Source: https://patents.google.com/patent/EP1046612A1/en
Timestamp: 2018-08-20 18:44:19
Document Index: 217271935

Matched Legal Cases: ['art 1', 'art 10', 'art 1', 'art 1', 'art 1', 'art 10', 'art 1', 'art 10']

EP1046612A1 - Hydrogen refinement apparatus - Google Patents
Hydrogen refinement apparatus Download PDF
EP1046612A1
EP1046612A1 EP20000108279 EP00108279A EP1046612A1 EP 1046612 A1 EP1046612 A1 EP 1046612A1 EP 20000108279 EP20000108279 EP 20000108279 EP 00108279 A EP00108279 A EP 00108279A EP 1046612 A1 EP1046612 A1 EP 1046612A1
shifting catalyst
EP20000108279
EP1046612B1 (en )
The present specification disclosed a hydrogen refinement apparatus comprising a reformed gas feeding part containing at least a hydrogen gas and water vapor, and a reaction chamber equipped with a carbon monoxide shifting catalyst body downstream said reformed gas feeding part, wherein said carbon monoxide shifting catalyst body comprises a carrier supporting Pt, the carrier being composed of at least one metal oxide having a BET specific surface area of 10 m2/g or more, and a method for operating the apparatus. The present invention provides improved heat-resistance of the CO shifting catalyst body, and can operate stably even if the apparatus is activated and stopped repeatedly.
The present invention relates to a hydrogen refinement apparatus, which refines a reformed gas containing hydrogen as the main component and, in addition, CO and provides a hydrogen gas of high purity.
As the hydrogen source for a fuel cell, a reformed gas obtained by reforming hydrocarbons, alcohols, ethers and the like. In the case of a solid polymer type fuel cell operating at a lower temperature of 100° C or less, there is a fear that a Pt catalyst used in an electrode is poisoned by carbon monoxide (CO) contained in the reformed gas. When a Pt catalyst is poisoned, the reaction of hydrogen is disturbed and the power generation efficiency of the fuel cell decreases remarkably, therefore, it is necessary to lower the concentration of CO to 100 ppm or less, preferably 10 ppm or less.
Conventionally, there have been used, as the CO shifting catalyst, copper-zinc-based catalysts, copper-chromium-based catalysts and the like for lower temperatures, which can be used at 150 to 300° C, and iron-chromium-based catalysts and the like for higher temperatures, which can function at 300° C or more. Further, there have been used CO shifting catalysts singly, or combinations of CO shifting catalysts for higher temperatures and for lower temperatures. depending on use conditions for chemical plants and hydrogen generating apparatuses for fuel cell.
The present invention relates to a hydrogen refinement apparatus comprising a reformed gas feeding part for feeding a reformed gas containing at least a hydrogen gas and water vapor and a reaction chamber equipped with a carbon monoxide shifting catalyst body positioned downstream from said reformed gas feeding part, wherein said carbon monoxide shifting catalyst body comprises a carrier composed of at least one metal oxide having a BET specific surface area of 10 m2/g or more and Pt supported or carried thereon.
Also, the present invention relates a method for operating the above-mentioned hydrogen refinement apparatus. Namely, the present invention relates to a method for operating a hydrogen refinement apparatus comprising a reformed gas feeding part for feeding a reformed gas containing at least a hydrogen gas and water vapor, and a reaction chamber equipped with a carbon monoxide shifting catalyst body positioned downstream from said reformed gas feeding part; aforementioned carbon monoxide shifting catalyst body comprising a carrier composed of at least one metal oxide having a BET specific surface area of 10 m2/g or more and Pt supported thereon, wherein the temperature of aforementioned carbon monoxide shifting catalyst body is controlled from 150 to 450° C.
Fig. 1 is a schematic longitudinal sectional view showing the constitution of a hydrogen generating apparatus containing a hydrogen refinement apparatus of the present invention.
The present invention will be illustrated with the following typical embodiments, by referring to drawings.
