KR100818592B1 - Module type compact hydrogen reformer including both exothermic reaction and endothermic reaction using catalytic combustion - Google Patents

Abstract

A module type hydrogen reformer is provided to maximize thermal efficiency of the system by direct use of heat generated by catalytic combustion or by supplying heat in a short distance within the reformer and to minimize the size of the hydrogen reformer at the same heat rate. A hydrogen reformer extracting hydrogen gas includes an exothermic device(1) for supplying a mixture of air and fuel for exothermic reaction of catalyst, an endothermic device(3) for supplying a gas mixture for endothermic reaction of catalyst to reform hydrogen, and a device(2) for generating both exothermic reaction as a secondary reaction and endothermic reaction as a primary reaction of hydrogen reforming by utilizing gas mixtures supplied from both the exothermic and endothermic devices.

Description

Modular type Compact Hydrogen Reformer Including both Exothermic Reaction and Endothermic Reaction Using Catalytic Combustion that enables simultaneous exothermic reaction for heat supply using catalytic combustion and endothermic reaction for hydrogen production

1 is an overall schematic diagram of an integrated hydrogen reformer device in which exothermic and endothermic events can occur simultaneously using the catalytic combustion of the module type proposed in the present invention.

Figure 2 is a schematic diagram showing the structure of the injection nozzle and the hop mixer of the air and fuel supplied for the catalytic combustion exothermic reaction of the part A-A 'in the basic combustion apparatus of the present invention shown in FIG.

3A is a schematic diagram of an exothermic / endothermic integrated reformer module type I in which heat generation and endotherm may simultaneously occur in the basic combustion apparatus of the present invention shown in FIG. 1,

FIG. 3B is a cross sectional view taken along the line B-B 'of the module type I shown in FIG. 3A;

FIG. 3C is a cross sectional view taken along the line C-C ′ in the module type I shown in FIG. 3A;

3D is a cross sectional view taken along the section D-D ′ in the module type I shown in FIG. 3A;

4A is a schematic diagram of an exothermic / endothermic integrated reformer module type II in which heat generation and endotherm may simultaneously occur in the basic combustion apparatus of the present invention shown in FIG. 1;

FIG. 4B is a cross sectional view taken along the line E-E 'in the module type II shown in FIG. 4A;

FIG. 5A is a schematic diagram of an exothermic / endothermic integrated reformer module type III in which heat generation and endothermic may occur simultaneously in the basic combustion apparatus of the present invention shown in FIG. 1;

FIG. 5B is a cross sectional view taken along the line F-F 'of the module type III shown in FIG. 5A;

6A is a schematic diagram of an exothermic / endothermic integrated reformer module type IV in which heat generation and endotherm may simultaneously occur in the basic combustion apparatus of the present invention shown in FIG. 1;

FIG. 6B is a cross sectional view taken along the line G-G ′ in the module type IV shown in FIG. 6A;

FIG. 6C is a cross sectional view taken along the line H-H ′ in the module type IV shown in FIG. 6A;

FIG. 6D is a cross sectional view taken along the line II ′ of the module type IV shown in FIG. 6A;

FIG. 7A is a schematic diagram of an exothermic / endothermic integrated reformer module type V in which heat generation and endotherm may simultaneously occur in the basic combustion device of the present invention shown in FIG. 1;

FIG. 7B is a cross sectional view taken along the section J-J ′ in the module type V shown in FIG. 7A.

<Description of the symbols for the main parts of the drawings>

(1): mixed gas supply unit for catalytic exothermic reaction (2): exothermic / endothermic simultaneous reaction unit

(3): Mixed gas supply part for catalytic endothermic reaction (4): Integrated module combination part

(5): exothermic / endothermic integrated reformer module (6): catalyst exothermic reaction air

(7): fuel for catalytic exothermic reaction (8): exhaust gas for catalytic exothermic reaction

(9): mixed gas for catalytic endothermic reaction (10): exhaust gas of catalytic endothermic reaction

(11): fuel injection nozzle for catalytic heating reaction

(12): air / fuel mixing device for catalytic heating reaction

(13) Mixer vanes 14 Mixer drive shaft

(15): air / fuel mixture gas for catalytic heating reaction

(16): fuel injection nozzle porous

(17): Mixer drive shaft support (21): Insulated appearance

(22): insulation

(23): appearance of heat generation / absorption integrated reformer module

(24): catalyst for exothermic reaction

(25): Inner tube of heating / absorption integrated reformer module

(26): catalyst for endothermic reaction

(27): heating / absorption integrated reformer module connection flange

(28): catalytic endothermic exhaust gas outlet

(29): catalyst exothermic exhaust gas outlet (31): fin

(32): corrugated board

(33): mixed gas passage for catalytic heating reaction

(34): Mixed gas passage for catalytic endothermic reaction

(41): final exit of catalyst exothermic reaction exhaust gas

(42): final exit of catalytic endothermic reaction exhaust gas

43: integrated module combination connection joint

(44): integrated module combination lock

45: integrated module combination sealing paper

(46): catalytic exothermic exhaust gas passage section

47: integral module combination section combustion section

(48): catalytic endothermic reaction exhaust gas passage section

The present invention relates to a modular integrated hydrogen reformer device capable of simultaneously performing an exothermic reaction for heat supply and an endothermic reaction for hydrogen production using catalytic combustion, and in particular, a combination technology of a device structure and system that can maximize the miniaturization and thermal efficiency of the device. It is about.

