, completely dried at a temperature of 105 ℃ and atmospheric pressure, Ce (NO ₃ ) ₂ ㆍ 6H ₂ O with Ce precursor dissolved in distilled water to prepare a Ce precursor solution and then evenly sprayed on the carrier and the carriers for 20-30 minutes Mix well and allow the sprayed solution to penetrate inside the support pores. This process was continued until the Ce precursor solution was consumed completely. Thereafter, the mixture was completely dried at a temperature of 105 ° C. and atmospheric pressure, and finally calcined for 6 hours at a temperature of 650 ° C. and an air atmosphere to support nickel-lanthanum-cerium on the SBA-15 carrier. At this time, the nickel was supported 10 wt%, lanthanum was supported 5 wt%, cerium was supported 5 wt%.

Step 3: The catalyst in which the nickel-lanthanum-cerium was supported on the SBA-15 carrier prepared in step 2 was hardly filled into a continuous reactor in powder form, and thus formed into pellets. First, a powdered catalyst, a binder, and distilled water are mixed to form a dough. The mixing ratio of catalyst, binder, and water was 13.8 wt% of methyl cellulose binder, 20.8 wt% of ammonium zironium (IV) carbonnate solution binder, and 247 wt% of water. The dough was placed in a compression molding apparatus or extrudator, compressed and molded into pellets of a predetermined size, dried at 105 ° C., and then calcined again at 650 ° C. in an air atmosphere to finally prepare a catalyst for steam reforming reaction of low carbon alcohol.

The catalyst was maintained at the maximum activity by reducing treatment in a hydrogen atmosphere at a temperature of 650 ° C. for at least 8 hours while being charged to the reactor immediately before the steam reforming experiment.

< Example  4> KIT-6 On the carrier  Nickel-lanthanum Supported  Preparation of the catalyst

A catalyst for steam reforming of low carbon alcohol was prepared in the same manner as in Example 2, except that the KIT-6 carrier other than the SBA-15 carrier was prepared and used.

< Example  5> KIT-6 On the carrier  Nickel-lanthanum-cerium Supported  Preparation of the catalyst

A catalyst for steam reforming of low carbon alcohol was prepared in the same manner as in Example 3, except that the KIT-6 carrier other than the SBA-15 carrier was prepared and used in Example 3.

< Experimental Example  1> Catalytic Characterization

In order to confirm the characteristics of the catalyst for the steam reforming reaction of the low carbon alcohol according to the present invention, the surface area characteristics were analyzed by nitrogen adsorption / desorption experiments using the Examples 1 to 3 and the SBA-15 carrier, and the results are shown in FIG. 4, FIG. 5 and Table 1 below. In addition, X-ray diffraction analysis (XRD) was performed using Examples 1 to 3 and SBA-15 carrier, and the results are shown in FIG. 6.

BET specific surface area
(m ² / g) Pore volume
(cm ³ / g) Average pore diameter
(nm) SBA-15 825.46 1.062 5.15 Example 1
(10Ni / SBA-15) 530.65 0.705 5.31 Example 2
(10Ni-5La / SBA-15) 562.60 0.758 5.39 Example 3
(10Ni-5La-5Ce / SBA-15) 451.91 0.517 4.57

As shown in Figures 4, 5 and Table 1, the catalysts of Examples 1 to 3 exhibited well developed mesopore adsorption / desorption behavior. The SBA-15 carrier had a high BET specific surface area of about 825 m ² / g as well as a mesoporous region with an average pore diameter of 5.15 nm. The catalyst having 10 wt% Ni on SBA-15 support (Example 1, 10Ni / SBA-15) had a BET specific surface area of 530 m ² / g, which was lower than that of SBA-15 but had an average pore diameter of 5.31 nm. Mesopoa areas were maintained. Catalysts carrying 10 wt% Ni and 5 wt% La on SBA-15 carrier (Example 2, 10Ni-5La / SBA-15) showed similar surface area characteristics as Example 1, and 10 wt on SBA-15 carrier Catalysts carrying% Ni, 5 wt% La and 5 wt% Ce (Example 3, 10Ni-5La-5Ce / SBA-15) showed lower BET surface areas than the catalysts of Examples 1 and 2 above. . This is because the catalysts partially trapped the micropores while adsorbing into the SBA-15 pores.

