JP5355946B2 - HYDROGEN GENERATION CATALYST, ITS MANUFACTURING METHOD, AND HYDROGEN GENERATOR - Google Patents

Description

  The present invention relates to a hydrogen generation catalyst for generating hydrogen from water vapor, a production method for producing the catalyst, and a hydrogen generation apparatus using the hydrogen generation catalyst.

The inventor of the present application uses a catalyst for hydrogen generation in which hydrogen is collected from water vapor by heating one kind of metal oxide and one kind of alkali metal hydroxide in Japanese Patent Application No. 2008-97501 and the catalyst. A hydrogen generator is disclosed. This application discloses the development and theoretical clarification of these technologies.
Japanese Patent Application No. 2008-97501

  In the above application, molybdenum oxide as a metal oxide and sodium hydroxide as a metal hydroxide are not specifically disclosed as catalyst materials, and the relationship between molybdenum oxide and titanium oxide is not disclosed. In addition, no specific examples are disclosed with respect to the details of the production method including these and further the pellet-shaped catalyst.

  The hydrogen generation catalyst of the present invention is obtained by heat-mixing molybdenum oxide with a metal hydroxide such as potassium hydroxide or sodium hydroxide, and then solidifying by heat treatment.

  Further, the hydrogen generation catalyst of the present invention is obtained by solidifying by heat treatment after titanium oxide is mixed with metal hydroxide such as potassium hydroxide and sodium hydroxide.

  Furthermore, the hydrogen generation catalyst of the present invention is obtained by adding molybdenum oxide or chromium oxide to the metal hydroxide and titanium oxide.

  Furthermore, the hydrogen generation catalyst of the present invention preferably has a weight ratio of the metal oxide to molybdenum oxide of 2 to 3: 1.

  Furthermore, the weight ratio of the metal hydroxide, titanium oxide, molybdenum oxide or chromium oxide is preferably 10: 5: 1.

  Furthermore, in the method for producing a hydrogen generation catalyst of the present invention, the mixture is heated to a melting point or higher of the metal hydroxide to form a liquid and then mixed while gradually supplying titanium oxide with stirring, and then at 300 to 400 ° C. The pellet is held for about 30 minutes, heated at this temperature for 4 to 5 hours, then cooled, and further raised to 600 ° C. or higher to be finally solidified.

  Furthermore, the method for producing a hydrogen generation catalyst according to the present invention comprises a steam chamber for producing steam at 300 ° C. or higher, a catalyst housing chamber for housing the catalyst and collecting hydrogen from the steam supplied from the steam chamber by a thermochemical reaction. A circulation device for separating only the water vapor from the hydrogen, oxygen and untreated water vapor discharged from the catalyst storage chamber and returning it to the catalyst storage chamber inlet; a hydrogen tank for storing collected hydrogen; The hydrogen tank has a heating device that supplies hydrogen and heats the steam chamber and the catalyst storage chamber. The heating device includes a water sealing device provided in a hydrogen supply path for preventing backfire, A demister provided on the downstream side of the sealing device for removing mist in the hydrogen gas.

  Furthermore, the method for producing a hydrogen generation catalyst according to the present invention comprises a steam chamber for producing steam and a catalyst housing chamber for collecting hydrogen from the steam contained in the catalyst and supplied from the steam chamber by a thermochemical reaction, Opening and closing valves are provided before and after the catalyst storage chamber, respectively, and after injecting water vapor into the catalyst storage chamber, both the opening and closing valves are closed, and the water vapor is retained for a predetermined time.

  Furthermore, it is preferable that a pellet-shaped catalyst is stored in the catalyst storage chamber, and the catalyst storage chamber is rotatable.

  Furthermore, a steam chamber for generating steam and a catalyst storage chamber for storing hydrogen from water vapor supplied from the steam chamber by thermochemical reaction by storing the catalyst, the catalyst storage chamber comprises a standing cylinder. In this cylinder, a pellet-shaped catalyst is accommodated, water vapor is supplied from the bottom surface to the top surface of the cylinder, and a separation member for separating the water vapor is provided on the outlet side of the cylinder.

