KR20070075613A - The selective co oxidation reactor for hydrogen-rich stream - Google Patents

Abstract

A reactor for oxidizing carbon monoxide in reformed gas is provided to stably reduce the carbon monoxide, by installing a vortex generating structure for inducing the mixture of reformed gas and air inside or outside the reactor. A first reactor(100) and a second reactor(200) are continuously connected to each other so as to induce two-step selective oxidation reaction. The first and second reactors are respectively composed of gas mixers(110,210), reacting units(120,220), and cooling units(130,230). The gas mixer uses a vortex generating structure for mixing air and reformed gas containing carbon monoxide. The reacting unit selectively oxidizes the carbon monoxide by making mixed gas of the reformed gas and the air pass through a catalyst layer. The cooling unit controls the temperature of the reactor unit.

Description

The selective CO oxidation reactor for hydrogen-rich stream

  1 is a schematic cross-sectional view of a mixer-containing selective oxidation reactor in the selective oxidation reactor according to the present invention

  2 is a schematic cross-sectional view of a mixer exterior type selective oxidation reactor according to the present invention;

  3 is a graph showing the performance of the selective oxidation reactor produced in accordance with an embodiment of the present invention by operating for three days in conjunction with a natural gas reforming system.

  Figure 4 is a graph showing the operation results according to the load variation of the natural gas reforming system connected to the selective oxidation reactor produced in accordance with an embodiment of the present invention.

*** Explanation of major symbols in drawings ***

100: primary reactor 200: secondary reactor

110, 210: gas mixer 111, 211: pipe

112, 212: static screw 120, 220: reaction part

121, 221: upper shelf 122, 222: lower shelf

123 and 223 catalyst layer 130. 230 cooling part

131, 231: coiled cooling tube 132, 232: cooling jacket

The present invention relates to a reactor for the selective oxidation of carbon monoxide in a hydrogen-rich reforming gas and to a method for operating the same, more particularly, to supplying as little oxygen as possible to selectively oxidize carbon monoxide in the reforming gas and to an appropriate reaction temperature. The present invention relates to a carbon monoxide selective oxidation reactor capable of maintaining CO in a composition of 10 ppm or less from a reforming gas mixture containing hydrogen and CO ₂ and H ₂ O.

In general, a natural gas reforming system for supplying hydrogen to polymer fuel cell (PEMFCs) systems for small and distributed power supplies consists of five unit processes: desulfurization, steam reforming, high temperature transition, low temperature transition, and selective oxidation.

The exit composition of the reformed gas passed through the low temperature transition process is generally 60% by volume H ₂ , 15% by volume CO ₂ , 20% by volume H ₂ O, 1-4% by volume CH ₄ , and 0.5-1% by volume CO. It includes.

However, since the CO poisons the polymer fuel cell anode catalyst (Pt) and causes a drastic drop in battery performance, there is a problem in that the CO concentration must be removed below 10 ppm in order to protect it. The Pd separation membrane, methanation, and selective oxidation (PrOx) may be considered as the method, and selective oxidation reaction is mainly studied.

As the catalyst used for the selective oxidation of carbon monoxide as described above, platinum-based metals (Pt, Rh and Ru) supported on alumina have been reported mainly as precious metals. These catalysts are housed in flat-bed reactors or concentric tubular, tubular, fixed-bed reactors to remove CO and, if necessary, install two or more reactors. In this case, the volume of the selective oxidation reactor is increased because a device for injecting air as an oxidant for the selective oxidation reaction and mixing it with a reforming gas and a heat exchanger that avoids oxidation of hydrogen and maintains an appropriate temperature range inducing oxidation of CO are required. There is a drawback to growing.

Therefore, in recent years, in order to solve the above problems, researches on a reactor integrating a mixing device and a heat exchanger and minimizing the amount of the catalyst accommodated in the catalyst bed have been actively conducted.

