KR100719486B1 - Micro Combustion / Reforming Reactor - Google Patents

Abstract

According to the present invention, in a system in which a metal thin plate having a micro flow path is laminated in a multi-layer, and a heating body and a heated body are cross-fed into a burning thin plate and a heat transfer thin plate, generation of heat required for heating is evenly performed in front of the reactor in which the heated body is present. In order to proceed, it relates to a micro-combustion / reforming reactor for inducing uniform mixing of fuel and air to minimize temperature differences in the reactor.

Starting device, micro combustion / reforming reactor, exothermic heater, catalytic coating mesh

Description

Micro combusting / reforming device

1 is a perspective plan view of each component of a hydrocarbon combustion / reforming reactor of the present invention.

2 is a cross-sectional view taken along the line A-B of FIG.

3 is a detailed view of the combustion reforming catalyst coating thin plate of FIG.

Figure 4 is a cross-sectional view A1-B1 of FIG.

5 is a functional diagram of a catalyst coated metal mesh

6 is a production completion picture according to the configuration of Figure 1

Figure 7 is a perspective view of a combined reactor of the hydrocarbon combustion layer and the reformed bed of the present invention separated

8 is a cross-sectional view taken along line A-B of FIG.

9 is a cross-sectional view taken along the line C-D of FIG.

10 is a detailed view of the burning thin plate used in FIG.

FIG. 11 is a cross-sectional view taken along the line A1-B1 of FIG.

12 is a detailed view of the modified thin plate 20 used in FIG.

13 is a cross-sectional view taken along the line A2-B2 of FIG.

14 is a plan view of a blank thin plate 70 used in FIG.

15 is an exploded perspective view of a micro reactor using a particle catalyst

FIG. 16 shows a reactor complete according to FIG. 15

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

10: thin plate 11: gas shift hole

12: gas discharge hole 19: fine flow path surface

20: modified sheet 21: gas moving hole

22: gas discharge hole 25: gas delivery hole

26: gas delivery hole 29: fine flow path surface

30: burning sheet 31: gas transfer hole

32: gas delivery hole 35: gas transfer hole

36: gas discharge hole 70: blank sheet

71,72,73,74: Gas connection hole 75: Blank sheet

76: hole 1 77: hole 5

78: fourth hole 79: third hall

80: second hole 100,101,103: upper plate

110: supply hole tube 111: first supply hole tube

112: second supply hole tube 113: supply hole tube

120: supply hole 121: first supply hole

122: second supply hole 200, 201, 203: lower plate

209: first discharge hole 210: discharge hole tube

211: first discharge hole tube 212: second discharge hole tube

213: second discharge hole tube 220: discharge hole

221: first discharge hole 222: second discharge hole

250,251: charging hole 253: first discharge hole tube

500: metal mesh 501: metal mesh for combustion

600,601: heating heater 610,611: insulator

620, 621, 622: wire 623: thermocouple mounting hole

700: first heat transfer thin plate 701: third gas transfer hole

702: first gas delivery hole 703: second gas delivery hole

709: first gas discharge hole 800: reforming metal mesh

900: second heat transfer thin plate 902: fourth gas transfer hole

904: sixth gas delivery hole 909: fifth gas delivery hole

950: third heat transfer thin plate 951: ninth gas transfer hole

953: eighth gas delivery hole 959: seventh gas delivery hole

1000: reforming sheet 1002: 10th gas delivery hole

1003: 11th gas delivery hole 1004: 12th gas delivery hole

The present invention relates to a micro-combustion / reforming reactor, and more particularly, to stacking a metal thin plate having a micro flow path in multiple layers, and required for heating in a system in which a heating body and a heated object are cross-fed with a burning thin plate and a heat transfer thin plate. The present invention relates to a micro-combustion / reforming reactor for minimizing the temperature difference in the reactor by inducing uniform mixing of fuel and air so that the generation of calories can proceed evenly in front of the reactor in which the heating element is present.

Recently, many researches have been conducted on microreactors for the purpose of preparing a synthesis gas using hydrocarbons or alcohols in order to utilize fuel gas and reducing gas for removing nitrogen oxides.

Looking at the reaction of the synthesis gas using a hydrocarbon it is possible to proceed using a variety of reactions, such as Scheme 1 to Scheme 3.

Attention is drawn to steam reforming according to Scheme 1, where the concentration of hydrogen in the product is very high.

In particular, partial oxidation (Scheme 3), which has fast response characteristics, is also drawing attention.

CH ₄ + H ₂ O → CO + 3H ₂ , ΔH ₂₉₈ = 206 kJ / mol

CO ₂ + CH ₄ → 2CO + 2H ₂ , ΔH ₂₉₈ = 247 kJ / mol

CH ₄ + 1 / 2O ₂ → CO + 2H ₂ , ΔH ₂₉₈ = -36 kJ / mol

As a hydrogen production system for small stationary fuel cells (RPGs), much research is being carried out in anticipation of the effectiveness of steam reforming with high hydrogen concentration rather than rapid response.

The difficulty in this process is the supply of the heat of reaction required for the reaction as shown in Scheme 1 is the key. In the case of the steam reforming reaction, since the conversion rate of hydrocarbon (methane) is more than 95% at a reaction temperature of more than 750 ℃, it requires a lot of effort to supply the heat of reaction with maintaining the high temperature.

CH ₄ + 2O ₂ → CO ₂ + 2H ₂ O, ΔH ₂₉₈ = -801 kJ / mol

The heat of reaction is generated through the combustion (catalytic oxidation or combustion) of hydrocarbons as in Scheme 4.

In this process, a material having a high temperature difference (ΔT), a large contact area (A), and a high heat transfer coefficient (k) is required to achieve heat transfer effectively.

However, in order to achieve such a high temperature difference, it is not only impossible to raise the temperature of the flame necessary for heating indefinitely, but also causes the generation of pollutants of nitrogen oxides (NOx) together with the problems of the constituent materials.

In addition, the heat transfer coefficient also has a limit that is fixed to a unique value of the constituent material.

