JPH049726B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method and apparatus for purifying hydrogen gas using metal hydrides.

<Conventional technology> Hydrogen storage alloys based on rare earths, titanium, magnesium, and other metals, or metal hydrides called metal hydrides, undergo a hydrogenation reaction and rapidly It is known that metal hydrides exothermically absorb hydrogen and that these metal hydrides undergo a reversible dehydrogenation reaction and endothermically release hydrogen.

This chemical reaction formula is shown by the following formula.

M+n/2H ₂ MH _o +ΔH M: Hydrogen storage alloy ΔH: Heat of reaction MH _o : Metal hydride However, once a hydrogenation reaction occurs and a metal hydride is formed, it must completely return to its original alloy state. is very difficult, so it may be expressed by the following equation.

MH _(n+o) MH _n +n/2H ₂ ±ΔH In other words, m represents a hydrogen atom that is usually combined with a hydrogen storage alloy to form a metal hydride, and n is a metal hydride in practice. It represents hydrogen that can be extracted from an alloy that has become a hydride.

In this specification, the above-mentioned M, M H _o ,
MH _(n+o) and MH _n are collectively called metal hydrides,
It is simply indicated by the symbol M.

In addition, the term "phase" as used herein refers to a certain state or position in one period of a periodic reaction or a moving object, and is interpreted in the broadest sense, particularly including the states of hydrogenation reactions and dehydrogenation reactions. shall be.

The metal hydride selectively stores hydrogen in hydrogen gas containing impurities during the hydrogen storage process,
Since impurities are difficult to be occluded, the hydrogen gas released in the hydrogen release process contains less impurities. Various hydrogen purification devices have been proposed that take advantage of the properties of metal hydrides.

For example, Special Publication No. 59-53201 and Special Publication No. 59-59-
Publication No. 53202 discloses that at least one set of hydrogen purification containers containing a metal hydride are connected to each other through a heat exchanger so as to be able to exchange heat with each other, and one container stores hydrogen gas to be purified while the other A hydrogen purification method and apparatus are described in which hydrogen stored in an alloy is released as purified hydrogen from a container. According to this conventional technology, the heat of storage of hydrogen in one container can be used to release hydrogen in the other container, so by alternately supplying the raw material hydrogen to be purified to these containers,
It has the advantage that it can be carried out continuously and with good thermal efficiency.

<Problems to be Solved by the Invention> However, in the above-mentioned conventional hydrogen purification method or apparatus, valves are used to alternately supply raw hydrogen to a set of containers and alternately take out purified hydrogen from these containers. Using a switching system, it is necessary to switch a large number of valves, which makes the operation complicated, and when hydrogen is stored in the alloy, impurities remain in the container, which may be entrained when hydrogen is released from the alloy. There is a drawback that it does.

Therefore, the present invention provides a hydrogen purification method and device that can be operated continuously using only rotary driving force without requiring complicated valve switching operations when supplying raw material hydrogen or taking out purified hydrogen, and which entrains few impurities. It was done for that purpose.

<Means for Solving the Problems> That is, the hydrogen purification method of the present invention uses a plurality of closed containers interconnected by hydrogen pipes and filled with metal hydride, and the hydrogen purification method is performed in the nth closed container. As a result of the hydrogenation reaction of the metal hydride, the degraded hydrogen gas containing impurities remaining in the sealed container (nth) is used to initiate the hydrogenation reaction of the metal hydride in the subsequent sealed container (n-1st). The purified hydrogen gas released by the dehydrogenation reaction of the metal hydride in the n-th sealed container is then returned to the sealed container (n-1st) in the next stage. The heating and cooling timings of the closed containers are staggered so that the hydrogenation reaction of the metal hydride in the (n+1) chamber advances to the next stage.

In addition, the hydrogen purification apparatus of the present invention has a plurality of rotating bodies each having a plurality of sealed containers filled with metal hydride disposed in the circumferential direction, arranged along a rotation axis, and each rotation as the rotating body rotates. A low-temperature heat medium chamber and a high-temperature heat medium chamber are provided around the rotating shaft so that the closed container of the body passes through the low-temperature heat medium chamber and the high-temperature heat medium chamber alternately and sequentially, and one rotating body (nth) When the m-th closed container ( _o R _n ) above is in the low-temperature heating medium chamber, as a result of the hydrogenation reaction of the metal hydride that takes place in the closed container, the metal hydride remains in the closed container ( _o R _n ). The degraded hydrogen gas containing impurities is transferred to the latter rotating body (n-1st)
As the hydrogenation reaction of the metal hydride starts in the m-th sealed container ( _o-1 R _n ) that has been rotated to the upper low-temperature heating medium chamber, the metal hydride is transferred to the subsequent sealed container ( _o-1 R _n ). While returning, the airtight container ( _o
R _n ) rotates into the high temperature heating medium chamber and the sealed container ( _o R _n )
The purified hydrogen gas released by the dehydrogenation reaction of the metal hydride in the
Along with the hydrogenation reaction of the metal hydride in the m-th sealed container ( _{o+1 R n )} located in the low-temperature heating medium chamber above In order to move forward, the closed containers of the rotating bodies are connected with hydrogen pipes with their phases shifted, and the hydrogen pipes exiting from each closed container of the final stage rotating body are connected to the purified hydrogen outlet, and the first stage The hydrogen pipes coming out of each sealed container of the rotating body are connected to the degraded hydrogen outlet, and the hydrogen pipes entering each sealed container of one rotating body at any stage are connected to the raw hydrogen supply port, and the purified hydrogen is connected to each of the hydrogen pipes. The connection with the outlet, the degraded hydrogen outlet, or the raw hydrogen supply port is characterized in that communication or interruption occurs as the rotating body rotates.