Fig. 1 is a schematic longitudinal sectional view showing the constitution of a hydrogen generating apparatus containing a hydrogen refinement apparatus of the present invention. In Fig. 1, a raw material gas feeding part 1 feeds a raw material gas comprising a fuel and water vapor. This hydrogen generating apparatus comprises a reforming reaction chamber 3, CO shifting chamber 6 and CO purifying chamber 11. The apparatus further comprises a heat exchange fin 2, reforming catalyst body 3a, heating burner 4, exhaust port 5, CO shifting catalyst body 6a, thermocouple 7, temperature controller 8, cooler 9, air feeding part 10, CO purifying catalyst body ha and discharge port 12. The periphery of necessary portions of the reaction chamber may be covered with a heat insulating material composed of ceramic wool to keep the reaction chamber at constant temperature (not shown).
The CO shifting catalyst body 6a is prepared by impregnating an alumina carrier in the form of a pellet shown in Fig. 2 with a Pt salt. As the reforming catalyst body 3a, a Ni-based catalyst usually used is employed, and as the CO purifying catalyst body 11a, a Pt-based catalyst is used.
In Fig. 1, the reforming catalyst body 3a and the CO purifying catalyst body ha are also shown for explanation of the basic mechanism of the hydrogen refinement apparatus of the present invention.
As the fuel used for generating a reformed gas to be fed to the hydrogen refinement apparatus, there are natural gas, methanol, gasoline and the like for example. As the reforming method, there are a vapor reforming method in which water vapor is added, a partial reforming method in which air is added, and the like. In this example, a case will be described in which natural gas is vapor-reformed to obtain a reformed gas.
A mixture of natural gas and water vapor is fed from the raw material gas feeding part 1 and preheated by passing through a route heat-exchanged by the heat exchange fin 2 and, then, allowed to contact with the reforming catalyst body 3a. The reforming catalyst body 3a has been heated at 500 to 800° C by the heating burner, and the raw material gas is converted into hydrogen and CO and carbon dioxide at a conversion ratio of approximately 100%.
The composition of the reformed gas somewhat changes depending on the temperature of the reforming catalyst body 3a. Usually, in terms of the average composition excepting water vapor, the reformed gas contains about 80% of hydrogen, about 10% of carbon dioxide and about 10% of carbon monoxide. This reformed gas is fed to the CO shifting catalyst body 6a, to cause a reaction of CO with water vapor. Since the CO shifting catalyst body 6a functions at about 150 to 450° C while the reforming catalyst body 3a is functions at about 500 to 800° C, the temperature of the reformed gas is controlled to make the temperature of the CO shifting catalyst body 6a optimum by detecting the temperature of the upstream side part of the CO shifting catalyst body 6a with the thermocouple 7 and controlling the output of a cooling fun attached to the cooler 9 with the temperature controller 8 having feed back mechanism.
The CO concentration of the gas (shifted gas) after passing through the CO shifting catalyst body 6a is about 0.5%. Therefore, after mixing the shifted gas with air containing an oxygen in an amount corresponding to 3-fold of the CO concentration of the shifted gas, the mixed gas is fed to the CO purufying catalyst body 11. In the CO purifying catalyst body 11, CO is removed to a level of 10 ppm or less, and the gas is fed through the discharge port 12 to a fuel cell.
Then, the operation theory of the hydrogen generating apparatus containing the hydrogen refinement apparatus of this example will be described. In this embodiment, the CO shifting catalyst body 11a, which is the feature of the present invention, will be illustrated in detail.
The CO shifting reaction is an equilibrium reaction depending on temperature, and the CO concentration can be decreased further when the reaction is conducted at lower temperature. On the other hand, the reaction rate is decreased at lower temperature, there exists a temperature at which the CO concentration is decreased as lowered as possible. Usually, copper-based shifting catalysts such as copper-zinc catalysts, copper-chromium catalysts and the like used as the CO shifting catalyst can cause a CO shifting reaction at around 150 to 250° C. Further, the CO concentration can be decreased to about from several hundreds to several thousands ppm depending on conditions. However, copper-based catalysts have to be activated by passing through of a reduction gas such hydrogen or reformed gas after filled in a reaction chamber, and the heat resistance of the copper based catalysts is as low as around 300° C. Therefore, so as not to exceed the heat-resistant temperature by the reaction heat in activation, the reduction gas should be diluted with an inert gas and the like before feeding, or the reaction should be proceeded gradually at a lower flow rate, requiring a longer period of time. Also in starting-up of an apparatus, heating should be effected slowly over a long period of time so as not to exceed the heat-resistant temperature by surplus heat increase, and a lot of problems occur in a use with a frequent repetition of starting-up and stopping.