As a representative example, Tokyo Gas uses a concentric tubular reactor in which reformed gas and air are mixed in a specific size space, introduced into the reactor, and the cooling water flows through the reactor inlet or the reactor wall to perform heat exchange. Gas and air are mixed and introduced into the reactor, and a flat reactor is cooled by the supplied air [Nishizaki, K., Kawamuram M., Osaka, N. Ito, K., Fujiwara, N., Nishizaka, Y. and Kitazawa, H .: Fuel Cell Seminar (2005), Mitsuaki, E., Shinske, N., Takami, S., and Tabata, T.: Journal of Power Sources , 132, 29 (2004).

However, in the reactor as described above, since the mixing of the reformed gas and air is not performed smoothly, the amount of air to be injected increases and the ratio of oxygen and carbon monoxide ([O ₂ ] / [CO]) increases to 2 to 3 There are disadvantages. Moreover, in the case of the reactor using Ru catalyst, the increase of the amount of air injected due to the methanation reactivity of the CO ₂ catalyst of Ru catalyst causes difficulty in temperature control, and the excess air reduces the consumption of H ₂ by oxidation reaction. It is reported to increase rapidly (Twigg, MV: Catalyst Handbook, 2nd edition, Wolfe Publishing Ltd., London, UK, 1989).

Therefore, there is an urgent need for a reactor and an operation method for selectively oxidizing carbon monoxide in the reformed gas by effectively mixing air with the reformed gas to maintain an appropriate reaction temperature.

SUMMARY OF THE INVENTION An object of the present invention for solving the above problems is to selectively oxidize carbon monoxide from a reforming gas mixture using as little oxygen as possible and using a relatively small amount of catalyst, and to exchange heat with the air and reforming gas mixing device. To provide a carbon monoxide selective oxidation reactor incorporating a group.

Another object of the present invention is to produce a small-volume reactor incorporating a complex mixing device and a cooler, simplifying the production process of the entire natural gas steam reforming system, and effectively operating a carbon monoxide selective oxidation reactor and its operation. To provide a way.

In the selective oxidation reactor according to the present invention, a gas mixer capable of effectively mixing hydrogen-rich reformed gas and air is installed inside or outside the reaction unit in which selective oxidation of carbon monoxide occurs, inducing selective oxidation of carbon monoxide, and Cooling unit that can effectively remove the heat generated in the oxidation reaction of the reaction mixture is installed on the gas inlet and the outer wall surface of the reaction section where the selective oxidation reaction occurs,

The present invention is to remove the carbon monoxide in the hydrogen-rich reforming gas through a two-stage oxidation reaction through the selective oxidation of carbon monoxide in two reactors, the first reactor in the reaction temperature 100 ~ 300 ℃, Preferably the reaction is carried out under the conditions of 140 ~ 190 ℃, space velocity is 10,000hr ^{- 1} or less, in the secondary reactor the reaction temperature is 100 ~ 200 ^o C, preferably 120 ~ 160 ^o C, space velocity 10,000hr ^- the reactor is provided for selectively oxidizing the carbon monoxide in the hydrogen-rich reformed gas at ¹ or less condition.

In addition, the present invention, by introducing a platinum (Pt) -based catalyst layer in a single stage of the reactor performs an oxidation reaction to reduce the carbon monoxide of 0.5 ~ 1% by volume contained in the reformed gas discharged from the low temperature water gas reactor to 300ppm or less, An effective mixing device of reformed gas and air is placed inside or outside the reactor to maintain the amount of oxygen contained in the air mixed with the reformed gas at a ratio of carbon monoxide and [O ₂ ] / [CO] = 1.5, wherein the catalyst bed By using a heat exchanger maintaining the reaction temperature at 140 ~ 190 ℃ is provided a reactor that suppresses the rapid rise of the temperature due to the exothermic reaction and the resulting consumption of H ₂ .

