KR102039045B1 - Methanol steam reforming catalysts, preparation method thereof, and methanol reforming apparatus comprising the same - Google Patents

Abstract

The present invention relates to a methanol steam reforming catalyst. The present invention includes a first catalyst adsorbed on the ceramic felt and a second catalyst adsorbed on the ceramic felt, wherein the second catalyst is different from the first catalyst, and the weight of the first catalyst adsorbed on the ceramic felt It is characterized in that it is larger than the weight of the second catalyst adsorbed on the felt.

Description

Methanol steam reforming catalyst, preparation method thereof and methanol steam reforming apparatus including same {METHANOL STEAM REFORMING CATALYSTS, PREPARATION METHOD THEREOF, AND METHANOL REFORMING APPARATUS COMPRISING THE SAME}

The present invention relates to a methanol steam reforming catalyst for submarines, and more particularly, to a submarine reforming catalyst for generating hydrogen supplied to a fuel cell of a submarine.

In general, submarines are divided into a diesel engine, a secondary battery, and nuclear power. Here, in the case of a submarine using a diesel engine and a secondary battery, it is necessary to snorkel to rise to sea level every certain time in order to recharge the secondary battery discharged during underwater navigation.

As snorkeling of such submarines causes a problem of lowering the confidentiality of the submarine, a system called Air Independent Propulsion (AIP) has recently been applied to satisfy a submersion, that is, a minimum snorkeling cycle for more time. Doing. There are closed-circuit diesel engines, Stirling engines, fuel cells, and the like. However, fuel cells with relatively high efficiency and quietness are most frequently used in submarines.

On the other hand, the fuel cell system requires hydrogen as a fuel to produce electricity. Hydrogen can be stored and supplied in a vessel using a hydrogen storage alloy, but with the recent technological development, hydrogen is produced and supplied directly in the vessel through a fuel reformer. The fuel reformer method has a higher hydrogen storage density than the conventional hydrogen storage alloy method, and has an advantage of improving submarine operability.

The fuel reformer may produce hydrogen from various hydrocarbon compounds such as liquefied petroleum gas (LPG), liquefied natural gas (LNG), diesel, gasoline, ethanol and methanol.

In particular, methanol has a high yield of hydrogen that can be produced per unit mole, and reforming can occur well at relatively low temperatures. In addition, since methanol has an advantage of easy storage and transportation, it is suitable as a hydrogen source of submarine fuel. Preferably, the methanol steam reforming is endothermic, so heat must be continuously supplied to the catalyst during the reforming reaction. Therefore, while reforming methanol to produce hydrogen, it is possible to increase the efficiency of the fuel reformer when effectively transferring heat generated from an external heat source to the inside of the catalyst.

The technical problem to be solved of the present invention is to improve the heat transfer efficiency inside the methanol steam reforming catalyst.

In addition, in the use of a catalyst having increased efficiency, it is to use a methanol steam reforming catalyst that can improve the operating temperature range of the catalyst without requiring a separate reduction device.

The methanol steam reforming catalyst according to the present invention includes a ceramic felt and a first catalyst and a second catalyst adsorbed on the ceramic felt, and the weight of the first catalyst adsorbed on the ceramic felt is the first adsorbed on the ceramic felt. 2 is greater than the weight of the catalyst.

In some embodiments, the first catalyst may include at least one of copper (Cu), zinc (Zn), nickel (Ni), manganese (Mn), and iron (Fe).

In example embodiments, the second catalyst may include at least one of platinum (Pt), palladium (Pd), and rhodium (Rh).

In an embodiment, the weight per unit volume of the first catalyst decreases from one end of the ceramic felt to the other end, and the weight per unit volume of the second catalyst increases from the one end of the ceramic felt to the other end.

In an exemplary embodiment, only a portion of the first catalyst is adsorbed to a portion of the ceramic felt, and only a portion of the second catalyst is adsorbed to a region different from the portion of the ceramic felt.

In an embodiment, the present invention is a methanol steam reforming catalyst for a fuel cell system or a hydrogen production apparatus used as an air independent propulsion engine in submarines and unmanned underwater systems.

