JP2002249032A - Hydrogen station - Google Patents

Abstract

PROBLEM TO BE SOLVED: To lengthen the service life of a second purifier used for achieving high-purity hydrogen. SOLUTION: This hydrogen station 1 is constituted of a hydro-electrolytic apparatus 4, a first purifier 6 capable of purifying hydrogen produced by the hydro-electrolytic apparatus 4 to obtain first purified hydrogen, a switching device 8 for switching the flowing direction of the first purified hydrogen to make the first purified hydrogen flow to either of storage side or re-purification side, a first storage device 12 for charging the first purified hydrogen, a second purifier 15 for re-purifying the first purified hydrogen to obtain second purified hydrogen, and a second storage device 16 for charging the second purified hydrogen.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a hydrogen station,
That is, the present invention relates to a hydrogen station having a function of producing hydrogen, storing the hydrogen, and supplying the produced hydrogen to, for example, a fuel cell vehicle.

[0002]

2. Description of the Related Art When carrying hydrogen in a vehicle equipped with a fuel cell, for example, a high-pressure container filled with high-pressure and relatively low-purity hydrogen, that is, low-purity hydrogen, or a low-pressure and relatively high-purity hydrogen is used. That is, a means of equipping a pressure vessel having a hydrogen storage material storing high-purity hydrogen is adopted.

[0003] Therefore, in a hydrogen station, for example, a first electrolysis apparatus for producing hydrogen is used to obtain low-purity hydrogen.
Attempts have been made to connect a purifying / compressing system and a second purifying / compressing system for obtaining high-purity hydrogen via a switching device to obtain two types of hydrogen from one water electrolysis device.

[0004]

The hydrogen obtained by the water electrolyzer contains a large amount of water, and its dew point is +40.
It is about ° C. On the other hand, high-purity hydrogen has a dew point of -10.
It is required to be about 0 ° C. For this reason, refiners are required to have strict refining capacity, but existing refiners do not have the durability to meet the above requirements for a long period of time. This has led to a decline in productivity.

On the other hand, the required purity of low-purity hydrogen is dew point -2.
Since the temperature is about 0 ° C., the purifying ability required for the purifier is relaxed, and the above-mentioned problem does not occur.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a hydrogen station capable of extending the life of a purifier used for obtaining high-purity hydrogen.

[0007] To achieve the above object, according to the present invention,
A hydrogen production apparatus, a first purifier for purifying hydrogen produced by the hydrogen production apparatus to obtain a first purified hydrogen, and a switch for determining a flow direction of the first purified hydrogen to one of a storage side and a repurification side An apparatus and a first charged hydrogen filled with the first purified hydrogen.
A hydrogen station is provided having a reservoir, a second purifier for repurifying the first purified hydrogen to obtain a second purified hydrogen, and a second reservoir filled with the second purified hydrogen.

[0008] With the above configuration, the second purified hydrogen,
Therefore, high-purity hydrogen is obtained through a two-stage purification process,
Therefore, since the refining capacity required for the second purifier is relaxed, it is possible to extend the life of the second purifier, thereby efficiently purifying the first and second purified hydrogen having different purities. Can be produced.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS As shown in FIG. 1, a hydrogen station 1 is a main facility 2 for producing, purifying and storing hydrogen.
And a refining facility 3 for the purifier. The main facility 2 will be described first, and then the regenerating facility 3 will be described.

A. Main Facility (Production, Purification and Storage of Hydrogen) The main facility 2 is provided with a water electrolysis device 4 as a hydrogen production device. The inlet side of the first supply pipe 5 is connected to the hydrogen supply section of the water electrolysis device 4.
The first purifier 6 and the compressor 7 are sequentially arranged from the water electrolysis device 4 side.
Is installed. The outlet side of the first supply pipe 5 is connected to a first port of a three-way valve 9 in the switching device 8.