In addition, the present invention, by introducing a ruthenium (Ru) -based catalyst layer in the secondary reactor to perform the oxidation reaction to reduce the carbon monoxide concentration of less than 300ppm contained in the reformed gas discharged from the first stage selective oxidation reactor to 10ppm or less, And a mixture of air and air are similarly arranged inside or outside the reactor to maintain the amount of oxygen contained in the air mixed with the reforming gas at a ratio of carbon monoxide and [O ₂ ] / [CO] = 1.5, wherein the reaction of the catalyst bed A reactor is provided where the temperature is maintained between 120 and 160 ^° C without the aid of special cooling.

In the reactor used in the present invention, a gas mixer for mixing the reformed gas and air may be used. There is no particular limitation as the gas mixer, but preferably, a mixer using an vortex generating structure may be selected and used.

The vortex generating structure is not limited to a static mixer, a honeycomb type mixer, a metal foam mixer, and the like, and it is preferable to use the following method.

The reformed gas passed through the low temperature water gas shift reactor contains 0.5 to 1% by volume of carbon monoxide, which contains air containing carbon monoxide and oxygen in a ratio of [O 2] / [CO] = 1.5. Inject at the inlet.

The reformed gas and air in the laminar flow state are introduced into the selective oxidation reactor of the present invention without being sufficiently mixed, but the oxygen is uniformly mixed in the reformed gas as a vortex occurs in the gas mixer installed inside or outside the reactor before reaching the catalyst bed of the reaction section. do. The mixed gas of air and reformed gas is introduced into the catalyst layer of the reaction unit to convert carbon monoxide and oxygen into carbon dioxide through a selective oxidation reaction. The vortex generating structure is preferably inserted into a tube installed outside or inside the reactor.

Subsequently, the cooling unit effectively removes the reaction heat generated in the selective oxidation reaction.

At this time, if the reactants do not effectively remove the heat of reaction at the inlet of the catalyst layer, the temperature of the catalyst layer increases rapidly, and the oxidation reaction of hydrogen is preferentially superior to the oxidation reaction of carbon monoxide. Therefore, the temperature of the catalyst bed must be maintained within an appropriate range, that is, in the range of 140 to 190 ° C. for the primary reactor and in the range of 120 to 160 ^o C for the secondary reactor. Install a cooling unit to remove the heat of reaction in the circulating cooling water to maintain the proper temperature.

The selective oxidation reactor according to the present invention having the configuration as described above will be described in detail with the accompanying drawings.

However, the terms or words used in the present specification and claims are regarded as concepts selected by the inventors as the best way to explain the present invention and the meanings consistent with the technical spirit of the present invention in grasping the technical contents of the present invention. It should be properly interpreted as a concept.

1 and 2 are schematic cross-sectional views of a selective oxidation reactor according to the present invention, Figure 1 is a mixer-type selective oxidation reactor, Figure 2 shows a mixer external selective oxidation reactor in cross-sectional view.

Built-in selective oxidation reactor according to the present invention is composed of a primary reactor 100 and a secondary reactor 200 to induce two-stage oxidation reaction, the primary reactor 100 is produced through a low temperature transition process A gas mixer 110 having a vortex generating structure for mixing the reformed gas containing carbon monoxide and air and a gas containing the reformed gas and air discharged from the gas mixer are passed through to selectively select carbon monoxide contained in the gas using a catalyst. It is composed of a reaction unit 120 having a catalyst layer filled with a catalyst by oxidizing and a cooling unit 130 which effectively removes the reaction heat generated by the selective oxidation reaction of carbon monoxide in the reaction unit to effectively advance the oxidation reaction of the reaction unit. . The gas mixer 110 is a mixing device for mixing the reformed gas and air, but there is no particular limitation, and preferably, a gas mixer 110 may be used by selecting a mixer in which the vortex generating structure is applied.

In addition, the gas mixer 110 to which the vortex generating structure is applied is not limited to a static mixer, a honeycomb type mixer, a metal foam mixer, and the like, and it is preferable to use the following method.

As shown in FIGS. 1 and 2, the static mixer 110 is formed by inserting the static screw 112 into the pipe 111 through which the reformed gas and the air are pumped.