In addition, the method for producing a methanol steam reforming catalyst according to the present invention comprises immersing one end of a ceramic felt in a first mixture in which a first catalyst is dispersed or dissolved to adsorb the first catalyst to the ceramic felt. Drying the ceramic felt to which a catalyst is adsorbed, inverting the ceramic felt and immersing the other end of the ceramic felt opposite to the one end in a second mixture in which a second catalyst is dispersed or dissolved, thereby displacing the second catalyst into the ceramic Adsorbing the felt, drying the ceramic felt to which the second catalyst is adsorbed, and calcining the ceramic felt.

In an embodiment, the region immersed in the first mixture in the step of adsorbing the first catalyst to the ceramic felt is part of the ceramic felt, and the second step in the step of adsorbing the second catalyst to the ceramic felt. Characterized in that it is another part of the ceramic felt which is the area immersed in the mixture.

In some embodiments, the first catalyst may include at least one of copper (Cu), zinc (Zn), nickel (Ni), manganese (Mn), and iron (Fe).

In example embodiments, the second catalyst may include at least one of platinum (Pt), palladium (Pd), and rhodium (Rh).

In some embodiments, the step of adsorbing the first catalyst to the ceramic felt and drying the ceramic felt with the first catalyst adsorbed may include 30 parts by weight of the first catalyst based on 100 parts by weight of the ceramic felt. It is repeated until it is abnormal.

In some embodiments, the adsorbing of the second catalyst to the ceramic felt and drying the ceramic felt to which the second catalyst is adsorbed may be performed in an amount of 1 to 5 based on 100 parts by weight of the ceramic felt. Repeat until parts by weight.

In addition, the methanol steam reforming apparatus according to the present invention comprises a ceramic felt, a methanol steam reforming catalyst including a first and a second catalyst, methanol steam and steam inlet, and the inlet and methanol arranged on one side of the ceramic felt Decomposition products including water vapor, hydrogen generated by the decomposition of the steam is released, and comprises a discharge portion disposed on the other side of the ceramic felt, the second catalyst decomposes methanol steam and steam introduced into the inlet portion To generate hydrogen, and the hydrogen generated by decomposition from the second catalyst activates the first catalyst.

In the methanol steam reforming catalyst according to the present invention, by using a catalyst including a ceramic felt support, heat transfer efficiency inside the methanol reforming catalyst can be improved. Conventional pellet-type catalysts are advantageous in reactant mixing, but the heat transfer efficiency is not good because the heat transfer between the pellets and the pellets occurs in point contact. On the other hand, the monolith type catalyst has better heat transfer than the pellet type, but it is difficult to fix the monolith catalyst in the stainless steel reactor and mix the reactants. Until now, a method of wrapping a monolith catalyst with a heat insulating material and fixing it to a case has been used. However, in view of a steam reformer requiring heat transfer from the outside, it is not a preferred method. Therefore, the present invention can effectively solve the existing problems by using a catalyst containing a ceramic felt support.

In addition, by using a heterogeneous catalyst for supplying hydrogen generated in a second catalyst having excellent catalytic efficiency but not requiring a separate reducing action to a first catalyst requiring a hydrogen reducing action, It does not require a reduction device of, and can be used for all of the different types of catalyst can be widened the operating temperature range of the catalyst. Due to this, the economics of the methanol reforming catalyst can be improved.

1 is a schematic diagram of a methanol steam reforming catalyst according to an embodiment of the present invention.
2A to 2D are schematic diagrams illustrating a manufacturing process of a methanol steam reforming catalyst according to an embodiment of the present invention.
3 is a schematic diagram of a methanol steam reforming apparatus according to another embodiment of the present invention.

Hereinafter, embodiments of the present disclosure will be described in detail with reference to the accompanying drawings, and the same or similar components are denoted by the same reference numerals regardless of the reference numerals, and redundant description thereof will be omitted. In addition, in describing the embodiments disclosed herein, when it is determined that the detailed description of the related known technology may obscure the gist of the embodiments disclosed herein, the detailed description thereof will be omitted. In addition, the accompanying drawings are intended to facilitate understanding of the embodiments disclosed herein, but are not limited to the technical spirit disclosed herein by the accompanying drawings, all changes included in the spirit and scope of the present invention. It should be understood to include equivalents and substitutes.

