KR100782125B1 - Purificaton catalyst of reformed gas and preparation method thereof - Google Patents

Abstract

The present invention relates to a reforming gas purification reactor containing a reforming gas purification catalyst, a method for preparing the same, and an electrical reforming gas purification catalyst. More specifically, selective carbon monoxide removal to reduce the carbon monoxide remaining after the aqueous reaction to 10 ppm or less after reforming the gas produced through hydrocarbon or alcohol reforming to obtain hydrogen, which is a driving material of a polymer electrolyte membrane fuel cell (PEMFC). It relates to a reforming gas refining reactor containing a catalyst for (preferential oxidation, PrOx), a method for producing the same and a catalyst for refining the reformed gas.

The first object of the present invention is to selectively remove carbon monoxide (PrOx) to reduce the carbon monoxide remaining after the aqueous reaction to reformate gas produced through hydrocarbon or alcohol reforming to obtain hydrogen, which is the driving material of the polymer fuel cell (PEMFC) up to 10ppm or less To provide a catalyst. A second object of the present invention is to provide a method for producing a catalyst for removing carbon monoxide, which can reduce carbon monoxide from the above-mentioned reformed gas. A third object of the present invention is to provide a reforming gas purification reactor containing a catalyst prepared by the above-mentioned selective carbon monoxide removal (PrOx) catalyst or a method for preparing carbon monoxide removal catalyst which can reduce carbon monoxide from reforming gas. to be.

Description

Reformed catalyst for reforming gas and its preparation method {Purificaton catalyst of reformed gas and preparation method

1 is a block diagram of a reforming gas purification system using a conventional catalyst.

2 is a configuration example of a reforming gas purification system containing the catalyst of the present invention.

3 is a process for producing a catalyst using a mixed support.

4 is the catalytic activity measured in Test Example 1. (A: Pt / HY catalyst used, B: Pt / HY-M catalyst, C: Pt / Bento catalyst used)

5 shows catalytic activity of Test Example 2. (D: Pt / MS4A-M catalyst, E: Pt / MS4A catalyst)

6 is an exploded perspective view showing the configuration of a reforming gas refining reactor having a carbon monoxide removal catalyst layer and a methanation catalyst layer of the present invention.

FIG. 7 is a cross-sectional view (I) of the catalyst bed separation zone boundary plate of the reactor of FIG. 6.

FIG. 8 is a cross-sectional view II of the catalyst bed separation zone boundary plate of the reactor of FIG. 6.

9 is a photograph showing an example of the reactor of FIG.

10 is a graph illustrating a measurement result of reformed gas purification performance using the reactor of FIG. 6.

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

100: upper plate 200: lower plate

300: upper heat dispersion plate 400: catalyst layer forming plate

500: lower heat dispersion plate 700: upper catalyst layer support plate

800: lower catalyst layer support plate

The present invention relates to a reforming gas purification reactor containing a reforming gas purification catalyst, a method for preparing the same, and an electrical reforming gas purification catalyst. More specifically, in order to obtain hydrogen as a driving material of a polymer electrolyte membrane fuel cell (PEMFC), the reformed gas, which is a synthesis gas produced through hydrocarbon or alcohol reforming, is reduced to 10 ppm or less after the aqueous reaction. It relates to a reforming gas refining reactor containing a catalyst for selective carbon dioxide removal (PrOx), a method for producing the same, and a catalyst for refining the reforming gas.

The concentration of carbon monoxide is reduced by 0.4 ~ 1.0% through reforming reaction of the hydrogen production process using hydrocarbon (refer to Scheme 1 below) and carbon monoxide aqueous reaction (see Scheme 2). The carbon monoxide (CO) concentration in the gas should be reduced to less than 10 ppm.

Recently, the development of an electrode catalyst capable of excluding effects up to 100 ppm has been announced, but when the concentration of carbon monoxide in the reformed gas is reduced to 10 ppm or less, preferably 1 ppm or less, it is possible to maximize output density and safety.

Reactions applicable for the purification of carbon monoxide are purification processes in which selective oxidation to carbon monoxide (see Scheme 3 below) and methanation (see Scheme 4 below) can be used in small polymer fuel cell systems.

CH ₄ + H ₂ O → CO + 3H ₂ Generation heat: +49.1 kcal / mol (Scheme 1)

CO + H ₂ O → CO ₂ + H ₂ Generated heat: -9.81 kcal / mol (Scheme 2)

CO + 1 / 2O ₂ → CO ₂ Generated heat: -69.76 kcal / mol (Scheme 3)

CO + 3H ₂ → CH ₄ + H ₂ O Heat generated: -49.1 kcal / mol (Scheme 4)

H₂ + 1 / 2O₂ → H₂O Generated heat: -68.1 kcal / mol (Scheme 5)

In order to remove carbon monoxide contained in the reformed gas after the aqueous reaction, research on carbon monoxide removal (PrOx) or methanation reaction is being conducted. However, in addition to minimizing the loss of hydrogen according to Scheme 4, in particular, when alcohol is used as a raw material, In order to simultaneously reduce alcohol, a carbon monoxide removal process involving an oxidation reaction is essential.