<Embodiments> The present invention will be described in detail below with reference to embodiments shown in the drawings.

FIG. 1 is an explanatory diagram schematically showing a hydrogen purification apparatus of the present invention, in which three disc-shaped rotating bodies 1a, 1
b and 1c are fixed to a rotating shaft 2, and this rotating shaft is supported by a bearing 3, so that the rotary body can rotate together with the rotation of the rotating shaft 2. As shown in the side view of FIG. 2, the interior of each rotating body 1 is divided into four sections by partition walls 4 and annular walls 5, 5 arranged in the radial direction, and each chamber has one sealed chamber. A container 6 is formed. The number of airtight containers 6 formed in each rotating body 1 does not necessarily have to be four, and any number of airtight containers 6, preferably three or more, may be formed.

Note that it is preferable that the partition wall 4 of each closed container 6 be a heat insulating wall using a heat insulating material, since the influence of heat transfer between the closed containers 6 can be prevented. Furthermore, the present invention incorporates conventional rotary heat exchanger technology in which means for enlarging the heat transfer surface such as heat transfer fins and heat transfer means such as heat pipes are provided on the inside and outside of each sealed container. can be used.

A metal hydride M is filled in the closed container 6 on each rotating body. Furthermore, each sealed container 6 on the rotating body 1b is connected to one of the sealed containers 6 on the rotating body 1a and one of the sealed containers 6 on the rotating body 1c, that is, two hydrogen conduits 7, 7.
They are connected in communication by. The pair of closed containers communicated by the hydrogen conduit 7 will be described in detail in the description of the operation of the apparatus below. In addition, in Fig. 1, two parts on one rotating body are shown for simplification.
One set of hydrogen conduits 7, 7 for only one closed container
Although shown in the figure, in reality, all closed containers are provided with one set of hydrogen conduits.

One end of the rotating shaft 2 is connected to each sealed container 6 through one of a set of hydrogen conduits in each sealed container 6 on the rotating body 1a as the rotating shaft 2 rotates. A raw hydrogen supply port 8 and a degraded hydrogen outlet 9 to be shut off are provided. On the other hand, the other end of the rotating shaft 2 is connected to each sealed container 6 on the rotating body 1c through one of a set of hydrogen conduits, which communicates with each sealed container 6 individually as the rotating shaft 2 rotates. Alternatively, a purified hydrogen outlet 10 to be shut off is provided.

That is, as shown in FIG. 3, an annular member 20 having a raw hydrogen supply port 8 and a degraded hydrogen outlet 9 opened at predetermined locations is attached to one end of the rotating shaft 2.
The rotating body 1a is fixed in the annular space formed by the annular member 20 and the rotating shaft 2.
A partition member 20 in which four cavities 21 corresponding to the four closed containers 6 are arranged in a radial direction from the rotating shaft 2.
The hydrogen conduit 7 from each closed container communicates with each cavity 21. Further, the annular partition member 71 is formed with an opening 22 that communicates with each cavity 21, and as the rotating shaft 2 rotates, each hydrogen conduit is connected to the cavity 21.
1, the cycle of communication with the raw hydrogen supply port 8, cutoff, communication with the degraded hydrogen outlet 9, and cutoff is repeated.

Similarly, at the other end of the rotating shaft 2, as shown in FIG. In the annular space formed by the rotating shaft 2 and the rotating shaft 2, the four parts of the rotating body 1c are separated by a partition member 74 arranged in a radial direction from the rotating shaft 2 and an annular partition member 75 that slides and rotates on the inner wall of the annular member 23. forming four cavities 24 corresponding to four airtight containers;
One opening 25 is formed at a location of the annular partition member 75 corresponding to each cavity. Thereby, each hydrogen conduit can communicate with the purified hydrogen outlet 10 once through the cavity 24 during one rotation of the rotating shaft 2.

