KR20060106778A - Hydrogen generating apparatus and hydrogen generating method using the hydrogen generating apparatus - Google Patents

Abstract

The present invention includes a unit reaction apparatus including a microchannel in which a combustion catalyst and / or a reforming catalyst are coated to supply hydrogen to a fuel cell system using alcohol such as methanol as a fuel, but with high thermal efficiency and high hydrogen conversion rate. A hydrogen production apparatus designed to produce hydrogen and a method for producing hydrogen using the same, the hydrogen production apparatus according to the present invention includes a plate assembly for combustion including a combustion catalyst and a reforming plate assembly including a reforming catalyst. At least one combustion / modification combined first unit reactor (11), wherein the plate assemblies face a pair of microchannel plates having microchannels formed on one surface thereof. By coupling to each other, For the plate assembly is the reforming plate assembly, comprising a combustion catalyst within the microchannel is characterized in yirueojim including the reforming catalyst within the microchannel.

Hydrogen Production, Reforming Reaction, Miniaturization, Microchannel, Conversion Rate, Reforming Catalyst, Combustion Catalyst

Description

Hydrogen generating apparatus and hydrogen producing method using same {Hydrogen generating apparatus and Hydrogen generating method using the hydrogen generating apparatus}

1 is a schematic diagram schematically showing the overall configuration of a hydrogen production apparatus according to the present invention.

FIG. 2 is an exploded perspective view illustrating the decomposition of a unit reaction apparatus used in the hydrogen production apparatus of FIG. 1.

3 is an exploded photograph of one specific embodiment of a hydrogen production apparatus according to the present invention.

FIG. 4 is an exploded perspective view showing only the plate assemblies constituting the unit reaction device of FIG.

5 is a plan view of a microchannel plate constituting the plate assemblies of FIG.

6 is a plan view of a gasket used in the plate assembly constituting the unit reaction apparatus according to the present invention.

7 is a side cross-sectional view of the plate assembly constituting the unit reaction device of FIG.

※ Explanation of codes for main parts of drawing

11: first unit reactor 12: third unit reactor

13: second unit reactor 14: primary oxidation reactor

15: fourth unit reaction device

21: hydrogen supply source 22: primary oxygen supply source

23: flow path change valve 24: primary fuel supply source

25: second oxygen supply source 26: second fuel supply source

27: raw material supply source 28: third oxygen supply source

* 31: Filter

41: unit reaction device 41´: plate assembly for combustion

41˝: Modified plate assembly 42, 42´: Upper, lower case

43: combustor inlet 43´: combustor outlet

44: reformer inlet 44´: reformer outlet

45, 45´: Microchannel plate 46, 46´: Entrance

47, 47´: Exit 48, 48´: First connector

49, 49´: Second connector

51, 51´: Microchannel 52, 52´: Bulkhead

53, 53´: blocking wall 54, 54´: Converging groove

55, 55´: convergence protrusion

61: gasket 62: opening

63: through hole

71: channel formation space 72: catalyst coating

The present invention relates to a hydrogen production apparatus and a hydrogen production method using the same. More specifically, the present invention includes a unit reaction apparatus including a microchannel in which a combustion catalyst and / or a reforming catalyst are coated to supply hydrogen to a fuel cell system using alcohol such as methanol as fuel, and high thermal efficiency and The present invention relates to a hydrogen production apparatus designed to produce hydrogen at a high hydrogen conversion rate and a hydrogen production method using the same.

Recently, as interest in environmental problems increases, the interest and demand for clean fuels using hydrogen are increasing.

As an alternative to the existing gasoline engine and fossil fuel power generation, research on fuel cells is being actively conducted. In order to increase the utilization of fuel cells, conditions for smooth production and / or supply of hydrogen used as raw materials should be provided. Hydrogen is very difficult to store and handle, as it is the lightest gas and can easily explode in air. Therefore, simply supplying hydrogen using a large capacity hydrogen storage tank and the like is the state of the art to date, such a hydrogen storage tank has the disadvantage that it is difficult to completely solve the above problems, and also the development and development of a large capacity hydrogen storage tank There is a drawback in that initial facility investment is enormous, such as the need to prepare a larger capacity hydrogen storage, etc., and it is a large-scale business that needs to be discussed as a national infrastructure.

Therefore, miniaturization of the hydrogen production apparatus that produces hydrogen to reduce the weight and volume can be said to be very desirable in that hydrogen can be used as a clean fuel without the need for the large-scale equipment investment described above.

In addition, in order to directly supply hydrogen produced from the miniaturized hydrogen production apparatus to a fuel cell, the content of carbon monoxide (CO) that inhibits the activity of the anode of the fuel cell must be reduced to a minimum.

As a method of producing hydrogen from methanol, a methanol steam reforming method has already been developed and widely used.

In order to proceed with the methanol steam reforming reaction, a vaporizer for vaporizing a mixture of methanol and water in a liquid state, a combustor for supplying heat to the reforming reactor, and a vaporizer for vaporizing liquid fuel for combustion are included. There is a separate need for a differential oxidation reactor to lower the concentration of carbon monoxide.

The reaction occurring in steam reforming of methanol is shown in Scheme 1 below.

CH ₃ OH + H ₂ O = CO ₂ + 3H ₂ ΔH = 49.4 kJ / mol (1)

CH ₃ OH = CO + 2H ₂ ΔH = 90.5 kJ / mol (2)

CO + H ₂ O = CO ₂ + H ₂ ΔH = -41.1 kJ / mol (3)

As described above, the methanol steam reforming reaction proceeds partially to reaction (1) of Scheme 1, and reaction (2) of Scheme 1, which is a methanol direct decomposition reaction, occurs partially at a high temperature. Reaction (1) of reaction scheme 1 and reaction (2) of reaction scheme 1 are endothermic reactions, and in order for these reactions to proceed, heat must be continuously supplied from the outside.

Methanol steam reforming is said to proceed optimally at around 300 ° C. If the temperature is higher than this, the direct reaction of methanol direct decomposition reaction and the reaction of (3) above proceeds, and the concentration of carbon monoxide in the product is increased. In order to lower the concentration of carbon monoxide, water-gas shift reaction, which is the reaction (3) of Scheme 1, is required, and therefore, the temperature of the reformer must be maintained accurately to lower the concentration of carbon monoxide in the product.

Republic of Korea Patent No. 0314829 describes a methanol reformer configured in a double tube method to maintain a constant temperature of the reformer. It is configured to arrange the honeycomb combustion catalyst at regular intervals in the inner tube and to carry out the reforming reaction by filling the reforming catalyst in the outer tube. By doing so, the local temperature rise of the reformer was prevented and the temperature was kept constant in the range of 200 to 300 ° C. However, the use of the reactor of such a configuration has a disadvantage in that there is a limit to downsizing the reformer.

Paper J. of Power source, 108 (2002) 21-27, of the Pacific North National Laboratory, describes a small methanol steam reformer that uses methanol simultaneously as a combustion fuel and as a reformate. However, it has a low output of about 200 kPa, and has a disadvantage in that the total thermal efficiency is very low as 5 to 10% due to the large amount of methanol entering the combustor to maintain the reaction temperature.