Therefore, research is underway due to the need for continuous development of catalyst materials having high activity, and it is known that high selectivity can be obtained when using zeolite as a precious metal support as a representative component. Although slightly different depending on the concentration of carbon monoxide, when the concentration of carbon monoxide is supplied as a 1% reactant, the use temperature is known to be 200 to 250 ° C.

On the other hand, in the conventional reactor for removing carbon monoxide, the reactor is installed in multiple stages (2-4 stages) and the temperature of the reactants is reduced by using a heat exchanger in the middle, or an inter cooler is provided inside the reactor to increase the maximum conversion rate. The system is configured to operate in the range which can be obtained (see FIG. 1).

On the other hand, when the catalyst composition is provided with excellent selectivity to carbon monoxide and a very wide active temperature range, a heat exchanger and / or an internal cooling device are unnecessary for the multi-stage reaction, thereby reducing the volume and weight of the device while ensuring ease of process configuration. Can be achieved (see FIG. 2). However, due to the lack of research on catalysts with good selectivity to carbon monoxide and very wide active temperature ranges, heat exchangers and / or internal cooling systems in addition to reactors are generally required for the system.

The first object of the present invention is to reduce the carbon monoxide remaining after the aqueous reaction of the reformed gas, which is a synthesis gas produced through hydrocarbon or alcohol reforming to obtain hydrogen as a driving material of the polymer fuel cell (PEMFC) up to 10ppm, preferably 1ppm It provides a catalyst for selective carbon monoxide removal (PrOx) to reduce.

A second object of the present invention is to provide a method for producing a catalyst for removing carbon monoxide, which can reduce carbon monoxide from the above-mentioned reformed gas.

A third object of the present invention is to provide a reforming gas purification reactor containing a catalyst prepared by the above-mentioned selective carbon monoxide removal (PrOx) catalyst or a method for preparing carbon monoxide removal catalyst which can reduce carbon monoxide from reforming gas. to be.

The reformed gas purification catalyst, which is the first invention of the present application for the above-mentioned purpose, is a reforming gas purification catalyst comprising an active ingredient and a support for supporting the active ingredient, wherein the support for supporting the active ingredient is a mixture of zeolite and bentonite. A mixed support is used.

As the active ingredient in the reforming gas purification catalyst of the present invention, any one or more precious metals selected from conventional Pt, Rh, Ru, Au, and Ir may be used. At this time, the active metal noble metal may be included 0.1 to 5.0 parts by weight based on 100 parts by weight of the mixed support.

In the reforming gas refining catalyst of the present invention, if the active ingredient is used in an amount less than 0.1 part by weight based on 100 parts by weight of the mixed support, the removal effect of carbon monoxide is minimal when the reforming gas is purified. There is no apparent effect on the removal. Therefore, it is preferable to use 0.1 to 5.0 parts by weight of the precious metal as the active ingredient in the catalyst for reforming gas purification of the present invention based on 100 parts by weight of the mixed support.

In the reforming gas purification catalyst of the present invention, the support supporting the active ingredient may be a mixed support comprising 1 to 50% by weight of bentonite and 50 to 99% by weight of zeolite. At this time, the zeolite is used as a catalyst support to improve the selectivity by increasing the residence time in the catalyst layer for the reformed gas, bentonite is used to secure the oxidizing power at low temperatures. That is, the reformed gas purification catalyst of the present invention can have high conversion rate and high selectivity of carbon monoxide in the reformed gas in a wide temperature range by using zeolite and bentonite as a support supporting the active ingredient.

In the present invention, a mixture of zeolite and bentonite in various contents is used as a support for the catalyst. In order to obtain a catalyst meeting the object of the present invention, a mixture of zeolite and bentonite of the aforementioned numerical content may be used as a support for the catalyst.

In the present invention, the zeolite, which is one component of the catalyst support, may use any one or more selected from A-type zeolite, Y-type zeolite, HY-type zeolite, and beta (β) zeolite.

Bentonite, which is one component of the catalyst support in the present invention, may have some differences in activity depending on acidity or degree of purification, but there is no particular limitation because there is no big difference in overall performance. However, since it is used as a support for the catalyst, each material is milled with a zeolite to be pulverized to 10 탆 or less, preferably 0.5 to 10 탆, and then uniformly mixed to granulate and carry a precious metal as an active ingredient. .

According to a second aspect of the present invention, there is provided a method of preparing a catalyst for refining a reformed gas, the method including preparing an active ingredient and a support for supporting the active ingredient.

Mixing zeolite and bentonite,

Extruding a mixture of zeolite and bentonite,

Drying the extrudate mixed with zeolite and bentonite and calcining to obtain a mixed support consisting of zeolite and bentonite,

The step of supporting the active ingredient on the mixed support.