Note that 73 and 76 in FIGS. 3 and 4 are parts constituting the annular members 20 and 21, and each hydrogen conduit connects the raw hydrogen supply port 8, the degraded hydrogen outlet 9, and the purified hydrogen outlet 10 to the respective inlets and cavities. The time and timing of communication via 21 and 24 is adjusted.

To further explain with reference to FIG. 1, each hydrogen conduit 7 has a resistance member 1 against the return flow of hydrogen
1 is provided. This resistance member 11 is configured so that, for example, hydrogen released as a result of a dehydrogenation reaction of metal hydride in a closed container of the rotating body 1b is transferred to a hydrogen conduit 7.
On the other hand, when hydrogen flows from the closed container of the rotating body 1c through the hydrogen conduit 7 to the closed container of the rotating body 1c, the resistance is small. works so that it becomes larger. As such a resistance member 11, for example, a type in which a nozzle-type orifice 30 as shown in FIG. 5 is inserted into the hydrogen conduit 7 via a flange portion 31 can be used. This makes it possible to have a small resistance to the hydrogen flow in the direction of the arrow, and a large resistance to the flow in the opposite direction. FIG. 6 shows a type of resistance member 11 having a swing valve that can be preferably adopted in the vertical part of the hydrogen conduit 7 when the rotating shaft 2 is configured to be approximately vertical. A swing valve 32 is swingably supported on a shoulder formed on the surface by a pivot 33, and a support protrusion 34 is provided at the free end of the swing valve. As a result, the swing valve is pushed up against the hydrogen flow in the direction of the arrow, so the resistance is reduced, and when the hydrogen flow is in the opposite direction, the swing valve closes the flow path and the support protrusion 34 and shoulder Since the flow only occurs through the gaps, the resistance increases.

Note that the resistance member 11 is not particularly required in the hydrogen conduit 7 that connects each closed container 6 of the rotating body 1c to the purified hydrogen outlet 10. Further, it is preferable that the resistance value of the resistance member 11 of the hydrogen conduit 7 connected from each closed container of the rotating body 1a to the degraded hydrogen outlet 9 is determined in accordance with the amount of degraded hydrogen gas (impurities).

As mentioned above, each sealed container 6 has a hydrogen conduit 7.
Two hydrogen pipes are connected to each other, but in order to prevent the hydrogen introduced from one hydrogen pipe from being discharged from the other hydrogen pipe in the same sealed container, the fine-grained metal hydride is connected to the hydrogen pipe. We need to prevent it from getting inside. Therefore,
As shown in FIG. 7, one hydrogen conduit 7a is arranged in a radial direction from the rotation axis center side along the side wall of the closed container 6 on the rear side with respect to the rotation direction of the rotating body,
The other hydrogen conduit 7b is arranged radially from the center of the rotating shaft along the side wall of the sealed container on the front side with respect to the rotating direction of the rotating body, and hydrogen enters and exits the two hydrogen conduits 7a and 7b. A large number of openings 40 are formed, and a filter 41 made of a laminated wire mesh or a porous metal sintered body is inserted into the hydrogen conduits 7a, 7.
Arranged around b. Note that the number of openings 40 formed in the hydrogen conduit is preferably increased toward the outer periphery of the rotating body in proportion to the amount of metal hydride.

FIG. 8 shows another example of arrangement of the hydrogen conduits, in which one hydrogen conduit 7c is arranged along the outer circumferential wall of the closed container, and the other hydrogen conduit 7d is arranged along the inner circumferential wall of the closed container. be. In this case as well, hydrogen 7
A large number of openings 40 through which hydrogen enters and exits are provided at ports c and 7d, and a filter 41 is provided around the hydrogen conduit.

Rotating body 1 assembled integrally as above
a, 1b, 1c and the rotating shaft 2 are surrounded by an outer duct 12 as shown in FIG.
3 into two duct parts.

The partition wall 13 connects the rotating shaft 2 and the rotating bodies 1a, 1
It is provided with a slight gap between the parts b and 1c so as not to hinder the rotation of parts b and 1c. In this case, the rotating shaft 2 is made hollow, and the hydrogen conduit 7 is placed inside the rotating shaft.
By allowing the ducts to pass through, the gap between the rotating shaft 2 and the partition wall 13 can be reduced, and the sealing performance between the respective duct parts can be improved. In this way, by flowing a high-temperature heat medium or a low-temperature heat medium through each duct, a high-temperature heat medium chamber 14 is formed on one side of the rotating shaft 2, for example, on the upper side, and a low-temperature heat medium is formed on the other side of the rotating shaft 2, for example, on the lower side. A heat medium chamber 15 is formed. With such a configuration, as the rotating shaft 2 is rotated by an external drive source (not shown), the closed containers 6 of each rotating body can alternately and sequentially pass through the high-temperature heat medium chamber 14 and the low-temperature heat medium chamber 15. It's like that.