Therefore, the need for the development of a hydrogen production apparatus capable of producing a large amount of hydrogen while being small in size and high in thermal efficiency and hydrogen in terms of weight and size is still high.

An object of the present invention comprises a unit reaction apparatus including a microchannel in which a combustion catalyst and / or a reforming catalyst is coated to supply hydrogen to a fuel cell system using alcohol such as methanol as fuel, and high thermal efficiency and high hydrogen. It is to provide a hydrogen production apparatus designed to produce hydrogen at a conversion rate and a hydrogen production method using the same.

The hydrogen production apparatus according to the present invention comprises a combustion unit comprising a combustion catalyst and at least one first unit reaction apparatus for both combustion and reforming comprising a reforming plate assembly including a reforming catalyst. Wherein the plate assemblies are configured by coupling a pair of microchannel plates having microchannels formed on a surface of one side to each other such that the microchannels face each other, the plate assembly for combustion being burned in the microchannel. And a catalyst, wherein the reforming plate assembly comprises reforming catalysts in the microchannel.

The hydrogen production apparatus according to the present invention includes at least one combustion / modification combined first unit reactor, at least one second unit reactor for vaporization, and at least one third unit reactor for heat exchange. Wherein, the first unit reactor comprises a combustion plate assembly comprising a combustion catalyst, and the reforming plate assembly comprising a reforming catalyst, the second unit reaction device for the heat exchange plate assembly and the heat exchange A plate assembly, wherein the third unit reactor includes plate assemblies for heat exchange, and the combustion plate assembly of the first unit reactor includes heat exchange plate assemblies of the third unit reactor. Connected to any one of, the other heat exchanger plate assembly of the three unit reactor is connected to the combustion plate assembly of the first unit reactor, and The plate assembly for heat exchange of the second unit reactor is connected to the reforming plate assembly of the first unit reactor.

The hydrogen production method using the hydrogen production apparatus according to the present invention, the first unit reaction of at least one combined combustion / reforming comprising a combustion plate assembly comprising a combustion catalyst and a reforming plate assembly comprising a reforming catalyst And the apparatus, wherein the plate assemblies are configured by coupling a pair of microchannel plates having microchannels formed on a surface of one side thereof so that the microchannels face each other so as to be bonded to each other. Is a combustion catalyst in the microchannels, and the reforming plate assembly is configured to produce hydrogen using a hydrogen production device comprising reforming catalysts in the microchannels. The combustion plate assembly by supplying a gaseous fuel and an oxidant together to the plate assembly for A first combustion step of burning inside and heating the reforming plate assembly adjacent to the combustion plate assembly using the heat; And (2) a reforming step of supplying and reforming the reformed raw material consisting of a mixture of methanol and water to the heated reforming plate assembly to produce hydrogen.

The hydrogen production method using the hydrogen production apparatus according to the present invention includes at least one combustion / reforming combined first unit reactor, at least one second unit reactor for vaporization, and at least one third unit for heat exchange. It comprises a reactor, wherein the first unit reactor comprises a combustion plate assembly comprising a combustion catalyst, and a reforming plate assembly including a reforming catalyst, the second unit reaction device for combustion It comprises a plate assembly and a heat exchange plate assembly, wherein the third unit reactor comprises a plate heat exchanger, the combustion plate assembly of the first unit reactor is the third unit of the reactor Is connected to any one of the heat exchanger plate assembly, the other heat exchanger plate assembly of the three unit reaction apparatus for the combustion of the first unit reaction apparatus In the production of hydrogen using a hydrogen production device is connected to the assembly, the heat exchange plate assembly of the second unit reactor is connected to the reforming plate assembly of the first unit reaction device, (1) A first combustion step of supplying gaseous fuel and oxidant to the combustion plate assembly of the one-unit reactor for combustion; (2) exhausting the exhaust gas discharged from the combustion plate assembly in the first combustion step via any one heat exchanger plate assembly of the third unit reaction device to discharge the third unit reaction device at 80 to 100 ° C. A first preheating step of preheating to a temperature range; (3) A liquid fuel is supplied and vaporized through another heat exchange plate assembly of the third unit reactor to the combustion plate assembly of the first unit reactor, and at the same time, an oxidant is supplied together to burn the fuel. A second combustion step of heating the first unit reactor to 260 to 320 ° C; (3) a third combustion step of heating the second unit reactor to 110 to 200 ° C. by supplying gaseous fuel and an oxidant to the combustion plate assembly of the second unit reactor to burn the fuel; (5) vaporizing the vaporized by passing a mixture of methanol and water as a raw material for reforming through the heat exchanger plate assembly of the second unit reactor and supplying it to the reforming plate assembly of the first unit reactor; And (6) a reforming step of passing the raw material vaporized in the vaporization step through the reforming plate assembly of the first unit reaction device and reforming it with hydrogen.

Hereinafter, with reference to the accompanying drawings, the present invention will be described in detail.

As shown in FIG. 1, the apparatus for producing hydrogen according to the present invention includes at least one combustion / modification combined agent comprising a combustion plate assembly including a combustion catalyst and a reforming plate assembly including a reforming catalyst. 1 unit reaction apparatus 11, wherein the plate assemblies are configured by coupling a pair of microchannel plates having microchannels formed on a surface of one side thereof so that the microchannels face each other and are coupled to each other. The combustion plate assembly includes combustion catalysts in the microchannels, and the reforming plate assembly includes reforming catalysts in the microchannels. Therefore, in the present invention, the heat for reforming can be obtained from the combustion plate assembly positioned adjacent to the reforming plate assembly including the reforming catalyst, thereby allowing the reforming reaction to be carried out at an optimum temperature, thereby increasing the thermal efficiency and hydrogen. One of the features is that it can increase the conversion rate. In addition, the combustor in which the combustion reaction occurs is composed of a combustion plate assembly, and the combustion reaction in the combustion plate assembly is performed in a microchannel, thereby miniaturizing the function of the combustor in the conventional hydrogen generator. The reformer plate assembly is composed of the reforming plate assembly and the reformer in which the reforming reaction takes place, and the reforming reaction in the reforming plate assembly is performed in a microchannel, while performing the function of the reformer in the conventional hydrogen generator. It is characterized by the fact that miniaturization is possible. Furthermore, according to the present invention, as shown in FIG. 2, the combustion unit includes the first unit reactor 11 comprising the combustion plate assembly 41 'and the reforming plate assembly 41'. The assembly 41 'and the reforming plate assembly 41' are alternately positioned and stacked so that the heat of combustion can be utilized in the reforming reaction as much as possible. In the above description, the first expression in the first unit reaction apparatus 11 is for distinguishing and displaying a unit reaction apparatus including both a combustion catalyst and a reforming catalyst. The combustion catalyst is a platinum group element such as platinum, rhodium, ruthenium, osmium, iridium, palladium, gold, silver, copper, or two of them. It may be selected from the group consisting of the above mixture. In particular, the combustion catalyst may be supported on the catalyst support. The supporting of the combustion catalyst is first coated with a catalyst support, and the aqueous solution of the combustion catalyst is added so that the amount of the combustion catalyst is 0.1 to 5% by weight relative to the catalyst support, followed by drying and calcining. The catalyst support may be selected from the group consisting of aluminum oxide, α-aluminum oxide, zirconium oxide (ZrO ₂ ), silica (SiO ₂ ) or a mixture of two or more thereof, preferably α-oxidation Aluminum can be used. However, it is to be understood that the present invention is not limited thereto, and other catalysts that may be used to promote oxidation of hydrocarbons or alcohols may also be used in the present invention.