In the production of the catalyst for reforming gas purification of the present invention, the support for supporting the active ingredient of the catalyst may be a mixed support consisting of 1 to 50% by weight of bentonite and 50 to 99% by weight of zeolite.

Particularly during the preparation of the catalyst for reforming gas purification of the present invention, the method may further include adding water to these mixtures before extrusion after mixing zeolite and bentonite in the preparation of the mixed support. In the present invention, 10 to 100 parts by weight of water may be added based on 100 parts by weight of the mixture of zeolite and bentonite. At this time, it is good to add gradually in small amounts while paying attention to the rapid heat generation by the addition of moisture. If less than 10 parts by weight of water is added to 100 parts by weight of the mixture of zeolite and bentonite, there is a problem of causing an overload of the extrusion process during extrusion, and if it is used more than 100 parts by weight, it is difficult to uniformly dry and take a lot of drying time. In the present invention, it is preferable to add 10 to 100 parts by weight based on 100 parts by weight of the mixture of zeolite and bentonite when water is added.

Meanwhile, the method may further include adding water to the mixture of zeolite and bentonite and then adding a process aid to facilitate the granulation process for the mixture of zeolite and bentonite when preparing the mixed support. In this case, 0.05 to 3 parts by weight of the process aid may be added to 100 parts by weight of the mixture of zeolite and bentonite. If the process aid is added less than 0.05 parts by weight with respect to 100 parts by weight of the mixture of zeolite and bentonite, the role is insignificant. If the process aid is used in excess of 3 parts by weight, the catalyst is lost due to the process aid combustion heat during the firing process. When adding the process aid in the invention it is preferable to add 0.05 to 3 parts by weight based on 100 parts by weight of the mixture of zeolite and bentonite. In the process aids may be used polyvinyl alcohol (PVA).

Zeolite, bentonite, water and process aids are ball milled for 12 to 48 hours to uniformly mix the respective materials and then extrude these mixtures. At this time, the extrusion conditions are slightly different depending on the content of the process aid, the mixing ratio of zeolite and bentonite, and the water content, but may be performed at 0.5 to 20 kgf / cm ² per unit area.

The mixture of zeolite and bentonite may be extruded from the above and then dried and calcined. In this case, drying of the extrudate mixed with zeolite and bentonite may be performed at 50 to 105 ° C. for 24 to 72 hours, and firing may be performed at 400 to 700 ° C. for 10 to 24 hours to remove the process aid. In the present invention, the catalyst for reforming gas purification according to the object of the present invention was carried out under various conditions for the drying and firing of an extrudate mixed with zeolite and bentonite when preparing a mixed support consisting of zeolite and bentonite. In order to obtain the above, it is preferable to obtain a mixed support supporting the active component of the catalyst under the above-described drying and firing conditions.

After completion of drying and firing, the mixed support consisting of zeolite and bentonite can be processed to have a desired size. Meanwhile, the catalyst may be prepared by supporting 0.1 to 5.0 parts by weight of any one or more precious metals selected from Pt, Rh, Ru, Au, and Ir as 100 parts by weight of the mixed support composed of zeolite and bentonite. At this time, any method of supporting the active ingredient on the mixed support may be used as long as it is possible to support the active ingredient on the support when preparing a conventional catalyst. In the present invention, both the initial wetting method or the method of impregnation may be used as a method of supporting the active ingredient in the mixed support.

As mentioned above, after preparing a mixed support of zeolite and bentonite, the active support is supported on the mixed support, followed by drying, calcining and reducing to obtain a catalyst for reforming gas purification. At this time, the active ingredient is supported on the mixed support and dried, and then the supporting and drying of the active ingredient are repeated several times to obtain a catalyst having the active ingredient supported on the mixed support. On the other hand, after supporting the active ingredient in a mixed support consisting of zeolite and bentonite, drying, firing and reduction can be applied to the conditions used in the production of a general catalyst. The mixed support catalyst on which the active ingredient is supported can be dried under the same conditions as the drying conditions in the process of preparing the mixed support, and the calcining is adsorbed on the catalyst by calcining at a temperature of 400 to 600 ° C. for 3 to 12 hours. Volatile residues can be decomposed and removed. At the time of firing, it takes a long time to incinerate the residual material under the conditions of 400 ° C. or lower, and at a temperature of 600 ° C. or higher, the dispersibility of the supported active metal decreases, and therefore, firing is performed in the temperature range of 400 ° C. to 600 ° C. The calcined catalyst is reduced for 0.5 to 5 hours at a temperature in the range of 200 to 400 ° C. using a reducing gas such as hydrogen. At temperatures below 200 ° C, the oxygen bound in the mixed support surface and the supported active metals and oxides cannot be removed effectively.At 400 ° C or higher, the dispersion degree decreases through recombination of dispersed active metals. Reducing in the temperature range of -400 degreeC is the most effective.