Recently, hydrogen fuel is a new energy that can replace fossil fuels, and has attracted great attention as a clean fuel that does not generate environmental pollutants in the combustion reaction. Since fuel cell technology, which is the most representative technology using hydrogen, is expected to be commercialized starting from 2010-2020, the importance of hydrogen producing, storing, and supplying systems is increasing. In particular, the demand for hydrogen stations that produce, store and supply hydrogen is expected to grow exponentially in the future. Existing oil companies have invested a lot of manpower and money to secure the technology. It has a hydrogen station base and built a system to supply eco-friendly cars.

The basic principle of a reforming system that produces hydrogen is to obtain hydrogen by supplying heat while simultaneously supplying water and steam with hydrocarbon-based materials such as propane, methane and carbon monoxide. Therefore, a large amount of heat must be supplied to complete such a reforming reaction.

As described above, the most common method of supplying the heat required for the reaction is to supply the reaction heat indirectly using a flame burner.

As described above, there are a number of patents that complete the reforming system by using a general flame burner. In US Patent US-5,229,102, the heat required for the reformer is supplied by a flame burner located at the center, and the burner is a ceramic tube. The high temperature combustion exhaust gas was allowed to flow between the burner tube and the annular space between the burner tube and the second reforming space arranged on the same axis.

Flame burner was also used as a heat source for reforming reaction in "Japanese Patent P2005-525984A", and flame burner was also used as a heat source supply in "Japanese Patent P2002-362901A". It has been proposed to be able to increase the heat transfer surface area.

As such, when the flame burner is used, it is easy to control and has a wide range of controllable range of the burner for supplying necessary heat amount.

However, it is common to use an indirect heating method because it is difficult to miniaturize the device due to the flame, and it is not easy to directly supply heat to the reforming reaction part due to the high flame temperature.

Recently, researches on a technology for supplying the combustion heat to the reforming apparatus using a catalyst burner to compensate for the disadvantage of the flame burner have been conducted.

In the case of a system for supplying reaction heat by using a catalytic combustion method, the amount of NOx generated at a high temperature can be reduced as compared with a general flame burner method, and it is advantageous to miniaturize the device because no flame is generated.

In addition, when using a two-stage hybrid catalyst-flame complex combustion method that can simultaneously generate catalytic combustion and flame combustion, it has the advantage of supplying high-temperature heat while reducing dependence on flame.

However, the catalytic combustion method has a disadvantage in that it is not easy to control compared to the flame burner.

Most of the above-mentioned flame burners and catalytic combustion methods are indirect heating methods, which limits the miniaturization of the apparatus, and there are many problems in establishing a system for maximizing thermal efficiency.

Therefore, some research groups are trying to develop a system capable of constructing a miniaturized device while improving the most thermal efficiency.A solution for this is an integrated hydrogen reformer device in which exothermic and endothermic (reforming) reactions can occur simultaneously. Although the research is being conducted, it seems that the technical perfection is not yet high enough to be used.

In conclusion, as described above, most of the prior art technologies for the hydrogen reformer system have a limitation in improving thermal efficiency because they need to supply heat obtained from a separate burner system as described above, although a burner device for heat supply is installed inside. Even if there is a problem in miniaturizing the system compared to the same calories.

An object of the present invention for solving the above problems is to generate a catalyst exothermic reaction in one device to directly use the heat or to supply heat at the shortest distance can maximize the thermal efficiency of the system, the size of the device Another object of the present invention is to provide a technology that can be miniaturized significantly in preparation for the same amount of heat.

In addition, another object of the present invention is to invent the above-described heat generating / endothermic integral hydrogen reformer device in a modular type, so that the system can be easily scaled up / down by using a combination of modules from one according to an application field. / down) to provide a combination system technology.

The present invention, which achieves the object as described above and the problem for removing the conventional drawbacks, in the hydrogen reformer device for producing hydrogen,

A mixed gas supply unit for a catalyst exothermic reaction, which injects or mixes air and fuel supplied for an exothermic reaction of the catalyst;

A mixed gas supply unit for catalytic endothermic reaction which is supplied for the Susori forming reaction (catalyst endothermic reaction);

 And an exothermic / endothermic simultaneous generating unit for generating a main reaction, a soris forming reaction (catalyst endothermic reaction) and a side reaction, a catalytic exothermic reaction, using the mixed gases supplied from the above.

Supply unit of the mixed gas for the catalytic endothermic reaction,

A fuel injection nozzle for catalyst heating reaction for injection of fuel for catalyst heating reaction;

And an air / fuel mixing device for catalytic exothermic reaction having a rotary mixer blade for mixing fuel / air.

The catalyst exothermic fuel injection nozzle for injecting the catalyst exothermic reaction has a donut-shaped circular structure, and a plurality of pores are drilled at equal intervals inside the circular structure, and a predetermined injection angle is provided at the lower end of each of the pores. It is configured to smoothly spread the fuel.

The catalyst exothermic fuel injection nozzle for injecting the catalyst exothermic reaction fuel has a donut-shaped circular structure, and a pore having a diameter of 1 mm is drilled at equal intervals along the circumferential direction inside the circular structure, and the number of pores. Depends on the total amount of flow rate supplied to the module. That is, the number of actual device manufacturing is not limited to a specific number because the injection speed may vary depending on the capacity of the reformer device.

In addition, the spray angle was 15 degrees at the lower end of each pore. The reason why the spray angle is given is to make the diffusion well for smooth mixing with air, and it is generally within 30 degrees. However, since the diameter of the pore is so small, the spray angle increases too much and thus the spray linear velocity Is limited to 15 degrees in the present invention because it may be excessively reduced so that the mixing may not be performed up to the center portion.