As the reforming catalyst, a composite of copper / cerium oxide / zirconium oxide (Cu / CeO ₂ / ZrO ₂ ), a composite of copper / zinc oxide / aluminum oxide (Cu / ZnO ₂ / Al ₂ O ₃ ), and copper / cerium oxide / Composite of aluminum oxide (Cu / CeO ₂ / Al ₂ O ₃ ), composite of copper / zirconium oxide / aluminum oxide (Cu / ZrO ₂ / Al ₂ O ₃ ), copper-zinc-aluminum oxide solid solution (solid-solution CuZnAl oxide) and the like, and preferably copper: zinc: aluminum oxide may be synthesized by coprecipitation using a weight ratio of 3 to 5: 3 to 5: 1 to 3. However, the present invention is not limited thereto, and it is naturally understood that other catalysts that may be used to produce hydrogen by reforming hydrocarbons or alcohols may also be used in the present invention.

As shown in FIG. 2, the unit reaction device 41 constituting the first unit reaction device 11 includes cases 42 and 42 ′ formed of two metal blocks. The combustion plate assembly 41 'and the reforming plate assembly 41' are alternately stacked and fixed to each other between 42 and 42 '. The upper case 42 of the cases 42 and 42 ', for example, is formed with a combustion outlet 43' and a reformer outlet 44 ', and the lower case 42' with a combustion inlet 43. And a reformer inlet 44 is formed. However, it is obvious to those skilled in the art that these quotation marks are for reference only and vice versa. However, it is obvious to those skilled in the art that these quotation marks are for reference only and vice versa. 3 shows a photograph taken by partially decomposing one specific example of the unit reaction apparatus. In one example of the actual configuration shown in FIG. 3, the thickness of the microchannel plate 45 was about 0.3 mm, and the depth of the microchannel was formed to be 10 to 150 mu m. Channels are formed on the metal plate in the form of parallelograms, and at each vertex of the metal plate holes are formed to enable the flow of fluid.

As shown in FIGS. 2, 4, and 5, the plate assemblies constituting the unit reactor 41 have a pair of microchannels 51, 51 ′ formed on a surface of one side in common. The microchannel plates 45 and 45 'are configured such that the microchannels 51 and 51' face each other and are coupled to each other, and the combustion plate assembly 41 'is connected to the microchannels ( 51, 51 ') and combustion catalysts, and the reforming plate assembly 41' comprises reforming catalysts in the microchannels 51, 51 '. Both the case and the microchannel plate may be formed of a metal, and preferably, may be formed of a material having excellent corrosion resistance and heat resistance, such as stainless steel. A gasket 61 as illustrated in FIG. 6 may be interposed between the microchannel plates 45 and 45 ′. The gasket 61 may be preferably made of a copper plate, and may include an opening 62 and through holes 63 for forming a predetermined space between the microchannel plates 45 and 45 '. Therefore, the plate assembly, as shown in FIG. 2 as an example, may be formed by stacking two or more of each other, such as a combustion plate assembly 41 'and a reforming plate assembly 41', and, if necessary, That is, the stacking number of the combustion plate assembly 41 ′ and the reforming plate assembly 41 ′ may be increased or decreased according to the amount of hydrogen to be produced. In each of the plate assemblies, as shown in FIG. 7, a plurality of channel forming spaces 71 are formed, and the inner walls of the catalyst coating unit 72 are coated with catalysts such as a catalyst for combustion or a reforming catalyst. Function as.

Among the microchannel plates 45 and 45 ', the upper microchannel plate 45 has one inlet 46 and one outlet 47 in a diagonal direction with respect to each other, as shown in FIGS. 4 and 5. And the first connector 48 and the second connector 49 are also positioned diagonally with respect to each other, and between the inlet 46 and the outlet 47 are connected to the inlet 46 and the outlet 47. It is formed as a groove which is dug to a predetermined depth from the surface, the wall of the groove functions as a barrier wall 53 for restricting the flow direction of fuel or raw material passing through the microchannels (51). The microchannels 51 are separated by the partitions 52 in the groove, and a plurality of the microchannels 51 are formed. Near the inlet 46 and the outlet 47, diffuse fuel or raw materials from these inlets 46 or outlets 47 into the plurality of microchannels 51 or these inlets 46 or outlets 47. Many converging grooves 54 and converging protrusions 55 are formed to restrict the flow of these fuels or raw materials so that fuel or raw materials are collected into the field. The lower microchannel plate 45 'of the microchannel plates 45 and 45' is the same as the upper microchannel plate 45, but has a mirror-symmetrical structure, and therefore, refers to the same reference numeral, And separated by (´).

In addition, as shown in Fig. 2, according to the present invention, at least two or more combustion plate assemblies 41 'and reforming plate assemblies 41' are alternately stacked with respect to each other. The flow of raw materials does not cross each other. Referring to FIG. 2, a portion of the fuel introduced into the combustion inlet 43 of the lower case 42 ′ is connected to the second connector 49 of the first reforming plate assembly 41 ′ located above. After passing through, it enters the inlet 46 of the first combustion plate assembly 41 'and burns while passing through the microchannels inside the first combustion plate assembly 41', and then burns the first combustion plate. After being discharged through the outlet 47 of the assembly 41 ', the second connector 49 and the second combustion plate assembly 41' of the second reforming plate assembly 41 'positioned above it. Passing through the outlet 47 is discharged through the combustor combustor outlet 43 'of the upper case 42. On the other hand, the other part of the fuel flowing into the combustion inlet 43 of the lower case 42 ′ and passed through the second connector 49 of the first reforming plate assembly 41 ′ located above is the first portion. Pass through the inlet 46 of the combustion plate assembly 41 'and the first connector 48 of the second reforming plate assembly 41' to the inlet 46 of the second combustion plate assembly 41 '. After entering and burning while passing through the microchannels inside the second burning plate assembly 41 ', after being discharged through the outlet 47 of the second burning plate assembly 41', the upper case 42 Is discharged through the combustor combustor outlet 43 '. The same applies to the flow of the raw material for the reforming plate assembly 41 ', so that the fuel and the raw material can flow separately from each other.