The third object of the present invention is to provide a heat exchanger or an intermediate cooler including the catalyst for reforming gas reforming of the first object of the present invention (including the catalyst for reforming gas purification obtained by preparing the catalyst for reforming gas reforming for the second purpose of the present invention) It provides a reactor for reforming the reformed gas is unnecessary.

In the reformed gas purification reactor of the present invention, the reformed gas purification reactor comprising a catalyst layer for inducing the oxidation reaction of carbon monoxide contained in the reformed gas and a methanation catalyst layer for inducing the methanation reaction of carbon monoxide,

Purification gas flow hole, catalyst layer for inducing oxidation reaction of carbon monoxide, catalyst inlet for introducing such catalyst, methanation catalyst layer for inducing methanation reaction of carbon monoxide, methanation catalyst inlet through which such methanation catalyst is introduced and separated A catalyst layer forming plate 400 separating the catalyst layer for inducing the oxidation reaction of carbon monoxide and the methanation catalyst layer for inducing the methanation reaction of carbon monoxide by the region boundary plate 407,

A lower catalyst support plate 800 having a reformed gas flow hole under the catalyst layer forming plate 400, a purified gas discharge hole formed through a catalyst layer and a methanation catalyst layer of the catalyst layer forming plate, and a reformed gas flow hole under the lower catalyst support plate; Lower heat distribution plate 500 having a purification gas discharge hole connected to the purification gas discharge hole of the lower catalyst support plate 800 on one side, and a reformed gas inlet and a flow hole under the lower heat distribution plate, and on one side of the lower heat dispersion plate A lower plate 200 having a purified gas discharge hole connected to the purified gas discharge hole,

An upper catalyst support plate 700 having a reformed gas flow hole on the catalyst layer forming plate 400 and a gas flow hole that induces a reformed gas flow in a catalyst layer inducing an oxidation reaction of carbon monoxide, and a reformed gas flow hole on the upper catalyst support plate; An upper heat dissipation plate 300 having a gas flow hole for inducing a flow of reformed gas to the upper catalyst support plate 700, and a reformed gas flow hole and an upper heat dissipation plate 300 to induce a flow of reformed gas on the upper heat dissipation plate 300. And an upper plate 100 having a gas flow hole.

The carbon monoxide oxidation catalyst layer space and carbon monoxide methanation reaction methanation catalyst layer space of the catalyst layer forming plate 400 may be separated by a separation area boundary plate 407 in a ratio of 5 to 9: 1 to 5.

In the separation region boundary plate 407, the gas moves from the catalyst space 402 to the catalyst space 403 through the flow holes 450 formed in the upper and lower portions thereof (see FIG. 7) or the multilayer thin plate 490. ) And through the flow holes 490 formed in each thin plate, gas can be moved from the catalyst space 402 to the catalyst space 403 (see FIG. 8).

The upper heat dissipation plate 300 and the lower heat dissipation plate 500 includes a heat dissipation action of the upper catalyst support plate 700 and the lower catalyst support plate 800 and a mixture of reformed gas and air. can do.

The catalyst layer forming plate 400 may have a thickness of 1.0 to 10.0 mm, and the catalyst for removing the reformed gas carbon monoxide charged in the catalyst layer forming plate 400 may be filled in the thickness of the catalyst layer forming plate 400. The particle size can be filled with 0.1 to 2.0 mm.

The catalyst layer forming plate 400 includes a catalyst space 402 filled with a catalyst for removing carbon monoxide to remove carbon monoxide contained in the reformed gas and a catalyst space filled with a methanation catalyst for promoting a methane reaction. The reformed gas introduced into the catalyst layer forming plate removes carbon monoxide contained in the reformed gas through a catalyst space 402 filled with a carbon monoxide removal catalyst and a catalyst space 403 filled with a methanation catalyst to obtain a purified gas. Can be.

Meanwhile, the reformed gas supplied to the reformed gas purification reactor of the present invention controls the ratio of H ₂ / CO in the reformed gas to 500 or more, preferably 500 to 700, while the ratio of O ₂ / CO is 0.4 to 2.5. The reformed gas may be purified as air as an oxidant to be supplied to the reactor for reforming gas purification, such as reformed gas, so that the carbon monoxide in the reformed gas is 10 ppm or less, more preferably 1 to 10 ppm of carbon monoxide in the reformed gas.

Hereinafter, the content of the present invention will be described in detail through examples and test examples. However, these are intended to explain the present invention in more detail, and the scope of the present invention is not limited thereto.

Comparative Example 1 Preparation of Pt / HY Catalyst

5.31 g of chloroplatinic acid (H ₂ PtCl ₆ .xH ₂ O, manufactured by HanGold Gold Co., Ltd.) was dissolved in 100 g of distilled water, and then supported by 100 g of HY zeolite (Aldrich) by initial wet method.