In describing each drawing, like reference numerals are used for like elements.

Terms including ordinal numbers such as first and second may be used to describe various components, but the components are not limited by the terms. The terms are used only for the purpose of distinguishing one component from another.

Singular expressions include plural expressions unless the context clearly indicates otherwise.

In this application, the terms "comprises" or "having" are intended to indicate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, and one or more other features. It is to be understood that the present disclosure does not exclude the possibility of the presence or the addition of numbers, steps, operations, components, components, or combinations thereof.

Hereinafter, with reference to the accompanying drawings, preferred embodiments of the present invention will be described to be easily carried out by those of ordinary skill in the art. In the following description of the embodiments of the present invention, when it is determined that the detailed description of the related known functions or known configurations may unnecessarily obscure the subject matter of the present invention, the detailed description thereof will be omitted.

Hereinafter, a methanol steam reforming catalyst according to an embodiment of the present invention will be described in detail with reference to the accompanying drawings.

1 is a schematic diagram of a methanol steam reforming catalyst according to an embodiment of the present invention.

Referring to FIG. 1, a methanol steam reforming catalyst 1 according to an embodiment of the present invention includes a ceramic felt 10, a first catalyst 11, and a second catalyst 12.

Methanol steam reforming catalyst (1) aims to supply hydrogen to a fuel cell by generating hydrogen by reforming reaction of methanol and steam. In particular, it is possible to supply hydrogen to the fuel cell of the air unnecessary propulsion system used in submarines.

Specifically, since the methanol steam reforming catalyst 1 generates hydrogen by endothermic reaction, heat must be supplied to the methanol steam reforming catalyst 1 from the outside. In particular, in the limited environment of submarines, unlike general methanol steam reforming catalysts used in commercial water, heat must be supplied to the reformer by indirect heating using saturated steam as a heat medium.

When saturated steam is used as the heat medium, the thermodynamics allow the saturated steam to supply 300 ° C of heat to the methanol steam reforming catalyst 1 when operated at a pressure of 80 bar or more. That is, the temperature of the heat source (saturated water vapor) which is a heat medium is determined by the pressure by thermodynamics. However, since there are limitations in supplying saturated steam above 80 bar in the limited environment of the submarine, the methanol steam reforming catalyst 1 in the submarine is preferably operated at a low temperature of 300 ° C or lower. However, when saturated steam is used as a heat medium, heat transfer may not be performed smoothly because the case thickness of the reformer surrounding the catalyst must be thick. Therefore, in order to improve the efficiency of the catalyst of the methanol steam reformer for submarines, it is important to select a catalyst support capable of transferring heat to the inside of the catalyst as much as possible.

To date, various types of catalysts have been introduced to solve the heat transfer problem of the catalyst itself. The pellet type catalyst is advantageous in reactant mixing, but the heat transfer efficiency is not good because the heat transfer between the pellet and the pellet occurs in point contact. On the other hand, the monolith type catalyst has better heat transfer than the pellet type, but it is difficult to fix the monolith catalyst in the stainless steel reactor and mix the reactants. Until now, a method of wrapping a monolith catalyst with a heat insulating material and fixing it to a case has been used. However, in view of a steam reformer requiring heat transfer from the outside, it is not a preferred method.

Therefore, in the embodiment, in order to efficiently transfer heat to the inside of the catalyst, the heat transfer efficiency may be improved by using the ceramic felt 10 in which the internal tissues are connected to each other. Furthermore, since the catalyst support in the form of a ceramic felt has a slight elasticity, the catalyst support can be in close contact with the case wall so that a separate wrapping insulation is not required. In addition, there is an advantage that the reactant mixing is easier than the monolith catalyst.

In addition, in the embodiment, the gas can be smoothly moved without the difference between the pressure of the methanol vapor and the steam and the methanol vapor, the steam and hydrogen introduced by the structure of the ceramic felt 10 is smooth passage of the gas. There is an advantage.