The catalyst exothermic air / fuel mixing device includes a rotary mixer blade for complete uniform mixing of the fuel for the catalytic exothermic reaction and the air for the catalytic exothermic reaction;

It consists of a drive shaft for supporting the mixer blades to be free to rotate in accordance with the flow rate.

The heating / absorption simultaneous generating unit includes an integrated module combination unit formed by combining two or more cases; It is composed of; heat generating / heat absorbing integrated reformer module that is installed in one or two or more combinations as needed in the integrated module combination unit,

The integrated module combination portion,

The outside is the final outlet of the exothermic reaction exhaust gas formed through one point of the lower case; A final outlet of the endothermic reaction exhaust gas formed through one of the upper ends of the other case; An integral module combination connecting joint formed on the upper and lower portions so as to be respectively connected to the upper portion of the catalyst exothermic reaction mixture gas supply portion and the lower portion of the catalyst endothermic reaction gas supply portion; Sealing paper mounted on the boundary between the casings of the integrated module assembly including at least two casings to prevent the exhaust gas from leaking; Composed of; integral module combination locking device for connecting between neighboring cases,

An inside of the catalyst exothermic reaction exhaust gas passage portion formed as a space so that the catalyst endothermic reaction exhaust gas of the exothermic / endothermic integrated reformer module is discharged from the upper portion; An integrated module combination combustion unit located below the unit; It is composed of a catalytic endothermic reaction exhaust gas passage portion formed in the space portion so that the catalyst exothermic reaction exhaust gas is discharged below.

The module type heat / absorption integrated reformer module has a circular cylindrical structure having a circular cross-section consisting of the heat / absorption integrated reformer module exterior and the heat / absorption integrated reformer module inner tube installed at a predetermined interval therein, and having a circular cross section. On both sides of the heating / absorption integrated reformer module connection flange is formed,

An exothermic reaction catalyst is coated on the outside of the inner tube of the exothermic / heat absorbing integrated reformer module and an inner side of the exothermic / heat absorbing integrated reformer module. ,

The exothermic / heat absorbing integrated reformer module exterior and the heat generating / heat absorbing integrated reformer module inner tube installed at a predetermined distance apart therein have a structure in which one end is blocked in different directions and thus exothermic or exothermic reaction At least one catalyst endothermic reaction exhaust gas outlet having a structure in which a reaction air / fuel mixed gas or a catalyst exothermic reaction gas flows in, but one end of the exothermic / endothermic integrated reformer module is formed to penetrate outwardly Is formed, at least one catalyst exothermic reaction exhaust gas outlet is formed around the exterior side of the exothermic / heat absorbing integrated reformer module with one end blocked outward,

A heat insulating exterior filled with a heat insulating material is formed around the exterior of the exothermic / heat absorbing integrated reformer module.

At least one fin is protruded in the outer diameter direction in order to widen the exothermic reaction surface area in the outer circumferential direction and the longitudinal direction of the exothermic / heat absorbing integrated reformer module inner tube, and the extruded fin is coated with an exothermic catalyst.

At least one fin is protruded in the inner diameter direction to extend the exothermic reaction surface area in the inner circumferential direction and the longitudinal direction of the exothermic / heat absorbing integrated reformer module exterior, and the extruded fin is coated with an exothermic catalyst.

The module type heat / absorption integrated reformer module is formed of a double rectangular clearance structure having a rectangular cross-section consisting of the heat / absorption integrated reformer module exterior and the heat / absorption integrated reformer module inner tube installed at a predetermined interval therebetween. On both sides of the heating / absorption integrated reformer module connection flange is formed,

An exothermic reaction catalyst is coated on the outside of the inner tube of the exothermic / heat absorbing integrated reformer module and an inner side of the exothermic / heat absorbing integrated reformer module, and at least one catalyst body for the endothermic reaction is installed inside the inner tube of the exothermic / heat absorbing integrated reformer module. ,

The exothermic / heat absorbing integrated reformer module exterior and the heat generating / heat absorbing integrated reformer module inner tube installed at a predetermined distance apart therein have a structure in which one end is blocked in different directions and thus exothermic or exothermic reaction At least one catalyst endothermic reaction exhaust gas outlet having a structure in which a reaction air / fuel mixed gas or a catalyst exothermic reaction gas flows in, but one end of the exothermic / endothermic integrated reformer module is formed to penetrate outwardly Is formed, at least one catalyst exothermic reaction exhaust gas outlet is formed around the exterior side of the exothermic / heat absorbing integrated reformer module with one end blocked outward,

A heat insulating exterior filled with a heat insulating material is formed around the exterior of the exothermic / heat absorbing integrated reformer module,

The exothermic / exothermic integrated reformer module expands the exothermic reaction surface area outside the inner tube and forms a corrugated plate for inducing turbulent flow of the air / fuel mixture gas for the catalytic exothermic reaction, and the extruded corrugated plate is coated with the exothermic catalyst. It is configured.