An inlet side of a second supply pipe 10 is connected to a second port of the three-way valve 9, and a first pressure reducing valve 11 for adjusting pressure belonging to the switching device 8 is connected to the second supply pipe 10. At the outlet side of the second supply pipe 10, a high pressure vessel 12 as a first storage is provided.
Are detachably connected. Further, the third port of the three-way valve 9 is connected to the inlet side of the third supply pipe 13.
3, a second pressure reducing valve 14 belonging to the switching device 8 and having a high pressure reducing ratio and a second purifier 15 are sequentially provided from the three-way valve 9 side. A pressure vessel 16 as a second storage is detachably connected to the outlet side of the third supply pipe 13.

The first purifier 6 is internally heated by heating.
Activated alumina and silica gel as regenerated adsorbents
Activated alumina 17 is provided in at least one of the embodiments.
On the other hand, the second purifier 15 is similarly heated inside.
Sieve 18 as adsorbent regenerated by water
It has. The pressure vessel 16 has a hydrogen storage material inside.
MH, and the hydrogen storage material MH is a hydrogen storage alloy
[For example, MmNi_{Four. 7}Al_0.3(Mm: Mishmeta
Le), Ti_1.2CrMn, etc.], nanostructured carbon, etc.
Can be.

Next, the operation of the main equipment 2 will be described.

Hydrogen is produced by the water electrolysis apparatus 4, and the hydrogen contains a large amount of moisture, and the purity is about + 40 ° C. of dew point. The hydrogen is supplied to the activated alumina 1 of the first purifier 6.
7, a purification treatment mainly involving dehydration is performed, whereby a first purified hydrogen is obtained. The purity of the first purified hydrogen is about -20 ° C.

The first purified hydrogen is several tens M by the compressor 7.
After being pressurized to Pa, it is introduced into the switching device 8. Since the three-way valve 9 of the switching device 8 is switched so as to determine the flow direction of the first purified hydrogen to the storage side, that is, to the high-pressure vessel 12 side, the first purified hydrogen of high pressure and low purity is supplied to the first pressure reducing valve 11. After the pressure is adjusted by the above, the high-pressure container 12 is filled. In this case, since the first purified hydrogen has a dew point of about −20 ° C. and contains sufficient moisture to lubricate the compressor 7, wear of the sliding portion of the compressor 7 is suppressed, and the life of the compressor 7 is extended. It is planned.

When the filling of the high-pressure vessel 12 with hydrogen is completed,
The three-way valve 9 is switched so as to determine the flow direction of the first purified hydrogen to the re-purification side, that is, to the second purifier 15 side, and the high-pressure vessel 12 is separated from the second supply pipe 10 to refill the hydrogen. The high-pressure vessel 12 is connected to the second supply pipe 10.

The switching of the three-way valve 9 causes the high pressure first
The purified hydrogen is decompressed to a few MPa by the second pressure reducing valve 14, and then subjected to a purification treatment mainly for dehydration by the molecular sieve 18 of the second purifier 15, whereby the second purified hydrogen is obtained. The purity of this second purified hydrogen is dew point -1.
The highly purified second purified hydrogen at about 00 ° C. and under reduced pressure is stored in the hydrogen storage material MH of the pressure vessel 16. When the occlusion is completed, the three-way valve 9 is switched so as to determine the flow direction of the first purified hydrogen to the high-pressure vessel 12, and the pressure vessel 16 is separated from the third supply pipe 13, so that a new hydrogen storage pressure is obtained. The container 16 is connected to the third supply pipe 13.

With the above configuration, the second purified hydrogen,
Therefore, high-purity hydrogen is obtained through a two-stage purification process,
Therefore, since the refining capacity required for the second purifier 15 is relaxed, it is possible to extend the life of the second purifier 15, whereby the first and second purified hydrogens having different purities can be removed. It can be produced efficiently.

If necessary, the compressor 7 may be omitted from the main equipment 2, and the storage tank may be filled with low-pressure, low-purity first purified hydrogen.

B. Regeneration equipment for refiner This regeneration equipment 3 heats activated alumina 17 of the first refiner 6 and molecular sieve 18 of the second refiner 15,
In addition, a heating-cooling device 19 capable of cooling, and both purifiers 6 and 1
A hydrogen circulating device 20 for circulating the hydrogen for regeneration between the five purifiers 5 enables the regeneration of the first purifier 6 to be performed during the regeneration of the second purifier 15.