The reaction unit 120 is formed in the upper shelf 121 and the lower shelf 122 made of a porous plate having a regular structure and a plurality of gas flow openings 120h formed in the cylinder to have a predetermined interval to form a space thereon. Then, a pebble-plated platinum (Pt) catalyst layer 123 is formed in the space between the upper and lower shelves 121 and 122.

The cooling unit 130 is a low-temperature cooling water is introduced from the outside to cool the reformed gas is first installed in the reformed gas outlet portion of the gas mixer 110 or the reformed gas introduction portion of the reaction unit 120 is a reaction unit ( Cooling water that forms a space in which the cooling water flows into the double wall so that the cooling water flows to the outer wall of the coil type cooling tube 131 and the reaction unit 120 by cooling the reformed gas flowing into the coil 120. It consists of a cooling jacket 132 of a cooling water jacket.

However, the selective oxidation reactor according to the present invention is divided into a mixer built-in type (FIG. 1) and a mixer exterior type (FIG. 2), as shown in FIGS. 1 and 2, so that the installation structure is different.

 The selective oxidation reactor built-in mixer has a pipe-shaped gas mixer 110 vertically penetrating the center of the reaction unit 120, and the lower end thereof is located directly below the lower shelf 122, and the cooling unit 130. Coil-shaped cooling tube 131 is provided in the space below the catalyst layer 123 in the reaction unit 120, that is, the inlet of the catalyst layer 123.

On the other hand, in the mixer external selective oxidation reactor, the gas mixer 110 is formed separately on the outside of the reaction unit 120 to introduce the end, that is, the mixed gas to the upper side of the reaction unit 120, and the coil type of the cooling unit 130. The cooling tube 131 is installed in the inlet space of the catalyst layer 123 of the reaction unit 120.

Therefore, when the primary reactor 100 having the configuration as described above is pressurized reformate gas and air to the gas mixer 110, the two gases are uniformly mixed while passing through the gas mixer 110 is introduced into the reaction unit 120 In the case of the built-in gas mixer, the mixed gas of the reformed gas and air, which is introduced and mixed at a relatively low temperature, is introduced into the lower space of the lower shelf 122 of the reaction unit 120 to provide a coil of the cooling unit 130. Cooled by the type cooling unit 131, the carbon monoxide is selectively reacted while passing through the catalyst layer 123 of the reaction unit 120 through the hole of the lower shelf 122 to generate carbon dioxide together with the reaction heat.

The cooling unit 130 is operated to assist the selective oxidation of the carbon monoxide. The coil type cooling unit 131 is installed at the inlet of the reaction unit 120, that is, the inlet of the catalyst layer 123 to cool the reformed gas and the air mixture gas. To let in. On the other hand, the jacket type cooling unit 132 of the cooling unit 130 removes the reaction heat generated directly from the catalyst layer 123 of the reaction unit 120.

The secondary reactor 200 performs a step of selectively oxidizing carbon monoxide that is still included in the mixed gas of the reformed gas and air discharged and selectively released carbon monoxide in the primary reactor 100.

The secondary reactor 200 is formed in the same structure as the primary reactor 100. That is, the secondary reactor 200 is composed of the same gas mixer 210, the reaction unit 220 and the cooling unit 230 as the primary reactor (100). However, unlike the first reactor, the catalyst layer 223 of the reaction unit 220 is composed of a ruthenium (Ru) catalyst layer.

The selective oxidation reactor according to the present invention having the above configuration prevents the performance of supplying the reformed gas to the polymer fuel cell stack by selectively oxidizing carbon monoxide in the hydrogen-rich reformed gas to carbon dioxide.

In particular, the jacket-type cooling unit of the cooling unit is not limited to the configuration surrounding the entire outer wall of the reactor, it is also possible to install a tube through which the cooling water passes. It is also preferable to use a method of controlling the temperature by providing a cooling tube at the inlet of the catalyst layer having a large amount of reaction heat.

Hereinafter, the features of the present invention will be described in more detail with reference to the following examples.