Note that the type of heat medium flowing into each heat medium chamber 14, 15 is not particularly limited as long as it is a fluid, but gas is generally preferably used. Furthermore, if the fluid heating medium is supplied to each heating medium chamber at substantially the same pressure, it is not necessary to strictly seal the heating medium chambers.

The operation of the hydrogen purification apparatus of the present invention configured as described above will be explained below. FIG. 9 is an expanded view of the three rotating bodies shown in _FIG .
Each represents a low temperature heat medium chamber 15 of T _L (< _TH ). In addition, the m-th sealed container on the n-th rotating body is expressed as _o R _n , and the four sealed containers on the first rotating body 1a are respectively ₁ R ₁ , ₁ R ₂ , ₁ R We will write it as ₃ , ₁ R ₄ . At this time, the first rotating body 1a
This means that the hermetic container ₁ R ₁ of the second rotating body 1b, the hermetic container ₂ R ₁ of the third rotating body 1c, and the hermetic container ₃ R ₁ of the third rotating body 1c are connected by the hydrogen conduits 7, 7. ing.

The raw material hydrogen to be purified is introduced from the supply port 8 and flows into the closed container _1R1 which is cooled in the low-temperature heating medium chamber ₁₅ , where it is occluded by metal hydride through a hydrogenation reaction. Ru. This hydrogenation reaction is an exothermic reaction, and this closed container is located in the low-temperature heating medium chamber.
As long as it rotates within the metal hydride, it is cooled, so the hydrogen concentration in the metal hydride increases, and it continues to absorb hydrogen until the equilibrium hydrogen pressure becomes equal to the system internal pressure.

In this way, the closed container ₁ R ₁ containing the metal hydride that has absorbed hydrogen is heated to a high temperature heat transfer medium chamber 1 as the rotating shaft rotates.
4 and reach position ₁ R ₃ in the diagram. When heated in _the high-temperature heating medium chamber 14, the metal hydride in the closed container _1R3 begins to release hydrogen through a dehydrogenation reaction. This dehydrogenation reaction is an endothermic reaction, but as long as this closed container rotates within the high-temperature heating medium chamber 15, it will be heated, so hydrogen will continue to be released until the equilibrium hydrogen pressure becomes equal to the system internal pressure. become. Most of the hydrogen released in the closed container _{1 R3} flows into the closed container _{2 R3} , which is cooled in the low-temperature heating medium chamber 15 on the rotating body 1b of the next stage, and at the same time hydrogen gas is released. A part of the hydrogen is discharged to the outside from the degraded hydrogen outlet 9.

In the next stage rotating body 1b, hydrogen released from the closed container ₁ R ₃ is occluded by the metal hydride in the closed container ₂ R ₃ through a hydrogenation reaction similar to that described above.
As the rotating shaft rotates, this sealed container becomes the high temperature heat transfer medium chamber 1.
When _{the 2} R ₁ position of 4 is reached, the metal hydride is heated and hydrogen is released from the metal hydride through a dehydrogenation reaction.
Most of the hydrogen released in the closed container ₂ R ₁ flows into the closed container ₃ R ₁ which is cooled in the low-temperature heating medium chamber 15 on the rotating body 1c of the next stage, and at the same time hydrogen gas is released. A part of it returns to the closed container _1R1 where it has started to be cooled in the low temperature heat medium chamber 15 on the rotating body _1a at the subsequent stage.
The forward flow and return flow of hydrogen are controlled as described above because the resistance of the return flow is increased by the resistor 11 in the hydrogen conduit 7 of the closed container ₃ R ₁ , ₂ R ₁ , ₁ R ₁ . The amount of return flow can be made smaller than the amount of forward flow to the next stage rotating body 1c.

In the final stage rotating body 1c, the closed container ₃ R ₁
The hydrogen released from the closed container ₂ R ₁ is stored in the metal hydride inside, and then this closed container is transferred to the high temperature heat transfer medium chamber 1.
When it rotates to the _4-3 R ₃ position, it is heated and hydrogen is released, and the released hydrogen is discharged from the outlet 10 as purified hydrogen. Further, a part of the hydrogen gas released here returns to the closed container _2R3 where it has started to be cooled in the low temperature heat medium chamber 15 on the rotating body 1b in _the latter stage.

In this way, the process of occluding and releasing hydrogen by the metal hydride in each closed container is repeated. When a metal hydride absorbs hydrogen, it is generally difficult for impurities to be occluded, so the more the occlusion and release steps are repeated, that is, the more rotating bodies are used, the more hydrogen can be purified. Purity will be increased.