The heating / cooling device 19 is configured as follows. The molecular sieve 18 is placed in the second purifier 15.
Is provided with an electric heater 21 capable of heating the heater. Further, a cooling water circulation path 22 provided with first and second purifiers 6 and 15 is provided.
In order to configure the circulation path 22, one of the first and second water pipes 23 and 24 connecting the first and second purifiers 6 and 15, that is, the first water pipe 23 is provided with a first purification pipe. First three-way valve 25, circulation pump 26, second three-way valve 2
7, radiator 28, third three-way valve 29 and fourth three-way valve 30
Is installed. First to fourth three-way valves 25, 27, 29, 3
0, the first and second ports are connected to the first water pipe 2
3 is connected. 2nd, 3rd three-way valve 2
A third water pipe 31 connects between the third ports 7 and 29, and the radiator 28 is bypassed by the third water pipe 31.

The second water pipe 24 is provided with a fifth three-way valve 32 and a sixth three-way valve 33 sequentially from the first purifier 6 side. The first and second ports of the fifth and sixth three-way valves 32 and 33 communicate with the second water pipe 24. A supply pipe 35 of a water reservoir 34 is connected to the second water pipe 24 between the three-way valves 32 and 33. The water reservoir 34 is used to fill the cooling water circulation path 22 with cooling water, and when the cooling water decreases with time, the reduced water is immediately replenished. First and fifth three-way valves 2
A fourth water pipe 36 connects between the third ports 5 and 32, and the first purifier 6 is bypassed by the fourth water pipe 36. Furthermore, the third ports of the fourth and sixth three-way valves 30 and 33 are connected by a fifth water pipe 37, and the fifth water pipe 37 bypasses the second purifier 15.

The hydrogen circulation device 20 is configured as follows. A hydrogen circulation path 38 provided with first and second purifiers 6 and 15 is provided.
One of the two conduits 39, 40 connecting the purifiers 6, 15
9, a circulating pump 41 and a condenser 42 are sequentially installed from the first purifier 6 side. In one conduit 39, a buffer container 43 filled with hydrogen is connected between the condenser 42 and the second purifier 15 via a supply pipe 44, and a two-way valve 45 is provided in the supply pipe 44. The buffer container 43 is used to fill the hydrogen circulation path 38 with hydrogen for regeneration, and when the hydrogen for regeneration decreases with time, the buffer vessel 43 is immediately replenished with the decrease.

Next, the operation of the regeneration equipment 3 will be described.

(1) Electric heater 2 of heating / cooling device 19
1, the molecular sieve 18 of the second purifier 15 is raised from room temperature to a regeneration treatment temperature, for example, 300 ° C., as shown by solid lines a and b in FIG. Thereby, the moisture adsorbed on the molecular sieve 18 evaporates. In addition, the circulation pump 41 of the hydrogen circulation device 20 is operated, and the regeneration hydrogen is supplied from the circulation pump 41 → the condenser 42 → the second purifier 15 → as indicated by an arrow in FIG.
The first refiner 6 is circulated in the order of the circulation pump 41, and the molecular sieve 1 is converted into dry hydrogen for regeneration through the condenser 42.
The second purifier 1 containing the water (steam) evaporated from 8
Discharge from 5 The regeneration hydrogen containing water is supplied to the condenser 42.
Is dehydrated and dried. This circulation of the hydrogen for regeneration is continued until the end of the regeneration process.