In an embodiment, methanol vapor may be used by supporting or adsorbing a catalyst containing a metal on the ceramic felt 10. As a method of producing hydrogen from methanol, steam reforming of Chemical Formula 1 is typical, and it consists of a continuous reaction of methanol decomposition of Chemical Formula 2 and water gas shift of Chemical Formula 3.

[Formula 1]

CH ₃ OH + H ₂ O ↔ 3H ₂ + CO ₂ ΔH ⁰ ₂₉₈ = +49.4 kJ / mol

[Formula 2]

CH ₃ OH ↔ CO + 2H ₂ ΔH ⁰ ₂₉₈ = +90.64 kJ / mol

[Formula 3]

CO + H ₂ O ↔ CO ₂ + H ₂ ΔH ⁰ ₂₉₈ = -41.1665 kJ / mol

Methanol steam reforming is mainly used in which a copper (Cu) catalyst having excellent catalyst efficiency is used. However, the copper catalyst has a low thermal stability at a high temperature, and there is a problem that the copper catalyst may serve as a catalyst after the copper catalyst is reduced in a hydrogen atmosphere before the catalytic reaction.

On the other hand, noble metal catalysts such as platinum (Pt), palladium (Pd) and rhodium (Rh) have excellent thermal stability at high temperatures, but relatively high operating temperatures at which hydrogen can be produced. However, there is an advantage that does not need to be reduced by using hydrogen, such as a copper (Cu) catalyst.

The present invention does not have a separate hydrogen atmosphere reduction apparatus, and can provide a catalyst capable of reforming methanol steam as well as extend the operating temperature range of the catalyst. That is, it does not require a separate reduction device for the initial use of the methanol reforming catalyst, it can be used both of the heterogeneous catalyst can be extended the operating temperature range of the catalyst.

To this end, the methanol steam reforming catalyst according to an embodiment of the present invention is for a fuel cell system or a hydrogen production apparatus used as an air independent propulsion engine in submarines and unmanned underwater systems. ), The first catalyst 11 and the second catalyst 12 adsorbed on the ceramic felt 10 may be included. The ceramic felt 10 has a porosity of 90% or more, and methanol steam and steam can pass through the ceramic felt 10 to be smoothly connected to the first catalyst 11 and the second catalyst 12. In addition, the ceramic felt 10 may be made of alumina or zirconia and may be a material on which a catalyst may be supported or adsorbed.

In detail, the first catalyst 11 includes copper (Cu), zinc (Zn), nickel (Ni), manganese (Mn), and iron (Fe), which may generate hydrogen by reforming methanol at a temperature of 300 ° C. or lower. It may include at least one. Preferably it may be a catalyst containing copper (Cu) or zinc (Zn). Since the first catalyst 11 is transferred in a form combined with oxygen immediately after synthesis, a reduction operation for removing oxygen is required to perform a catalyst role. This requires the supply of a reducing agent such as hydrogen. Furthermore, the activated first catalyst 11 may serve as a catalyst for decomposing methanol vapor into hydrogen. Reducing hydrogen required for the initial use of the first catalyst 11 may be hydrogen produced by the reforming reaction of methanol and steam reactants of the second catalyst 12 described later.

In addition, the second catalyst 12 is a catalyst capable of producing hydrogen by methanol and steam reforming without being reduced by hydrogen, and may include platinum (Pt), palladium (Pd), and rhodium (Rh). That is, the first catalyst 11 and the second catalyst 12 are different catalysts, and hydrogen generated by the second catalyst 12 from the methanol and steam reforming reaction is supplied to the first catalyst 11 to supply the first catalyst. The catalyst 11 can be reduced.

The second catalyst 12 is essential for activating the first catalyst 11, but since the catalytic reaction of most of the methanol vapor occurs in the first catalyst 11 having excellent catalyst efficiency, the weight of the first catalyst 11 It is more efficient that silver is larger than the weight of the second catalyst. Specifically, the first catalyst 11 may be 30 parts by weight or more based on 100 parts by weight of the ceramic felt, and the second catalyst 12 may be 1 to 5 parts by weight based on 100 parts by weight of the ceramic felt.