The supported catalyst was dried for 24 hours in a 105 ° C. air atmosphere, calcined for 5 hours in a 400 ° C. air atmosphere, and reduced to 2 hours in a 300 ° C. hydrogen atmosphere. The prepared catalyst was designated Pt / HY.

In the above HY zeolite, Y-type zeolite (NH ₄ Y) substituted with an ammonium group was calcined at 550 ° C. for 3 hours, and used by pulverizing to 80/120 mesh particle size.

<Comparative Example 2> Preparation of Pt / Bento Catalyst

Bentonite (Aldrich) was used as a support for the catalyst, and the catalyst was prepared in the same manner as in Comparative Example 1 except that the bentonite was loaded with platinum and calcined at 500 ° C for 3 hours. The prepared catalyst was designated Pt / Bento.

<Comparative Example 3> Preparation of Pt / MS4A Catalyst

A catalyst was prepared in the same manner as in Comparative Example 1 except that the support of the catalyst was used as an A-type zeolite (Aldrich). The prepared catalyst was designated Pt / MS4A.

Example 1 Preparation of Pt / HY-M Catalyst

A catalyst was prepared in the same manner as in Comparative Example 1 except that a mixed support consisting of HY zeolite (Aldrich) and bentonite was used as a support of the catalyst. The prepared catalyst was designated Pt / HY-M.

The mixed support is mixed with 90 parts by weight of HY zeolite and 10 parts by weight of bentonite and milled for 24 hours, extruded at a pressure of 0.7kgf / cm ² , dried at 85 ℃ for 24 hours and baked at 500 ℃ for 12 hours It was then used to grind to 80/120 mesh (see Figure 3).

Example 2 Preparation of Pt / MS4A-M Catalyst

 A catalyst was prepared in the same manner as in Example 1, except that a mixed support consisting of 80 parts by weight of A-type zeolite and 20 parts by weight of bentonite was used. The prepared catalyst was designated Pt / MS4A-M.

<Test Example 1>

The performance of the catalysts prepared in Comparative Examples and Examples was measured using an internal diameter 4 mm micro fixed bed reactor. The composition of the reaction gas is 1.0% by volume of carbon monoxide (CO), 0.75% by volume of oxygen (O ₂ ) (O / C = 1.5), 2.5% by volume of water, 20.0% by volume of carbon dioxide (CO ₂ ), and the remainder is hydrogen. It was.

The reaction gas was supplied at 100 ml / min, and each catalyst was charged with 0.15 g of space velocity (GHSV) of 20,000 hr ⁻¹ . The removal rate of carbon monoxide was analyzed 2 hours after the reaction supply to reach a steady state. The carbon monoxide concentration on the reactor inlet and outlet side was measured to define the CO conversion rate as shown in Equation 1 below.

[Equation 1]

CO conversion rate = [1- (Reactor outlet CO concentration / reactor inlet CO concentration)] ㅧ 100

The analysis of CO, O ₂ and CO _{2 used} Hewlett-Packard's HP-6890 gas chromatography (GC) equipped with two thermal conductivity detector (TCD) detector. Carbon monoxide and oxygen were separated into Molecular sieve 5A capillary column (length 30m, inner diameter 500㎛), and carbon dioxide was separated by Porapak Q, using mobile gas as hydrogen.

Activity for three catalysts of Pt / HY catalyst (A) prepared in Comparative Example 1, Pt / Bento catalyst (B) prepared in Comparative Example 2, and Pt / HY-M catalyst (C) prepared in Example 1 The measurement result is as showing in FIG.

As shown in FIG. 4, the activity of the Pt / HY catalyst (A) showed a maximum conversion at around 200 ° C. as shown in the existing zeolite related literature, and the Pt / Bento catalyst (B) using bentonite as a support was 99 at 130 ° C. Carbon monoxide conversion was more than% and the conversion was linearly decreased with increasing temperature. However, in the case of the Pt / HY-M catalyst (C) using the mixed support member, the carbon monoxide removal tendency was similar to that of using bentonite alone as a support, but there was a big difference in the high temperature portion. Pt / Bento (B) catalysts have a temperature range of 130-150 ° C, while Pt / HY-M (C) catalysts using mixed supports are 130-190 ° C. Appeared. From this point of view, it was found that there is a difference in activity of the catalyst depending on the constituent conditions of the support.

<Test Example 2>

In the same manner as in Test Example 1, the activities of the two catalysts of Pt / MS4A-M catalyst (D) prepared in Example 2 and Pt / MS4A catalyst (E) prepared in Comparative Example 3 were measured. However, the oxygen concentration of oxidant was supplied at 0.6% to maintain the O / C ratio of 1.2, and the space velocity (GHSV) of the reaction gas was 15,000 hr ⁻¹ .