The module type heat / absorption integrated reformer module is formed of a double rectangular clearance structure having a rectangular cross-section consisting of the heat / absorption integrated reformer module exterior and the heat / absorption integrated reformer module inner tube installed at a predetermined interval therebetween. On both sides of the heating / absorption integrated reformer module connection flange is formed,

An exothermic reaction catalyst is coated on the outside of the inner tube of the exothermic / heat absorbing integrated reformer module and an inner side of the exothermic / heat absorbing integrated reformer module. ,

The exothermic / heat absorbing integrated reformer module exterior and the heat generating / heat absorbing integrated reformer module inner tube installed at a predetermined distance apart therein have a structure in which one end is blocked in different directions and thus exothermic or exothermic reaction At least one catalyst endothermic reaction exhaust gas outlet having a structure in which a reaction air / fuel mixed gas or a catalyst exothermic reaction gas flows in, but one end of the exothermic / endothermic integrated reformer module is formed to penetrate outwardly Is formed, at least one catalyst exothermic reaction exhaust gas outlet is formed around the exterior side of the exothermic / heat absorbing integrated reformer module with one end blocked outward,

A heat insulating exterior filled with a heat insulating material is formed around the exterior of the exothermic / heat absorbing integrated reformer module,

The inner surface of the exothermic / endothermic integrated reformer module expands the exothermic reaction surface area and forms a corrugated plate for inducing turbulent flow of the air / fuel mixture gas for the catalytic exothermic reaction, and the extruded corrugated plate is coated with an exothermic catalyst. It is configured.

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

FIG. 1 shows an overall schematic diagram of an integrated hydrogen reformer device in which exothermic and endothermic events can occur at the same time using the catalytic combustion of the module type proposed in the present invention.

The apparatus of the present invention comprises a mixed gas supply unit (1) for a catalytic exothermic reaction, a mixed gas supply unit (3) for a catalytic endothermic reaction, and a mixed gas supply unit (1) for a catalytic exothermic reaction and a mixed gas supply unit (3) for a catalytic endothermic reaction It is located at is composed of a simultaneous exothermic / endothermic generating unit (2) that generates a catalytic exothermic reaction and a catalytic endothermic reaction at the same time. The catalyst exothermic reaction mixture gas supply unit 1 includes a catalyst exothermic reaction fuel injection nozzle 11 for injecting and mixing air and fuel supplied to the exothermic unit and an air / fuel mixture device 12 for the catalytic exothermic reaction. This is illustrated in FIG. 2.

In the catalyst exothermic reaction mixture gas supply unit 1, the catalyst exothermic reaction fuel injection nozzle 11 has a circular structure, and the fuel injection nozzle pores 16 are disposed at the same interval in the inner portion toward the center of the supply pipe. It is characterized in that the drilled to be injected. As the catalyst exothermic fuel 7 injected through the catalyst exothermic fuel injection nozzle 11, a fuel such as methane, propane or carbon monoxide is mainly used, and the catalyst exothermic air 6 supplied from the upper side is used. Primary mixing takes place in the same structure. At this time, the catalyst exothermic reaction air (6) supplied is supplied at room temperature according to the fuel used for the exothermic reaction, preheated with equipment such as an electric heater, or heat-exchanged using waste heat used in the process, which is necessary for the exothermic initiation temperature. It is necessary to raise the temperature as much as possible. The catalyst exothermic reaction air / fuel mixture device for the final uniform mixing of the catalyst exothermic reaction air (6) and the catalyst exothermic reaction (7) at the bottom of the catalyst exothermic reaction fuel injection nozzle (11) ( 12) is installed. The catalyst exothermic reaction air / fuel mixing device 12 has a structure in which a mixer blade 13 rotatable is attached to the mixer drive shaft 14, and the mixer blade 13 has an air / fuel for catalyst exothermic reaction. Located at the top of the mixing device 12, the mixing device drive shaft 14 is the catalyst heating by the mixing device drive shaft support 17, which is four thin rods at the bottom of the air / fuel mixing device 12 for the catalytic heating reaction It has a structure fixed to the inner wall of the reaction air / fuel mixing device 12. Swivel blade mixer 13 is the primary mixing based on the principle of automatically rotating around the mixer drive shaft 14 according to the total flow rate of the incoming catalyst exothermic reaction air (6) and the catalyst exothermic reaction fuel (7) The catalytic exothermic reaction air (6) and the catalytic exothermic reaction fuel (7) are made into the catalyst exothermic reaction air / fuel mixture gas (15) uniformly completely mixed.

The catalyst endothermic reaction mixture gas supply unit 3 is supplied with a catalyst exothermic reaction fuel 7 for the catalytic endothermic reaction, which is a reforming reaction, and the catalyst exothermic reaction air 6 is not supplied, so a separate mixing device is required. Not. When saturated vapor is supplied, additional equipment such as a vaporizer and a supply pump are required.

The simultaneous heating / absorption unit 2 includes an integrated module combination unit 4 formed by combining two or more cases; An exothermic / absorption integrated reformer module (5) installed in one or two or more forms as necessary in the integrated module combination unit (4) is installed in combination; The endothermic reaction and endothermic reaction of the mixed gas 9 for the catalytic endothermic reaction and the air / fuel mixed gas for the catalyst exothermic reaction 15, which are the mixed gases supplied from the endothermic reaction mixed gas supply unit 3, After the reaction, the catalyst exothermic reaction exhaust gas 8 and the catalyst endothermic reaction exhaust gas 10, which are the exhaust gases generated after the reaction, are catalyzed exothermic reaction exhaust gas final outlet 41 and the catalyst endothermic reaction exhaust gas final outlet ( 42).

The core part of the integrated module combination unit 4 is a heating / absorption integrated reformer module 5 which is a reaction device that generates heat / absorption at the same time, and forms a structure capable of combining a plurality of modules from one according to a required capacity.

In addition, the integrated module combination unit 4 has three casings composed of a catalyst exothermic reaction exhaust gas passage 46, an integrated module combination combustion unit 47, and a catalytic endothermic reaction exhaust gas passage 48. The structure is coupled to the case by the integrated module combination locking device 44, and the integrated module combination sealing paper 45 is inserted therebetween to prevent the exhaust gases from leaking.