Therefore, it is possible to secure the heat transfer area of the heating part and the heat absorbing part as an adjustable item in the construction of the reactor.

For use in this application, a reactor having a microchannel in a thin metal sheet can be used.

The reactor having a micro channel in the thin metal plate can secure a large contact area per unit volume by stacking a multi-layer metal plate processed to have a micro channel in multiple layers.

However, the combustion reaction of hydrocarbons (LNG, LPG, alcohols) necessary for generating the heat of reaction may be carried out through catalytic combustion or non-catalytic combustion in a violent reaction that generates a very large calorific value.

In addition, the mixture of hydrocarbons and air undergoes oxidation through self-combustion from above a certain temperature (for example, 650 ° C. when carbon monoxide is present in air).

Therefore, even in a reactor having a micro-channel, localized heat of combustion is generated at the position where the reactant is introduced, which leads to a loss of uniformity of the reactor temperature, which in turn causes non-uniformity in the combustion catalyst or the to-be-heated portion, resulting in deactivation of the reforming catalyst. do.

To solve this problem, the researchers have applied for a patent on the construction of a separate supply line to supply fuel to each metal sheet (Park Jong-soo et al., “Microfluidic heater for uniform heating”, Korea Patent Application No. 10-2004-0080918).

On the other hand, Anna Lee Tonkovich et al. Discloses a metal microfluidic reactor having a heat exchange zone adjacent to a hydrocarbon combustion zone and an endothermic layer using heat generation thereof (US Patent 2004/0033455 A1, "Integrated combustion reactors"). and methods of conducting simultaneous endothermic and exothermic reactions ").

In addition, since Ehrfeld Wolfgang of Germany discloses the construction of a microfluidic heat exchanger using a metal sheet, it can be used for producing heat through hydrocarbon combustion and enabling endothermic reactions using the same (US Pat. No. 6,230,408). 2001), “Process for producing micro-heat exchangers”).

However, all the reactors are focused on the construction of the reactor in consideration of the steady-state operating conditions.

That is, a separate external heating device is required for start up, which is a start step of the reactor. When hydrogen or methanol is used as the fuel for heating the reactor, it is possible to start the oxidation reactor from normal temperature.

At this time, however, since the oxidation power of the catalyst is not high at a low temperature of less than 100 ° C, attempts to shorten the heating time by supplying an excessive amount of fuel at the beginning of the operation are not possible, and at the same time, to suppress the discharge of unburned fuel. The device or process is necessary.

An object of the present invention devised to solve the above problems is to laminate a multi-layer metal thin plate having a micro flow path, and to heat the heating body and the heated object in a system in which the heating plate and the heat transfer plate are cross-fed to heat the required amount of heat required for heating. It is to provide a micro combustion / reforming reactor for minimizing the temperature difference in the reactor by inducing uniform mixing of fuel and air so that the production can proceed evenly in front of the reactor in which the heating element is present.

At this time, since the electric heating element can be cooled by air and fuel at room temperature, a heating element manufactured to produce high energy per unit area is used.

However, in order to obtain locally high heat, a heater manufactured to produce high energy in a narrow heating area is required. That is, since a large amount of heat energy is generated when the heat generating area is large, initial ignition is impossible because cooling by air and fuel supplied when the surface temperature of the heat generating heater is lower than a predetermined temperature proceeds.

Therefore, it is equipped with a local heating heater that can produce more than a certain energy per unit area, and by applying electrical energy to the heater before the supply of the reactant, using less electrical energy than when starting to supply fuel after heating the heater surface You can complete the initial maneuver.

It is necessary to design the reactor so that the heating element having the above characteristics is located in the air and fuel flow region inside the body of the reactor.

The present invention for achieving the above object, the upper plate is formed with a supply hole in which the raw material gas is introduced; A lower plate having a discharge hole through which reformed gas is discharged; A plurality of thin plates laminated between the upper plate and the lower plate each having a combustion catalyst-coated microfluidic surface, and a gas movement hole and a gas discharge hole extending to the supply and discharge holes, respectively, and connected to the microfluidic surface; A metal mesh coated with an oxidation / modification catalyst inserted into a hole formed by the supply hole and the gas moving hole and a hole formed by the discharge hole and the gas discharge hole; And an exothermic heater installed at a predetermined gap in the metal mesh inserted into the hole formed by the supply hole and the gas moving hole to supply heat.

Another invention, the upper plate formed with a first supply hole into which the combustion gas flows and the second supply hole into which the reforming gas flows; A lower plate having a first discharge hole through which combustion waste gas is discharged and a second discharge hole through which reformed gas is discharged; A microfluidic surface coated with a combustion catalyst, a gas movement hole and a gas discharge hole extending to the first supply hole and the first discharge hole, respectively, and connected to the microfluidic surface, and isolated from the microfluidic surface; A plurality of combustion thin plates having gas delivery holes extending in each of the second supply hole and the second discharge hole; A microfluidic surface coated with a reforming catalyst, a gas movement hole and a gas discharge hole extending to the second supply hole and the second discharge hole, respectively, and connected to the microfluidic surface, and isolated from the microfluidic surface; A plurality of reforming thin plates having gas delivery holes extending in each of the first supply hole and the first discharge hole; A plurality of blank thin plates each having a gas connection hole extending from and respectively isolated from the first supply hole, the second supply hole, the first discharge hole, and the second discharge hole; A combustion metal mesh coated with an oxidation catalyst inserted into the hole in which the first supply hole extends and the hole in which the first discharge hole extends; A reforming metal mesh coated with a reforming catalyst inserted into a hole formed by extending the second supply hole and a hole formed by extending the second discharge hole; And a heating heater installed at a predetermined gap in the combustion metal mesh inserted into the hole formed by extending the first supply hole to supply heat, and a burning thin plate between the upper plate and the lower plate. A reforming thin plate is alternately stacked, and a micro-combustion / reforming reactor in which the blank thin plate is interposed between the adjacent combustion thin plate and the reforming thin plate.