In addition, as shown in FIG. 6, the hard silica (SiO ₂ ) crystals and active substances of SBA-15 were added to both the completed catalyst after firing (left graph of FIG. 6) and the catalyst after reduction firing (right graph of FIG. 6). I could see that it was well supported.

< Experimental Example  2> Steam reforming reaction experiment analysis

1. Experimental Materials

Ethanol and glycerol (purity> 99%) were used as low carbon alcohols for the steam reforming reaction. These alcohols were mixed with distilled water in stoichiometric ratios to prepare reactants. The catalyst prepared in Examples 1 to 5 was used as the catalyst.

2. Experiment apparatus and method

Steam reforming reaction experiments were performed using the hydrogen production apparatus 101 shown in FIG. 1. The apparatus 101 includes a raw material supply unit 200 including a first preheater 260, a reaction unit 500 and a cooling unit 600 including a reactor 520 including the catalyst of Examples 1-5. And a separator 700.

Raw material input was performed using a reciprocating pump (Waters 515). The first preheater was operated at 550 ° C., at 450 ° C. at the reactor inlet and at 650 ° C. at the reactor outlet. The reactor was made of SS316 SML tubes and the catalyst fill volume was 21.3 mL. The product leaving the reactor was cooled to 20 ° C. or lower in a cooling section (condenser), and then separated into a gas phase and a liquid product in a separation section (G-L separator). The separated gas product was passed through a gas flow meter to measure the amount of production per hour. A gas sample was taken from the gas line between the gas-liquid separator and the gas flow meter to analyze its composition. The separated liquid effluent was also recovered and analyzed for the flow rate and the degree of gasification.

3. Analysis method

The product gas was sampled between the gas-liquid separator and the wet test meter of the hydrogen generating device and analyzed using gas chromatograph (GC, Agilent, DS Scientific iGC7200). Hydrogen, carbon monoxide, methane, and carbon dioxide of the produced gas were quantitatively analyzed using a thermal conductivity detector (TCD), and C _{2+ and} higher hydrocarbons and other gases using a flame ionization detector (FID). An analytical column was used Caroxen-1000 packed column. The carrier gas was a gas in which 8 vol% of hydrogen was mixed with helium. Quantitative analysis was determined by a calibration curve prepared for each gas component using a standard gas.

The preheating temperature of the reactant and water, the reactor inlet and outlet temperature and pressure were collected and stored at 5 second intervals through the data logger and used to set the operating conditions by monitoring the change over the reaction time.

4. Result Analysis

(1) Steam Reforming of Ethanol

The catalytic effect on the steam reforming reaction of ethanol in low carbon alcohol is shown in FIG. 7. The reaction material was prepared by mixing ethanol with distilled water in the stoichiometric ratio of Scheme 1 below, wherein the ethanol concentration was 46 wt%.

<Scheme 1>

C ₂ H ₅ OH + 3H ₂ O-> 2CO ₂ + 6H ₂

The reactant input rates were WHSV 20.3h ^-1 and 46.7h ^-1 . Here, the weight hourly spave velocity (WHSV) is defined as the amount of metal catalyst charged to the reactor (g / h) mass flow rate of ethanol.