The type of exothermic / endothermic integrated reformer module 5, which is a reaction device in which exothermic / absorption occurs simultaneously, may be modified in various embodiments as shown in FIGS. 3 to 7 according to heat transfer characteristics and the shape of the module.

FIG. 3A is a schematic diagram of a type I of a heat / absorption integrated reformer module 5 in which heat and endotherm may simultaneously occur in the basic combustion apparatus of the present invention shown in FIG. 1, and FIG. 3B is a module type shown in FIG. 3A. FIG. 3C is a cross-sectional view of the cross-section B-B 'in the module type I shown in FIG. 3A, and FIG. 3D is a cross-sectional view of the cross-section D in the module type I shown in FIG. -It shows sectional drawing about D '.

The catalyst exothermic reaction air / fuel mixture gas 15 of the catalyst exothermic reaction air 6 and the catalyst exothermic reaction fuel 7 supplied for the catalytic exothermic reaction of the exothermic / endothermic integrated reformer module 5 is catalytically exothermic. It is introduced through the reaction mixture gas passage 33.

The exothermic reaction catalyst 24 is coated on the inner part of the exothermic / endothermic integrated reformer module exterior 23 and the inner part of the exothermic / endothermic integrated reformer module inner tube 25. As the catalyst for the exothermic reaction, platinum (Pt) and palladium (Pd), which are noble metal catalysts, are used. When hydrogen or propane is used as the catalyst exothermic reaction fuel 7, platinum and palladium are coated in a ratio of 1: 1, and when methane is used as the fuel, only palladium is used as the exothermic catalyst 24.

In order to uniformly coat the exothermic reaction catalyst 24 on the metal surface of the exothermic / endothermic integrated reformer module 5 tube, ZrO ₂ is first washed and coated on the metal surface. After the coating was fired at 120 ° C. for 12 hours, and reduced to 6 hours at 550 ° C. using a reducing gas containing hydrogen within 5 vol% of the total amount of nitrogen and hydrogen to finish coating the catalyst for the exothermic reaction 24. The reason for limiting such a single value is that the effect of the present invention appears in such a value.

Propane or methane is mainly used as the mixed gas 9 for the endothermic reaction for the endothermic reaction. In processes where steam is required, such as steam reforming, water is supplied in the form of saturated vapor.

As the endothermic catalyst 26, Al ₂ O ₃ is first washed with a general ceramic honeycomb or a metal honeycomb, and then a reforming catalyst such as ZnO or CuO is prepared thereon.

The shape of the ceramic honeycomb or the metal honeycomb used as the catalyst support may be selected from a circle or a quadrangle according to the structure of the heating / absorption integrated reformer module 5, and the size of the reforming capacity and the heating / absorption integrated reformer module 5 may be selected. It can be decided selectively considering the SV (space velocity) according to the size.

The exothermic / endothermic integrated reformer module 5 of FIG. 3 has a circular basic structure, and heat is generated by surface reaction in the exothermic reaction catalyst 24 prepared above, and the heat is generated by the endothermic reaction catalyst 26. The main heat transfer principle is achieved by conduction through the exothermic / endothermic integrated reformer module inner tube 25 of the exothermic / endothermic integrated reformer module 5.

The catalyst endothermic reaction exhaust gas 10 generated by the endothermic reaction of the endothermic reaction catalyst 26 is the catalyst exothermic reaction toward the air / fuel mixture gas 15 for the catalytic exothermic reaction which is supplied for the exothermic reaction as shown in FIG. 3B. The catalyst exothermic reaction exhaust gas 8 generated by the exothermic reaction of the catalyst endothermic reaction exhaust gas outlet 28 installed in the mixed gas passage 33 for the exothermic reaction is shown in FIG. As shown, it is discharged to the outside through the exothermic reaction exhaust gas outlet 29 provided in the catalyst endothermic reaction gas mixture 33 for the catalytic endothermic reaction gas 9 which is supplied for the endothermic reaction.

Wherein the endothermic and exothermic reaction of the heat generating / endothermic integrated reformer module 5 of the present invention is provided with a heat insulating layer as shown in Figure 3c, the heat insulating layer is characterized by consisting of the heat insulating material 22 and the heat insulating exterior 21. The heat / absorption integrated reformer module 5 type is configured as a heat / absorption integrated reformer connection flange 27 type on both sides for connection with the integrated module combination unit 4.

FIG. 4A is a schematic diagram of an exothermic / endothermic integrated reformer module type II in which heat generation and endotherm may simultaneously occur in the basic combustion apparatus of the present invention shown in FIG. 1, and FIG. 4B is a cross-sectional view of the module type II shown in FIG. 4A. A cross-sectional view of 'E'. Type II is characterized in that the structure of the fin (31) in the exothermic / endothermic integrated reformer module exterior 23 in the type I device is configured to increase the amount of heat by increasing the surface area for the catalytic exothermic reaction.

The structure of the present invention serves to increase the exothermic heat of the externally supplied through the convective transfer to the catalytic exothermic heat generated outside the exothermic / endothermic integrated reformer module inner tube 25 which directly transfers heat to the endothermic reaction. Since the fin 31 is installed in the exothermic / endothermic integrated reformer module exterior 23 and does not directly take heat away from the endothermic reaction, the catalyst exothermic reaction in the pin 31 may occur more stably. have.