As mentioned above, when a metal hydride stores hydrogen, it is difficult to store impurities, so when moving from a low-temperature heating medium chamber to a high-temperature heating medium chamber, in other words, it moves from a hydrogen storage process to a hydrogen release process. The gas remaining in the sealed container is hydrogen gas (depleted hydrogen) with many impurities. Therefore, it is necessary to return this degraded hydrogen to the subsequent stage rather than flowing it to the next stage. Also,
The hydrogen gas released into the closed container during the hydrogen release process in the high-temperature heating medium chamber has few impurities, so it is necessary to move most of it forward to the closed container on the next rotating body. .

Therefore, in the present invention, the closed containers on each rotating body connected by hydrogen conduits are made to be out of phase with each other. That is, in the illustrated embodiment,
When one closed container _o R _n on the n-th rotating body is in a low-temperature heating medium chamber and the metal hydride in this sealed container absorbs hydrogen, at the end of the storage process, the closed container _o R _n Degraded hydrogen containing impurities will remain. At this time, the latter stage, that is, the (n-1)th
If the closed vessel _o-1 R _n in which the hydrogen storage process is started on the th rotating body and the above-mentioned closed vessel _o R _n are connected by a hydrogen conduit, degraded hydrogen will be transferred from _o R _n to _o-1 R _n It becomes easier to return to. The final stage of this return flow is the degraded hydrogen outlet 9.
is discharged from. On the other hand, 1 on the nth rotating body
When two closed containers _o R _n are in the high-temperature heating medium chamber and hydrogen is being released in these closed containers, the next step, that is, the (n+1)th closed container _o If ₁ R _n and _{the o} R _n are connected by a hydrogen conduit, the released hydrogen will easily flow to the next stage, and the final stage of this released hydrogen will be discharged from the purified hydrogen outlet 10. Such quantitative control of the return flow and forward flow of hydrogen gas can be performed more reliably by the action of the resistance member 11 provided in the middle of the hydrogen conduit 7.

Thus, in the illustrated embodiment, closed containers _o-1 R _n , _o R _n , _o+1 R _n are connected to each other by hydrogen conduits.
, _o R _n is ahead in phase than _o-1 R _n , and _o
The relationship is such that _o+1 R _n is ahead of R _n in phase.

To explain the phase relationship in more detail,
The method of shifting the phase of sealed containers connected to each other by hydrogen pipes depends on the number of sealed containers on one rotating body, the size of each sealed container, thermal conductivity, reactivity of metal hydride, presence or absence of a resistance member, and its It depends on the performance, etc., and there are cases where it is better to delay the phase of the next stage, so it cannot be absolutely specified.
However, in general, in the closed containers _o+1 R _n , _o R _n , _o-1 R _n that are connected through hydrogen pipes, the tip of the closed container _o R _n is , the positional relationship where the tips of the subsequent sealed container _o-1 R _n and the next sealed container _o+1 R _n enter the low-temperature heating medium chamber (in Fig. 10, _o+1 R _n , _o R _n , _o-1 R _n are mutually
Since the phase is shifted by 180 degrees), the closed container
_o When R _n is between the low-temperature heating medium chamber and the high-temperature heating medium chamber, the subsequent closed container _o-1 R _n has just completely entered the low-temperature heating medium chamber, and the next closed container _o+1
The positional relationship where the tip of R _n is just before entering the low-temperature heating medium chamber (in Figure 11, _o+1 R _n , _o R _n , _{and o-1} R _n are out of phase by 135° from each other) It is preferable that the closed container _o R _n is between the low-temperature heat medium chamber and the high-temperature heat medium chamber, and the volume of the metal hydride in the closed container is between the low-temperature heat medium chamber side and the high-temperature heat medium chamber. When it is equal to the medium chamber side, the airtight container _o-1 in the latter stage
Immediately after R _n has completely entered the low-temperature heating medium chamber, the tip of the next closed container _o+1 R _n is positioned just before entering the low-temperature heating medium chamber, _{so that} Positional relationship before reaching the positional relationship just before the tips of the rear and next closed containers _o+1 R _n , _o-1 R _n reach the position just before they enter the low-temperature heating medium chamber, just before the tips leave the low-temperature heating medium chamber A good range is up to

Note that the timing for discharging degraded hydrogen from the closed container 6 of the rotating body 1a to the degraded hydrogen outlet 9 is such that the hydrogen released by the dehydrogenation reaction is discharged before it goes to the next stage, as described above. Therefore, it is preferable to provide an automatic valve or a suction means at the degraded hydrogen outlet 9 so that the timing of discharging the degraded hydrogen and its discharge amount can be finely adjusted.