The combustion plate assembly 41 'of the first unit reactor 11 is connected to the hydrogen supply source 21 and the first oxygen supply source 22 via the combustor inlet 43. The combustion heat is generated by simultaneously supplying hydrogen and supplying an oxidant, preferably oxygen or air, and burning it in the combustion plate assembly 41 ′, and using this to modify the adjacent plate assembly 41. ) To supply heat and to the reforming plate assembly (41) to the raw material supply source (27) to supply a reforming material, which is a mixture of methanol and water for reforming, to convert methanol into hydrogen to produce hydrogen. . Instead of using combustion heat, the reforming plate assembly 41 'of the first unit reactor 11 can generate a reforming reaction by passing a heat fluid therein. It is obvious to those skilled in the art that a thermofluid having such waste heat may be used. In this case, the combustion catalyst may not be included in the combustion plate assembly 41 ′.

As shown in FIG. 1, a third unit reaction device 12 may be further connected to the first unit reaction device 11. The third unit reaction device 12 includes heat exchanger plate assemblies, and the heat exchanger plate assemblies allow the microchannels to face each other with a pair of microchannel plates having microchannels formed on one surface thereof. By combining them with each other. The heat exchanger plate assemblies do not contain any catalysts such as combustion catalysts or reforming catalysts, and only function to allow fluids to pass through the microchannel, thereby allowing heat exchange between fluids passing through adjacent plate assemblies. Except that it can be understood to have the same or similar structure as the burning plate assembly or reforming plate assembly as described above. In the above, the third expression in the third unit reaction device 12 is for distinguishing and displaying unit reaction devices that do not include both the combustion catalyst or the reforming catalyst. The third unit reactor 12 is connected to the combustion plate assembly 41 'of the first unit reactor 11, and the combustion plate assembly 41' of the first unit reactor 11 is carried out. It may be connected to the inlet of any one heat exchange plate assembly of the third unit reactor 12 at the outlet of. Therefore, the exhaust gas discharged from the combustion plate assembly 41 ′ of the first unit reaction device 11 passes through one of the heat exchanger plate assemblies of the third unit reaction device 12 and the other one adjacent thereto. By heating the plate assembly for heat exchange, it becomes possible to heat the fluid passing through the inside. At this time, when the first fuel supply source 24 is circulated to the other heat exchange plate assembly, and the liquid fuel supplied therefrom passes through the other heat exchange plate assembly, the liquid fuel is vaporized. In addition, the vaporized fuel may be connected to the combustion plate assembly 41 ′ of the first unit reaction device 11 to continue the combustion reaction. Thus, during the initial preheating, the first unit reactor 11 and the third unit reactor 12 are operated at a predetermined temperature, for example, using the gaseous fuel. To a temperature range of 320 ° C., and the third unit reaction device 12 is preheated to a temperature range of 80 to 100 ° C., after which the gaseous fuel is shut off and vaporized by the third unit reaction device 12. The spent fuel can be used to continue the reforming reaction while continuing the combustion reaction. This can minimize the use of gaseous fuels, which are inconvenient to handle and store, while operating the miniaturized hydrogen generator, and allow the use of liquid fuel that is easier to handle and store. The liquid fuel may preferably be methanol. The configuration as described above makes it possible to vaporize the liquid fuel using at least the waste heat of the exhaust gas generated from the first unit reactor 11 so that it can be efficiently used as fuel.

The second unit reaction device 13 may be further connected to the first unit reaction device 11.

The second unit reaction device 13 includes a plate assembly for combustion and a plate assembly for heat exchange. The second unit reaction device 13 is connected to the reforming plate assembly 41 'of the first unit reaction device 11, and the outlet of the heat exchange plate assembly of the second unit reaction device is the first unit. It may be connected to the inlet of the reforming plate assembly of the reactor. In the above description, the combustion plate assembly of the second unit reaction device 13 may be understood to have the same or similar configuration as the combustion plate assembly 41 'of the first unit reaction device 11. In addition, the plate assembly for heat exchange of the second unit reactor 13 may be understood to have the same or similar configuration as the plate assembly for heat exchange of the third unit reactor 12. In the above description, the second expression in the second unit reaction device 13 is used to distinguish and display a unit reaction device including only a combustion catalyst. The second unit reactor (13) heats and vaporizes a mixture of methanol and water as raw materials supplied to the first unit reactor (11) to promote the reforming reaction in the first unit reactor (11). Function That is, the hydrogen supply source 21 and the second oxygen supply source 25 are connected to the combustion plate assembly of the second unit reaction device 13 to supply the gaseous fuel and the oxidant together to burn the second fuel as the combustion heat. The heat exchanger plate assembly adjacent to the combustion plate assembly in the unit reaction apparatus 13 is heated, and a raw material source 27 is connected to the heat exchanger plate assembly so that the raw material passes therethrough, so that the mixture of methanol and water as a raw material. It passes through and vaporizes, and the vaporized raw material is supplied to the reforming plate assembly 41 'of the first unit reactor 11 to be reformed. The second unit reaction device 13 may be maintained at a temperature range of, for example, 110 to 200 ° C.

A fourth unit reaction device 15 may be further connected between the second unit reaction device 13 and the first unit reaction device 11. The fourth unit reactor 15 includes plate assemblies for heat exchange. In the above description, the fourth expression in the fourth unit reaction device 15 is for distinguishing and displaying unit reaction devices that do not include both the combustion catalyst or the reforming catalyst. That is, the inlet of the heat exchanger plate assembly of the heat exchanger plate assembly of the fourth unit reactor 15 is connected to the inlet of the combustion plate assembly of the second unit reactor 13, and at the same time A second fuel supply 26, which is a liquid fuel supply source, is connected to an inlet of the heat exchanger plate assembly, and an inlet of the other heat exchanger plate assembly of the fourth unit reactor 15 is connected to the first unit reaction device ( By connecting the outlet of the reforming plate assembly 41 'of 11), the liquid fuel is vaporized using the heat of the product flow discharged therefrom for the combustion of the second unit reactor 13 The plate assembly may be supplied to allow combustion reactions to occur. As a result, the gaseous fuel supplied from the hydrogen supply source 21 can be shut off, and the combustion reaction can be continued by using the fuel vaporized by the fourth unit reactor 15. This can minimize the use of gaseous fuels, which are inconvenient to handle and store, while operating the miniaturized hydrogen generator, and allow the use of liquid fuel that is easier to handle and store. The liquid fuel may preferably be methanol. The configuration as described above makes it possible to vaporize the liquid fuel using at least the waste heat of the product stream generated from the first unit reactor 11 so that it can be efficiently used as fuel.

A primary oxidation reactor 14 may be connected to an outlet of the reforming plate assembly 41 ′ of the first unit reactor 11. The primary oxidation reactor 14 functions to perform a carbon monoxide oxidation reaction to remove carbon monoxide that may be included in hydrogen as a product produced by the first unit reaction apparatus 11 and is produced separately. In the process of supplying hydrogen produced in the hydrogen generating apparatus according to the present invention directly to the fuel cell without refining process, it is possible to directly remove and use carbon monoxide that may affect the electrode of the fuel cell. . The primary oxidation reactor 14 is also used as a plate assembly according to the present invention as described above, and instead of the combustion catalyst of the combustion plate assembly as described above or the reforming catalyst of the reforming plate assembly as described above. It may have the same or similar structure as the plate assembly except that it further comprises a catalyst. The primary oxidation reactor 14 is connected to a third oxygen source 28 for supplying oxygen or air for oxidation of carbon monoxide.