FIG. 5A is a schematic diagram of an exothermic / endothermic integrated reformer module type III in which heat generation and endotherm may simultaneously occur in the basic combustion apparatus of the present invention shown in FIG. 1, and FIG. 5B is a cross-sectional view of the module type III shown in FIG. 5A. A cross-sectional view of -F '. Type III is characterized in that the heat generation by increasing the surface area for the catalytic exothermic reaction by forming the fin 31 structure in the heat generating / endothermic integrated reformer module inner tube 25 in the type I device.

The structure of the present invention has the advantage that the fin is installed in the exothermic / endothermic integrated reformer module inner tube 25 in which the endothermic reaction occurs, and can supply more heat directly to the endothermic reaction heat, whereas the change in the amount of reaction heat of the endothermic reaction Accordingly, the degree to which the exothermic reaction at the fin 31 is directly affected may increase as compared with Type II of FIG. 4, which may make operation control difficult.

FIG. 6A is a schematic diagram of an exothermic / endothermic integrated reformer module type IV in which heat generation and endotherm may simultaneously occur in the basic combustion apparatus of the present invention shown in FIG. 1, and FIG. 6B is a cross-sectional view G in the module type IV shown in FIG. 6A. -C 'is a cross sectional view, and FIG. 6C is a cross sectional view of section H-H' in module type IV shown in FIG. 6A, and FIG. 6D is a cross sectional view of section I-I 'in module type IV shown in FIG. This is a cross section.

The exothermic / heat absorbing integrated reformer module 5 type of the structure of the present invention constituted an overall appearance in a rectangular structure.

The internal structure of the exothermic / endothermic integrated reformer module 5 is provided with a corrugated plate 32 inside the exothermic / endothermic integrated reformer module exterior 23 to increase the surface area for the exothermic reaction and to generate air for the catalytic heating reaction. To the turbulent flow of the fuel mixture gas (15) to the exothermic / exothermic integrated reformer module inner tube (25) and the exothermic reaction catalyst (24) coated on the corrugated plate (32) of the exothermic / heat absorbing integrated reformer module exterior (23). It is characterized by a structure in which the combustion conversion rate due to the surface reaction can be improved by increasing the contact time.

The catalyst exothermic reaction mixture gas passage 33 and the catalyst endothermic reaction gas mixture 34 having the structure of the present invention are also formed in a square shape, and the endothermic catalyst is also coated on the catalyst support having a rectangular honeycomb structure. .

The processes related to the overall exothermic reaction and endothermic reaction and heat transfer of the reaction heat are similar to the above-mentioned exothermic / endothermic integrated reformer module 5 of circular structure.

FIG. 7A is a schematic diagram of an exothermic / endothermic integrated reformer module type V in which heat generation and endotherm may simultaneously occur in the basic combustion apparatus of the present invention shown in FIG. 1, and FIG. 7B is a cross-sectional view of the module type V shown in FIG. 7A. The cross section for J-J 'is shown.

The present invention is characterized in that the corrugated plate 32 is configured outside the heat generating / heat absorbing integrated reformer module inner tube 25 of the heat generating / heat absorbing integrated reformer module 5, and all principles and process characteristics are shown in FIG. Similar to type IV.

In the heat transfer method of the present invention, the catalyst exothermic reaction fuel 7 and the catalyst exothermic reaction air 6 have a porous structure in which the fuel exothermic reaction fuel injection nozzle 11 has a porous structure and a rotary type. It has the principle of spraying and mixing in the air / fuel mixture device 12 for the catalyst exothermic reaction equipped with the swing wing, wherein the air / fuel mixture gas 15 for the catalytic exothermic reaction is the mixed gas passage for the catalytic exothermic reaction A catalytic exothermic reaction occurs in contact with the exothermic reaction catalyst (24) coated on (33), and the reaction heat thus obtained is conducted by conduction heat transfer through the exothermic / endothermic integral reformer module inner tube 25 of the integrated reformer device for catalytic endothermic reaction. Although used as heat, the endothermic reaction is carried out in earnest while the mixed gas for catalytic endothermic reaction 9 flowing into the mixed gas passage 34 for the endothermic catalytic contact with the endothermic catalyst 26.

The present invention is not limited to the above-described specific preferred embodiments, and various modifications can be made by any person having ordinary skill in the art without departing from the gist of the present invention claimed in the claims. Of course, such changes will fall within the scope of the claims.

The present invention as described above is that the heat generated in the exothermic portion can be used directly as the heat of reaction of the endothermic portion, by generating a catalytic exothermic reaction in one device can be directly used to heat or supply heat at the shortest distance to maximize the thermal efficiency of the system And the size of the device can be significantly reduced in preparation for the same amount of heat,

In addition, it is composed of module type, and it is a combination system that can easily scale up / down the system by using a combination of modules from one according to the application field.

In addition, the integrated system of the present invention is not only a reforming system for producing hydrogen, but also a technology that can be actively used in a system of kW or more, such as the heat exchanger industry, which is a traditional industry, and in particular, the nano / micro technology has recently been rapidly interested. In the gathering situation, since the demand for miniaturization or miniaturization of the system is expected to increase, the integrated thermal system such as the present invention is a useful invention that can be applied to a system of less than 50W, such as a micro reactor, a micro fuel cell, and the like. It is an invention that is expected to be greatly used in the industry.