The experimental results are summarized in FIG. The catalyst (E) using the A-type zeolite as the support of the catalyst showed typical zeolite characteristics showing high conversion (80%) and selectivity in the region of 180 to 200 ° C. On the other hand, the catalyst (D) using type A zeolite and bentonite as a support of the catalyst showed a maximum conversion rate (96%) at 130 ° C., and also a range showing a high conversion rate of 90% or more. It was found that there was a significant performance improvement compared to the MS4A catalyst (E). In this regard, when a mixture of zeolite and bentonite having a separation ability for oxygen and carbon monoxide is used as a support for the catalyst, there is a synergistic effect on the carbon monoxide (PrOx) reaction compared to the catalyst using the zeolite or bentonite, respectively. It can be seen.

<Test Example 3> Reforming home purification reactor containing a catalyst for removing carbon monoxide and a catalyst for methanation reaction

The configuration and performance of the reforming home purification reactor containing the carbon monoxide removal catalyst and the methanation catalyst, which are the objects of the present invention, will be described with reference to FIG. 6.

6 is an exploded perspective view showing the configuration of a reforming gas refining reactor having a carbon monoxide removal catalyst layer and a methanation catalyst layer of the present invention.

The reactor for reforming gas purification of the present invention includes a lower heat dissipation plate 500, a lower catalyst support plate 800, a catalyst layer forming plate 400, an upper catalyst support plate 700, between the upper plate 100 and the lower plate 200. The upper heat dissipation plate 300 is configured.

The lower plate 200 has an inlet through which reformed gas and air flow and a flow hole 201 through which reformed gas and air flow, and has a purified gas discharge hole 202 on one side.

The lower heat dissipation plate 500 has flow holes 506 and 505 through which the reformed gas and air flowing from the lower plate flow, and the reformed gas and air are mixed between the flow holes 506 and the flow holes 506. It has a heat dissipation plate to induce heat dissipation of the catalyst support plate 800, one side is provided with a purified gas discharge hole 502 purified from the catalyst layer forming plate 400.

The lower catalyst support plate 800 is formed with a flow hole 801 through which reformed gas and air flow, and at one side, a purified gas discharge hole 805 purified from the catalyst layer forming plate 400 is formed.

The catalyst layer forming plate 400 includes a catalyst layer space 402 filled with a catalyst for removing carbon monoxide contained in the reformed gas and a catalyst layer space 403 filled with a methanation catalyst, and a separation zone boundary for separating the two layers. It is separated by the plate 407. Meanwhile, one side of each catalyst bed space is provided with catalyst inlets 405 and 405 ′ for introducing each catalyst. At this time, since the hole can be processed after joining according to the thickness of the catalyst layer forming plate, the processing of the holes 405 and 405 'can be omitted in the state of each component.

The shape of the separation area boundary plate 407 can be configured as shown in FIG. 7, and can also be configured in the form of FIG. That is, in the case of FIG. 7, the gas flow holes 450 are provided on both upper and lower surfaces of the single plate, and as shown in FIG. 8, when the microchannel is processed in the plane of the thin plate 490 and stacked thereon, the reactant supply holes are proportional to the number of stacked layers. Since 480 is increased, the reaction gas is supplied to the entire catalyst layer as compared to the single layer. Therefore, the separation zone boundary plate 407 also serves to redistribute the reaction gas in addition to the simple division of the catalyst layer.

The upper catalyst support plate 700 includes a flow hole 701 through which the reformed gas and air flow in communication with the reformed gas and the flow hole 401 through which the catalyst layer forming plate 400 flows. 100, a flow hole 705 through which reformed gas and air flow into the catalyst layer forming plate 400 through the upper heat dissipation plate 300 is provided.

The upper heat dissipation plate 300 has flow holes 301 and 302 through which reformed gas and air flow through the flow holes 705 of the upper catalyst support plate 700, and between the flow holes 301 and the flow holes 302. The reformed gas and air are mixed and have a heat dissipation plate for inducing heat dissipation of the upper catalyst support plate 700, and on one side, a flow hole 303 through which the reformed gas and air flow through the hole 102 of the upper plate 100. It is provided.

The upper plate 100 includes a hole 101 through which reformed gas and air flow through the hole 302 of the upper heat dissipation plate 300, and a hole 102 through which reformed gas and air flow through the hole 101. Equipped.

The lower heat dissipation plate 500, the lower catalyst support plate 800, the catalyst layer forming plate 400, the upper catalyst support plate 700, and the upper heat dissipation plate 300 between the upper plate 100 and the lower plate 200. Each component of can be joined and formed as shown in FIG. In this case, the diameters of the catalyst inlets 405 and 405 ′ may be processed to match the diameters of the catalysts flowing into the respective catalyst bed spaces. For example, when the diameter of the catalyst is 1.5 mm or less, the diameter of the catalyst may be processed to 1.5 mm or more. The Pt / MS4A-M catalyst (0.9 g) prepared in Example 2 was introduced into the catalyst layer space 402 through the catalyst inlet through the catalyst inlet 405 and then sealed with a plug. Also, for the methanation reaction, a Ru / TiO ₂ catalyst (0.5 g) was supplied into the catalyst layer space 403 through the opposite catalyst inlet 405 'and sealed with a plug.