Another invention, the upper plate is formed with a supply hole into which the source gas is introduced and the second discharge hole through which the reformed gas is discharged; A lower plate having a first discharge hole through which combustion waste gas is discharged; A first hole, a second hole, and a third hole extending in each of the supply hole, the first discharge hole, and the second discharge hole are formed at one side, and the fourth hole and the fifth hole are formed at the other side, and the first hole is formed. A plurality of blank thin plates which are separated from each other by the hole, the second hole, the third hole, the fourth hole, and the fifth hole; A first gas flow passage surface having a first gas discharge hole extending in the first discharge hole and a first groove extending in the fifth hole, wherein a combustion catalyst is coated between the first gas discharge hole and the first groove And a plurality of first gas transfer holes extending in the supply hole, a second gas delivery hole extending in the second discharge hole, and a third gas delivery hole extending in the fourth hole. Heat transfer thin plate; A second gas flow passage surface having a second gas discharge hole extending in the second discharge hole and a second groove extending in the fourth hole, and a combustion catalyst coated between the second gas discharge hole and the second groove; And a plurality of second gas transfer holes extending in the supply hole, a fifth gas transfer hole extending in the first discharge hole, and a sixth gas delivery hole extending in the fifth hole. Thermal transfer sheet; A third groove having a first gas movement hole extending in the supply hole and a third groove extending in the fifth hole, and a combustion catalyst coated with a third catalyst path surface formed between the first gas movement hole and the third groove; And a plurality of thirds including a seventh gas delivery hole extending in the first discharge hole, an eighth gas delivery hole extending in the second discharge hole, and a ninth gas delivery hole extending in the fourth hole. Heat transfer thin plate; A fine flow path surface is coated with a particle catalyst having a third gas discharge hole extending in the first discharge hole and a third groove extending in the fourth hole, and between the third gas discharge hole and the third groove. A plurality of reforming thin plates having a tenth gas transfer hole extending from the supply hole, an eleventh gas transfer hole extending from the second discharge hole, and a twelfth gas transfer hole extending from the fifth hole; A combustion metal mesh coated with an oxidation catalyst inserted into a hole formed by extending the supply hole and a hole formed by extending the first discharge hole; A reforming metal mesh coated with a reforming catalyst inserted into a hole formed to extend the second supply hole; And a heating heater installed at a predetermined gap in the combustion metal mesh inserted into the hole formed by extending the supply hole, and supplying heat, and a first heat transfer thin plate between the upper plate and the lower plate. It is a micro-combustion / reformation reactor in which a plurality of tanks are laminated in the order of a reforming thin plate, a second heat transfer thin plate, and a third heat transfer thin plate, and the blank plate is interposed between the thin plates.

The heating heater is characterized by having a capacity of 500W / cm ² or more.

In addition, the gap is characterized in that 0.5-10mm.

In addition, the raw material gas or the combustion gas is characterized by being supplied after heating the exothermic heater for at least 3 seconds.

Hereinafter, the present invention will be described in detail through examples and drawings.

Depending on the reaction to proceed, the form of the micro-combustion / reforming reactor may be configured in various ways, but the configuration and location of the initial starting device follow the same principle.

The metal mesh used in the present invention may be supplied with reactants to each catalyst layer without disturbing the gas flow depending on the height and at the same time providing the outer surface area for the catalyst coating.

The preheating temperature of the heating element and the catalyst used in the present invention is variable depending on the fuel to be used.

When using hydrogen alone or hydrogen mixed fuel of more than 10% by volume, the proper heating temperature can be started if it is preheated at 100-300 ℃. If methanol is used as fuel, preheating in the range of 150-400 ℃ is sufficient. Preheating is required in the range of 300-500 ° C for fuel and preheating up to 400-600 ° C for LNG.

1 is a plan view of a first hydrocarbon combustion / reforming reactor of the present invention, and FIG. 2 is a cross-sectional view along A-B of FIG. 1.

A plurality of combustion thin plates 10 are laminated between the upper plate 100 and the lower plate 200 to provide a catalyst coating surface for performing a combustion / reforming reaction.

One side of the upper plate 100 is formed with a supply hole 120 is charged with a mixture of combustion air and hydrocarbon gas, the supply hole 120 is extended to the supply hole tube (110).

In addition, one side of the lower plate 200 is formed with a discharge hole 220 through which the mixed gas reacts to discharge the reformed gas, and the discharge hole 220 extends to the discharge hole tube 210.

It is preferable that the distance between the supply hole 120 and the discharge hole 220 is formed to have the longest projection distance on the horizontal plane to increase the residence time of air therein.

As shown in FIG. 3, the thin plate 10 has a fine flow path surface 19 widely distributed at a central portion thereof, and a gas movement hole 11 and a gas discharge hole 12 at both ends of the micro flow path surface 19, respectively. ) Is formed.

A groove is formed between the micro flow path surface 19, the gas moving hole 11, and the gas discharge hole 12, so that a movement direction of air passes through the micro flow path surface 19 from the gas moving hole 11 to discharge the gas. To be a hole (12).

The gas movement hole 11 should be identical in position and size to the supply hole 120, and the gas discharge hole 12 should be identical in position and size to the discharge hole 220.

4 is a side view of the thin plate 10.

The surface combustion / reforming catalyst coating method of the micro channel surface 19 of the thin plate is as follows.

The microchannel surface 19 was calcined at 800 ° C. for 12 hours using a stainless steel plate (SS 316) to form an oxide, and an undercoat of an aluminum oxide on the surface thereof was coated with a noble metal oxidation / modification catalyst thereon.

In the aluminum coating solution, an aqueous solution was prepared by adjusting the precursor input amount so that aluminum isoproxide was made into a 5% by weight aqueous solution in a 5% by weight oxalic acid solution.

After 24 hours of normal temperature drying, after 105 hours 24 hours of baking at 500 ℃ for 12 hours, 2% by weight of cerium oxide solution was coated, dried and calcined in the same order as in the aluminum.