In addition, a filter 31 may be connected between the reforming plate assembly 41 ′ of the first unit reactor 11 and the primary oxidation reactor 14. The filter 31 may be a conventional mechanical filter.

As shown in FIGS. 1 to 7, the hydrogen production apparatus according to the present invention includes at least one combustion / reforming combined first unit reactor 11 and at least one vaporization second unit reactor 13. ) And at least one third unit reactor 12 for heat exchange, wherein the first unit reactor 11 includes a combustion plate assembly 41 ′ comprising a combustion catalyst and a reforming catalyst. A reforming plate assembly (41˝) is included, and the second unit reactor (13) comprises a combustion plate assembly and a heat exchange plate assembly, and the third unit reaction device (12) And plate assembly for heat exchange, wherein the combustion plate assembly 41 ′ of the first unit reactor 11 is disposed on any one of the plate assemblies for heat exchange of the third unit reactor 12. Connected to another heat exchanger of the 3-unit reactor 12 An assembly is connected to the combustion plate assembly 41 ′ of the first unit reactor 11, and the heat exchange plate assembly of the second unit reactor 13 is connected to the first unit reactor 11. It is characterized in that it is made connected to the reforming plate assembly (41˝).

A flow path change valve 23 is connected to the combustion plate assembly 41 ′ of the first unit reactor 11, and a hydrogen supply source 21 is connected to the flow path change valve 23. The flow path changing valve 23 may preferably be a four-way valve, whereby the first plate reactor for combustion of the first unit reactor 11 is used for reducing hydrogen supplied from the hydrogen supply source connected thereto. 41 '), and then to the reforming plate assembly (41') for reduction, and finally supplied to the combustion plate assembly of the second reactor (13) sequentially. Thereby, if the temperature of the first reactor 11 and the third reactor 12 connected thereto by using the hydrogen rises above the boiling point of methanol as fuel, the fuel is replaced by hydrogen to methanol. After raising the temperature of the first reactor 11 to a reduction temperature (about 300 ° C.) by subsequent combustion of methanol, the reforming catalyst in the reforming plate assembly 41 can be reduced by hydrogen. have

According to the configuration as described above, according to the present invention, the reforming reaction is carried out by carrying out the combustion reaction in the combustion plate assembly of the unit reaction apparatus including the microchannel, and placing the reforming plate assembly adjacent thereto. By maintaining a stable operating temperature of the resulting reforming plate assembly can increase the high methanol conversion and the composition of hydrogen in the product, lower the content of carbon monoxide can exhibit high thermal efficiency and high hydrogen productivity, miniaturization, carbon monoxide content Low, it is directly attached to the fuel cell, etc. provides the advantage of supplying hydrogen. In addition, by further removing the carbon monoxide as possible by including a primary oxidation reactor, the fuel cell can be operated without deactivation of the electrode of the fuel cell.

The hydrogen production method using the hydrogen production apparatus according to the present invention, the first unit reaction of at least one combined combustion / reforming comprising a combustion plate assembly comprising a combustion catalyst and a reforming plate assembly comprising a reforming catalyst Device 11, wherein the plate assemblies are configured by coupling a pair of microchannel plates having microchannels formed on a surface of one side with the microchannels facing each other so as to be bonded to each other. The plate assembly includes combustion catalysts in the microchannels, and the reforming plate assembly includes hydrogen in a hydrogen production apparatus including reforming catalysts in the microchannels. The combustion plate assembly 41 'of (11) is supplied with a gaseous fuel and an oxidant together for the combustion. A first combustion step of burning in the plate assembly 41 'and using the heat to heat the reforming plate assembly 41' adjacent to the combustion plate assembly 41 '; And (2) a reforming step of supplying a reformed raw material consisting of a mixture of methanol and water to the heated reforming plate assembly (41˝) to produce hydrogen by reforming. Using the heat of combustion generated in the first combustion step to supply heat to the reforming plate assembly (41), it is possible to perform the reforming reaction using this heat. Therefore, the combustion reaction is carried out in the combustion plate assembly 41 'of the unit reaction apparatus including the microchannel, and the reforming plate assembly 41' is placed adjacent to the stacking element. By maintaining the plate assembly (41˝) at a constant operating temperature range of 260 to 320 ° C., high methanol conversion and hydrogen composition in the product, and carbon monoxide content can be lowered, resulting in high thermal efficiency and high hydrogen productivity. It is characterized by one point. When the temperature of the first unit reactor 11 is less than 260 ° C., there may be a problem in that the conversion rate to hydrogen is lowered due to a low temperature of the reforming reaction. On the contrary, when the temperature exceeds 320 ° C., the content of carbon monoxide in the product This may cause a problem that the concentration of carbon monoxide is not sufficiently lowered even by the subsequent primary oxidation reaction, and the yield of hydrogen is lowered. When the concentration of carbon monoxide becomes relatively high, there may be a problem that hydrogen as a product cannot be directly introduced into a fuel cell material.

Between the first combustion step of (1) and the reforming step of (2), the heat exchanger plate assembly includes a pair of microchannels in which microchannels are formed on a surface of one side. A third unit reactor 12 is connected to the combustion plate assembly 41 ′ of the first unit reactor 11 by coupling the plates to each other so that the microchannels face each other. A first connection step of connecting the inlet of any one heat exchanger plate assembly of the third unit reactor 12 to the outlet of the combustion plate assembly 41 'of the unit reaction device 11; And connecting exhaust gas exhausted from the combustion plate assembly 41 ′ of the first unit reactor 11 to one of the heat exchanger plate assemblies of the third unit reactor 12, and the other heat exchanger. A first vaporization step of vaporizing by supplying a liquid fuel to the plate assembly may further include. The third unit reactor 12 is connected to the first unit reactor 11 by the first connection step, and the liquid fuel is discharged using the exhaust gas discharged from the first unit reactor 11. And vaporize the gas and supply the vaporized fuel to the first unit reactor 11 to be used as fuel to start operation once the third unit reactor is a predetermined temperature, preferably 80 to 100 ° C. When it reaches the temperature range of, the gaseous fuel is no longer used and the liquid fuel can be used to minimize the use of gaseous fuel, which is inconvenient to store and handle, and the liquid fuel which is easier to store and handle. It is characterized in that it can be used. If the temperature of the third unit reaction apparatus is less than 80 ℃, there may be a problem that a sufficient amount of liquid fuel is not vaporized, in practice, the process does not exceed 100 ℃.