The completed reactor was mounted in a heater and the temperature of the catalyst bed inlet and outlet was monitored and the reaction temperature was defined as the catalyst bed outlet temperature.

The reformed gas and air are supplied to the hole 201 of the lower plate, and locally heated by the oxidation reaction and the methanation reaction while passing through the heat dispersion plate through the hole 506 of the lower heat dissipation plate 500. Induction of thermal equilibrium. Subsequently, after passing through the gas holes 505, 801, 401, 701, and 301 sequentially, the air and the reformed gas are mixed together with the heat dissipation of the upper catalyst support plate 700 while moving the upper heat transfer plate 300. . The mixed gas passes through the holes 303 of the heat dissipation plate 300 via the holes 101 and 102 of the upper plate 100, and then passes through the holes 705 in the upper catalyst support plate 700, and the catalyst is mounted. The oxidation reaction of carbon monoxide proceeds by contacting the catalyst for removing carbon monoxide (PrOx) provided in the catalyst space 402. Then, through the holes 450 and 480 of the separation zone boundary plate 407, the catalyst is moved to the catalyst space 403 in which the methanation catalyst is mounted, and the unreacted carbon monoxide is purified by the methanation reaction. .

Thereafter, the purified gas is discharged through the hole 805 of the lower catalyst support plate 800, the hole 502 of the lower heat dissipation plate 500, and the hole 202 of the lower plate 200. Each of the holes 705 and 805 processed in the upper catalyst layer support plate 700 and the lower catalyst layer support plate 800 necessary for forming the catalyst layer forms a large diameter and preferably a plurality of gas flow passages in a range where the catalyst particles are supported. It was prevented from acting as a resistive layer in the.

The reaction gas was supplied at 1600ml / min (GHSV 30,000 / hr), and the composition of the gas was 79% hydrogen, 1% carbon monoxide, 20% carbon dioxide, and 10% moisture before the reaction. Infused occasionally. Prior to the reaction, a reduction pretreatment of the catalyst was performed by supplying 200 ml / min of 10% H ₂ / N ₂ gas at 250 ° C. for 3 hours. After the reaction was cooled to 85 ° C. under a reducing atmosphere and the reaction gas was added and stabilized for 1 hour, heating was performed at a heating rate of 0.1 ° C./min. Oxygen, methane and carbon monoxide remaining in the exhaust gas in the range of 85 to 275 ° C were analyzed. The conversion rate of carbon monoxide and oxygen was calculated by [Equation 1].

As shown in FIG. 10, the results of carbon monoxide concentration of 1 ppm or less were obtained in the region of 115 to 245 ° C., and carbon monoxide 1 to 10 pm was purified in the region of 245 to 275 ° C. In particular, according to the use of this reactor, the area which can be reduced to 1 ppm or less of carbon monoxide was evaluated as a purifier that can ignore the effect on PEMFC in a very wide range of 115 to 245 ° C. When comparing the following Experimental Example 4, in order to achieve the third object of the present invention, it can be seen that the role of the low-temperature, high activity PrOx catalyst according to the first and second objects is very important.

<Test Example 4>

Reactor performance was evaluated in the same order as in Example 8. However, Pt / MS4A catalyst prepared in Comparative Example 3 was used as the PrOx catalyst.

As a result of the experiment, as shown in FIG. 10, the temperature range that can satisfy the range of 10 ppm of residual carbon monoxide concentration in the refined gas is very narrow, 224 to 241 ° C. In addition, it was found that it is impossible to reduce the residual concentration of carbon monoxide to less than 1 ppm. According to Test Example 3, the results can not be compared with the carbon monoxide removal Pt / MS4A-M catalyst (▼) adoption. This phenomenon is a phenomenon in which the temperature range showing the maximum activity of the Pt / MS4A catalyst (●) and the main activity range of the methanation reaction are the same. The results indicate the importance of the / MS4A-M catalyst. That is, the reactor simply can not achieve the purification efficiency to the carbon monoxide by the configuration as shown in FIG. 6 shows that the low-temperature activity of the catalyst is to be preceded.

The reforming gas purification catalyst according to the present invention has excellent performance of selective oxidation reaction for carbon monoxide in a wide temperature range. Thus, in the configuration of the reformed gas purification process using the catalyst, the process is simplified, downsized, and lightweight.

As described above, although described with reference to a preferred embodiment of the present invention, those skilled in the art will be variously modified and modified within the scope of the present invention without departing from the spirit and scope of the present invention described in the claims below. It will be appreciated that it can be changed.