  If molybdenum oxide is heated and mixed with metal hydroxide, the temperature at which hydrogen is generated is reduced to about 600 ° C. If titanium oxide is used instead of molybdenum oxide, the hydrogen generation temperature is reduced and the production is similar to molybdenum oxide. Easy handling. Since titanium oxide is difficult to dissolve in metal hydroxide, it is necessary to use molybdenum oxide or chromium oxide as a binder.

  As a method for producing a catalyst using titanium oxide, heat treatment is performed at 300 ° C. to 400 ° C., and once cooling, solidification is performed without releasing water, so that pellets can be easily formed.

  In addition, if only water vapor is circulated in the catalyst storage chamber as a hydrogen generator, the hydrogen collection efficiency is remarkably improved. Similarly, if the water vapor is retained in the catalyst storage chamber for a certain period of time, the hydrogen collection efficiency from the water vapor is increased. Remarkably improved. In order to circulate the water vapor, it is necessary to separate the water vapor and hydrogen at the top of the pellet storage cylinder, and if the pellet storage cylinder is rotated as necessary, the water vapor uniformly touches the surface of each pellet. become.

  The best mode for carrying out the present invention will be described below with reference to the drawings.

  First, the hydrogen generation catalyst will be described.

The hydrogen generation catalyst of the present invention comprises at least one alkali metal hydroxide such as potassium hydroxide (KOH), sodium hydroxide (NaOH), and calcium hydroxide (Ca (OH) ₂ ), and titanium oxide (TiO ₂ ). ₂ ), and produced by heating and mixing at least one metal oxide such as molybdenum oxide (MoO ₃ ) and chromium oxide (Cr ₂ O ₃ ).

  That is, first, an alkali metal hydroxide is heated and melted and mixed while adding the metal oxide little by little (titanium oxide, molybdenum oxide, etc.). From the beginning, the alkali metal hydroxide and the metal oxide are mixed. Some are mixed with other materials (such as chromium oxide). During catalyst production, generally, when an alkali metal hydroxide and a metal oxide are heated and mixed, a metal acid metal (for example, a bond between a metal oxide such as potassium titanate and sodium titanate and a metal in the metal hydroxide) Water).

This reaction is considered as follows.
(1) In the case of titanium oxide and potassium hydroxide (sodium) 2TiO ₂ + 2KOH (NaOH) → K ₂ Ti ₂ O ₅ (Na ₂ Ti ₂ O ₅ )
+ H ₂ O ↑ (a)
(2) In the case of molybdenum oxide and potassium hydroxide (sodium) MoO ₃ +2 KOH (NaOH) → K ₂ MoO ₄ (Na ₂ MoO ₄ )
+ H ₂ O ↑ (b)
(3) In the case of chromium oxide and potassium hydroxide (sodium) In this case, oxygen in the air is required.

2Cr ₂ O ₃ + 8KOH (NaOH) + 3O ₂
→ 4K ₂ CrO ₄ (Na ₂ CrO ₄ ) + 4H ₂ O ↑ (c)
In the case of (1) and (2), first, after melting the hydroxide, powdered titanium oxide or molybdenum oxide is added and heated and mixed at 200 ° C. to 400 ° C., and the temperature is maintained for 1 to 2 hours. After solidifying to a certain degree and once cooled to room temperature (substantially solidifies when cooled), when the temperature is gradually raised to about 700 ° C., it is completely solidified without melting and water vapor is not generated.

  In the case of (3), potassium hydroxide 2 (weight ratio) is mixed with chromium oxide powder 1 (weight) at the same time, melted and mixed at 400 ° C. to 500 ° C. for several hours, and at 500 ° C. until solidified. After completion of heating for 3 to 3 hours at 600 ° C. for 2 to 3 hours and 700 ° C. for 2 to 3 hours, no water vapor is produced.