However, the baking temperature was advanced at 800 degreeC. Undercoating platinum was coated on the microfluidic surface 19 by using 1 wt% aqueous chloroplatinic acid solution. Its drying and firing was carried out under the same conditions as the cerium oxide coating.

A metal mesh 500 coated with an oxidation catalyst is mounted in the hole formed by the supply hole 120 and the plurality of gas movement holes 11, and a heating heater 600 is mounted in the center of the hole.

In addition, the heating heater 600 is electrically connected to the wire 620 for supplying electrical energy for heat generation through the insulator 610.

The exothermic heater 600 requires a heat generation amount of 500W / cm ² or more per unit area so as not to be cooled by the supply combustion gas.

That is, local heating is required to a temperature range where combustion of hydrocarbons supplied at room temperature may proceed by generating high heat per unit area rather than the calorific value of the exothermic heater 600. In other words, there is no requirement in terms of the total calorific value of the heater, and the meaning of the calorific value generated per unit area (local high temperature) is an important requirement of the heating element.

At this time, the heated exothermic heater 600 complexes the supplied hydrocarbon and the heat generated at this time heats the metal mesh 500 nearby to achieve a full-scale oxidation / modification reaction.

The heating heater 600 may be configured in various forms depending on the type of system to be used, but a heating element generating high energy in a small cross-sectional area is required.

However, in consideration of the shape of the stacked reactor, it is possible to minimize the increase in the reactor volume due to the heating medium when using the rod shape having a diameter of 3-10 mm in order to be mounted in the tube through which the reactants are moved.

The heating heater 600 is preferably a ceramic heater in consideration of durability, such as high temperature stability, corrosion resistance and ease of control.

In addition, a metal mesh 500 coated with an oxidation catalyst is mounted through the charging hole 250 in the hole formed by the discharge hole 220 and the plurality of gas discharge holes 12.

The catalytically coated metal mesh 500 serves to actively suppress unburned / reformed emissions of fuel.

Therefore, as the metal mesh 500 coated with the oxidation catalyst is used, the supply of the hydrocarbon for combustion can be uniformly supplied to the thin plate 10 located in the middle of the upper plate 100 and the lower plate 200.

As shown in FIG. 5, the metal mesh 500 is formed by rolling a mesh formed of a metal material into a cylindrical shape.

The wall surface of the metal mesh 500 is formed of a thin film or a fine catalyst layer.

In addition, the metal mesh 500 may maintain an interval of about 1 mm so as not to contact the gas moving hole 11, the gas discharge hole 12, and the heating heater 600.

If the metal mesh 500 is in contact with the gas movement hole 11 or the gas discharge hole 12, heat transfer proceeds to the thin plate 10, and thus, the catalyst layer heating rate is lowered.

In addition, when the metal mesh 500 is in contact with the heater may cause problems in the durability of the catalyst.

In the metal mesh 500 used in the present invention, the reactant may be supplied to each catalyst layer without disturbing the gas flow depending on the height as shown in FIG. 5 at the same time as providing the outer surface area for the catalyst coating.

The metal mesh 500 manufacturing method is as follows.

First, an aluminum oxide is formed on the surface of the metal mesh made of the iron-chromium-aluminum alloy by baking for 10 hours at 950 ° C. to increase the surface roughness.

5 g of a titanium isoproxide solution and 5 g of oxalic acid were added to 100 g of distilled water, followed by stirring at room temperature for 24 hours to prepare a coating solution.

The pretreated metal mesh is soaked in the coating solution and the excess solution is removed using high pressure air.

After 12 hours of drying at room temperature and 12 hours of baking at 800 ℃ to form a titanium oxide (TiOx). A 1% by weight solution of chloroplatinic acid is wetted with a metal mesh surface on which TiOx undercoating is completed, and the excess platinum solution is removed.

Drying at room temperature for 12 hours and firing at 800 ° C. for 12 hours to complete the coating of platinum, and cut it into a predetermined length so as to be hollowed so as to be charged into the supply hole 120 and the discharge hole 220.

The coating method of the catalyst on the surface of the metal mesh may be any method known in the art, and in particular, a woven form using a noble metal fiber having catalytic activity (oxidation / modification) may be used.

The completed reactor external shape having the configuration as described above is shown in FIG. 6.

Its driving method is as follows.

First, power is applied through the conductive wire 620 to heat the surface temperature of the heating heater 600 to 600 ° C. or more.

In addition, a mixed gas in which hydrocarbon and air, which are raw material gases, is mixed is supplied through the supply hole 120, and the mixed gas is a gas movement hole of the thin plate 10 having the same position and size as the supply hole 120. Pass (11).

Therefore, fuel is supplied to the center of the metal mesh 500 installed in the gas moving hole 11, and the mixed gas passing through the metal mesh 500 is present in the micro channel 19 existing in the thin plate 10. Combustion / reforming proceeds in contact with the catalysts while passing through.

Gas passing through the micro-channel is in contact with the oxidation / reforming catalyst coating mesh 500 mounted on the discharge hole 220 to achieve a high conversion rate.

In addition, activation of the oxidation / modification catalyst coated on the microchannels in the thin plate 10 proceeds with the start of the oxidation reaction.

If a fine powder catalyst is used, a large amount of air flows toward the upper thin plate 10 near the supply portion of air and hydrocarbons, and the gas flow decreases on the lower thin plate 10 near the lower plate 200. Although the temperature of the reactor becomes nonuniform, in the case of the present invention, this phenomenon can be eliminated because the metal mesh 500 that rolls the mesh coating catalyst into the hollow type is used.

When the ignition of the hydrocarbon proceeds and the temperature of the combustion gas discharge hole 220 starts to rise, the power supply is stopped.

Even if the power supply is stopped, the catalyst-coated metal mesh 500 is maintained in high temperature due to self-heating, and thus the combustion reaction continues.

When the temperature of the discharge unit 220 reaches 750 ° C. (when diesel, gasoline, or liquefied natural gas is used as the fuel), the fuel supply amount is increased to switch the operation to the reducing gas production mode by partial oxidation (POX).