While in the hydrogen refinement apparatus of the present invention, a Pt catalyst is used as the CO shifting catalyst body 6 and this catalyst has higher heat-resistance as compared with copper-based catalysts, therefore, no significant deterioration occur even in the case of high temperatures around 500° C in starting-up of the apparatus. Further, there is no need for activation for a long period of time in a reduction gas like in the case of copper-based catalysts. Even if air is introduced into an apparatus when the apparatus is stopped, no catalyst deterioration due to oxidation occur as in case of the copper-based catalyst.
Any of noble metal catalysts such as Pt, Pd, Rh, Ru and the like can cause a CO shifting reaction. however, the reaction selectivity thereof is relatively low due to the high activity. Further, a methanization reaction of CO or carbon dioxide proceeds as the side reaction of the CO shifting reaction, depending on conditions. Then the methanization reaction proceeds, hydrogen is consumed to decrease efficiency of the whole apparatus. Usually, in the temperature range from 150 to 450° C in which the CO shifting reaction is conducted, the methanization reaction proceeds further at higher temperatures, and the methane yield varies also depending on the kind of a noble metal. The reason for this is that a CO adsorption mechanism varies depending on the kind of a noble metal. In case of the Pd, Rh and Ru, the temperature range, in which a CO shifting reaction easily proceeds, is narrow because Pd, Rh and Ru having the CO adsorption mechanism facilitating the methanization reaction generate methane at relatively lower temperature.
Further, when cerium oxide is complicated with zirconia (Zr), lanthanum (La) and/or zinc (Zn) and the like, lattice failures increase facilitating transfer of oxygen in the lattice. In other words, in an oxide of cerium and Zr, La and /or Zn, oxygen transfers easily. Also, the heat resistance of cerium oxide having relatively low heat resistance can be improved.
As described above, since cerium oxide itself has relatively lower heat resistance, the heat resistance is improved by complication with Zr. Namely, composite metal oxides containing Ce and Zr are preferable. Also, there is no specific restriction on the method to complicate cerium oxide with Zr, and there can be used, for example, a co-precipitation method, sol-gel method, alkoxide method and the like. Further, Zr may be incorporated into cerium oxide, or cerium may be incorporated into zirconium oxide.
Further, when one selected from Pd, Rh and Ru is added in an amount of 0.1 to 0.05-fold based on the weight of Pt, further higher activity is obtained. Since these noble metal elements facilitate a methanization reaction, they alone cannot easily obtain higher ability as the CO shifting catalyst, but complication thereof with Pt can improve the ability of a Pt catalyst. For smooth reaction of CO on the Pt, there needs some active points remained on the Pt. However, CO has higher affinity to Pt than the other molecules and tends to close the active points on the Pt. Such tendancy is remarkable as the temperature is lower. By adding the slight amount of Pd, Rh and /or Ru, the above-mentioned phenomenon can be inhibited.
The hydrogen refinement apparatus of the present invention exhibits particularly high ability if the temperature of the CO shifting catalyst body 6a is controlled from 150 to 450° C. In the CO shifting reaction, the CO concentration decreases further at lower temperature from the equilibrium point of view. And, when over 450° C, the CO concentration cannot be fully decreased and an amount of the methane generated increases to reduce the efficiency of hydrogen generation. On the other hand, at a lower temperature of less than 150° C, the CO concentration increases from the viewpoint of the reaction rate.
Further, when the temperature of the downstream side part of the CO shifting catalyst body 6a is controlled to be lower than the temperature of the upstream side part thereof by cooling the downstream side part of the CO shifting catalyst body 6a, particularly high ability is obtained. Since the CO shifting reaction is an exothermic reaction, the reaction heat generated in the upstream side part of the CO shifting catalyst body 6a is transmitted via the reformed gas to the downstream side part. Therefore, the temperature of the downstream side part of the CO shifting catalyst body 6a is easy to be higher than that of the upstream side part, and even if the CO concentration is fully decreased in the upstream side part, the CO concentration increases in the downstream side part having higher temperature again by a reverse reaction. Therefore, by controlling the temperature of the downstream side part to be lower than the temperature of the upstream side part, the reverse reaction can be suppressed or inhibited.