In detail, the first catalyst 11 may reduce the weight per unit volume of the ceramic felt 10 from one end to the other end of the ceramic felt 10. On the other hand, the second catalyst 12 may increase in weight per unit volume of the ceramic felt 10 from one end to the other end of the ceramic felt 10.

In addition, only a portion of the first catalyst 11 may be adsorbed to the partial region A of the ceramic felt 10, and only a portion of the second catalyst 12 may be adsorbed to the other region B of the ceramic felt 10. In detail, in some regions A of the ceramic felt 10, the first catalyst 11 having the same weight per unit volume may be supported. In another region B of the ceramic felt 10, the second catalyst 12 having the same weight per unit volume may be supported. In addition, another region C between the partial region A and the other region B may be supported by mixing the first catalyst 11 and the second catalyst 12.

Looking at the supporting of the first catalyst 11 in detail, the first region (a) and the first region of the first catalyst to which the first catalyst 11 is adsorbed at the same weight per unit volume of the ceramic felt 10 ends The arrangement from the region to the other end may be divided into the second region a 'of the first catalyst. In detail, the amount of the first catalyst 11 adsorbed by the concentration gradient of the first catalyst 11 is generated in the second region a 'of the first catalyst from one end to the other end due to the osmotic pressure caused by the ceramic support. This can be reduced. The first region a of the first catalyst may be formed from one end of the ceramic felt 10 to the other end up to 80% of the total length.

On the other hand, the adsorption of the second catalyst 12 is once in the region where the first region (b) and the first region of the second catalyst in which the second catalyst 12 is adsorbed at the same weight per unit volume of the ceramic felt 10 end. Therefore, the arrangement may be divided into a second region b ′ of the second catalyst. In detail, the amount of the second catalyst 12 adsorbed by the concentration gradient of the second catalyst 12 is generated in the second area b 'of the second catalyst from one end to the other by the osmotic pressure caused by the ceramic support. This can be reduced. That is, the amount of the second catalyst 12 adsorbed from one end to the other end may increase. The first region (b) of the second catalyst may be formed from the other end of the ceramic felt 10 to one end up to 20% of the total length.

Furthermore, the methanol steam reforming catalyst 1 may include a first catalyst 11 and a second catalyst 22 having different use temperature ranges of the catalyst, thereby widening the use temperature range of the catalyst.

2A to 2D are schematic diagrams illustrating a manufacturing process of a methanol reforming catalyst according to an embodiment of the present invention.

2A to 2D, a first step of immersing one end of a ceramic felt in a first mixture in which a first catalyst is dispersed or dissolved to adsorb the first catalyst to the ceramic felt (see FIG. 2A), wherein A second step of drying the ceramic felt in which the first catalyst is adsorbed in the first step (see FIG. 2B), the second catalyst is dispersed in the other end opposite to the one end by inverting the ceramic felt dried in the second step. Or a third step (see FIG. 2C) of adsorbing the second catalyst to the ceramic felt by immersing in the dissolved second mixture, and a fourth step of drying the ceramic felt to which the second catalyst is adsorbed in the third step. A step (see FIG. 2D) and a fifth step (not shown) of calcining the ceramic felt dried in the fourth step at 400 ° C.

Referring to FIG. 2A, in the first step, the ceramic felt 20a may be wound and fixed with copper or stainless steel wire. In addition, the first catalyst 21 is immersed at a height of H _α in the first mixed solution 21s from one surface of the wound ceramic felt 20a, and a vacuum environment is formed in the vacuum chamber for one hour. The first step of adsorbing is carried out.

In addition, the first catalyst 21 of the first mixed solution 21s may include at least one of copper (Cu), zinc (Zn), nickel (Ni), manganese (Mn), and iron (Fe). Preferably it may be a catalyst comprising copper (Cu) or zinc (Zn), more preferably copper nitrate (copper nitrate) and zinc nitrate (zinc nitrate).