Between the first combustion step of (1) and the reforming step of (2), the first unit reaction device 11 includes a second unit reaction device 13 including a combustion plate assembly and a heat exchange plate assembly. Is connected to a reforming plate assembly (41˝), and the outlet of the heat exchanger plate assembly of the second unit reaction device (13) is connected to the reforming plate assembly (41˝) of the first unit reaction device (11). A second connecting step of connecting to the inlet; A gaseous fuel and an oxidant are supplied together to the combustion plate assembly of the second unit reactor 13 to burn in the combustion plate assembly, and the heat exchange plate is adjacent to the combustion plate assembly using the heat. A second combustion step of heating the assembly; A second vaporization step of supplying and reforming a reforming material consisting of a mixture of methanol and water to the heat exchange plate assembly of the second unit reactor 13; And a first supplying step of supplying the reformed raw material vaporized in the second vaporization step to the reforming plate assembly 41 'of the first unit reaction device 11. The second unit reaction device 13 is connected to the first unit reaction device 11 by the second connecting step, and the combustion reaction in the combustion plate assembly of the second unit reaction device 13 is performed. By using the heat of combustion by vaporizing the raw material to be introduced into the first unit reactor 11 to be reformed first so that the reforming reaction can occur smoothly, the thermal efficiency and the conversion rate to hydrogen can be increased.

Between the first combustion step of (1) and the reforming step of (2), a combustion unit of the second unit reaction device 13 includes a fourth unit reaction device 15 including plate assembly for heat exchange. Connected to an assembly, wherein an outlet of the heat exchanger plate assembly of the fourth unit reactor 15 is connected to an inlet of the combustion plate assembly of the second unit reactor 13, and the heat exchanger plate assembly A third connection step of connecting an inlet of the liquid phase to a fuel supply source; The inlet of the other heat exchanger plate assembly of the fourth unit reactor 15 is connected to the outlet of the reforming plate assembly of the first unit reactor 11 and the outlet of the heat exchanger plate assembly is a product collector. A fourth connection step of connecting to the; And a third vaporization step of vaporizing a liquid fuel supplied to the second unit reactor 13 by using the heat of the product stream discharged from the reforming plate assembly of the first unit reactor 11. Can include them. Accordingly, the second unit reaction device 13 reaches a predetermined temperature, preferably a temperature range of 110 to 200 ° C., and the fourth unit reaction device 15 is discharged from the first unit reaction device 11. Operate using gaseous fuel, i.e., hydrogen, until it is sufficiently preheated by the resulting product stream, and after the second unit reactor 13 reaches a predetermined temperature, preferably 1110 to 200 ° C. Supplies a liquid fuel, that is, methanol, to the fourth unit reactor 15, and vaporizes it in the fourth unit reactor 15, and converts the vaporized fuel into the second unit reactor 13. It is possible to minimize the use of gaseous fuel, which is inconvenient to store and handle, and to use liquid fuel, which is easier to store and handle, by supplying it so that it can vaporize liquid fuel without using gaseous fuel anymore. To point There is a characteristic. When the temperature of the third unit reaction apparatus is less than 110 ° C, there may be a problem that a sufficient amount of liquid fuel is not vaporized, and actually does not exceed 200 ° C during process operation.

The hydrogen production method using the hydrogen production apparatus according to the present invention includes at least one combustion / reforming combined first unit reactor, at least one second unit reactor for vaporization, and at least one third unit for heat exchange. A first unit reaction apparatus includes a reforming plate assembly including a reforming catalyst, and a combustion plate assembly including a combustion catalyst, and the second unit reaction apparatus includes a combustion unit. It comprises a plate assembly and a heat exchange plate assembly, the third unit reactor comprises a plate assembly for heat exchange, the combustion plate assembly of the first unit reactor is the third unit reactor Is connected to any one of the heat exchanger plate assemblies, and the other heat exchanger plate assembly of the three unit reactor is used for the combustion of the first unit reactor. In producing hydrogen using a hydrogen production apparatus connected to the assembly, wherein the heat exchange plate assembly of the second unit reactor is connected to the reforming plate assembly of the first unit reactor (1) the first A first combustion step of supplying a gaseous fuel and an oxidant to the combustion plate assembly of the unit reactor for combustion; (2) exhausting the exhaust gas discharged from the combustion plate assembly in the first combustion step via any one heat exchanger plate assembly of the third unit reaction device to discharge the third unit reaction device at 80 to 100 ° C. A first preheating step of preheating to a temperature range; (3) A liquid fuel is supplied and vaporized through another heat exchange plate assembly of the third unit reactor to the combustion plate assembly of the first unit reactor, and at the same time, an oxidant is supplied together to burn the fuel. A second combustion step of heating the first unit reactor to 260 to 320 ° C; (3) a third combustion step of heating the second unit reactor to 110 to 200 ° C. by supplying gaseous fuel and an oxidant to the combustion plate assembly of the second unit reactor to burn the fuel; (5) vaporizing the vaporized by passing a mixture of methanol and water as a raw material for reforming through the heat exchanger plate assembly of the second unit reactor and supplying it to the reforming plate assembly of the first unit reactor; And (6) a reforming step of passing the raw material vaporized in the vaporization step through the reforming plate assembly of the first unit reaction device and reforming it with hydrogen.

The above method may be used as an optimal embodiment in producing hydrogen using the hydrogen production apparatus according to the present invention as described above.

That is, in order to start the reforming reaction, first, a mixed gas of hydrogen and air or oxygen is supplied to the first unit reactor 11 to combust in the combustion plate assembly 41 ′, and the heat generated at this time is exhaust gas and Together with the third unit reactor 12, the exhaust is exhausted, and the third unit reactor 12 is supplied with methanol as a liquid fuel to vaporize the methanol, and then again the first unit reactor 11 Supply it to the furnace to sustain the combustion reaction. Here, when the combustion reaction by methanol is started, hydrogen, which is a gaseous fuel, is stopped, and hydrogen is converted into the second unit reactor 13 together with air or oxygen mixed gas. On the other hand, the combustion reaction is continued by adjusting the injection amount of methanol until the temperature of the first unit reactor (11) reaches 260 to 320 ° C, and when the temperature reaches the temperature, the first unit reactor (11) A reforming reaction is carried out by supplying a mixture of methanol and water as a raw material to the reforming plate assembly 41 ', and a flow of hydrogen, which is a product flow thereof, is supplied to the fourth unit reactor 15. The fourth unit reactor 15 also vaporizes methanol as a liquid fuel and supplies it to the second unit reactor 13. In the second unit reactor 13, the combustion reaction is also performed, and when the temperature reaches 110 to 200 ° C, the operation start step of the hydrogen production apparatus according to the present invention ends, and only methanol, which is a liquid fuel, is continuously used. While the combustion reaction is continued in the first unit reactor 11 and the second unit reactor 13, methanol as a raw material in the reforming plate assembly 41k of the first unit reactor 11 The mixture of water is reformed to produce hydrogen continuously.

Hereinafter, preferred embodiments and comparative examples of the present invention will be described.

The following examples are intended to illustrate the invention and should not be understood as limiting the scope of the invention.