The preheating temperature of the exothermic heater and the catalyst is variable depending on the fuel to be used. When using hydrogen alone or hydrogen mixed fuel of more than 10% by volume, the proper heating temperature can be started if it is preheated at 100-300 ℃. If methanol is used as fuel, preheating in the range of 150-400 ℃ is sufficient. Preheating is required in the range of 300-500 ° C for fuel and preheating up to 400-600 ° C for LNG.

Operation of the system initially heats the exothermic heater for 3-20 seconds and supplies fuel and air. At this time, the fuel supply is kept below 30% of the steady state supply, and the air supplies 100-200% of the theoretical air ratio required for combustion.

When the temperature of the reactor exhaust gas reaches 105 ° C or higher, the fuel supply amount is increased to 50% while maintaining the same mixing ratio of fuel and air. However, the fuel supply speed may vary depending on the type of fuel used or the type of reaction (SR, POX, ATR).

That is, the fuel / air ratio (mass ratio) required for complete combustion at the start of the start is maintained at 1.05-2.0, and the fuel / air ratio (mass ratio) is maintained at the range of 0.3-1.0 when the temperature of the reactor exhaust gas rises above 100 ° C. It is desirable to adjust the supply amount of hydrocarbon or air.

For example, in the reforming reaction using methanol as a fuel, since the catalytic combustion temperature of methanol is 150 degrees or less, even if the supply rate of the reactants is increased to a steady state value within a short time, unburned methanol is not emitted.

Of course, while supplying fuel after the preheating of the catalyst layer, the continuous supply of electric energy to the heating element also has no problems in terms of system stability and operation, and has a merit of shortening start-up time. It is not a preferred method of operation in large systems.

The raw material gas may be selected from one or two or more of white kerosene, gasoline, diesel, or one or more selected from methane, LNG, propane, butane, LPG, and DME.

Alternatively, it is also possible to use methanol and / or ethanol as the source gas.

However, the presence or absence of fuel supply using an independent supply hole according to the fuel used may be selected according to the characteristics of the fuel.

In addition, it may be configured in the form shown in Figures 7 to 9 to generate the heat of combustion using the above configuration and to proceed the endothermic reaction using the same.

This also follows the same configuration in that the ignition is embedded within the fuel and air flow conduits.

However, in order to cause a combustion reaction and an endothermic reaction separately on the flow path, the plurality of combustion thin plates 30 and the plurality of reforming thin plates 20 are laminated and stacked, respectively, with independent first supply holes 121 and second supply. It has a hole 122, and the first discharge hole 221 and the second discharge hole 222, between the combustion thin plate 30 and the reforming thin plate 20 so that the combustion region and the reforming region can be operated independently The addition of the blank thin plate 70 is required.

Unlike the metal mesh 500 used above, the combustion metal mesh 501 corresponding to the main reaction of the fuel and the reforming metal mesh 800 with the reforming role are used.

The combustion metal mesh 501 is mounted through the charging hole 250.

The heating heater 601 is formed in a hole in which the first supply hole 121 extends, and a wire 621 is electrically connected to the heating heater 601 through an insulator 611.

10 and 11 are plan and cross-sectional views of the reforming thin plate 20.

Similar to the thin plate 10, there are differences that two more holes are formed.

The thin plate 20 is such that the fine flow path surface 29 is widely distributed in the center, and the gas movement hole 21 and the gas discharge hole 22 are farthest apart from both ends of the fine flow path surface 29, respectively. It is formed diagonally to each other.

A groove is formed between the micro flow path surface 29, the gas moving hole 21, and the gas discharge hole 22, so that a movement direction of air passes through the micro flow path surface 29 at the gas moving hole 21. To be the discharge hole 22.

The hydrocarbon reforming catalyst is applied to the fine flow path surface 29 of the reforming thin plate 20. Alternatively, it may be used to make a space and to charge a catalyst in the form of 0.1-1.0mm particles.

The gas movement hole 21 must be identical in position and size to the second supply hole 122, and the gas discharge hole 22 must be identical in position and size to the second discharge hole 222.

In addition, gas delivery holes 25 and 26 are formed on a diagonal line intersecting an imaginary straight line connecting the gas moving hole 21 and the gas discharge hole 22.

The gas delivery holes 25 and 26 only serve to deliver a mixed gas or a mixed gas of hydrocarbon and water above or below it.

Of course, the gas delivery holes 25 and 26 should be identical in position and size to the first supply hole 121 and the first discharge hole 221, respectively.

That is, it is possible to apply to the reactor of various configurations for the purpose of using the heat generated by the catalytic combustion after the initial startup according to the present invention. It is applicable to steam reforming (SR) in which the exothermic region and the endothermic region are separated, or partial oxidation reaction (POX) and spontaneous partial oxidation reaction (ART), which are reforming reactions through self-heating.

12 and 13 are a plan view and a cross-sectional view of the combustion thin plate 30.

Similar to the thin plate 10, there are differences that two more holes are formed.

The combustion thin plate 30 has a fine flow path surface 39 is widely distributed in the center, and the gas movement hole 35 and the gas discharge hole 36 at the both ends of the micro flow path surface 39 have the greatest distance between them. It is formed diagonally to each other far.

A groove is formed between the micro flow path surface 39, the gas moving hole 35, and the gas discharge hole 36 so that the movement direction of air passes through the micro flow path surface 39 at the gas moving hole 35. To be the discharge hole 36.

An oxidation catalyst is applied to the fine flow path surface 39 of the thin plate 30 for combustion. Alternatively, a certain space may be secured and charged with a catalyst in the form of 0.1-1.0 mm particles.

The gas movement hole 35 should be identical in position and size to the first supply hole 121, and the gas discharge hole 36 should be identical in position and size to the first discharge hole 221.

In addition, gas delivery holes 31 and 32 are formed on a diagonal line intersecting an imaginary straight line connecting the gas moving hole 35 and the gas discharge hole 36.