Claims (16)

In the reforming gas purification catalyst comprising the active ingredient and a support for supporting the active ingredient, A catalyst for reforming gas purification, characterized in that a mixed support consisting of a mixture of zeolite and bentonite is used as a support for supporting at least one active ingredient selected from Pt, Rh, Ru, Au, and Ir. The catalyst for reforming gas purification according to claim 1, wherein the active ingredient comprises 0.1 to 5.0 parts by weight based on 100 parts by weight of the mixed support. The catalyst for reforming gas purification according to claim 1, wherein the mixed support comprises bentonite 1 to 50% by weight and zeolite 50 to 99% by weight. In the production of a catalyst applied to the reformed gas purification and consisting of an active ingredient and a support for supporting the active ingredient, Mixing zeolite and bentonite, Extruding a mixture of zeolite and bentonite, Drying the extrudate mixed with zeolite and bentonite and calcining to obtain a mixed support consisting of zeolite and bentonite, A method for producing a reforming gas purification catalyst comprising the step of supporting at least one active ingredient selected from Pt, Rh, Ru, Au, and Ir on a mixed support. The method for producing a catalyst for reforming gas purification according to claim 4, wherein 1 to 50% by weight of bentonite and 50 to 99% by weight of zeolite are mixed. The method of claim 4, further comprising adding 10 to 100 parts by weight of water to 100 parts by weight of the mixture of zeolite and bentonite. The method according to claim 4, further comprising adding 0.05 to 3 parts by weight of polyvinyl alcohol (PVA) as a processing aid based on 100 parts by weight of the mixture of zeolite and bentonite. The method of claim 4, wherein the drying of the mixture of zeolite and bentonite is carried out at 50 to 105 ° C. for 24 to 72 hours. The method of claim 4, wherein the firing of the mixture of zeolite and bentonite is performed at 400 to 700 ° C. for 10 to 24 hours. The method for producing a reforming gas purification catalyst according to claim 4, wherein the active ingredient is supported on 0.1 to 5.0 parts by weight in 100 parts by weight of the mixed support. In a reforming gas purification reactor comprising a catalyst layer for inducing an oxidation reaction of carbon monoxide contained in a reformed gas and a methanation catalyst layer for inducing a methanation reaction of carbon monoxide, A catalyst layer for inducing the oxidation reaction of carbon monoxide comprising a refinery gas flow hole, the catalyst for reforming gas reformed according to any one of claims 1 to 3, a catalyst inlet for introducing such a catalyst, and a methanation reaction of carbon monoxide. A catalyst for reforming gas reforming according to any one of claims 1 to 3 is provided by a separation zone bounding plate 407 having a methanation catalyst layer for inducing and a methanation catalyst inlet through which the methanation catalyst is introduced. A catalyst layer forming plate 400 in which a catalyst layer inducing an oxidation reaction of carbon monoxide and a methanation catalyst layer inducing a methanation reaction of carbon monoxide are separated; A lower catalyst support plate 800 having a reformed gas flow hole under the catalyst layer forming plate 400, a purified gas discharge hole formed through a catalyst layer and a methanation catalyst layer of the catalyst layer forming plate, and a reformed gas flow hole under the lower catalyst support plate; Lower heat distribution plate 500 having a purification gas discharge hole connected to the purification gas discharge hole of the lower catalyst support plate 800 on one side, and a reformed gas inlet and a flow hole under the lower heat distribution plate, and on one side of the lower heat dispersion plate A lower plate 200 having a purified gas discharge hole connected to the purified gas discharge hole, An upper catalyst support plate 700 having a reformed gas flow hole on the catalyst layer forming plate 400 and a gas flow hole that induces a reformed gas flow in a catalyst layer inducing an oxidation reaction of carbon monoxide, and a reformed gas flow hole on the upper catalyst support plate; An upper heat dissipation plate 300 having a gas flow hole for inducing a flow of reformed gas to the upper catalyst support plate 700, and a reformed gas flow hole and an upper heat dissipation plate 300 to induce a flow of reformed gas on the upper heat dissipation plate 300. Reactor for reforming gas purification comprising a top plate having a gas flow hole (100). 12. The reformed gas purification according to claim 11, wherein the carbon monoxide oxidation catalyst layer space and carbon monoxide methionization methanation catalyst layer space of the catalyst layer forming plate are separated by a separation zone boundary plate 407 at a ratio of 5-9: 1-5. Reactor. 12. The separation zone boundary plate 407 has a gas flow from the catalyst space 402 to the catalyst space 403 through a flow hole formed in the upper and lower portions, or formed into a thin layer of each of the thin plate Reactor for reforming gas purification gas is moved from the catalyst space (402) to the catalyst space (403) through a flow hole formed in the. 12. The reactor of claim 11, wherein the upper heat dissipation plate and the lower heat dissipation plate include a heat dissipation action of the upper catalyst support plate and the lower catalyst support plate and a mixture of the reformed gas and air. The reactor of claim 11, wherein the catalyst layer forming plate has a thickness of 1.0 to 10.0 mm. delete

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