In each of the cases (1), (2), and (3), the release of water vapor is completed, and when the catalyst itself dries, hydrogen begins to be released even if water is not newly injected. This is because hydrogen atoms of residual water vapor in the catalyst vessel are once taken into the potassium positions of the generated K ₂ Ti ₂ O ₅ , K ₂ MoO ₄ , and K ₂ CrO ₄ atomic arrangements, and the atmosphere is high at this time. It is considered that this reaction is repeated by releasing the incorporated hydrogen and further incorporating hydrogen in the water vapor.

That is,
In the case of (1) K ₂ Ti ₂ O ₅ + H ₂ O → (K, H) Ti ₂ O ₂ + KOH (d)
In the case of (2) K ₂ MoO ₄ + H ₂ O → (K, H) MoO ₃ + KOH (e)
In the case of (3) K ₂ CrO ₄ + H ₂ O → (K, H) CrO ₄ + KOH (f)
It seems that this reaction is repeated.

  These reactions are the same when sodium hydroxide is used instead of potassium hydroxide.

Here, when a large amount of water vapor enters, the reaction of the formulas (d), (e), and (f) proceeds to release hydrogen. At the same time, a reverse reaction such as the reverse of the equations (a), (b) and (c) occurs,
In the case of (1) K ₂ Ti ₂ O ₅ + H ₂ O → 2Ti ₂ O ₅ +2 KOH (g)
In the case of (2) K ₂ MoO ₄ + H ₂ O → MoO ₄ +2 KOH (h)
In the case of (3) 4K ₂ CrO ₄ + 4H ₂ O → 2CrO ₃ +8 KOH + 3O ₂ (i)
Furthermore, the reverse reactions (a), (b), and (c) of (g), (h), and (i) occur in a high-temperature atmosphere, and K ₂ Ti ₂ O ₅ , K ₂ MoO ₄ and K ₂ CrO ₄ are produced, and these compounds undergo the reactions (d), (e), and (f), and hydrogen is released.

  These reactions (a) to (f) occur instantaneously and hydrogen is generated, but the amount of hydrogen changes according to the amount of water up to the capacity limit of the catalyst, and when the capacity limit is exceeded, it is released as water vapor. The

In the case of mixing the potassium hydroxide (sodium) and titanium oxide (TiO ₂ ) described in (1) above, it is necessary to mix about 5 titanium oxides with respect to potassium hydroxide 10 (weight ratio). Even if titanium oxide is added after heating to 300 to 500 ° C. to make it liquid, only about 2 to 3 (weight ratio) is mixed as it is, so molybdenum oxide (MoO ₃ ) or chromium oxide (Cr ₂ O) is used as a binder. ₃ ) Addition of about 1 (weight ratio) enables mixing.

  In the case of (1), in the case of potassium hydroxide and molybdenum oxide, a ratio of potassium hydroxide 2-3: molybdenum oxide 1 in weight ratio is preferable.

FIG. 1 shows a state of making a pellet as a catalyst. First, potassium hydroxide (KOH) is put in a heating container 1 (FIG. 1 (a)) around which a heater 2 is wound, and the melting point or more is exceeded. after the heated to 300 ° C. to 400 ° C. the temperature liquid, allowed to mixing powders of titanium oxide (TiO ₂₎ is a metal oxide. At this time, if chromium oxide (Cr ₂ O ₃ ) is slightly added as a binder, titanium oxide can be mixed with about 1/2 weight of potassium hydroxide. Further, sodium hydroxide may be used instead of potassium hydroxide, and molybdenum oxide (MoO ₃ ) may be mixed instead of titanium oxide. The weight ratio of the metal hydroxide, titanium oxide, and molybdenum oxide or chromium oxide as a binder is preferably 10: 5: 1.