The gas delivery holes 31 and 32 only serve to transfer a mixed gas or a mixed gas of a hydrocarbon and a water up or down.

Of course, the gas delivery hole 32 and the gas delivery hole 31 should be identical in position and size to the second supply hole 122 and the second discharge hole 222, respectively.

The method for manufacturing the combustion thin plate 30 and the reforming thin plate 20 is as follows.

FIG. 14 is a plan view of the blank thin plate 70, in which four gas connection holes 71, 72, 73, and 74 which only transfer gas up and down are provided in the first supply hole 121 and the second supply hole ( 122, the first discharge hole 221, the second discharge hole 222 is formed to match the size and position.

Its driving method is as follows.

First, power is applied through the conductive wire 621 to heat the surface temperature of the heating heater 601 to 600 ° C or more.

In addition, a fuel gas in which a hydrocarbon, which is a fuel gas, and air is mixed is supplied through the first supply hole 121, and the mixed gas is a gas moving hole having the same position and size as that of the first supply hole 121. Pass 35 and the gas delivery hole 25.

Accordingly, fuel is supplied to the center of the combustion metal mesh 501 installed in the gas movement hole 35 and the gas delivery hole 25, and the combustion gas that has passed through the combustion metal mesh 501. Combustion proceeds in contact with the catalysts while passing through the microchannel 39 present in the combustion thin plate 30.

At the same time, a gas including hydrocarbon and moisture, which are reforming gases, is supplied through the second supply hole 122, and the reforming gas is a gas moving hole having the same position and size as the second supply hole 122. Pass 21 and the gas delivery hole 31.

Therefore, the reforming gas is supplied to the center of the reforming metal mesh 800 installed in the gas moving hole 21 and the gas delivery hole 31, and the reforming gas passes through the reforming metal mesh 800. The molten gas is contacted with the catalysts while passing through the microchannel 29 present in the reforming thin plate 20 to undergo a reforming reaction.

The fuel gas passing through the micro flow path surface 39 is in contact with the combustion metal mesh 501 mounted in the first discharge hole 221 to achieve a high conversion rate.

In addition, the reforming gas passing through the micro flow path surface 29 is in contact with the reforming metal mesh 800 mounted in the second discharge hole 222 to achieve a high conversion rate.

In accordance with the start of the oxidation / reforming reaction, activation of the oxidation / reforming catalyst coated on the microfluidic surfaces 29 and 39 in the combustion thin plate 30 and the reforming thin plate 20 is performed.

When the ignition of hydrocarbon proceeds and the temperature of the first discharge hole 221 of the combustion gas starts to rise, the power supply is stopped.

Even if the power supply is stopped, the combustion metal mesh 501 is maintained in high temperature by self-heating, and thus the combustion reaction is continued, and the reforming reaction is maintained by the combustion heat caused by the combustion reaction.

Alternatively, it is possible to take a method in which fuel is mixed and supplied to the air supply hole at the beginning of the operation, and after the catalytic combustion reaches a temperature at which the combustion can proceed vigorously, the hydrocarbon supply position is switched to be supplied through an independent hole.

Finally, the third reactor has a similar configuration to the second reactor, but has one supply hole (not shown), a second discharge hole (not shown) through which reformed gas is discharged, and a first discharge hole 209 through which combustion waste gas is discharged. do.

The supply hole (not shown) extends by the supply hole tube 113, the second discharge hole (not shown) extends by the second discharge hole tube 213, and the first discharge hole 209. Is extended to the first discharge hole tube 253.

Further, the heat transfer thin plates 700, 900, 950 and the modified thin plate 1000 are installed as shown in FIG. Installed.

Therefore, a part of the mixed gas inputted is combusted and discharged to the first discharge hole 209, and the other part is reformed and discharged to the second discharge hole (not shown).

That is, the mixed gas to be burned is used as a heat source necessary for reforming, and the heat transfer thin plates 700, 900, and 950 are installed to transfer the heat amount.

The reformed mixed gas is separated from the reforming thin plate 1000.

The blank thin plate 75 has a first hole 76 and a second hole 80 extending at each side of the supply hole (not shown), the first discharge hole 209, and the second discharge hole (not shown). ), A third hole 79 is formed, and the fourth hole 78 and the fifth hole 77 are formed at the other side, and the first hole 76, the second hole 80, and the third hole ( 79), the fourth hole 78, the fifth hole 77 is isolated from each other.

The first heat transfer thin plate 700 has a first gas discharge hole 709 extending in the first discharge hole 209 and a first groove extending in the fifth hole 77, and the first gas discharge is performed. A first gas passage surface coated with a combustion catalyst is formed between the hole 709 and the first groove, the first gas transfer hole 702 extending in the supply hole (not shown), and the second discharge hole. A second gas delivery hole 703 extending in (not shown) and a third gas delivery hole 701 extending in the fourth hole 78 are formed.

The second heat transfer thin plate 900 has a second gas discharge hole extending in the second discharge hole (not shown) and a second groove extending in the fourth hole 78, and the second gas discharge hole and the second gas discharge hole. A second micro flow path surface coated with a combustion catalyst is formed between the second grooves, and extends in the fourth gas delivery hole 902 extending in the supply hole (not shown) and the first discharge hole 209. The fifth gas delivery hole 909 is formed, and the sixth gas delivery hole 904 extending in the fifth hole 77 is formed.

The third heat transfer thin plate 950 has a first gas moving hole extending in the supply hole (not shown) and a third groove extending in the fifth hole 77. Between the three grooves, a third fine flow path surface coated with a combustion catalyst is formed, and extends to the seventh gas transfer hole 959 extending in the first discharge hole 209 and the second discharge hole (not shown). The eighth gas delivery hole 953 and the ninth gas delivery hole 951 extending in the fourth hole 78 are formed.

The reforming thin plate 1000 has a third gas discharge hole 1009 extending in the first discharge hole 209 and a third groove extending in the fourth hole 78, and the third gas discharge hole ( 1009) and a fine flow path surface coated with a particle catalyst is formed between the third groove, the tenth gas transfer hole 1002 extending with the supply hole (not shown), and the second discharge hole (not shown). And an eleventh gas transfer hole 1003 extending therefrom and a twelfth gas transfer hole 1004 extending from the fifth hole 77.