As shown in FIG. 7, in Example 1 (IW-NS), Example 2 (IW-NLS), and Example 3 (IW-NLCS), a catalyst including an SBA-15 carrier was used. IW-NLK) and Example 5 (IW-NLCK) showed a higher concentration of hydrogen in the synthesis gas than in the case of using a catalyst containing a KIT-6 carrier. The highest hydrogen yield is 64.5 mol%, using the catalyst of Example 2. This corresponds to 86% of the theoretical maximum of 75 mol%. As the WHSV increased, the hydrogen concentration of syngas tended to decrease somewhat. Other gases carbon monoxide, carbon dioxide, methane was produced, C ₂ or more hydrocarbons is not substantially generated. The catalyst supported on KIT-6 showed a relatively high methane production rate. Therefore, it can be confirmed that the SBA-15 carrier is a suitable catalyst carrier for steam reforming of ethanol.

8 shows the total gas generation rate for each catalyst according to the operation time of the hydrogen generating device in the steam reforming reaction of ethanol in low carbon alcohol.

As shown in FIG. 8, the total gas generation rate was highest when the catalyst of Example 2 was used, and the total gas generation rate was lowest when the catalyst of Example 1 was used. When the catalyst of Example 3 was used, the hydrogen concentration in the generated gas was lower than when the catalyst of Example 1 was used (see FIG. 7), but the total gas generation rate was higher. This is the result of all gasification of ethanol by Ce inhibiting the coking reaction which is the main side reaction in ethanol steam reforming reaction. On the other hand, in the case of using the catalyst of Examples 4 and 5, it was confirmed that the total gas generation rate is significantly lower than when using the catalyst of Examples 1 to 3.

(2) Steam Reforming of Glycerol

The catalytic effect on the steam reforming reaction of glycerol in low carbon alcohol is shown in FIGS. 9-11. The reaction material was prepared by mixing glycerol in distilled water in a stoichiometric ratio of the following scheme 2 wherein the ethanol concentration is 63 wt%.

<Scheme 2>

C ₃ H ₅ (OH) ₃ + 3H ₂ O-> 3CO ₂ + 7H ₂

Reactant dosing rate was performed at WHSV 7.9h ⁻¹ to 37.8h ⁻¹ . Here, the weight hourly spave velocity (WHSV) is defined as the amount of metal catalyst charged to the reactor (g / h) mass flow rate of ethanol.

As shown in FIG. 9, the lower the WHSV, the higher the hydrogen concentration in the generated gas, but the effect of the WHSV on the hydrogen concentration in the range of 9.45 to 37.8h ⁻¹ was not significant. Other gases produced carbon monoxide, carbon dioxide, and methane. Due to the very low content of methane, it can be said that the methanation reaction of hydrogen produced on the catalyst of Example 1 occurred very limitedly. Synthetic gas having a composition produced using the catalyst of Example 1 (composition of FIG. 9) can be used as a fuel such as a solid oxide fuel cell (SOFC) or a gas turbine without any special treatment. The liquid effluent from steam reforming was colorless and transparent, mostly water.

In addition, as shown in Figure 10, WHSV can be confirmed that there is no significant effect on the composition gas composition in the range of 8.4 to 33.6h ^-1 . Unlike ethanol, in the case of glycerol, when lanthanum (La) was added as an active material to the catalyst (Example 2), the concentration of hydrogen in the generated gas was slightly lower. As a result, it is possible that the steam reforming of glycerol proceeds in a rather complicated reaction pathway compared to ethanol, and side reactions such as coking are activated in the process. The liquid phase effluent of the reactor was slightly yellow in WHSV 33.6h ^-1 , which appears to be an intermediate of the coking reaction. Glycerol can be said to have a rather complicated steam reforming reaction path than ethanol.

Furthermore, as shown in FIG. 11, in the case of using the catalyst of Example 3, unlike in the case of ethanol, the concentration of hydrogen in the generated gas was hardly reduced as compared with the case of using the catalyst of Example 1. Especially high WHSV (about 31.5h ^-1 ) was confirmed that the amount of hydrogen produced more than when using the catalyst of Example 1. Through this, various side reactions may be more likely to occur in the steam reforming of the polyhydric alcohol having a high molecular weight, and it may be said that the steam reforming reaction by the Ni catalyst is more actively progressed by inhibiting side reactions such as coking as Ce. The liquid effluent obtained in this reaction was colorless and transparent, confirming again that the catalyst of Example 3 was a more effective catalyst for the steam reforming reaction of glycerol than the catalyst of Example 2.