(2) The power supply to the electric heater 21 of the second purifier 15 is stopped, and the circulation pump 26 of the heating / cooling device 19 is operated. Thus, the cooling water is supplied to the circulation pump 26 → the second three-way valve 27 → the third water pipe 31 → the third three-way valve 29 → the fourth three-way valve 30 → the second
The purifier 15 → the sixth three-way valve 33 → the fifth three-way valve 32 → the first purifier 6 → the first three-way valve 25 → the circulation pump 26 is circulated in this order. As a result, as shown by the solid line c in FIG. 2, the temperature of the molecular sieve 18 decreases, while the cooling water whose temperature has risen by removing the residual heat of the second purifier 15 flows through the first purifier 6. As shown by a dotted line d in FIG. 2, the temperature of the activated alumina 17 increases from room temperature. (3) When the temperature of the molecular sieve 18 drops to about 50 ° C., the temperature of the activated alumina
Is the regeneration processing temperature as shown by the dotted line e, for example, 10
Increase to 0 ° C. (this is the same for silica gel). Therefore, the electric heater 21 of the second purifier 15 is energized to raise the temperature of the molecular sieve 18 by a predetermined value from 100 ° C. as shown by solid lines f and g in FIG. Thereby, activated alumina 17
Is maintained at a regeneration processing temperature of 100 ° C. for a predetermined time to evaporate the moisture adsorbed on the activated alumina 17. Since most of the water in the molecular sieve 18 has been removed in the process of maintaining the regeneration processing temperature at 300 ° C.,
The hydrogen for regeneration that has passed through the second purifier 15 is in a substantially dry state,
The hydrogen for regeneration contains moisture (steam) evaporated from the activated alumina 17 and is discharged from the first purifier 6.

(4) The energization of the electric heater 21 of the second purifier 15 is stopped, and the second and third three-way valves 27 and 29 are switched, as shown by a thin arrow x of a white triangular arrowhead in FIG. Then, the cooling water is supplied to the circulation pump 26 → the second three-way valve 27 → the radiator 28.
→ 3rd 3-way valve 29 → 4th 3-way valve 30 → 2nd purifier 15 →
Sixth three-way valve 33 → fifth three-way valve 32 → first purifier 6 → first
Circulation is performed in the order of the three-way valve 25 and the circulation pump 26. As a result, the temperatures of the molecular sieve 18 and the activated alumina 17 decrease as shown by the solid line h and the dotted line i in FIG.

(5) The temperature of the molecular sieve 18 is 50
Immediately before the temperature drops to 4 ° C., the fourth and sixth three-way valves 30,
33, the cooling water is supplied from the circulation pump 26 to the second three-way valve 27 as shown by the thick arrow y of the black triangle arrowhead in FIG.
Radiator 28 → third three-way valve 29 → fourth three-way valve 30 → fifth water pipe 37 → sixth three-way valve 33 → fifth three-way valve 32 → first purifier 6 → first three-way valve 25 → circulation pump 26 Circulate in order. As a result, the temperature of the activated alumina 17 drops to room temperature as shown by a dotted line j in FIG. Thereafter, the operation of the circulation pump 26 is stopped.

(6) Immediately after the switching of the fourth and sixth three-way valves 30 and 33, the electric heater 21 of the second purifier 15
To maintain the temperature of the molecular sieve 18 at about 50 ° C. for a predetermined time, as indicated by the solid line k in FIG. Thereby, the molecular sieve 18 is dried.

(7) Electric heater 21 of second purifier 15
Is stopped, the first and fifth three-way valves 25 and 32 are switched, and the fourth and sixth three-way valves 30 and 33 are switched.
Further, the circulation pump 26 is operated, and as shown by the thick arrow z of the white triangle arrowhead in FIG.
Second three-way valve 27 → heat radiator 28 → third three-way valve 29 → fourth three-way valve 30 → second purifier 15 → sixth three-way valve 33 → fifth three-way valve 32 → fourth water pipe 36 → first three-way valve The circulation is performed in the order of 25 → circulation pump 26. Thereby, as shown by the solid line m in FIG. 2, the temperature of the molecular sieve 18 decreases to room temperature.

Through the above steps (1) to (7), the first,
The regeneration processing of the second purifiers 6 and 15 ends.

As described above, the regeneration processing of the first and second purifiers 6 and 15 is performed by one regeneration facility 3, and
Since the regenerating process of the first purifier 6 is performed in the regenerating process of the refining device 15, the regenerating process time can be reduced as compared with the case where the regenerating processes of the two refining devices 6 and 15 are performed separately. Further, since the residual heat of the regeneration processing heat of the molecular sieve 18 is used for the regeneration processing of the activated alumina 17, the heat energy required for the regeneration processing can be reduced.

As described above, according to the regenerating equipment 3, the regenerating process of the first and second purifiers 6, 15 can be performed efficiently at low cost.