In the examples and comparative examples, the reformed gas concentration was compared with the amount of air supplied.

Comparative example  One

Comparative Example 1 is a result of the operation of ZBT GmbH, Germany, reported to be excellent among natural gas reforming systems independently installed with selective oxidation reactors similar to the present invention [Mathiak, J., Heinzel, A., Roes, J., Talk , Th., Kraus, H., and Brandt, H .: Journal of Power Sources , 131, 112 (2004). In a low temperature water gas shift reactor, a reforming gas containing about 1% by volume of carbon monoxide is introduced into the selective oxidation reactor at a temperature of 80 ^° C., and in normal operation the reactor reduces the concentration of carbon monoxide below 50 ppm. At this time, the air supplied is an amount in which oxygen maintains a ratio of carbon monoxide and [O ₂ ] / [CO] = 3.5, which has a disadvantage in that the hydrogen concentration is reduced due to the oxidation of additional hydrogen. In addition, since the concentration of carbon monoxide is higher than the target concentration of 10 ppm, which is 50 ppm, the polymer fuel cell electrode prevents poisoning of carbon monoxide through inflow of air, thereby causing deterioration of battery performance.

Table 1 shows the concentration and the CO conversion of the reformed gas obtained through the reactor as described above. In addition, the performance of the selective oxidation reactor mentioned in Comparative Example 2 and the performance of the selective oxidation reactor provided in the present invention were also presented.

Comparative example  2

In the case of Comparative Example 2 is the performance of the reactor similar to the reactor proposed in the present invention, but without a mixing device of air and reformed gas.

First, a platinum catalyst layer 123 was installed in the primary reactor 100 and air was injected to remove 0.2% by volume of carbon monoxide contained in the reformed gas discharged from the low temperature water gas shift reactor. While maintaining the temperature of the reactor at 160 ~ 180 ^o C, the amount of air was injected to maintain the ratio of carbon monoxide and [O ₂ ] / [CO] = 3.5 ~ 5. At this time, the concentration of carbon monoxide was reduced to 0.07% by volume. In the secondary reactor 200, the ruthenium catalyst layer 223 was installed, and the amount of air was injected to maintain the ratio of [O ₂ ] / [CO] = 3.5 to 5 while maintaining the temperature at 140 to 160 ^o C. The concentration of carbon monoxide decreased below 10 ppm. Reducing the carbon monoxide concentration to less than 10 ppm was successful, but the increased amount of air supplied caused additional hydrogen combustion. Similarly, the oxidation reactor performance of Comparative Example 2 is shown together in Table 1.

Table 1. Concentration of reformed gas and feed air ratio according to the embodiment of the selective oxidation reactor

     Comparative Example 1      Comparative Example 2      Example 1 [O ₂ ] / [CO] ratio 3.5 3.5 1.5 CO conversion rate (%) 99 ~ 99.5 99.7 99.8  Reforming gas concentration (drybase,%) H ₂ 72 71 74 CH ₄ 3 4 One CO 50 ppm 10 ppm 10 ppm CO ₂ 19 19 20 N ₂ 5 5 5

Example  One

In actual operation of the selective oxidation reaction process, it is required to supply a proper amount of oxygen for the complete oxidation of CO and to design a reactor for controlling the temperature range.

Therefore, in the case of Example 1, a reactor was designed as shown in FIGS. 1 and 2 to remove carbon monoxide with an appropriate amount of catalyst.

1 is a built-in selective acid reactor, which is a system in which an air and reforming gas mixing device is installed therein.