The catalytic effect on the total gas evolution rate in the steam reforming reaction of glycerol in low carbon alcohol is shown in the graph of FIG.

As shown in FIG. 12, at WHSV of 7.9h ⁻¹ and 15.8h ⁻¹ , almost similar total gas evolution rates were obtained with three catalysts (Examples 1 to 3). However, in the WHSV of 31.5h ⁻¹ , the catalyst of Example 1 and the catalyst of Example 3 showed almost the same total gas generation rate, but the catalyst of Example 2 showed a relatively low total gas generation rate. These results are different from the results of steam reforming of ethanol, which may be due to the different unit reactions occurring during steam reforming depending on the type of reactants.

Through this, it was possible to confirm the characteristics of the catalyst according to the present invention. Specifically, using a SBA-15 carrier as a regular mesoporous silica carrier and the active material of Ni, Ni-La or Ni-La-Ce by the initial wet method By supporting, it was confirmed that excellent activity in the steam reforming reaction.

Further, in the steam reforming reaction of ethanol, it is more preferable to apply Ni-La or Ni-La-Ce as the active substance, and in the steam reforming reaction of glycerol, it is more preferable to apply Ni or Ni-La-Ce as the active substance. Could confirm.

101: hydrogen gas generator
110: supercritical water gasifier
200: raw material supply
220: organic material raw material chamber
240: first pump
260: first preheater
300: steam supply
320: water chamber
340: second pump
360: second preheater
400: mixing part
420: connector
500: reaction part
520: reactor
600: cooling unit
620: cooler
640: after pressure controller
700: separation
720: separator
740: flow meter

Claims (20)