Referring to FIG. 2B, a second step of taking out the ceramic felt 20b having the first catalyst 21 adsorbed therein and drying it in a dry oven 24 having a temperature of 110 to 120 ° C. is performed in the first step. The ceramic felt 20b dried in the second step may form a first region α of the first catalyst to which the first catalyst 21 is adsorbed at the same weight per unit volume. In addition, the second region α ′ of the first catalyst is disposed at the other end in the region where the first region α of the first catalyst ends, and the first catalyst 21 is formed due to the osmotic pressure of the first mixture 21s. It can be adsorbed forming a gradient of concentration. In detail, the amount of the first catalyst 21 adsorbed decreases from one end to the other end of the second region α ′ of the first catalyst.

In addition, by measuring the weight of the ceramic felt 20b dried in the second step, the first catalyst 21 to 30 parts by weight or more with respect to 100 parts by weight of the ceramic felt, the first to second Steps can be repeated. When the first catalyst 21 is 30 parts by weight or less per 100 parts by weight of the ceramic felt, the efficiency of methanol steam reforming by the first catalyst 21 may be reduced.

Referring to FIG. 2C, the second mixture 22s is immersed at a height of H _β from the other surface of the ceramic felt 20b in the second step, and a vacuum environment is formed in the vacuum chamber 25 for a second time. A third step of adsorbing the catalyst 22 on the ceramic felt 20b is performed. When manufacturing the ceramic felt 20c in which the second catalyst 22 is adsorbed, the ceramic felt 20b is made in order to make the weight of the second catalyst 22 less than the weight in which the first catalyst 21 is adsorbed. 2 mixed solution (22s) that is height H is immersed _β is preferably lower than the height H of the above described _α. In detail, the second catalyst 22 of the second mixed liquid 22s may include at least one of platinum (Pt), palladium (Pd), and rhodium (Rh). Preferably it may be a catalyst containing platinum (Pt) or palladium (Pd), more preferably platinum nitrate (platium nitrate) or palladium nitrate (palladium nitrate).

Referring to FIG. 2D, a fourth step of taking out the ceramic felt 20c to which the second catalyst 22 is adsorbed in the third step and drying it in a dry oven 26 having a temperature of 110 to 120 ° C. is performed. The ceramic felt 20d dried in the fourth step may form the first region β of the second catalyst on which the second catalyst 22 is adsorbed at the same weight per unit volume. In addition, the second region β 'of the second catalyst is disposed at the other end in the region where the first region β of the second catalyst ends, and the second catalyst 22 is formed due to the osmotic pressure of the second mixture 22s. It can be adsorbed forming a gradient of concentration. In detail, the amount of the second catalyst 22 adsorbed increases from one end to the other end of the second region β 'of the second catalyst.

In addition, by measuring the weight of the ceramic felt dried in the second step, the third to fourth steps are repeated until the second catalyst 22 to 1 to 5 parts by weight based on 100 parts by weight of the ceramic felt Can be. Since the second catalyst 22 is a more expensive catalyst than the first catalyst 21, a small amount may be adsorbed in consideration of economical efficiency. The weight part of the second catalyst 22 may be smaller than the weight of the first catalyst 11 described above. The first catalyst 21 is a catalyst capable of generating hydrogen by reforming methanol at a temperature of 300 ° C. or lower, and thus serves as a catalyst mainly reforming methanol vapor. Thus, a sufficient amount may be adsorbed or supported. In addition, since the second catalyst 22 serves as a catalyst for reforming methanol steam without reduction, generating hydrogen, and supplying hydrogen for reduction to the first catalyst 21, the second catalyst 22 is supported in a smaller amount than the first catalyst 21. Or preferably adsorbed.

3 is a schematic diagram of a methanol steam reforming apparatus 300 according to another embodiment of the present invention.

Referring to FIG. 3, the methanol steam reforming unit includes a methanol steam reforming catalyst 3 including a ceramic felt 30, an inlet part 33 disposed on one side of the ceramic felt so that methanol steam and steam are introduced therein, and the methanol. Steam, and a discharge portion 34 disposed on the other side of the ceramic felt so as to release hydrogen generated by the methanol steam reforming catalyst 3. Specifically, the methanol steam reforming catalyst 3 can be wound and inserted into a tube in the form of a tube. At this time, the ceramic support may be in close contact with the inner diameter of the tube-shaped tube. That is, the ceramic support may be used by cutting the ceramic support so as to be in close contact with the reformer wall.