  When metal hydroxide and metal oxide are mixed in the above ratio, a viscous gel is formed. The temperature at this time is 300 ° C to 400 ° C, and after holding for about 30 minutes, this is rinsed with a spoon or the like. The pellet 3 is rounded and heated by a heater 5 in an open state on a shallow container 4 to remove water vapor from the pellet 3 (FIG. 1B). At this time, it heats at 300 to 400 degreeC for 4 to 5 hours. Then, it is once cooled to room temperature (Fig. 1 (c)) and further heated at 400 ° C for 2-3 hours, 500 ° C for 2-3 hours, 600 ° C for 2-3 hours, and 700 ° C for 2-3 hours. (FIG. 1 (d)) and stored in the sealed container 6.

  FIG. 2 shows a case where the pellets of the present invention are incorporated into an air boiler B. A furnace cylinder 11 is provided at the lower part of the boiler body 10, and a hydrogen burner 12 faces the furnace cylinder 11. A heat exchanging portion 13 is provided at the upper portion of the furnace tube 11, and hot air from the hydrogen burner 12 exchanges heat with air in the air flow path 15 through the passage 14, and the hot air is formed on the upper surface of the boiler body 10. The discharged outlet 16 is discharged to the outside. Only hot steam and air exit from the outlet 16.

  On the other hand, a hydrogen generation unit 20 is provided on the back surface of the boiler body 10. The hydrogen generation unit 20 is provided with a steam chamber 21 and a catalyst storage chamber 22, and a valve 24 is provided in the communication passage 23. It has been. A hollow cylindrical steam cylinder 25 is provided in the steam chamber 21, and the steam cylinder 25 is heated by hot air from the hydrogen burner 12 to generate steam at 700 ° C. This vapor comes into contact with the pellet catalyst 26 in the catalyst storage chamber 22 to generate hydrogen. The catalyst pellets act at 300 ° C. or higher to decompose water and generate hydrogen, but it is more efficient to set the temperature to about 700 ° C.

  A separation part 27 for separating water vapor and hydrogen is formed in the upper part of the catalyst storage chamber 22. As shown in FIG. 3, the separation unit 27 is provided with a filter 28 that allows only hydrogen made of a palladium alloy to pass therethrough and prevents water vapor from passing therethrough, and the water vapor is returned from the periphery of the separation unit 27 into the catalyst storage chamber 22. A punching plate 29 that allows water vapor to pass therethrough is provided at the bottom of the catalyst storage chamber 22, and a pellet catalyst 26 is supported thereon. The separation unit 27 and the circulation furnace form a circulation device.

  As shown in FIG. 4, the catalyst storage chamber may be a fluidized bed type in which the catalyst is finely divided and moved up and down by steam. In this case, a filter 30 for holding the fine catalyst and a filter 28 for separating the water vapor and hydrogen are provided in the upper part of the catalyst storage chamber 31, and the water vapor is returned from the middle of the filters 28, 30 to the inlet of the catalyst storage chamber 31. In this case, a fluidized bed plate 32 is provided below the catalyst storage chamber 31.

  As shown in FIG. 2, the hydrogen discharged from the catalyst storage chamber is stored in a cylinder 50, sent to the water sealing device 52 through the valve 51, and sent to the hydrogen burner 12 through the demister 53 that removes moisture.

  Thus, by making the hydrogen generating catalyst into a pellet, the continuous time of hydrogen generation can be extended as compared with the plate-like hydrogen generating catalyst. In the case of a plate-like hydrogen generating catalyst, when a part of a metal hydroxide such as potassium hydroxide or sodium hydroxide evaporates, the hydrogen generated as it is is discharged to the outside of the catalyst storage chamber 22 and the like. The performance is reduced. However, by making the hydrogen generating catalyst into a pellet form, the metal hydroxide evaporated from the surface of a certain pellet is not directly taken out of the catalyst storage chamber, but is trapped on the surface of another pellet. It is thought that the continuous time of hydrogen generation can be extended.