Fig. 12 shows another embodiment of the device of the present invention, which differs from the embodiments shown in Figs. 1 and 9 in which the feedstock hydrogen supply port and the discharge of degraded hydrogen are carried out on the same rotating body. The point is that a hydrogen recovery device is provided to recover hydrogen from degraded hydrogen. In FIG. 12, reference numeral 50 indicates a hydrogen purification device, and 51 indicates a hydrogen recovery device for depleted hydrogen from the purification device 50. Since the hydrogen purification apparatus 50 has the same structure as in FIG. 1, the same members as in FIG. 1 are given the same reference numerals and a description thereof will be omitted. The hydrogen recovery device 51 has a rotating shaft 2 that is common to the rotating shaft of the purifying device 50, and rotary bodies 53a and 53b similar to the rotating body of the purifying device 50 can rotate together with the rotation of the rotating shaft 2. ing. The rotating shaft 2 and the rotating bodies 53a and 53b are surrounded by an outer duct 54, and the inside of the outer duct is divided into two duct parts by a partition wall 55 extending across the rotating shaft 2.
A low temperature heat medium chamber 56 and a high temperature heat medium chamber 57 are formed. In addition, in order to flow the degraded hydrogen from the closed container ₁ R ₃ on the rotating body 1 a of the purification device 50 to the closed container ₁ S ₁ on the rotating body 53 a on the same side (for example, the upper side) as this closed container In the illustrated example, the low temperature heat medium chamber 56 of the recovery device 51 is arranged on the same side as the high temperature heat medium chamber 14 of the refining device 50.

In an apparatus with such a configuration, degraded hydrogen from the closed container ₁ R ₃ on the rotating body 1a of the purification apparatus 50 is
The rotating body 53a of the recovery device 51 is passed through the hydrogen conduit 7.
The hydrogen flows into the closed container ₁ S ₁ which is located in the upper low-temperature heating medium chamber 56 and is cooled, and hydrogen is occluded by the metal hydride in this closed container. While this sealed container ₁ S ₁ rotates to the high-temperature heating medium chamber 57 and reaches the position ₁ S ₃ in the figure, the degraded hydrogen containing many impurities remaining in this sealed container is transferred to the low-temperature heat on the rotating body 53b. Media room 5
On the other hand _, hydrogen with few impurities released in the closed container ₁ S ₃ joins with the raw hydrogen stream flowing in from the supply _port 8 and is purified. It is introduced into the closed container ₁ R ₁ on the rotating body 1a of the device 50. _The hydrogen gas contained in the contaminated hydrogen that has leaked into the closed container ₂ S ₃ is absorbed by _the metal hydride. While rotating to the chamber 57 and reaching the ₂ S ₁ position, the depleted hydrogen is sent to the depleted hydrogen outlet 9 and discharged from there. On the other hand, hydrogen with few impurities released from the closed container ₂ S ₁ is returned to the closed container ₁ S ₁ of the rotating body 53a. Thus, the closed container on the rotating body 1a of the purification device 50
₁ Compared to directly discharging degraded hydrogen from _R3 , hydrogen in degraded hydrogen can be recovered. Also in this case, the more the number of rotating bodies in the recovery device 51 is increased, the more the hydrogen recovery rate in degraded hydrogen can be improved.

Still another embodiment of the hydrogen purification apparatus of the present invention is shown in FIGS. 13 and 14. Figure 13 shows a plurality of rotating bodies 1a, 1a, which have the same phase and have the same action.
1a is set as a stage corresponding to the rotating body 1a in FIG. 1, and similarly, a plurality of rotating bodies 1b, 1b, 1b are set as a stage corresponding to the rotating body 1b in FIG. This allows the heat transfer volume of the closed container to be increased. Although only a part of the hydrogen conduit 7 is shown in FIG. 13, as the number of rotating bodies increases, the number of hydrogen conduits also increases and the piping becomes complicated. 2
It is preferable that the rotating shaft is hollow and the hydrogen conduit 7 is disposed within the rotating shaft.

FIG. 14 differs from the high temperature heat medium chamber 14 and the low temperature heat medium chamber 15 in which the high temperature heat medium chamber and low temperature heat medium chamber of each rotating body of FIG. An embodiment is shown in which heat medium chambers 14 and 15 are provided for each of 1b and 1c. In this case, as shown in the figure, the high temperature heat medium chamber 14 (T _H ) and the low temperature heat medium chamber 15 (T _L )
By providing the hydrogen conduits 7 alternately, the hydrogen conduits 7 that connect the closed containers that are approximately symmetrical with respect to the rotation axis as shown in FIG. It is only necessary to connect the closed containers located on the upper side), and the piping of the hydrogen conduit 7 becomes easier because it does not cross the rotation axis. Note that although the temperatures of the high-temperature heat medium chambers are all expressed as T _H , these may have different temperatures. The same applies to the low-temperature heat medium room, and it is sufficient if the relationship T _H > T _L holds true.

In addition, in the examples shown in FIGS. 1 and 14, the partition walls 13 extending across the rotating shaft 2 do not necessarily have to be on the same plane on both sides of the rotating shaft 2, but in the radial direction on both sides of the rotating shaft 2. The rotating bodies may be provided so as to extend at different angles, and the above-mentioned phase shift between the rotating bodies may be provided by adjusting the angle in the radial direction. Furthermore,
A large number of partition walls 13 may be extended in the radial direction from the rotating shaft 2 to provide a plurality of pairs of high-temperature heat medium chambers and low-temperature heat medium chambers around the rotating shaft.