Herein, the temperature of the upstream side part of the CO shifting catalyst body 6a and the temperature of the downstream side part of the CO shifting catalyst body 6a are average temperatures of the upstream side half and the downstream side half, respectively, or in the case of division into the upstream, middle stream and downstream, the average temperatures of the upstream and downstream, respectively. When the temperature of the most upstream part lowers exceptionally by cooling only the most upstream part, the average temperature of the upstream part excepting the this most upstream part is regarded as the temperature of the upstream part.
Further, when the amount of water vapor contained in a reformed gas is from 24 to 50% by volume, particularly high activity is obtained. It is more preferable from the equilibrium point of view when the average content of water vapor in the reformed gas s higher, and specifically, the CO concentration fully decreases when water vapor is contained in an amount of 24% by volume or more. On the other hand, when the water vapor content increases, the flow rate increases causing a disadvantage in the reaction rate, and specifically. when the content is more than 50% by volume, the CO concentration cannot be decreased sufficiently.
In this embodiment, the case has been illustrated in which a carrier is in the form of a pellet, and the CO shifting catalyst body 6a is produced by impregnation of a Pt salt, however, the CO shifting catalyst body 6a may be obtained by making a slurry of a catalyst body, which had been prepared previously by supporting Pt onto an alumina powder, and by coating this slurry on a carrier composed of a heat-resistant metal material such as cordierite, mullite and the like. Also in this case, a shifting catalyst body having the same ability is obtained. In this case, the amount of a metal powder may be decreased for coating only on the surface. Alternatively, by using a material having strong heat impact-resistance as the carrier, cracking or break of a catalyst body caused by heat impact due to starting-up and stopping is inhibited.
Moreover, there is no specific restriction also on the catalyst constituting the reforming catalyst body 3a, and those catalysts which can reform a fuel such as noble metal-based catalysts, other transition metal-based catalysts and the like can be widely used. Also as the fuel and reforming method, other fuels may be used, and a partial reforming method in which a part of a fuel is oxidized by addition of air may be used.
Metal oxides or composite metal oxides 1 to 34 having compositions shown in Table 1 were molded into pellets having a diameter of 6mm and a height of 3 mm. Then, these pellets were mixed into a 4 wt% (on the basis of Pt weight) solution of dinitrodiammineplatinum (Pt(NO2)2(NH3)2) in nitric acid, placed in an electric oven as they were, and sintered at 500° C for 1 hour in air to prepare CO shifting catalyst bodies comprising samples 1 to 34. The BET specific surface areas of these samples measured previously are shown in Table 1.
Then, the samples 1 to 34 were used as the CO shifting catalyst body 6a in the hydrogen refinement apparatus shown in Fig. 1, and the catalytic abilities thereof were evaluated.
First, methane, which is the main component of natural gas, was used as a fuel and water vapor in a volume 3-fold based on methane was mixed and introduced into the raw material gas feeding part 1. The reformed gas after passing through the heated reforming catalyst body 3a contained 80% of hydrogen, 11% of CO and 9% of carbon dioxide. The content of water vapor was measured by the dew point of the reformed gas to find it was 25%. This reformed gas was fed to the CO shifting catalyst body 6a, and the CO concentration of the shifted gas after passing through the CO shifting catalyst body 6a was measured by gas chromatography. The results are shown in Table 1.