At the inlet of the primary reactor 100, the air and the reformed gas introduced through the static screw 112, which is a vortex generating structure of the gas mixer 100 inserted through the reactor, is uniformly mixed. After passing through the pipe 111 and flowing in the reverse direction is introduced into the catalyst layer 123 of the reaction unit 120. At this time, the reformed gas is cooled to 120 ^° C. from 150 ^° C. and introduced into the catalyst layer 123 while passing through the coil-shaped cooling tube 131 of the cooling unit 130 installed at the introduction of the catalyst layer 123. At the inlet of the catalyst layer 123, the temperature of the catalyst layer 123 rises rapidly because carbon monoxide and oxygen start an intense exothermic reaction. In order to control this temperature, a cooling tube or a cooling jacket 132 is installed on the outer wall of the reactor to induce the temperature to be kept stable in the range of 140 to 190 ° C. In addition, the reformed gas flowing through the internal mixing device also serves to cool the catalyst layer 123 from being rapidly overheated. 2 illustrates a method in which a gas mixer 110 that is a mixture of air and reformed gas is installed outside the reaction unit 120. In this case, the volume of the reactor is reduced by the volume occupied by the gas mixer 110, and the coil type cooling tube 131 installed at the introduction of the catalyst layer 123 and the cooling tube or cooling jacket installed at the outer wall for effective removal of the reaction heat ( 132) should be designed to optimize the contact surface of the reactor. The mixed reformed gas and air undergo a selective oxidation reaction in the catalyst layer 123. The reactor performance of Figures 1 and 2 is similar and the reformed gas composition obtained at this time is shown in Table 1 together.

Example  2

In order to examine the long-term stability of the selective oxidation reactor, a reactor consisting of two stages was installed and the concentration of the reformed gas discharged was measured through three days of operation. The reaction temperature was maintained in the proper temperature range of each reactor, and the amount of air supplied was 10 ppm or less while the amount of air supplied was maintained in the ratio of oxygen and carbon monoxide while maintaining [O ₂ ] / [CO] = 1.5. Was maintained.

According to this, in the case of using the reactor of the present invention, the long-term performance test results show that carbon monoxide in the hydrogen-rich reformed gas is stably removed for a long time. The results are shown in FIG.

Example  3

In order to determine the performance of the selective oxidation reactor for the load variation of the natural gas reformer, the concentration of the reformed gas discharged from the selective oxidation reactor was measured while changing the load of the reformer to 75%, 50%, and 30%. When the load was lowered to 50% or less, the heat generation amount of the catalyst layer was reduced, so temperature control was easier, and the amount of air supplied was maintained at a ratio of [O ₂ ] / [CO] = 1.5 in the ratio of oxygen and carbon monoxide. The reformed gas concentrations at each load are shown in FIGS. 4 and 2. 4 shows the flow rate of hydrogen produced at each load.

Table 2. Performance of Selective Oxidation Reactor with Load Variation

Load (%) 100 75 50 30 Production hydrogen flow rate (Nm ³ / hr) 1.2 0.9 0.6 0.4 [O ₂ ] / [CO] ratio 1.5 1.5 1.5 1.5 CO conversion rate (%) 99.8 99.8 99.8 99.8  Reforming gas concentration (dry base,%) H ₂ 73.5 73.5 73.2 72.8 CO ₂ 20.0 19.9 19.0 18.5 CH ₄ 1.5 1.5 2.1 3.0 CO <10 ppm <10 ppm <10 ppm <10 ppm N ₂ 5.0 5.1 5.0 5.2

As a result, it was found that even when the load of the reformer changed from 100% to 30%, it was possible to maintain the carbon monoxide concentration in the reformed gas at 10 ppm or less while injecting an appropriate amount of air.

Therefore, when the reactor of the present invention is used, stable operation can be performed even under load fluctuation without concern for poisoning of the polymer fuel cell electrode.

While the invention has been shown and described with respect to specific embodiments thereof, it will be appreciated that the invention can be variously modified and modified without departing from the spirit or scope of the invention as provided by the following claims. It will be clear to those skilled in the art that they can easily know.

In the drawings, reference numeral 210 is a gas mixer, 211 is a pipe, 212 is a static screw, 220 is a reaction part, 221 is an upper shelf, 222 is a lower shelf, 223 is a catalyst layer, 230 is a cooling part, and 231 is a coil type. Cooling tube 232 is a cooling jacket.