The hydrogen purification container of the present invention is not limited to the above-described embodiments, and various modifications can be made within the scope of the claims. For example, the rotating body does not necessarily have to be disc-shaped, but may be spherical or polygonal. In addition, a plurality of closed containers filled with metal hydrides are rotors 1a, 1b, 1c shown in the figure.
It is not necessary to have an integral structure like this, but it is sufficient that they are arranged radially in the circumferential direction of the rotating shaft so that they can rotate together with the rotating shaft.

Furthermore, as shown in FIG. 15, for example, a plurality of cylindrical closed containers 60 filled with metal hydride are arranged in parallel to each other in an annular manner and mounted on an endless transfer line member 61 such as a chain or belt. One annular row arranged in the above may be one rotating body 62a. In this case, a pair of rotating gears 64 having a notch 63 into which the lower half of the airtight container 60 fits
If several rows of endless transfer row members 61 are installed between them, the number of rotating bodies 62a, 62 corresponding to the number of rows is
b, 62c will be formed. Then, the closed containers on adjacent rotating bodies are connected in a straight line with hydrogen conduits 7, and a resistance member 11 is placed in the middle of each hydrogen conduit 7.
By arranging the high-temperature heat medium chambers 65 and the low-temperature heat medium chambers 66 alternately in the feeding direction and the column direction of the endless rotation transfer row member 61, the embodiment of FIG. It can be operated in the same way as the device.

In addition, in this example, the raw material hydrogen supply port,
The hydrogen conduit connected to the degraded hydrogen outlet or the purified hydrogen outlet is partially made of flexible material, and is connected to the cavity 21 (24) in FIG. 3 (or FIG. 4), or the cavity is endlessly rotating. The annular member 20 in FIGS. 3 and 4 is moved in parallel with the feeding member 61.
(23) and the rotating shaft 2 are replaced with members having a similar shape to the endless rotation transfer row member 61, that is, the annular member 20 (23) shown in FIGS. ) and the rotating shaft 2, and a chamber formed with a cavity having an opening in the space is preferably moved.

<Effects of the Invention> As explained above, according to the present invention, the timing of heating and cooling of the closed containers interconnected by the hydrogen pipes is shifted, that is, the phase of the hydrogenation reaction and the dehydrogenation reaction is adjusted. Since the storage and release of hydrogen gas is repeated by shifting the hydrogen gas, impurities remaining in the container when hydrogen is stored in the alloy are not entrained with the purified hydrogen gas, and the closed container on the adjacent rotating body is Since they are connected by a hydrogen conduit with a phase shift between them, hydrogen gas generated by the metal hydride inside the sealed container is In addition to being able to repeatedly and continuously perform occlusion and release of hydrogen, it is also possible to automatically control the flow of purified hydrogen gas and the flow of degraded hydrogen gas containing many impurities.

In addition, since the hydrogen dissociation pressure of the metal hydride used in this invention varies greatly with temperature, the temperature difference between the high temperature heat medium chamber T _H and the low temperature heat medium chamber T _L is approximately several tens of degrees (°C). That's fine. Therefore, hydrogen gas can be efficiently purified using cooling water and waste heat from heated waste water.

In addition, in the apparatus of the present invention, if various adsorbents such as silica gel, activated carbon, zeolite, etc. are filled in the closed container instead of filling the metal hydride, and various gases containing impurities are passed through, it can be used as a purification apparatus for various gases. It is also possible to use it as

[Brief explanation of drawings]

Fig. 1 is an explanatory diagram showing an embodiment of the hydrogen purification apparatus of the present invention; Fig. 2 is a side view of the rotating body in Fig. 1; Figs. 3 and 4 respectively show the feedstock hydrogen supply port and Cross-sectional view of purified hydrogen outlet;
Figures 5 and 6 are cross-sectional views showing examples of resistance members in the hydrogen conduit; Figures 7 and 8 are explanatory views showing examples of the structure inside the closed container; Figure 9 is the rotation of Figure 1. A developed view of the body; Figures 10 and 11 are explanatory diagrams showing the phase shift of the closed container of each rotating body;
FIG. 12 is an explanatory diagram showing another embodiment of the device of the present invention, which is equipped with a device for recovering hydrogen from degraded hydrogen;
FIGS. 13, 14, and 15 are explanatory diagrams showing still another embodiment of the device of the present invention. 1...Rotating body, 2...Rotating shaft, 6...Airtight container, 7...
Hydrogen conduit, 8... Raw hydrogen supply port, 9... Degraded hydrogen outlet, 10... Purified hydrogen outlet, 11... Resistance member, 12
...outer duct, 13...partition wall, 14...high temperature heat medium chamber, 15...low temperature heat medium chamber.