Sample No. (Composite) Metal oxide BET specific surface area (m2/g) CO conc. (%)
1 MgO 52 0.30
2 Al2O3 121 0.20
3 SiO2 84 0.25
4 CaO 32 0.50
5 TiO2 93 0.20
6 Cr2O3 41 0.30
7 Fe2O3 21 0.80
8 ZnO 74 0.40
9 Y2O3 42 0.60
10 ZrO2 111 0.15
11 NbO2 86 0.30
12 MoO3 15 0.80
13 SnO2 35 0.70
14 BaO 12 0.90
15 La2O3 81 0.40
16 Pr2O3 75 0.35
17 Nd2O3 88 0.45
18 Sm2O3 62 0.40
19 Eu2O3 55 0.35
20 Gd2O3 45 0.55
21 Tb2O3 61 0.70
22 Dy2O3 79 0.60
23 Ho2O3 75 0.40
24 Er2O3 82 0.40
25 Tm2O3 77 0.50
26 Yb2O3 43 0.65
27 Lu2O3 34 0.70
28 Type A zeolite 415 0.20
29 Type X zeolite 253 0.30
30 Type Y zeolite 325 0.25
31 Mordenite 151 0.35
32 ZSM-5 132 0.20
33 Type β zeolite 255 0.30
34 Silica alumina 212 0.15
Mixtures of an alumina powder with a saturated aqueous solution of cerium nitrate were placed in an electric oven, sintered at 500° C for 1 hour in air, to complicate alumina with Ce. Then, the mixing ratios of an alumina powder with an aqueous cerium nitrate solution were varied corresponding to the compositions of the metal oxides shown in Table 2 to prepare samples 35 to 37 having compositions shown in Table 2.
The samples were molded into pellets having a diameter of 6 mm and a height of 3 mm, then, these pellets were mixed into a 4 wt% solution of dinitrodiammineplatinum (Pt(NO2)2(NH3)2) in nitric acid, and sintered in an electric oven at 500° C for 1 hour in air to prepare CO shifting catalyst body comprising samples 35 to 37.
Then, the CO shifting catalyst bodies were filled into the hydrogen refinement apparatus shown in Fig. 1, the reformed gas was fed, and the CO concentrations after passing through the CO shifting catalyst bodies 6a were measured by gas chromatography, in the same manner as in Example 1. The results are shown in Table 2.
Ammonia was added to a saturated aqueous solution of cerium nitrate to cause co-precipitation, and the product was sintered in an electric oven at 500° C for 1 hour in air atmosphere, to prepare a sample 38 (cerium oxide). Then, zirconyl nitrate and cerium nitrate were mixed corresponding to the compositions of metal oxides shown in Table 2 and ammonia was added thereto for co-precipitation to prepare samples 39 and 40.
These samples were molded into pellets having a diameter of 6 mm and a height of 3 mm, then, mixed into a 4 wt% solution of dinitrodiammineplatinum (Pt(NO2)2(NH3)2) in nitric acid in the same manner as in Example 1. Then, these mixtures were sintered in an electric oven at 500° C for 1 hour in air atmosphere to prepare CO shifting catalyst bodies comprising samples 38 to 41. They were filled as the CO shifting catalyst body 6a into the hydrogen refinement apparatus shown in Fig. 1, the reformed gas was fed, and the CO concentrations after passing through the CO shifting catalyst bodies 6a were measured by gas chromatography, in the same manner as in Example 1. The results are shown in Table 2.
This hydrogen refinement apparatus was operated for 2000 0 hours, and the CO concentrations after passing through the CO shifting catalyst bodies 6a were measured again, to find that the CO concentrations after passing through the CO shifting catalyst bodies 6a when the samples 38, 39 and 40 were used were 0.19%, 0.15% and 0.15%, respectively.
35 Al9CeOx 115 0.18
36 Al5Ce5Ox 100 0.17
37 Al3Ce7Ox 90 0.16
38 CeO2 80 0.13
39 Ce9ZrOx 85 0.14
40 Ce7Zr3Ox 90 0.15
41 CeZr4Ox 88 0.15
The CO shifting catalyst bodies 6a were produced in the same manner as in Example 1 except that cerium oxide carriers having different BET specific surface areas as shown in Table 3 were produced by controlling the sintering temperature. Then, the reformed gas was fed to the CO shifting catalyst bodies 6a, and the CO concentrations of the shifted gas after passing through the CO shifting catalyst bodies 6a were measured by gas chromatography, in the same manner as in Example 1. Also after operation of the hydrogen generating apparatus for 1000 hours continuously, the CO concentrations of the shifted gas after passing through the CO shifting catalyst bodies 6a were measured by gas chromatography. The results are shown in Table 3.