In addition, in one embodiment, the methanol steam and steam is decomposed by the methanol steam reforming catalyst (3), the methanol steam and the steam introduced through the inlet 33 as shown by the arrow (D) to produce hydrogen, The hydrogen may be released to the discharge section 34. Meanwhile, in another embodiment, the inlet may be disposed at the top and the discharge unit may be disposed at the bottom, depending on the location where the methanol steam reformer 300 is installed.

In detail, the reaction product discharged to the discharge part 34 may include some methanol which is not decomposed, including hydrogen, water, carbon dioxide and carbon monoxide, which are decomposed by the methanol steam reforming catalyst 3.

Further, a second catalyst 32 capable of producing hydrogen from methanol steam is adsorbed to one side of the ceramic felt 30 close to the inlet portion 33 without being reduced by hydrogen. On the other hand, the other side of the ceramic felt close to the discharge portion 34 may be reduced by hydrogen to act as a catalyst, the first catalyst 31 is adsorbed when generating hydrogen by reforming methanol at a temperature below 300 ℃. .

The second catalyst 32 on one side supplied with methanol and steam may produce hydrogen and reduce the first catalyst 31 on the other side. Therefore, since the first catalyst 31 is reduced and activated by hydrogen generated through the second catalyst 32, the methanol steam reforming catalyst 3 can operate efficiently.

In addition, only a portion of the first catalyst 31 may be adsorbed to the partial region A ′ of the ceramic felt 30, and only a second catalyst 32 may be adsorbed to the other region B ′ of the ceramic felt 30. Furthermore, in some areas A ′ of the ceramic felt 30, the first catalyst 31 may have the same weight per unit volume of the ceramic felt 30. In addition, in another region B ′ of the ceramic felt 30, the second catalyst 32 may have the same weight per unit volume of the ceramic felt 30. In addition, the first catalyst 31 and the second catalyst 32 may be mixed and adsorbed in another region C ′ between the partial region A ′ and the other region B ′.

The second catalyst 32 is essential for activating the first catalyst 31, but since the catalytic reaction of most of the methanol vapor occurs in the first catalyst 31 having excellent catalyst efficiency, the weight of the first catalyst 31 is increased. It is more efficient that silver is larger than the weight of the second catalyst. Specifically, the first catalyst 31 may be 30 parts by weight or more based on 100 parts by weight of the ceramic felt, and the second catalyst 32 may be 1 to 5 parts by weight based on 100 parts by weight of the ceramic felt.

That is, one side of the ceramic felt of FIG. 3 corresponds to the other end of the ceramic felt 10 described above in FIG. 1, and the other side of the ceramic felt of FIG. 3 corresponds to one end of the ceramic felt 10 described above in FIG. 1.

In addition, in order for the methanol steam reforming apparatus 300 to operate, heat must be supplied to the methanol steam reforming catalyst 3. The heating unit 35 uses saturated steam of high pressure as a heat source, and receives saturated steam of high pressure through a connection port (not shown) to supply heat of 300 ° C. or lower to the methanol steam reforming catalyst 3.

In detail, the saturated steam gas phase and the liquid phase coexist, and there is a limit to supplying saturated steam of 80 bar or more in the limited environment of the submarine, so that the methanol steam reforming catalyst 3 in the submarine has a temperature of 300 ° C. or less. It is desirable to operate at low temperatures.

It will be apparent to those skilled in the art that the invention may be embodied in other specific forms without departing from the spirit and essential features thereof.

In addition, the above detailed description should not be interpreted as limiting in all aspects and should be considered as illustrative. The scope of the invention should be determined by reasonable interpretation of the appended claims, and all changes within the equivalent scope of the invention are included in the scope of the invention.