Example  One

The reforming catalyst was synthesized by coprecipitation at a weight ratio of 4/4/2 of copper / zinc / aluminum oxide, and coated in an amount of 0.6 g per microchannel plate of the reforming plate assembly of the first unit reactor. A reforming plate assembly is constructed, and α-aluminum oxide is first coated on the microchannel plate as a combustion catalyst, and the amount of platinum is about 3% by weight relative to α-aluminum oxide, followed by the addition of an aqueous platinum solution, followed by drying and firing. The burned plate assembly was used to construct the burned plate assembly. Six reforming plate assemblies and five combustion plate assemblies are alternately stacked to form the first unit reaction device, and the first unit reaction device is about weak in the state where no primary oxidation reactor is attached. The operation was started by adjusting to 300 ° C., and the reforming reaction was performed. At this time, the mixing ratio of methanol and water as a reforming material was 50:50, the flow rate of the reforming material supplied into the first unit reactor was adjusted to 3 kW / min, and the flow rate of methanol as fuel was 1.1 kW / min. Adjusted to. Under these operating conditions, the time required for the first unit reactor to reach the above temperature was approximately 90 minutes. When the first unit reactor was operated at 300 ° C., the composition ratio of the product after the reforming was analyzed to be 74.8% hydrogen, 24.4% carbon dioxide, and 0.84% carbon monoxide based on the dry weight of water removed.

Based on the amount of methanol involved in the reforming reaction, the conversion of methanol was 99.5%.

The thermal efficiency to determine the operating efficiency was calculated by the following equation. Equation 1 is described in the paper J. of Power source, 108 (2002) 21-27 of the Pacific North National Laboratory, which describes a small methanol steam reformer referred to as prior art in the present invention. Based on this, objective preparation was made.

Operating efficiency = (ΔH _c H ₂ ) / (ΔH _c total CH ₃ OH)

CH ₃ OH (Liquid) + 1.5O ₂ = CO ₂ + 2H ₂ O (Liquid) ΔH = -726 kJ / mol

H ₂ + 0.5 O ₂ = H ₂ O (gas) ΔH = -242 kJ / mol

Where ΔH _c H ₂ is the total enthalpy of hydrogen produced and ΔH _c total CH ₃ OH is the total enthalpy of the methanol involved in the reforming and combustion reactions.

As a result of the calculation, the thermal efficiency of the hydrogen production apparatus according to the present invention was 59.5%. In addition, after connecting the primary oxidation reactor, it was confirmed that the carbon monoxide content in the hydrogen product is lowered to 70ppm. At this time, the thermal efficiency was shown to be reduced to 56.7% due to the reaction of some hydrogen during the primary oxidation reaction.

According to the present invention, there is provided a hydrogen production apparatus including a unit reaction apparatus including a microchannel on which a combustion catalyst and / or a reforming catalyst is coated, and a hydrogen production method using the same, for reforming including a reforming catalyst on a microchannel. Using a unit reaction apparatus including a plate assembly and a plate assembly for combustion, which also includes a combustion catalyst on a microchannel, they are stacked adjacent to each other, and a combustion reaction and a reforming reaction are performed to carry out a reforming reaction in a constant temperature range. It proceeds while maintaining the combustion reaction, and the combustion reaction is configured to be adjacent to the reforming reaction so that the heat generated from the combustion reaction is transferred to the reforming reaction quickly, and the combustion reaction and the reforming reaction are performed while maintaining a high reaction rate in the microchannel. Methanol conversion of more than 99%, higher than 59.5% In efficiency it has an effect of making it possible to produce hydrogen. In addition, both combustion and reforming reactions are possible using microchannels, and the hydrogen production apparatus itself can be extremely miniaturized by allowing evaporation by heat exchange, etc., and using hydrogen such as methanol as fuel as fuel. Supplying, but has an effect of providing a hydrogen production apparatus and a hydrogen production method using the same designed to produce hydrogen with high thermal efficiency and high hydrogen conversion rate. In addition, by configuring the combustion plate assembly and the reforming plate assembly in units, there is an effect of arbitrarily controlling the amount of hydrogen produced by simply controlling the number of stacked sheets of these plate assemblies.

Claims (29)