Claims (11)

In the hydrogen reformer apparatus for producing hydrogen, A mixed gas supply unit (1) for catalytic exothermic reaction, which injects or mixes air and fuel supplied for exothermic reaction of the catalyst; A mixed gas supply unit (3) for catalytic endothermic reaction which is supplied for a Susori forming reaction (catalyst endothermic reaction);  By using the mixed gases supplied from the mixed gas supply unit (1) and the catalytic endothermic reaction mixture gas supply unit (3) for the catalytic exothermic reaction, the main reaction of the Susori forming reaction (catalyst endothermic reaction) and the catalytic exothermic reaction A modular type integral hydrogen reformer device capable of simultaneously generating exothermic reaction for heat supply and endothermic reaction for producing hydrogen using catalytic combustion, characterized in that it comprises an exothermic / endothermic simultaneous generating unit (2). The method of claim 1, The supply unit 1 of the mixed gas for the catalytic exothermic reaction, A catalyst exothermic fuel injection nozzle 11 for injecting the catalyst exothermic fuel 7; An exothermic reaction for heat supply and an endothermic reaction for hydrogen production using a catalytic combustion comprising: an air / fuel mixing device for a catalyst exothermic reaction having a rotary mixer blade 13 for mixing fuel / air; Modular all-in-one hydrogen reformer unit available at the same time. The method of claim 2, The catalyst exothermic fuel injection nozzle 11 for injecting the catalyst exothermic fuel 7 has a donut-shaped circular structure, and a plurality of fuel injection nozzle pores 16 are arranged at the same interval inside the circular structure. A modular type integral hydrogen reformer capable of simultaneously performing exothermic reaction for heat supply and endothermic reaction for hydrogen production using catalytic combustion, characterized by having a predetermined injection angle at the lower end of each porous hole to facilitate fuel diffusion. Device The method of claim 2, The catalyst exothermic reaction fuel injection nozzle 11 for injecting the catalyst exothermic reaction 7 has a donut-shaped circular structure, and the fuel injection nozzle pore 16 having a diameter of 1 mm is circumferentially inside the circular structure. The number of perforations according to the total amount of flow rate supplied to the module at equal intervals along the heat, using the catalytic combustion, characterized in that the fuel diffusion is smoothly achieved by the injection angle of 15 degrees to the lower end of each pore Modular integrated hydrogen reformer device capable of exothermic reaction for supply and endothermic reaction for hydrogen production. The method of claim 2, The catalyst exothermic reaction air / fuel mixing device 12 includes a rotary mixer blade 13 for complete uniform mixing of the catalyst exothermic reaction fuel 7 and the catalyst exothermic reaction air 6; A module capable of simultaneously performing exothermic reaction for heat supply and endothermic reaction for hydrogen production using a catalytic combustion, characterized in that the mixer blade 13 is composed of a mixer drive shaft 14 supporting the mixer blade 13 to rotate freely according to the supply flow rate. Type integral hydrogen reformer device. The method of claim 1, The heat generation / endothermic simultaneous generation unit 2, An integrated module combination part 4 formed by combining two or more cases; Heat-absorbing / heat absorption integrated reformer module (5) that is installed in combination in one or more than two forms as needed in the integrated module combination unit (4); The integrated module combination part 4, The outside is the final outlet 41 of the exothermic reaction exhaust gas formed through one point of the bottom of one side case; A final outlet 42 of the endothermic reaction exhaust gas formed through one of the upper ends of the other case; An integrated module combining part connecting joint 43 formed respectively at the upper and lower ends thereof so as to be connected to the upper portion of the catalyst exothermic reaction mixture gas supply portion and the lower portion of the catalyst endothermic reaction gas supply portion; An integrated module combination sealing paper 45 mounted on the inter-case boundary of the integrated module combination 4 composed of at least two cases to prevent the exhaust gas from leaking; Composed of an integrated module combination locking unit 44 for connecting between neighboring cases, An inner portion of the catalyst exothermic reaction exhaust gas passage portion 46 formed as a space for discharging the catalytic endothermic reaction exhaust gas of the exothermic / endothermic integrated reformer module 5 from the upper portion; An integrated module combination part combustion unit 47 located below the unit; A modular type integral type capable of simultaneously performing exothermic reaction for heat supply and endothermic reaction for hydrogen production using catalyst combustion, characterized in that the catalyst endothermic reaction exhaust gas passage portion 48 formed as a space portion to discharge the catalyst exothermic reaction exhaust gas at the lower portion thereof. Hydrogen reformer device. The method of claim 6, The module type heat / absorption integrated reformer module 5 has a circular cross-section consisting of the heat / absorption integrated reformer module exterior 23 and the heat / absorption integrated reformer module inner tube 25 installed at a predetermined interval therein. Consists of a double cylindrical tube structure, the both ends of the heating / heat absorbing integrated reformer module connection flange 27 is formed, An exothermic reaction catalyst 24 is coated on the outside of the exothermic / heat absorbing integrated reformer module inner tube 25 and the inside of the exothermic / heat absorbing integrated reformer module exterior 23, and the exothermic / heat absorbing integrated reformer module inner tube 25 At least one end catalyst for the endothermic reaction is installed inside, The exothermic / absorption integrated reformer module exterior 23 and the exothermic / absorption integrated reformer module inner tube 25 installed at a predetermined interval apart therefrom have a structure in which one end is blocked in different directions, thereby exothermic reaction or It has a structure in which the air / fuel mixed gas for the catalytic endothermic reaction or the mixed gas for the catalytic exothermic reaction flows in for the endothermic reaction, but is formed to penetrate outwardly around the inner tube 25 side of the exothermic / endothermic integrated reformer module with one end blocked. At least one catalytic endothermic exhaust gas