Claims (12)

Applied to fuel cell systems or hydrogen production equipment used as Air Independent Propulsion in submarine and underwater unmanned systems.
Wound ceramic felt; And
A first catalyst and a second catalyst adsorbed on the ceramic felt; Including,
The weight of the first catalyst adsorbed on the ceramic felt is greater than the weight of the second catalyst adsorbed on the ceramic felt,
The ceramic felt is formed to have a close contact with the inner diameter of the tube-shaped tube,
The second catalyst is supplied with methanol and steam to produce hydrogen, and the first catalyst is reduced and activated by hydrogen produced from the second catalyst,
The ceramic felt,
Only the first catalyst is adsorbed to a partial region provided at one end,
Methanol steam reforming catalyst, characterized in that only the second catalyst is adsorbed to a region different from the partial region provided at the other end. The method of claim 1,
The first catalyst is a methanol steam reforming catalyst comprising at least one of copper (Cu), zinc (Zn), nickel (Ni), manganese (Mn) and iron (Fe). The method of claim 1,
The second catalyst is a methanol steam reforming catalyst comprising at least one of platinum (Pt), palladium (Pd) and rhodium (Rh). The method of claim 1,
The weight per unit volume of the first catalyst decreases from one end to the other end of the ceramic felt,
Methanol steam reforming catalyst characterized in that the weight per unit volume of the second catalyst increases from the one end to the other end of the ceramic felt. delete delete Applied to fuel cell systems or hydrogen production equipment used as Air Independent Propulsion in submarine and underwater unmanned systems.
Immersing one end of the wound ceramic felt in a first mixture in which the first catalyst is dispersed or dissolved to adsorb the first catalyst to the ceramic felt;
Drying the ceramic felt to which the first catalyst is adsorbed;
Inverting the ceramic felt and immersing the other end of the ceramic felt provided in the opposite direction to the one end in a second mixture in which the second catalyst is dispersed or dissolved to adsorb the second catalyst to the ceramic felt;
Drying the ceramic felt to which the second catalyst is adsorbed; And
Calcination of the ceramic felt; and
The ceramic felt is formed to have a close contact with the inner diameter of the tube-shaped tube,
The second catalyst is supplied with methanol and steam to produce hydrogen,
The first catalyst is reduced and activated by hydrogen produced from the second catalyst,
The ceramic felt,
In the step of adsorbing the first catalyst to the ceramic felt, a part of the ceramic felt is immersed in the first mixture,
Only the first catalyst is adsorbed to a partial region provided at one end,
A method for producing a methanol steam reforming catalyst, wherein only the second catalyst is adsorbed to another region provided at the other end of the ceramic felt opposite to the one end. The method of claim 7, wherein
The first catalyst is a method for producing a methanol steam reforming catalyst comprising at least one of copper (Cu), zinc (Zn), nickel (Ni), manganese (Mn) and iron (Fe). The method of claim 8,
Adsorbing the first catalyst to the ceramic felt and drying the ceramic felt to which the first catalyst is adsorbed until the first catalyst is 30 parts by weight or more based on 100 parts by weight of the ceramic felt Method for producing a methanol steam reforming catalyst, characterized in that it is repeated. The method of claim 7, wherein
The second catalyst is a method for producing a methanol steam reforming catalyst, characterized in that it comprises at least one of platinum (Pt), palladium (Pd) and rhodium (Rh). The method of claim 10,
Adsorbing the second catalyst to the ceramic felt and drying the ceramic felt to which the second catalyst is adsorbed until the second catalyst is 1 to 5 parts by weight based on 100 parts by weight of the ceramic felt. Method for producing a methanol steam reforming catalyst, characterized in that it is repeated. In a methanol steam reforming apparatus applied to a fuel cell system or a hydrogen production apparatus used as an air independent propulsion engine in a submarine and an unmanned underwater system,
Methanol steam reforming catalyst comprising a wound ceramic felt, a first catalyst and a second catalyst;
Methanol steam and steam is introduced, the inlet is disposed on one side of the ceramic felt; And
And a discharge part configured to discharge the reformed product of the methanol steam including hydrogen and disposed on the other side of the ceramic felt.
The ceramic felt is formed to have a close contact with the inner diameter of the tube-shaped tube,
The second catalyst generates hydrogen by decomposing methanol and steam introduced into the inlet,
The hydrogen generated by decomposition from the second catalyst activates the first catalyst
Only the second catalyst is adsorbed to the end of the ceramic felt disposed in the inlet,
Methanol steam reformer, characterized in that only the first catalyst is adsorbed to the end of the ceramic felt disposed in the discharge portion.

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