Sample No. (Composite) Metal oxide BET specific surface area (m2/g) CO conc. (%) CO conc. after 1000 hours (%)
38a CeO2 7 3.2 3.2
38b CeO2 9 1.8 1.8
38c CeO2 12 0.45 0.45
38 CeO2 80 0.13 0.14
38d CeO2 240 0.14 0.14
38e CeO2 310 0.66 0.66
38f CeO2 390 0.09 0.89
The CO shifting catalyst bodies (samples 38g and 38h) were produced in the same manner as in the case of the CO shifting catalyst body (sample 38) of example 2, except that cerium oxide was obtained by employing cerium carbonate or cerium hydroxide in place of cerium nitrate. Then, the reformed gas was fed to the CO shifting catalyst bodies 6a in the same manner as in example 1, and the CO concentrations after passing through the CO shifting catalyst bodies 6a were measured by gas chromatography. The results were 0.16% in case of sample 38g and 0.18% in case of 38h.
The metal oxides shown in Table 4 were produced by heating alumina in an electric oven. These metal oxides were molded into pellets having a diameter of 6mm and a height of 3 mm, then, these pellets were mixed into a 4 wt% solution of dinitrodiammineplatinum (Pt(NO2)2(NH3)2) in nitric acid. These mixtures were sintered in an electric oven at 500 ° C for 1 hour in air atmosphere to prepare CO shifting catalyst bodies (samples 42 to 46).
Then, they were filled as the CO shifting catalyst bodies 6a into the hydrogen refinement apparatus shown in Fig. 1, the reformed gas was fed, and the CO concentrations after passing through the CO shifting catalyst bodies 6a were measured by gas chromatography, in the same manner as in Example 1. The results are shown in Table 4.
42 Al2Ox 0.9 9.5
43 Al2Ox 9.5 1.8
44 Al2Ox 9 5
45 Al2Ox 0.9 9.5
46 Al2Ox 8.5 3.0
Alumina, sample 2 produced in Example 1 was molded into a pellet having a diameter of 6mm and a height of 3 mm, then, this molded article was mixed into a solution prepared by mixing a Pd salt, Rh salt or Ru salt in given ratio into a 4 wt% solution of dinitrodiammineplatinum (Pt(NO2)2(NH3)2) in nitric acid, these mixtures were sintered in an electric oven at 500° C for 1 hour in air atmosphere to prepare CO shifting catalyst bodies (samples 47 to 61) shown in Table 5. These CO shifting catalyst bodies comprising samples 47 to 61 were used as the CO shifting catalyst bodies 6a in the hydrogen refinement apparatus shown in Fig. 1, and evaluated, in the same manner as in Example 1. The results are shown in Table 5.
Sample No. Noble Metal added Weight per 1 g of Pt CO conc. (%) Methane conc.(%)
47 Pd 0.08 0.20 0.01
48 Pd 0.1 0.17 0.01
49 Pd 0.3 0.15 0.02
50 Pd 0.5 0.16 0.04
51 Pd 0.6 0.50 1.8
52 Rh 0.08 0.20 0.01
53 Rh 0.1 0.18 0.01
54 Rh 0.3 0.17 0.04
55 Rh 0.5 0.13 0.08
56 Rh 0.6 0.60 3.01
57 Ru 0.08 0.20 0.01
58 Ru 0.1 0.15 0.01
59 Ru 0.3 0.13 0.04
60 Ru 0.5 0.16 0.09
61 Ru 0.6 0.80 4.05
The sample 2 comprising platinum supported by the alumina pellet in Example 1 was filled in the hydrogen refinement apparatus shown in Fig. 1 as the CO shifting catalyst body 6a. 50 liter/min. of methane and 150 liter/min. of water vapor were introduced at the raw material feeding part 1, and they were heated by the heating burner 4 so that the temperature of the reforming catalyst body 3a reached about 800° C to cause reaction. The produced gas after passing through the reforming catalyst body 3a was measured by gas chromatography to find that it contained, excepting water vapor, about 80% of hydrogen, about 11% of CO, about 9% of carbon dioxide, and 300 ppm of methane. When this reformed gas was passed through the CO shifting catalyst body 6a, the CO concentration changed to about 0.20%, and air was introduced through the air feeding part 10 so as to obtain an oxygen concentration of 2% to cause a reaction over the CO purifying catalyst body 11, to obtain a CO concentration of 5 ppm.