The assembling method includes a first heat transfer thin plate 700, a reforming thin plate 1000, a second heat transfer thin plate 900, and a third heat transfer thin plate between the upper plate 103 and the lower plate 203. A plurality of tanks are stacked with the order of 950 as one set, and the blank thin plate 75 is interposed between the thin plates.

In the above, in order to charge the particle catalyst in the reactor, a charging hole may be formed in the upper plate 103 or the lower plate 203, and the charging hole may be closed with a plug after the catalyst loading.

The configuration of the other devices is the same as in the second reactor. That is, although not shown in the drawings, the supply holes (not shown) and the first discharge hole 209 are formed to extend, respectively, the combustion metal mesh (not shown) to which the combustion catalyst is applied, and the second discharge hole ( (Not shown) is provided with a metal mesh for reforming (not shown) to which a reforming catalyst is applied.

A heating heater (not shown) is provided inside the combustion metal mesh (not shown) provided in the hole in which the supply hole (not shown) is extended.

The reforming thin plate 1000 was crushed to 60 / 40mesh active aluminum particles having a diameter of 3-5mm on the support to support the oxidation / reforming catalyst. As a catalyst, a noble metal catalyst having known hydrocarbon reforming activity was prepared.

Next, supporting of the precursor aqueous solution was repeated so that the support was 5% by weight using an aqueous solution of magnesium nitrate on the support.

The finished support was calcined at 1300 ° C. for 12 hours (Mg (Al) O _x formed) to give thermal durability, and rhodium and magnesium components were simultaneously supported on the surface thereof using rhodium chloride and magnesium nitrate aqueous solution (Rh-Mg / Mg (Al) O _x ).

At this time, rhodium was 1% of the total weight of the catalyst, and the amount of precursor was added to the supported aqueous solution so that magnesium was 3%. The particles carrying rhodium and magnesium were dried at 105 ° C. for 12 hours, calcined at 900 ° C. for 5 hours, and reduced at 300 ° C. with 10 vol.% H ₂ / N ₂ gas.

Coating of the reforming catalyst on the metal mesh used in the third reactor was performed like the metal mesh 500 of the first reactor. However, the same coating solution was used to obtain the same composition as the particle catalyst (Rh-Mg / Mg (Al) O _x ).

The method of operation of the third reactor is as follows.

A mixture gas of air and fuel gas is supplied through a supply hole (not shown), which is preheated in the third heat transfer thin plate 950 along a connection passage existing in each plate, and again, the first heat transfer thin plate 700. While preheating at the same time while cooling the reactor via the first gas discharge hole 709, the reforming catalyst filled with the reforming catalyst (1000) is supplied and reformed to preheat the reactants in the second heat transfer sheet (900) It is discharged through the two discharge holes 213.

In addition, the remaining combustion waste gas is discharged to the first discharge hole tube 253.

The igniter required for initial operation is mounted in a conduit formed by the connection of successive 709, 1009, 909, 959, 209 holes.

The plate 1000 forming the catalyst layer was laminated with 7 sheets of 0.3 mm thick thin film to have a space of about 2.1 mm thick so that the volume of the catalyst layer was 1 ml.

The heat exchange plates 700, 900, and 950 were stacked in seven sheets, respectively, to secure a heat exchange area. At this time, the heat exchange plate was configured to repeat the flow of 900, 70, 950, 70.

In FIG. 16, reference numeral 623 denotes a thermocouple mounting hole for temperature measurement.

Through the following examples look at the characteristics of the present invention. This embodiment cannot be determined in the sense that it is intended to impose the limitation condition of the invention.

Example 1

The propane reforming reaction was carried out using the first reactor.

12V power was applied to the ignition igniter for 30 seconds, and air and propane mixed gas were supplied.

The temperature change of the reactor and the concentration of hydrogen and carbon monoxide under the corresponding conditions while changing the supply amount of propane and air with time are summarized in Table 1. The reactor was heated using an ignition apparatus and the reforming reaction was carried out to confirm the production of hydrogen and carbon monoxide.

Reaction condition result O / C molar ratio Feed rate, ml / min Reactor exhaust temperature, ℃ H ₂ , CO concentration, volume% in product gas air Propane H ₂ CO 0.57 1000 70 510 3.2 1.8 0.76 1900 100 715 7.2 8.3 0.63 1900 121 720 4.2 5.6 0.55 1900 138 715 4.5 5.8 0.70 2400 138 750 6.0 6.5

(Reactant Space Velocity (GHSV): 50,000-20,000 / hr)

Example 2

Mounted in the third reactor and carried out propane reforming reaction.

The experimental sequence is as follows. Using a reactor (volume 47ml, weight 312g) of FIG. 16, 12V power was applied to the ignition igniter for 30 seconds, and air and propane mixed gas were supplied.

The temperature change according to the reaction gas conditions and the concentrations of hydrogen and carbon monoxide at the corresponding temperatures are summarized in Table 2.

Reaction condition result O / C molar ratio Feed rate, ml / min Reactor exhaust temperature, ℃ H ₂ , CO concentration, volume% in product gas air Propane H ₂ CO 1.3 2050 240 (200 W) 736 19.4 14.2 1.1 1892 240 (200 W) 714 19.2 14.5 1.0 1710 240 (200 W) 706 17.4 13.7 0.9 1537 240 (200 W) 691 14.2 12.0 0.8 1367 240 (200 W) 686 13.4 11.5

(Reactant Space Velocity (GHSV): 125,000-87,000 / hr)

Example 3

A third reactor was used for partial oxidation of light oil with hydrocarbons. Other experimental conditions were kept the same as in Example 2.

The experimental results are summarized in <Table 3>.