As described above, according to the present invention, in a reactor for selectively oxidizing carbon monoxide in a hydrogen-rich reformed gas, a vortex generating structure for inducing the mixing of the reformed gas and air is installed inside or outside, and maintained at an appropriate temperature. By installing a heat exchanger to the outer wall of the reactor and the introduction portion of the catalyst layer it can be stably removed to 10ppm or less carbon monoxide.

In particular, even under long-term operation and load fluctuations of 3 days or more, 0.5-1% by volume of carbon monoxide emitted from the low temperature water gas shift reaction can be selectively oxidized to remove up to 10 ppm or less, and the efficiency of the stack of polymer fuel cells is reduced. It is possible to drive for a long time without problems.

Claims (12)

In the oxidation reactor for selectively oxidizing the carbon monoxide contained in the reformed gas obtained when the natural gas is reformed through the desulfurization process, steam reforming process, high temperature transition process, low temperature transition process, A gas mixer using a vortex generating structure for mixing the reformed gas containing carbon monoxide with air; A reaction unit for selectively oxidizing the carbon monoxide included by passing the mixed gas of the reformed gas and air obtained by the gas mixer through the catalyst layer; Carbon monoxide contained in the hydrogen-rich reformed gas characterized in that the two reactors consisting of a cooling unit for controlling the temperature of the reaction section, that is, the primary reactor and the secondary reactor are continuously connected to cause a two-stage selective oxidation reaction. Selective oxidation reactor. 2. The carbon monoxide selective oxidation reactor as recited in claim 1, wherein the gas mixer using the vortex generating structure includes a static mixer, a honeycomb type mixer, or a metal foam mixer. 2. The carbon monoxide selective oxidation reactor as recited in claim 1, wherein the gas mixer has a structure that penetrates the catalyst layer of the reaction part and introduces a mixed gas in a reverse direction to the reaction part. The carbon monoxide selective oxidation reactor according to claim 1, wherein the gas mixer is separately installed outside the reaction unit and configured to have a mixer exterior to introduce a mixed gas into the reaction unit. 2. The cooling unit is a double-ply-walled opening in the outer wall of the reactor and the coil-shaped cooling tube made of a coiled tube through which the cooling water for lowering the temperature of the mixed gas of the reformed gas and air introduced into the catalyst layer of the reaction unit is stored. A carbon monoxide selective oxidation reactor included in a reformed gas rich in hydrogen, characterized in that it comprises a cooling jacket having a space and cooling the reaction heat generated in the catalyst layer of the reaction section. 2. The carbon monoxide selective oxidation reactor as recited in claim 1, wherein the reaction part catalyst layer of the primary reactor is a platinum (Pt) catalyst layer. 2. The carbon monoxide selective oxidation reactor as recited in claim 1, wherein the reaction part catalyst layer of the secondary reactor is a ruthenium (Ru) catalyst layer. The method according to claim 1, wherein the reformed gas introduced into the primary reactor contains carbon monoxide at a concentration of 0.5 to 1% by volume and the carbon monoxide contained in the reformed gas discharged from the secondary reactor is reduced to 10 ppm or less. Carbon monoxide selective oxidation reactor in abundant reformate gas. The method of claim 1, wherein the amount of air required to selectively oxidize the carbon monoxide contained in the reforming gas introduced into the primary reactor is [O ₂ ] / [CO] = 1.5 in the ratio of oxygen and carbon monoxide. Carbon monoxide selective oxidation reactor in abundant reformate gas. The carbon monoxide selective oxidation reactor according to claim 1, wherein the space velocity of the mixed gas of the reformed gas and the air in the catalyst layer of the reaction unit is maintained at 10,000 hr ⁻¹ or less. [Claim 2] The carbon monoxide selective oxidation reactor according to claim 1, wherein the reaction part temperature of the primary reactor is controlled to maintain a temperature range of 140 to 190 ° C. 2. The carbon monoxide selective oxidation reactor according to claim 1, wherein the temperature of the reaction section of the secondary reactor is controlled to maintain a temperature range of 120 to 160 ^° C.

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