The hydrogen generating apparatus was once stopped, and started-up again. This stopping and starting-up operation was repeated 1200 times, and the reformed gas composition was measured to find that the CO concentration after passing through the reforming catalyst body 3a was 11%, which had not changed, and after passing through the CO shifting catalyst body 6a, the CO concentration was 0.22%, and after passing through the CO purifying catalyst body 11, the CO concentration was 6 ppm.
A commercially available copper-zinc-based CO shifting catalyst (C18 manufactured by Toyo CCI) in the form of a pellet having a diameter of 6 mm and a height of 3mm was filled in the hydrogen refinement apparatus shown in Fig. 1 as the CO shifting catalyst body 6a. 50 liter/min. of methane and 150 liter/min. of water vapor were introduced at the raw material feeding part 1, and they were heated by the heating burner 4 so that the temperature of the reforming catalyst body 3a reached about 800° C to cause reaction. The produced gas after passing through the reforming catalyst body 3a was measured by gas chromatography to find that it contained, excepting water vapor, about 80% of hydrogen, about 11% of CO, about 9% of carbon dioxide, and 300 ppm of methane. When this reformed gas was passed through the CO shifting catalyst body 6a, the CO concentration changed to about 0.11%, and air was introduced through the air feeding part 10 so as to obtain an oxygen concentration of 2% to cause a reaction over the CO purifying catalyst body 11, to obtain a CO concentration of 11 ppm.
The hydrogen generating apparatus was once stopped, and started-up again. This stopping and starting-up movement was repeated 1200 times, and the reformed gas composition was measured to find that the CO concentration after passing through the reforming catalyst body 3a was 11%, which had not changed, and after passing through the CO shifting catalyst body 6a, the CO concentration was 1.52%, and after passing through the CO purifying catalyst body 11, the CO concentration was 520 ppm.
A hydrogen refinement apparatus comprising a reformed gas feeding part for feeding a reformed gas containing at least a hydrogen gas and water vapor, and a reaction chamber equipped with a carbon monoxide shifting catalyst body positioned downstream from said reformed gas feeding part,
wherein said carbon monoxide shifting catalyst body comprising a carrier composed of at least one metal oxide having a BET specific surface area of 10 m2/g or more and Pt supported thereon.
The hydrogen refinement apparatus in accordance with claim 1, wherein the BET specific surface area of said carrier is 250 m2/g or less.
The hydrogen refinement apparatus in accordance with claim 1, wherein said metal oxide is at least one oxide of one selected from the group consisting of Mg, Al, Si, Ca, Ti, Cr, Fe, Zn, Y, Zr, Nb, Mo, Sn, Ba and lanthanoid.
The hydrogen refinement apparatus in accordance with claim 1, wherein said metal oxide contains Ce.
The hydrogen refinement apparatus in accordance with claim 4, wherein said metal oxide contains Zr.
The hydrogen refinement apparatus in accordance with claim 1, wherein said carbon monoxide shifting catalyst body comprises a carrier supporting Pd, Rh or Ru in an amount of 0.1 to 0.5% by weight based on Pt, in addition to Pt.
A method for operating a hydrogen refinement apparatus comprising a reformed gas feeding part for feeding a reformed gas containing at least a hydrogen gas and water vapor and a reaction chamber equipped with a carbon monoxide shifting catalyst body positioned downstream from said reformed gas feeding part; said carbon monoxide shifting catalyst body comprising a carrier composed of at least one metal oxide having a BET specific surface area of 10 m2/g or more and Pt supported thereon,
comprising the step of controlling the temperature of said carbon monoxide shifting catalyst body from 150 to 450° C.
The method for operating a hydrogen refinement apparatus in accordance with claim 7, further comprising the step of controlling the temperature of the upstream side part of said carbon monoxide shifting catalyst body to more than the temperature of the downstream side part thereof.
The method for operating a hydrogen refinement apparatus in accordance with claim 7, wherein said reformed gas containing 24 to 50% by volume of water vapor is fed.
EP20000108279 1999-04-22 2000-04-14 Hydrogen refinement apparatus Expired - Fee Related EP1046612B1 (en)
JP11510199 1999-04-22
EP1046612A1 true true EP1046612A1 (en) 2000-10-25
EP1046612B1 EP1046612B1 (en) 2011-11-30
EP20000108279 Expired - Fee Related EP1046612B1 (en) 1999-04-22 2000-04-14 Hydrogen refinement apparatus
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