The supply of air was fixed at 2500 ml / min, and the amount of diesel oil was increased to measure the reactor temperature change and the concentration of H ₂ , CO, and CH _{4 accordingly} . When the oxygen to carbon mole ratio was 1: 1, the highest hydrocarbon concentration was obtained and the concentration of syngas (H ₂ , CO) was 38%.

Reaction condition result O / C molar ratio flow Reactor exhaust gas temperature (℃) H ₂ , CO concentration, volume% in product gas Air (ml / min) Diesel (μl / min) H ₂ CO CH ₄ 2.2 2500 244 (150 W) 920 4.3 5.7 ND 1.9 2500 270 (170 W) 891 5.5 7.8 1.4 1.5 2500 360 (220 W) 882 12.0 15.0 2.9 1.2 2500 450 (280 W) 876 15.5 19.0 4.2 1.0 2500 540 (330 W) 840 18.9 19.0 4.2

(Reactant Space Velocity (GHSV): 170,000-90,000 / hr)

The micro-hydrocarbon combustion / reforming apparatus according to the present invention is equipped with an ignition device in the inner hole for forming the flow path to provide a system that can be started quickly with a compact configuration.

Claims (6)

An upper plate having a supply hole into which source gas is introduced; A lower plate having a discharge hole through which reformed gas is discharged; A plurality of thin plates laminated between the upper plate and the lower plate each having a combustion catalyst-coated microfluidic surface, and a gas movement hole and a gas discharge hole extending to the supply and discharge holes, respectively, and connected to the microfluidic surface; A metal mesh coated with an oxidation / modification catalyst inserted into a hole formed by the supply hole and the gas moving hole and a hole formed by the discharge hole and the gas discharge hole; And And a heating heater provided with a gap in the metal mesh inserted into the hole formed by the supply hole and the gas moving hole to supply heat. An upper plate having a first supply hole through which combustion gas is introduced and a second supply hole through which reforming gas is introduced; A lower plate having a first discharge hole through which combustion waste gas is discharged and a second discharge hole through which reformed gas is discharged; A microfluidic surface coated with a combustion catalyst, a gas movement hole and a gas discharge hole extending to the first supply hole and the first discharge hole, respectively, and connected to the microfluidic surface, and isolated from the microfluidic surface; A plurality of combustion thin plates having gas delivery holes extending in each of the second supply hole and the second discharge hole; A microfluidic surface coated with a reforming catalyst, a gas movement hole and a gas discharge hole extending to the second supply hole and the second discharge hole, respectively, and connected to the microfluidic surface, and isolated from the microfluidic surface; A plurality of reforming thin plates having gas delivery holes extending in each of the first supply hole and the first discharge hole; A plurality of blank thin plates each having a gas connection hole extending from and respectively isolated from the first supply hole, the second supply hole, the first discharge hole, and the second discharge hole; A combustion metal mesh coated with an oxidation catalyst inserted into the hole in which the first supply hole extends and the hole in which the first discharge hole extends; A reforming metal mesh coated with a reforming catalyst inserted into a hole formed by extending the second supply hole and a hole formed by extending the second discharge hole; And And a heating heater installed at a gap in the combustion metal mesh inserted into the hole formed by extending the first supply hole to supply heat. A combustion thin plate and a reforming thin plate are alternately stacked between the upper plate and the lower plate, and the blank thin plate is interposed between the adjacent combustion thin plate and the reforming thin plate. An upper plate having a supply hole into which source gas is introduced and a second discharge hole from which reformed gas is discharged; A lower plate having a first discharge hole through which combustion waste gas is discharged; A first hole, a second hole, and a third hole extending in each of the supply hole, the first discharge hole, and the second discharge hole are formed at one side, and the fourth hole and the fifth hole are formed at the other side, and the first hole is formed. A plurality of blank thin plates which are separated from each other by the hole, the second hole, the third hole, the fourth hole, and the fifth hole; A first gas flow passage surface having a first gas discharge hole extending in the first discharge hole and a first groove extending in the fifth hole, wherein a combustion catalyst is coated between the first gas discharge hole and the first groove And a plurality of first gas transfer holes extending in the supply hole, a second gas delivery hole extending in the second discharge hole, and a third gas delivery hole extending in the fourth hole. Heat transfer thin plate; A second gas flow passage surface having a second gas discharge hole extending in the second discharge hole and a second groove extending in the fourth hole, and a combustion catalyst coated between the second gas discharge hole and the second groove; And a plurality of second gas transfer holes extending in the supply hole, a fifth gas transfer hole extending in the first discharge hole, and a sixth gas delivery hole extending in the fifth hole. Heat transfer thin plate; A third groove having a first gas movement hole extending in the supply hole and a third groove extending in the fifth hole, and a combustion catalyst coated with a third catalyst path surface formed between the first gas movement hole and the third groove; And a plurality of thirds including a seventh gas delivery hole extending in the first discharge hole, an eighth gas delivery hole extending in the second discharge hole, and a ninth gas delivery hole extending in the fourth hole. Heat transfer thin plate; A fine flow path surface is coated with a particle catalyst having a third gas discharge hole extending in the first discharge hole and a third groove extending in the fourth hole, and between the third gas discharge hole and the third groove. A plurality of reforming thin plates having a tenth gas transfer hole extending from the supply hole, an eleventh gas transfer hole extending from the second discharge hole, and a twelfth gas transfer hole extending from the fifth hole; A combustion metal mesh coated with an oxidation catalyst inserted into a hole formed by extending the supply hole and a hole formed by extending the first discharge hole; A reforming metal mesh coated with a reforming catalyst inserted into a hole formed to extend the second supply hole; And And a heating heater installed at a gap in the combustion metal mesh inserted into the hole formed by extending the supply hole to supply heat. Between the upper plate and the lower plate, a plurality of groups are stacked in the order of the first heat transfer thin plate, the modified thin plate, the second heat transfer thin plate, and the third heat transfer thin plate in a set, and between the thin plates, Micro-combustion / reformer reactor with intervening rank sheet. delete The microcombustion / reformation reactor according to any one of claims 1 to 3, wherein the gap is 0.5-10 mm. delete

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