At least one combustion / reforming combined unit unit comprising at least one combustion plate assembly including a combustion catalyst and a reforming plate assembly including a reforming catalyst, wherein the plate assemblies have one surface And a pair of microchannel plates having microchannels formed thereon so that the microchannels face each other so as to be coupled to each other, wherein the combustion plate assembly includes combustion catalysts in the microchannel, and the reforming plate And the assembly comprises reforming catalysts in the microchannels. The method of claim 1, wherein the first unit reactor comprising the combustion plate assembly and the reforming plate assembly is characterized in that the combustion plate assembly and the reforming plate assembly are alternately positioned to be laminated to each other. Hydrogen production equipment. The method of claim 1, wherein the combustion catalyst is a platinum group element such as platinum, rhodium, ruthenium, osmium, iridium, palladium, gold, silver, copper or the like. Hydrogen production apparatus, characterized in that selected from the group consisting of two or more of these mixtures. The method according to claim 3, wherein the combustion catalyst is formed by first coating the catalyst support, adding the combustion catalyst so that the amount of the combustion catalyst is 0.1 to 5% by weight relative to the catalyst support, and then drying and calcining the supported catalyst. Hydrogen production apparatus characterized in that. 5. The hydrogen production apparatus according to claim 4, wherein the catalyst support is selected from the group consisting of aluminum oxide, α-aluminum oxide, zirconium oxide (ZrO ₂ ), silica (SiO ₂ ) or a mixture of two or more thereof. . The method of claim 1, wherein the reforming catalyst is a composite of copper / cerium oxide / zirconium oxide (Cu / CeO ₂ / ZrO ₂ ), a composite of copper / zinc oxide / aluminum oxide (Cu / ZnO ₂ / Al ₂ O ₃ ), Composite of copper / cerium oxide / aluminum oxide (Cu / CeO ₂ / Al ₂ O ₃ ), composite of copper / zirconium oxide / aluminum oxide (Cu / ZrO ₂ / Al ₂ O ₃ ), copper-zinc-aluminum oxide solid solution Hydrogen production apparatus, characterized in that selected from the group consisting of solid-solution CuZnAl oxide). 7. The hydrogen production apparatus according to claim 6, wherein the reforming catalyst is synthesized by a coprecipitation method with a weight ratio of 3: 5: 3-5: 1-3 of copper: zinc: aluminum oxide. The unit reaction apparatus of claim 1, wherein the unit reaction apparatus constituting the first unit reaction apparatus includes a case composed of two metal blocks, and the combustion plate assembly and the reforming plate assembly alternate between each other. Hydrogen generator characterized in that the stack is made of. The method of claim 8, wherein the plate assembly constituting the unit reaction device is made by combining a pair of microchannel plate formed with microchannels on the surface of one side so that the microchannels face each other and bonded to each other Hydrogen production equipment. 9. The hydrogen production apparatus according to claim 8, further comprising a gasket made of a copper plate. 10. The apparatus of claim 9, wherein the microchannel plates are positioned at one inlet and one outlet in a diagonal direction with respect to each other, and a first connector and a second connector are also at a diagonal direction with respect to each other, and between the inlet and the outlet. Hydrogen production apparatus characterized in that it is formed by forming a groove to the predetermined depth from the surface including these inlet and outlet. The flow of these fuels or raw materials in accordance with claim 11 wherein the fuels or raw materials are diffused from these inlets or outlets to the plurality of microchannels near the inlets and outlets or the fuel or raw materials are collected at these inlets or outlets. Hydrogen production apparatus characterized in that a plurality of converging grooves and converging protrusions are formed to limit the. The hydrogen production apparatus according to claim 1, wherein a third unit reaction device (12) is further connected to the first unit reaction device. The apparatus of claim 13, wherein the third unit reactor comprises plate assemblies for heat exchange, and the plate assemblies for heat exchange comprise a pair of microchannel plates having microchannels formed on one surface thereof. It is made by coupling to each other to face each other, wherein the heat exchange plate assembly is characterized in that it is configured not to include catalysts such as combustion catalyst or reforming catalyst. The hydrogen production apparatus of claim 1, wherein a second unit reaction device is further connected to the first unit reaction device. 16. The hydrogen production apparatus according to claim 15, wherein the second unit reaction device comprises a combustion plate assembly and a heat exchange plate assembly. 16. The hydrogen production apparatus according to claim 15, wherein a fourth unit reactor is further connected between the second unit reactor and the first unit reactor. 18. The hydrogen production apparatus according to claim 17, wherein the fourth unit reactor comprises plate assemblies for heat exchange. The hydrogen production apparatus of claim 1, wherein a primary oxidation reactor is further connected to the first unit reactor. 20. The hydrogen production apparatus according to claim 19, wherein a filter is connected between the first unit reactor and the primary oxidation reactor. The first unit reactor comprising at least one combustion / reformation combined first unit reactor, at least one second unit reactor for vaporization and at least one third unit reactor for heat exchange; And a plate assembly for combustion including a combustion catalyst and a plate assembly for reforming including a reforming catalyst, wherein the second unit reactor includes a plate assembly for combustion and a plate assembly for heat exchange. The third unit reactor includes a plate assembly for heat exchange, the combustion plate assembly of the first unit reactor is connected to any one of the plate assembly for heat exchange of the third unit reactor, The other heat exchange plate assembly of the unit reactor is connected to the combustion plate assembly of the first unit reactor, and the heat exchange plate of the second unit reactor is Hydrogen producing apparatus, characterized by yirueojim connected to the lip body is modified plate assembly of the first reactor unit. In producing hydrogen using the hydrogen production apparatus of claim 1, (1) A reforming plate adjacent to the combustion plate assembly using the heat by supplying a gaseous fuel and an oxidant to the combustion plate assembly of the first unit reaction apparatus together and burning them in the combustion plate assembly. A first combustion step of heating the assembly; And (2) a reforming step of producing hydrogen by supplying a reforming raw material comprising a mixture of methanol and water to the heated reforming plate assembly; 23. The method of claim 22, wherein the first unit reactor is kept constant in the temperature range of 260 to 320 ℃. 23. The method of claim 22, wherein between the first combustion step of (1) and the reforming step of (2), the plate assemblies for heat exchange are comprised, wherein the plate assemblies for heat exchange are microchannels on a surface of one side. A pair of microchannel plates on which the plurality of microchannel plates are formed are coupled to each other so that the microchannels face each other, and the third unit reactor is connected to the combustion plate assembly of the first unit reactor, wherein the first unit reactor A first connection step of connecting the inlet of any one heat exchanger plate assembly of the third unit reactor to the outlet of the combustion plate assembly of the first unit reaction apparatus; And The exhaust gas exhausted from the combustion plate assembly of the first unit reactor is connected to one of the heat exchange plate assemblies of the third unit reactor, and the liquid is supplied to the other heat exchange plate assembly to vaporize the liquid. A first hydrogenation step; Hydrogen production method characterized in that it further comprises. 25. The method of claim 24, wherein the third unit reactor is kept constant in the temperature range of 80 to 100 ℃. 23. The first unit reaction according to claim 22, wherein between the first combustion step of (1) and the reforming step of (2), a second unit reaction device comprising a plate assembly for combustion and a plate assembly for heat exchange is performed. A second connection step connected to the reforming plate assembly of the apparatus, wherein an outlet of the heat exchanger plate assembly of the second unit reactor connects to an inlet of the reforming plate assembly of the first unit reactor; A gaseous fuel and an oxidant are supplied together to the combustion plate assembly of the second unit reactor to combust in the combustion plate assembly, and the heat exchanger plate assembly adjacent to the combustion plate assembly is heated using the heat. A second combustion step of making; A second vaporization step of vaporizing and supplying a reforming material consisting of a mixture of methanol and water to the heat exchange plate assembly of the second unit reactor; And And a first supplying step of supplying the reforming raw material vaporized in the second vaporization step to the reforming plate assembly of the first unit reaction apparatus. 23. The combustion plate of claim 22, wherein the fourth unit reactor including the heat exchange plate assemblies between the first combustion step of (1) and the reforming step of (2). A heat exchange plate outlet of the fourth unit reactor connected to an inlet of the combustion plate assembly of the second unit reactor, and an inlet of the heat exchanger plate assembly to a liquid fuel A third connecting step for connecting with a source; A fourth connection connecting the inlet of the other heat exchanger plate assembly of the fourth unit reactor to the outlet of the reforming plate assembly of the first unit reactor and the outlet of the heat exchanger plate assembly to the product collector step; And And a third vaporization step of vaporizing a liquid fuel supplied to the second unit reactor by using the heat of the product stream discharged from the reforming plate assembly of the first unit reactor. Hydrogen production method 28. The method of claim 27, wherein the second unit reactor is maintained at a constant temperature range of 110 to 200 ° C. In producing hydrogen using the hydrogen production apparatus of claim 21, (1) a first combustion step of supplying a gaseous fuel and an oxidant to the combustion plate assembly of the first unit reactor for combustion; (2) exhausting the exhaust gas discharged from the combustion plate assembly in the first combustion step via any one heat exchanger plate assembly of the third unit reaction device to discharge the third unit reaction device at 80 to 100 ° C. A first preheating step of preheating to a temperature range; (3) A liquid fuel is supplied and vaporized through another heat exchange plate assembly of the third unit reactor to the combustion plate assembly of the first unit reactor, and at the same time, an oxidant is supplied together to burn the fuel. A second combustion step of heating the first unit reactor to 260 to 320 ° C; (4) a third combustion step of heating the second unit reactor to 110 to 200 ° C. by supplying a gaseous fuel and an oxidant to the combustion plate assembly of the second unit reactor to burn the fuel; (5) vaporizing the vaporized by passing a mixture of methanol and water as a raw material for reforming through the heat exchanger plate assembly of the second unit reactor and supplying it to the reforming plate assembly of the first unit reactor; And (6) a hydrogen production method comprising: a reforming step of passing the raw material vaporized in the vaporization step through the reforming plate assembly of the first unit reactor to be reformed with hydrogen.

Images