An ordered mesoporous silica (OMS) carrier is supported with an active material comprising at least one member selected from the group consisting of nickel, nickel-lanthanum and nickel-lanthanum-cerium, and is in a pellet form. A catalyst for steam reforming of C ₁ to C ₅ low carbon alcohols.
The method of claim 1,
The regular mesoporous silica carrier is SBA (Santa Barbara), the catalyst for steam reforming reaction of C ₁ to C ₅ low carbon alcohol.
The method of claim 1,
The content of nickel in the active material is a catalyst for steam reforming reaction of C ₁ to C ₅ low carbon alcohol, characterized in that 10 wt% to 30 wt% with respect to the total catalyst.
The method of claim 1,
The content of lanthanum in the active material is a catalyst for steam reforming of C ₁ to C ₅ low carbon alcohol, characterized in that 5 to 10% by weight based on the total catalyst.
The method of claim 1,
The content of cerium in the active material is a catalyst for steam reforming reaction of C ₁ to C ₅ low carbon alcohol, characterized in that 5 wt% to 10 wt% with respect to the total catalyst.
Preparing a ordered mesoporous silica (OMS) carrier;
Spraying a solution containing a metal precursor as an active material onto the prepared regular mesoporous silica carrier to support the active material; And
A method of preparing a catalyst for steam reforming of C ₁ to C ₅ low carbon alcohols according to claim 1, comprising the step of forming a regular mesoporous silica carrier carrying an active substance into pellets.
The method of claim 6,
The supporting of the active material may include spraying a solution containing a metal precursor as an active material onto regular mesoporous silica carriers, mixing and drying the carriers, and then steaming C ₁ to C ₅ low carbon alcohol. Method for producing a catalyst for reforming reaction.
The method of claim 6,
The step of supporting the active material is repeatedly carried out by the nickel, nickel in the active material-lanthanum and nickel-lanthanum-low-carbon of that of supporting the one active substance selected from the group consisting of cerium, characterized in C ₁ to C ₅ Method for producing a catalyst for steam reforming reaction of alcohol.
The method of claim 6,
The C ₁ to C production method of the ₅ catalyst for the steam reforming reaction of the low-carbon alcohols are C ₁ to C _5, comprising the step of calcining at a temperature of 500 ℃ to 700 ℃ after performing the step of supporting the active material A method for producing a catalyst for steam reforming reaction of low carbon alcohols.
The method of claim 6,
Forming the regular mesoporous silica carrier carrying the active material into a pellet form,
Method for producing a catalyst for steam reforming reaction of C ₁ to C ₅ low carbon alcohol, characterized in that the compression is carried out after mixing the regular mesoporous silica carrier, the binder and water on which the active material is supported.
The method of claim 10,
After performing the compression molding, the method of producing a catalyst for steam reforming reaction of C ₁ to C ₅ low carbon alcohol further comprising the step of firing at a temperature of 500 ℃ to 700 ℃.
A raw material chamber including a raw material chamber including a C ₁ to C ₅ low carbon alcohol and a first preheater for preheating (first preheating) the raw material; And
An ordered mesoporous silica (OMS) carrier is supported with an active material comprising at least one member selected from the group consisting of nickel, nickel-lanthanum and nickel-lanthanum-cerium, and is in a pellet form. comprises a C ₁ to C ₅ catalyst for steam reforming of a low carbon alcohols, and the reaction unit comprises a reactor for performing steam reforming reaction of the mixture; the steam reforming reaction of the C ₁ to a low-carbon alcohols, C ₅ containing Hydrogen gas generating device through.
The method of claim 12,
The hydrogen gas generating device,
A steam supply unit for steam reforming reaction including a water chamber and a second preheater for preheating (second preheating) the water; And
Hydrogen gas generation through the steam reforming reaction of the C ₁ to C ₅ low carbon alcohol comprising a; mixing section for producing a mixture of the raw material and steam containing a low carbon alcohol of C ₁ to C ₅ through the raw material supply and steam supply Device.
The method of claim 13,
The first preheating is carried out at a temperature of 200 ℃ to 500 ℃, the second preheating is carried out at a temperature of 600 ℃ to 800 ℃ hydrogen through the steam reforming reaction of C ₁ to C ₅ low carbon alcohol Gas generating device.
The method of claim 12,
The reactor is a hydrogen gas generating device through the steam reforming reaction of C ₁ to C ₅ low carbon alcohol, characterized in that the fixed bed reactor or fluidized bed reactor.
The method of claim 12,
The hydrogen gas generating device,
Hydrogen gas generating device through the steam reforming reaction of C ₁ to C ₅ low carbon alcohol further comprising a cooling unit connected to the reactor.
The method of claim 16,
The hydrogen gas generating device,
Hydrogen gas generating device through the steam reforming reaction of C ₁ to C ₅ low carbon alcohol further comprising a separator connected to the cooling unit.
The method of claim 12,
The C ₁ to the hydrogen gas generator is a hydrogen gas generator through the steam reforming reaction of the low-carbon alcohols, C ₁ to C _5, characterized in that the fuel of the fuel cell generation accepted through the steam reforming reaction of the low-carbon alcohols, C _5.
A fuel cell electric production system including a hydrogen gas generating device and a fuel cell through steam reforming of C ₁ to C ₅ low carbon alcohols of claim 13.
To claim 13 C ₁ to the hydrogen gas generated through a steam reforming method of the low carbon alcohols, C ₁ to C ₅ using the hydrogen gas generator through the steam reforming reaction of the low-carbon alcohols, C _5,
First preheating the raw material comprising C ₁ to C ₅ low carbon alcohol;
Preheating the water to produce water vapor;
Mixing a raw material and water vapor including the C ₁ to C ₅ low carbon alcohol generated above to produce a mixture, and continuously introducing the mixture into a reactor; And
Steam reforming method of the C ₁ to C ₅ low carbon alcohol comprising the step of performing a steam reforming reaction of the mixture in the reactor.

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