  Moreover, by making the hydrogen generating catalyst into a pellet form, the number of surfaces in contact with water vapor can be increased, and the amount of water vapor to be processed can be improved.

  Here, the shape and size of the pellet are not particularly limited, and examples thereof include a spherical shape, a cylindrical shape, and a cubic shape. Moreover, pellets of various sizes and shapes may be mixed. In short, any shape or size that allows water vapor to pass between the pellets when the catalyst storage chamber is filled with the pellet-shaped catalyst may be used. Any shape or size that is easy to manufacture may be used.

  Further, the hydrogen generation catalyst may have a structure in which the entire catalyst is made porous so that water vapor can pass therethrough instead of the pellet form.

  As shown in FIG. 5, if the valves 61 and 62 are provided above and below the catalyst storage chamber 60 and are opened and closed to keep the water vapor in the catalyst storage chamber 60 for a certain period of time, the water decomposition efficiency is improved. .

  In addition, as shown in FIG. 6, when a gear 71E is provided in the catalyst storage chamber 70, and the gear 72 is engaged with the gear 71 and the catalyst storage chamber 70 is rotated, the catalyst pellet moves to move the catalyst pellet. The front surface of the can operate uniformly and can separate hydrogen efficiently.

  Further, as shown in FIG. 7, water is supplied from a water tank 80 to a steam chamber 81, and a catalyst storage chamber 82 equipped with a water vapor circulation device (not shown) is connected to the steam chamber 81, and these are connected to hydrogen serving as a heating device. You may heat with the burner 83,84. The hydrogen burners 83 and 84 are provided with a hydrogen sealing device 87 for preventing backfire from a cylinder 86 for storing compressed hydrogen by a compressor 85 and a demister 88 for removing moisture (mist) from oxygen dampened by the water sealing device 87. Is supplied.

It is process drawing which shows the manufacturing process of the catalyst of this invention. It is a schematic block diagram at the time of applying this invention to an air boiler. It is a block diagram of a catalyst storage chamber. It is another block diagram of a catalyst storage chamber. FIG. 6 is still another configuration diagram of the catalyst chamber. FIG. 6 is still another configuration diagram of the catalyst chamber. It is another block diagram of the hydrogen generator of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Heating container 3 ... Pellet 6 ... Sealed container 10 ... Boiler main body 12 ... Hydrogen burner 16 ... Outlet 22 ... Catalyst storage chamber 28 ... Filter 29 ...・ Punching plate 30 ... Filter

Claims (5)

A steam chamber connected to the furnace tube and heated by hot air, and a catalyst storage chamber for storing the catalyst and collecting hydrogen from water vapor supplied from the steam chamber, and in the catalyst storage chamber, potassium hydroxide and water One kind of sodium oxide, titanium oxide, and one kind of molybdenum oxide (MoO ₃ ) and chromium oxide (Cr ₂ O ₃ ) as a binder are added in a smaller amount than the other two and heated to form a pellet. Hydrogen generator in which the catalyst is stored.   The hydrogen generator according to claim 1, wherein a weight ratio of one of the potassium hydroxide and sodium hydroxide, titanium oxide, and one of molybdenum oxide and chromium oxide as a binder is 10: 5: 1. .   The hydrogen generation apparatus according to claim 1, wherein the catalyst storage chamber has a fluidized bed type in which the catalyst flows up and down by water vapor sent by atomizing the catalyst.   2. The hydrogen generator according to claim 1, further comprising an on-off valve before and after the catalyst storage chamber, wherein after the water vapor is injected into the catalyst storage chamber, the on-off valve is closed and water vapor is retained for a predetermined time.   The hydrogen generator according to claim 1, further comprising a circulation device for separating only water vapor from the gas discharged from the catalyst storage chamber and returning it to the catalyst storage chamber inlet.

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