In the first purifier 6, a vortex tube as a dehumidifying means can be used instead of activated alumina.

[0035]

According to the first aspect of the present invention, there is provided a hydrogen station capable of extending the life of a second purifier used for obtaining high-purity hydrogen by having the above-described structure. Can be.

According to the second aspect of the present invention, in addition to the above-mentioned effects, it is possible to provide a hydrogen station which can extend the life of the compressor and reduce the equipment cost by eliminating the need for the second purified hydrogen compressor. it can.

According to the third, fourth and seventh aspects of the present invention, the first and second purified hydrogen can be reliably obtained, and an economical hydrogen station can be provided.

According to the fifth and sixth aspects of the present invention, it is possible to provide a hydrogen station having a regenerating facility capable of efficiently and efficiently regenerating the first and second purifiers at low cost. it can.

[Brief description of the drawings]

FIG. 1 is a schematic explanatory view of a hydrogen station.

FIG. 2 is a graph showing temperature changes over time of molecular sieve and activated alumina in a regeneration treatment.

[Explanation of symbols]

 1 ... hydrogen station 3 ... regenerator for purifier 4 ... water electrolyzer (hydrogen production device) 6 ... first purifier 7 ... compressor 8 ... Switching device 12 High pressure vessel (first storage) 14 Second pressure reducing valve 15 Second purifier 16 Pressure vessel (second storage) 17 Active alumina 18 ...... Molecular sieve

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) B01J 20/34 B01J 20/34 FH B67D 5/01 B67D 5/01 C01B 3/00 C01B 3/00 B Z 3/56 3/56 A // H01M 8/04 H01M 8/04 N 8/06 8/06 RF term (reference) 3D026 CA00 3E083 AA18 4G040 AA25 AA43 AA45 BA03 BB03 FA02 FB02 FC02 FD04 FE01 4G066 AA02B AA04B AA20B AA22B CA38 CA43 DA01 EA09 GA02 GA04 GA08 5H027 AA02 BA11 BA13 BA14 BA16

Claims (7)

[Claims] 1. A hydrogen production device (4), a first purifier (6) for purifying hydrogen produced by the hydrogen production device (4) to obtain a first purified hydrogen, A switching device (8) for determining the flow direction to one of the storage side and the re-purification side, a first storage (12) filled with the first purified hydrogen, and a second refiner for re-purifying the first purified hydrogen. A hydrogen station comprising: a second purifier (15) for obtaining purified hydrogen; and a second storage (16) filled with the second purified hydrogen. 2. A compressor (7) for compressing the first purified hydrogen is provided between the first purifier (6) and the switching device (8), and the switching device (8) is provided on a re-purification side. The first reservoir is a high-pressure container (12) corresponding to the high-pressure first purified hydrogen, and the second reservoir is a high-pressure container (12) corresponding to the high-pressure first purified hydrogen. 2. The hydrogen station according to claim 1, wherein the hydrogen station is a pressure vessel having a hydrogen storage material (MH) for storing the second purified hydrogen. 3. 3. The first and second purifiers (6, 15).
Are adsorbents (17, 1) regenerated by heating, respectively.
The hydrogen station according to claim 1 or 2, further comprising (8). 4. The adsorbent of the first purifier (6) is at least one of activated alumina and silica gel (17).
The hydrogen station according to claim 3, wherein the adsorbent of the second purifier (15) is a molecular sieve (18). 5. The hydrogen station according to claim 4, further comprising a regeneration facility (3) capable of performing a regeneration process of the first refiner (6) during a regeneration process of the second refiner (15). . 6. In the regeneration equipment (3), a regeneration treatment temperature of the molecular sieve (18) is set higher than a regeneration treatment temperature of the activated alumina and silica gel (17).
The hydrogen station according to claim 5, wherein the regenerative processing of (7) uses residual heat of the regenerative processing heat of the molecular sieve (18). 7. The first purifier (6) includes a vortex tube as a dehumidifying means, and the second purifier (15).
The hydrogen station according to claim 1 or 2, wherein the hydrogen station comprises a molecular sieve (18) as an adsorbent.