outlet 28 is formed, and at least one catalytic endothermic exhaust gas outlet 29 is formed so as to penetrate outwardly around the exterior 23 of the exothermic / endothermic integrated reformer module with one end blocked. ) Is formed, An exothermic reaction for heat supply and an endothermic reaction for hydrogen production using catalytic combustion, characterized in that the heat insulation / exterior heat absorber 22 is filled with a heat insulating exterior 21 is formed around the outer module 23 of the reforming integrated module module Modular all-in-one hydrogen reformer unit available at the same time. The method of claim 7, wherein At least one fin 31 protrudes in the outer diameter direction to expand the exothermic reaction surface area in the outer circumferential direction and the longitudinal direction of the exothermic / heat absorbing integrated reformer module inner tube 25, and exothermic reaction to the protruding fin 31. Modular integrated hydrogen reformer device capable of simultaneously exothermic reaction for heat supply and endothermic reaction for hydrogen production using a catalytic combustion, characterized in that the catalyst 24 is coated. The method of claim 7, wherein At least one fin 31 protrudes in the inner diameter direction to widen the exothermic reaction surface area in the inner circumferential direction and the longitudinal direction of the exothermic / heat absorbing integrated reformer module exterior 23, and the exothermic reaction to the protruding fin 31. Modular integral hydrogen reformer device capable of simultaneously performing an exothermic reaction for heat supply and an endothermic reaction for hydrogen production using a catalyst combustion, characterized in that the catalyst 24 is coated. The method of claim 6, The module type heat / absorption integrated reformer module 5 has a rectangular cross-section consisting of the heat / absorption integrated reformer module exterior 23 and the heat / absorption integrated reformer module inner tube 25 installed to be spaced apart at a predetermined interval therein. It is made of a double rectangular clearance structure, the both ends of the heating / heat absorbing integrated reformer module connection flange 27 is formed, An exothermic reaction catalyst 24 is coated on the outside of the exothermic / heat absorbing integrated reformer module inner tube 25 and the inside of the exothermic / heat absorbing integrated reformer module exterior 23, and the exothermic / heat absorbing integrated reformer module inner tube 25 At least one endothermic reaction catalyst 26 is installed therein, The exothermic / absorption integrated reformer module exterior 23 and the exothermic / absorption integrated reformer module inner tube 25 installed at a predetermined interval apart therefrom have a structure in which one end is blocked in different directions, thereby exothermic reaction or It has a structure in which the air / fuel mixed gas for the catalytic endothermic reaction or the mixed gas for the catalytic exothermic reaction flows in for the endothermic reaction, but is formed to penetrate outwardly around the inner tube 25 side of the exothermic / endothermic integrated reformer module with one end blocked. At least one catalytic endothermic exhaust gas outlet 28 is formed, and at least one catalytic endothermic exhaust gas outlet 29 is formed so as to penetrate outwardly around the exterior 23 of the exothermic / endothermic integrated reformer module with one end blocked. ) Is formed, A heat insulation exterior 21 filled with a heat insulating material 22 is formed around the exothermic / heat absorption integrated reformer module exterior 23, On the outside of the exothermic / heat absorption integrated reformer module inner tube 25, a corrugated plate 32 is formed to widen the exothermic reaction surface area and induce turbulent flow of the air / fuel mixture gas 15 for the catalytic exothermic reaction, and the protrusion Modular integral hydrogen reformer device capable of simultaneously performing exothermic reaction for heat supply and endothermic reaction for hydrogen production using catalytic combustion, characterized in that the corrugated plate (32) is coated with an exothermic reaction catalyst (24). The method of claim 6, The module type heat / absorption integrated reformer module 5 has a rectangular cross-section consisting of the heat / absorption integrated reformer module exterior 23 and the heat / absorption integrated reformer module inner tube 25 installed to be spaced apart at a predetermined interval therein. It is made of a double rectangular clearance structure, the both ends of the heating / heat absorbing integrated reformer module connection flange 27 is formed, An exothermic reaction catalyst 24 is coated on the outside of the exothermic / heat absorbing integrated reformer module inner tube 25 and the inside of the exothermic / heat absorbing integrated reformer module exterior 23, and the exothermic / heat absorbing integrated reformer module inner tube 25 At least one endothermic reaction catalyst 26 is installed therein, The exothermic / absorption integrated reformer module exterior 23 and the exothermic / absorption integrated reformer module inner tube 25 installed at a predetermined interval apart therefrom have a structure in which one end is blocked in different directions, thereby exothermic reaction or It has a structure in which the air / fuel mixed gas for the catalytic endothermic reaction or the mixed gas for the catalytic exothermic reaction flows in for the endothermic reaction, but is formed to penetrate outwardly around the inner tube 25 side of the exothermic / endothermic integrated reformer module with one end blocked. At least one catalytic endothermic exhaust gas outlet 28 is formed, and at least one catalytic endothermic exhaust gas outlet 29 is formed so as to penetrate outwardly around the exterior 23 of the exothermic / endothermic integrated reformer module with one end blocked. ) Is formed, A heat insulation exterior 21 filled with a heat insulating material 22 is formed around the exothermic / heat absorption integrated reformer module exterior 23, The inner surface of the exothermic / heat absorption integrated reformer module exterior 23 expands the exothermic reaction surface area, and a corrugated plate 32 is formed to induce turbulent flow of the air / fuel mixture gas 15 for the catalytic exothermic reaction. Modular integral hydrogen reformer device capable of simultaneously performing exothermic reaction for heat supply and endothermic reaction for hydrogen production using catalytic combustion, characterized in that the corrugated plate (32) is coated with an exothermic reaction catalyst (24).

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