Claims (1)

[Scope of Claims] 1. Using a plurality of sealed containers filled with metal hydride and interconnected by hydrogen conduits, a hydrogenation reaction of the metal hydride carried out in the n-th sealed container results in the sealing. The degraded hydrogen gas containing impurities remaining in the container (nth) is transferred to the subsequent sealed container (nth
With the start of the hydrogenation reaction of the metal hydride in the n-th sealed container, the dehydrogenation reaction of the metal hydride is carried out in the n-th sealed container. The timing of heating and cooling of each closed container is staggered so that the purified hydrogen gas released advances to the next stage along with the hydrogenation reaction of the metal hydride in the next stage closed container (n+1th). Characteristic hydrogen purification method. 2 A plurality of rotating bodies each having a plurality of sealed containers filled with metal hydride arranged in the circumferential direction are arranged along a rotating shaft, and as the rotating bodies rotate, the sealed containers of each rotating body open into a low-temperature heat medium chamber. and a low-temperature heat medium chamber and a high-temperature heat medium chamber are provided around the rotating shaft so as to pass through the high-temperature heat medium chamber alternately and sequentially, and an m-th sealed container on one rotating body (n-th) When ( _{oRn )} is in the low-temperature heating medium chamber, as a result of the hydrogenation reaction of the metal hydride carried out in the sealed container, degraded hydrogen gas containing impurities remaining in the sealed container ( _{oRn )} is transferred to the subsequent stage. The m-th rotating body (n-1st) rotates into the low-temperature heating medium chamber
With the start of the hydrogenation reaction of the metal hydride in the second sealed container ( _o-1 R _n ), the subsequent sealed container ( _o- 1 R n )
₁ R _n ), the closed container ( _o R _n ) on the nth rotating body rotates to the high temperature heating medium chamber, and the metal hydride produced in the closed container ( _o R _n ) is rotated. The purified hydrogen gas released by the dehydrogenation reaction is transferred to the metal hydride in the m-th sealed container ( _o+ 1 R _n ) located in the low-temperature heating medium chamber on the next rotating body (n+1-th). Along with the hydrogenation reaction, the next stage of the closed container ( _o+1
The closed containers of the rotating bodies are connected with hydrogen pipes with their phases shifted so that the rotating bodies move forward toward R _n ), and the hydrogen pipes exiting from each closed container of the final stage of the rotating body are connected to the purified hydrogen outlet. , connect the hydrogen pipes coming out of each sealed container of the rotating body of the first stage to the degraded hydrogen outlet, connect the hydrogen pipes entering each sealed container of one rotating body of the arbitrary stage to the raw hydrogen supply port, and connect each hydrogen pipe to the raw hydrogen supply port. A hydrogen purification apparatus characterized in that the connection between the conduit and the purified hydrogen outlet, the degraded hydrogen outlet, or the raw hydrogen supply port is communicated or cut off as the rotating body rotates. 3. A resistance member that has a high resistance to the return flow of degraded hydrogen gas and a low resistance to the forward flow of purified hydrogen gas is disposed in the hydrogen conduit connecting the sealed containers. The hydrogen purification apparatus according to claim 2, characterized in that: 4. The above-mentioned phase is characterized in that in closed containers ( _o+1 R _n , _o R _n , _o-1 R _n ) that are interconnected by hydrogen pipes, the tip of one closed container ( _o R _n ) is connected to a low-temperature heat medium. Immediately before leaving the chamber, the tips of the subsequent sealed container ( _o-1 R _n ) and the next sealed container ( _o+1 R _n ) are located just before entering the low-temperature heating medium chamber, so that one sealed container is sealed. When the container ( _o R _n ) is between the low-temperature heat medium chamber and the high-temperature heat medium chamber, immediately after the subsequent sealed container ( _o-1 R _n ) has completely entered the low-temperature heat medium chamber, and 3. The hydrogen purification apparatus according to claim 2, wherein the end of the closed container ( _o+1 R _n ) extends to a certain positional relationship immediately before entering the low-temperature heating medium chamber. 5 A hydrogen conduit connecting the sealed containers is arranged so as to cross the rotation axis, and the high temperature heat medium chamber and the low temperature heat medium chamber of each rotating body are connected to each other to form an integrated high temperature heat medium chamber and low temperature heat medium chamber. Claim 2, characterized in that the phase is shifted by
Hydrogen purification equipment described in section. 6. The phase is shifted by alternately arranging the high-temperature heat medium chambers and the low-temperature heat medium chambers of each of the rotating bodies, and arranging the hydrogen pipes connecting the closed containers so that they do not cross the rotation axis. The hydrogen purification apparatus according to claim 2, characterized in that: