JP6516393B1 - Hydrogen generator and hydrogen filling device - Google Patents

Abstract

The present invention provides a hydrogen generator capable of generating hydrogen with a simple and small-scale configuration without requiring a two-step heat treatment as in the prior art. SOLUTION: Methane and water are supplied to a heating unit 31. The first reaction chamber 33 downstream of the heating unit 31 is a catalytic reactor, and is filled with the first catalyst. The first catalyst is, for example, Ru. The second reaction chamber 35 is a catalytic reactor and is filled with a second catalyst. The second catalyst is, for example, an oxidation catalyst CuO / CeO2 in which CuO nanoparticles are deposited on ceria (CeO2 beads). In the downstream of the second reaction chamber 35, the CO concentration of the residual hydrogen can be made 1 ppm or less. [Selected figure] Figure 2

Description

  The present invention relates to a hydrogen generator and a hydrogen filler.

  Conventionally, a temperature of 800 to 900 ° C. is required for steam reforming, and a temperature of 200 to 300 ° C. for CO conversion processes. Do.

The overall flow of methane reforming is roughly divided into four stages.
1) Desulfurization mechanism
2) Fuel reformer
3) CO metamorphic stage
4) CO remover

[Desulfurization mechanism Desulfurizer removes sulfur components because sulfur compounds that are mixed in with fuel degrade the performance of fuel reformer and fuel cell. A sulfur compound is reacted with hydrogen over a catalyst (Ni-Mo system, Co-Mo system) to convert it into hydrogen sulfide (250 ° C to 400 ° C). It can be expressed by the equation (1).

H ₃ C-S + CH ₃ + 2H ₂ → 2CH ₄ + H ₂ S (1)

[Fuel reformer]
In a steam reforming reaction (Methane Steam Reforming Reaction) using methane as a raw material, 1 mol of methane and 1 mol of steam are reacted to generate 1 mol of carbon monoxide and 3 mol of hydrogen. This steam reforming reaction is an endothermic reaction, and the heat of reaction corresponds to about 85% of the heat of combustion of hydrogen (57.792 kcal / mol).

_{CH 4 + H 2 O = CO} + 3H 2 + 49.271kcal / mol ··· (2)

  In the combination of these two reactions, hydrocarbons such as methane are reformed into hydrogen and carbon monoxide. Since the reaction is endothermic overall, the reaction can not be continued unless heat is externally applied.

[CO Transformer]
When the carbon monoxide (CO) is mixed, the battery performance is reduced, so the concentration of CO generated in the reforming section is reduced. At the same time, a conversion reaction of carbon monoxide proceeds, and 1 mol of carbon monoxide and 1 mol of steam react to generate 1 mol of carbon dioxide and 1 mol of hydrogen. This reaction is different from steam reforming reaction and is exothermic reaction by reacting carbon monoxide (CO) and steam (H ₂ O) on a catalyst (Cu-Zn, Fe-Cr, or Pt) Convert to (H ₂ ) and carbon dioxide (CO ₂ ).

_{CO + H 2 O = CO 2} + H 2 - 9.755kcal / mol ··· (3)

In general, the concentration of CO is lowered by dividing into two stages, a high temperature shift reactor and a low temperature shift reactor.
The first stage lowers the concentration of carbon monoxide (CO) by several tens of percent in high temperature zone (350 ~ 420 ° C) with high reaction rate, and the second stage lowers the reaction temperature to about 200 ° C and outlet CO Reduce the concentration to 0.5 to 1%.

[CO remover]
Air is added to the CO converter outlet gas, and carbon monoxide (CO) and oxygen (O2) are reacted on a noble metal catalyst such as Pt (platinum) or Ru (ruthenium) iron oxide (FeO) to produce carbon dioxide (CO 2) Convert to CO) and remove CO by oxidation.

  CO + O → CO 2 + Q (exothermic reaction) ... (4)

In the conventional catalyst, CO can not be removed to 10 ppm or less without increasing to [O ₂ ] / [CO] = 3. Therefore, in general, the CO selective oxidation removal device has two stages, and the first stage CO is roughly removed at about O ₂ ] / [CO] = 1, and CO is removed to 10 ppm or less at about [O ₂ ] / [CO] = 3 in the second stage.

  The conventional problem is that in the fuel reformer, if the city gas is a boiler, the fuel gas will generate CO 2 if methane gas is used as the combustion gas.

CH ₄ + O ₂ → CO ₂ + 2H ₂ O (5)

Since this is a city gas, it is not a bio-derived gas, so it will increase CO ₂ .
Also, even if bio-derived methane gas is used, two stages (steam reforming process (operating at 800 ° C to 900 ° C) and CO oxidation process (200 ° C to 300 ° C) and processes are required to remove CO, and the temperature is raised to high temperature Heat loss occurs by cooling to the low temperature part.

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a hydrogen generation apparatus and a hydrogen filling apparatus capable of generating hydrogen with a simple and small-scale configuration without requiring two-stage heat treatment as in the prior art. It is to do.

In order to solve the problems of the prior art mentioned above and to achieve the above-mentioned purpose, the hydrogen generator according to the present invention comprises heating means for mixing and heating CH ₄ and H ₂ O, and mixing by the heating means And reforming a first mixed fluid of heated CH ₄ and H ₂ O (steam) with a first catalyst to form a second mixed fluid of 3H ₂ and CO. A reaction chamber and CO of the second mixed fluid supplied from the first reaction chamber are reacted with a second catalyst to generate a third mixed fluid of CO ₂ and H ₂ . A reaction chamber and a hydrogen separation unit for removing CO ₂ from the second mixed fluid to obtain H ₂ , wherein the first catalyst is Ru, Ni / Al ₂ O ₃ , or Rh / Al. ₂ O _3, and the second catalyst is an oxidation catalyst CuO / C with a deposit of CuO nanoparticles on ceria (CeO ₂ beads) An O _2, wherein the oxidation catalyst CuO / CeO ₂ of the second catalyst, cracking by depositing Cu plasma without introducing oxygen into CeO ₂ on the beads, the water adsorbed on the vacuum chamber are used CuO obtained by oxidizing the Cu by using the ^{H +} and ^- in which the OH.

Preferably, the shape of CuO of the oxidation catalyst CuO / CeO ₂ of the _second catalyst is flat.

Preferably, the heating means is provided with a plurality of circumferential grooves on the side surfaces of the columns so as to surround the columns, and the circumferential grooves are connected to each other between the adjacent circumferential grooves which are side surfaces of the columns. A plurality of connecting grooves are provided, and each of the plurality of connecting grooves is arranged such that the position on the periphery of the peripheral groove does not overlap with another connecting groove adjacent to the peripheral groove. The fluid in which the CH ₄ and H ₂ O are mixed flows from the inlet to the outlet of the inner wall of the cylinder in which the column is closely attached and stored and the channel formed by the column flows, the connection The fluid is caused to collide with the inner wall of the circumferential groove from the groove so that the column and the fluid exchange heat.

Preferably, it further comprises an adiabatic catalytic reactor located downstream of the heating means and upstream of the hydrogen separation unit and housing the first reaction chamber and the second reaction chamber.

Hydrogen filling apparatus of the present invention includes a hydrogen generator according to any one described above and a hydrogen filling machine for filling with H ₂ generated in the Hydrogen generating apparatus to the hydrogen filled container.

  According to the present invention, it is possible to provide a hydrogen generation device and a hydrogen filling device capable of generating hydrogen with a simple and small-scale configuration without the need for a two-step heat treatment as in the prior art.

FIG. 1 is a view for explaining a hydrogen filling apparatus according to an embodiment of the present invention. FIG. 2 is an external view of the hydrogen generator shown in FIG. FIG. 3 is a functional block diagram of the hydrogen generator shown in FIGS. 1 and 2. FIG. 4 is an external view of a hydrogen filled container. FIG. 5 is a schematic cross-sectional view of a fluid heating device showing the entire case containing the heating unit of the hydrogen generation device shown in FIG. FIG. 6 is an external view of the heating unit. FIG. 7 is an external view of an arc plasma deposition source used to manufacture a second catalyst housed in a second reaction chamber. FIG. 8 is a diagram showing the measurement results of the amount of residual CO gas when using only the first catalyst in the first reaction chamber. FIG. 9 shows the measurement results of the amount of remaining CO gas in the case of a two-stage configuration using the second catalyst of the second reaction chamber 35 subsequent to the first catalyst of the first reaction chamber, as a result of measurement with a gas chromatometer. FIG.

  An embodiment of the present invention forms hydrogen monoxide into carbon monoxide by endothermic reaction using hydrogen gas and water for producing hydrogen. The carbon monoxide is oxidized to carbon dioxide, and the carbon dioxide is separated by hydrogen and carbon dioxide through a permeable membrane, and used for a polymer fuel cell, hydrogen power generation, and the like. In particular, even if carbon dioxide is generated by oxidizing carbon monoxide by using methane gas derived from bio-methane which is a weight loss methane gas, it becomes a carbon neutral hydrogen generator and hydrogen filling device as a total system.

  The hydrogen generation device and the hydrogen filling device according to the present embodiment are improved in operating efficiency by reducing heat loss and using bio-derived methane gas, and carbon neutral by using bio-derived methane gas, as compared to the prior art. An apparatus can be provided.

In the present embodiment, a heater (heating unit 31) is used at 800 to 900 ° C. to reform methane. This heater (also called a heat beam) can conduct heat to the gas with an efficiency approaching 100% of the power. In the case of constant operation at 800 to 900 ° C., it is possible to replace the heater with a burner to obtain almost the same efficiency as the boiler 80.
Since it can be maintained at 90% and the heat transfer efficiency is close to 100%, the energy efficiency during operation is also higher than that of a normal boiler.

As described above, conventionally, a two-stage system for removing CO (high temperature reforming: Ni / Al ₂ O ₃ and low temperature CO removing catalyst: Pt / Al ₂ O ₃ , Ru / Al ₂ O ₃ , FeO / Al ₂ O _{Although 3 is} adopted (CO remains at 0.2%), in this embodiment, CO remaining in steam reforming can be removed to 1 ppm or less in one stage by using a CuO / CeO ₂ catalyst .

This is usually the _{Pt / Al 2 O 3, Ru} / Al 2 O 3, FeO / Al 2 O 3 is a wet method (impregnation method, a coprecipitation method) are prepared by such, Al ₂ O ₃ on the carrier in Pt, Ru and FeO become spherical. On the other hand, the shape of CuO deposited by the arc plasma deposition source becomes flat on the CeO ₂ carrier as in the present embodiment, and the catalytic activity is high because the locality of the ball and pole portion is small. In addition, since being flat is buried in the CeO ₂ carrier by the anchor effect, aggregation due to heat or the like is hard to occur and it is hard to become large, so that the catalyst activity is maintained while being high.

[Configuration of hydrogen filling apparatus 1]
FIG. 1 is a view for explaining a hydrogen filling apparatus 1 according to an embodiment of the present invention.
As shown in FIG. 1, the hydrogen filling device 1 has, for example, a methane cylinder 3, a hydrogen generator 5 and a hydrogen filling machine 131.
As shown in FIG. 1, a tube of a methane gas pump 3 is connected to the methane inflow portion 21 of the hydrogen generator 5.
The hydrogen generator 5 is connected to the hydrogen filler 131 by a tube, and the hydrogen generated by the hydrogen generator 5 is supplied to the hydrogen filler 131.

[Hydrogen generator 5]
FIG. 2 is an external view of the hydrogen generator 5 shown in FIG.
FIG. 3 is a functional block diagram of the hydrogen generator 5 shown in FIGS. 1 and 2.
As shown in FIG. 3, the hydrogen generator 5 includes, for example, a methane inflow unit 21, a water tank 23, a water pump 25, a water supply pipe 27, an inlet 29, a heating unit 31, a first reaction chamber 33, a second The reaction chamber 35, the CO ₂ removal unit 41, the heat exchanger 45, and the hydrogen separation unit 47 are provided.

The methane inflow unit 21 supplies CH 4 gas from the methane cylinder 3 shown in FIG. 1 to the inlet 29. For example, bio-derived methane gas flows into the methane inflow portion 21.
The methane cylinder 3 contains CH 4 (methane) gas.
The hydrogen generator 5 uses the CH ₄ gas supplied from the methane cylinder 3 to generate H 2 (hydrogen).
The hydrogen generator 5 supplies the generated H 2 to the hydrogen filler 131.

The water tank 23 contains water for steam reforming.
The water pump 25 controls the supply of water from the water tank 23 toward the inlet 29 via the water supply pipe 27. The water supply pipe 27 is heated in part, and the flowing water is supplied to the inlet 29 as steam.
For example, at inlet 29, methane gas: 0.8 L / min. Is diluted with water at 20 ° C .: 10 mL / min., Ar: 4.3 L / min., And introduced into heating unit 31.

  The heat insulating material 28 is disposed around the pipe 28 a and has the function of reducing the heat radiation from the pipe.

The inflow port 29 mixes the CH 4 from the methane inflow section 21 and the water vapor from the water supply pipe 27 and supplies the mixture into the heating section 31.
The heating unit 31 is, for example, a heat beam that mixes and heats the CH 4 flowing from the inlet 29 and the water vapor.

The first reaction chamber 33 is a catalytic reactor and is filled with a first catalyst.
The first catalyst is, for example, Ru. The first catalyst is, for example, a 4 mm diameter alumina coated with Ru by a wet method. As the first catalyst, Ni / Al ₂ O ₃ or Rh / Al ₂ O ₃ may be used in addition to Ru.

The first reaction chamber 33 reacts and reforms the heated first mixed fluid from the heating unit 31 with the first catalyst to generate a second mixed fluid of 3H ₂ and CO.

The second reaction chamber 35 is a catalytic reactor and is filled with a second catalyst.
The second catalyst is, for example, an oxidation catalyst CuO / CeO ₂ in which CuO nanoparticles are deposited on ceria (CeO ₂ beads).

The second reaction chamber 35 reacts CO of the second mixed fluid from the first reaction chamber 33 with the second catalyst to generate a third mixed fluid of CO ₂ and H ₂ .

The second catalyst oxidation catalyst CuO / CeO ₂ stores CeO ₂ bee in a container under vacuum, plasmatizes copper (Cu) with an arc plasma deposition source from the top, and moves the storage vessel up and down onto the CeO ₂ bee It is a catalyst obtained by vapor deposition while shaking and stirring.
Oxidation catalyst CuO / CeO ₂ of the second catalyst, by depositing a copper (Cu) plasma without introducing oxygen into CeO ₂ on the beads, the water adsorbed on the vacuum chamber was cracked OH ^- and It oxidizes Cu using H ⁺ to obtain CuO.

The shape of CuO of the oxidation catalyst CuO / CeO ₂ of the _second catalyst is not spherical but flat.
In addition to CuO / CeO ₂ , for example, FeO / Al ₂ O ₃ may be used as the second catalyst.

The CO ₂ removing unit 41 is, for example, a molecular sieve (synthetic zeolite), and absorbs CO ₂ .

  The heat exchanger 95 cools the third mixed fluid from the second reaction chamber 35 and supplies it to the hydrogen separation unit 47.

  The hydrogen separation unit 47 is a hydrogen selective permeation membrane that selectively permeates the hydrogen of the mixed fluid from the heat exchanger 45, and accommodates water in the water tank 49.

The hydrogen separated by the hydrogen separation unit 47 is supplied to the hydrogen filling machine 131 shown in FIG.
A hydrogen filling container 161 shown in FIG. 4 is attached to the caster of the hydrogen filling machine 131, and the hydrogen filling container 161 is filled with hydrogen. The hydrogen filling container 161 is filled with a hydrogen storage alloy.

  FIG. 5 is a schematic cross-sectional view of a fluid heating device showing the entire case containing the heating unit 31 of the hydrogen generator 5 shown in FIG. FIG. 6 is an external view of the heating unit 31.

  The heating unit 31 is obtained by putting the fluid heating mechanism unit 400 in a heat insulating case. The fluid heating mechanism 400 is thermally insulated by a thermal insulator case 502 containing a thermal insulator 501.

  There is a stainless steel outer case 503 outside the heat insulating case 502, and its end is connected to the flange 504.

  The cylindrical part is heated by the heater 403 fed from the heater feeder 402. The temperature of the cylindrical part is measured by a thermocouple not shown, and the power is controlled to be maintained at that temperature. This temperature was taken to 500 ° C. to produce heated nitrogen at 500 ° C. The heater 403 is 3 kW.

The first mixed fluid is supplied from the gas introduction pipe 505 in communication with the inlet 29 at 100 SLM. The first mixed fluid flows via the circumferential groove 506 and the connection groove not visible in this figure, and is instantaneously heated in the fluid heating mechanism 400. Nitrogen heated to 500 ° C. exits from the gas outlet pipe 507 communicating with the first reaction chamber 33.
A gas pipe is wound around the heater 403. The surrounding area is covered with insulation. Water and methane gas are allowed to flow into the inflow port 29, and steam and methane gas (heated first mixed fluid) become about 800 to 900 ° C. at the outlet of the heating unit 31, and Ru is coated on alumina beads. Steam reforming of methane is performed on the first catalyst in the reaction chamber 33.

The heating unit 31 has a plurality of circumferential grooves on the side surfaces of the column so as to surround the column. Further, a plurality of connection grooves for connecting the circumferential grooves are provided in each of the side surfaces of the column and between the adjacent circumferential grooves.
Each of the plurality of connection grooves is disposed such that the position on the circumference of the upper circumferential groove does not overlap with the other connection grooves adjacent to each other across the circumferential groove.
A first mixed fluid flows from the inner wall of the cylinder in which the column is in close contact and stored to the inlet to the outlet of the flow channel formed by the column, and the first mixed fluid flows from the connection groove to the inner wall of the circumferential groove. The mixed fluid collides, and the column and the first mixed fluid exchange heat.

[Second catalyst]
The second catalyst contained in the second reaction chamber 35 is manufactured as follows.
FIG. 7 is an external view of an arc plasma deposition source 601 (hereinafter referred to as an APD deposition source) used for producing the second catalyst housed in the second reaction chamber 35.
As shown in FIG. 7, copper (Cu) plasma is deposited on ceria beads 605 of about Φ 4 mm. In FIG. 7, when ceria beads (about 30 pieces) of φ4 mm (about 30) are irradiated with 1 wt% copper plasma in a stirring vessel 603, several nm of CuO nanoparticles are formed on the ceria beads 605. Water is adsorbed on the inner wall of the chamber under vacuum (× 10 ^-3 Pa or less), and when the plasma is irradiated, water adhering to the wall surface in the chamber is cracked and O (oxygen) is present, Cu Oxidizes in a vacuum.

  The second catalyst can be disposed downstream of the first catalyst to reduce the concentration to below the detection limit (1 ppm) of gas chromatography CO by oxidizing CO.

[methane gas]
For example, methane gas derived from bio (for example, sewerage) is used as the methane gas flowing from the methane inflow portion 21.
For example, sewage sludge generated in the process of sewage treatment is reduced stepwise by treatment such as concentration, digestion, dehydration and the like and finally incinerated.
The sludge concentrated by the concentrator is accumulated in the digestion tank and stirred at about 36 ° C. for about 30 days in the digestion tank. In the digestion tank, the action of anaerobic microorganisms is used to decompose the organic matter in the sludge without feeding air. This action is called digestion, and the decomposed organic matter generates digestive gas and water.

  Because sewage sludge contains a large amount of water, the water is first removed using a concentrator. Next, digestion treatment is carried out to reduce organic matter and stabilize properties. About 60% of the digestion gas is methane and about 35% carbon dioxide, which contains harmful hydrogen sulfide as an impurity component. Therefore, hydrogen sulfide is adsorbed to the absorbing liquid and removed using a desulfurizer containing the absorbing liquid. Furthermore, since the siloxane is contained, the activated carbon removes the siloxane to increase the purity of the methane gas.

The removal of siloxane mentioned above uses the adsorption agent for siloxane gas removal comprised with activated carbon fiber, for example. The activated carbon fiber has, for example, a BET specific surface area of 1,000 to 3,000 m 2 / g, and an integrated pore volume of pores having a radius of 0.2 to 1.8 nm according to the MP method of 0.4 to 2 cm 3 / g have. The average fiber diameter of the activated carbon fiber is preferably 1 to 50 μm.
In addition, the activated carbon fiber has pores with a pore radius of 0.3 to 0.6 nm by MP method, and the total volume of the pores is 0.2 to 1.8 nm of pore radius by MP method 10 to 80% by volume with respect to the integrated pore volume of the pores of

FIG. 8 is a view showing the measurement result of the amount of residual CO gas in the case of using only the first catalyst of the first reaction chamber 33 by the gas chromatometer.
FIG. 9 shows the measurement results of the amount of residual CO gas in the case of a two-stage configuration using the second catalyst of the second reaction chamber 35 following the first catalyst of the first reaction chamber 33 as the measurement result of FIG. FIG.

As shown in FIG. 8, when only the first catalyst in the first reaction chamber 33 was used, 0.2% CO remained after passing through the first catalyst at 300 ° C.
On the other hand, as shown in FIG. 9, in the case of the two-stage configuration using the second catalyst of the second reaction chamber 35 following the first catalyst of the first reaction chamber 33, the CO after passing The residual content of H.sub.2 was reduced below the detection limit (1 ppm) of the gas chromatometer.

In the present embodiment, hydrogen, water and CO ₂ of 1 ppm or less are separated into water and hydrogen · CO ₂ by a heat exchanger 45 shown in FIG.
Then, although not shown, hydrogen and CO ₂ is separated into hydrogen and CO ₂ separation permeable membrane, and supplying only the hydrogen charging device 131 shown in FIG. 1 hydrogen, where 0.99 MPa (high pressure gas method: The pressure is increased by a compressor at a pressure of less than 1 MPa, and hydrogen is filled in a hydrogen-filled container 161 shown in FIG.
In addition, in the fuel cell, platinum can not be poisoned unless the residual CO is reduced to 10 ppm or less.

  As described above, according to the hydrogen generation device 5 and the hydrogen filling device 6, the heat treatment is only the first catalyst in the first reaction chamber 33, and is not necessary for the second catalyst in the second reaction chamber 35. Therefore, hydrogen can be generated with a simple and small scale configuration.

That is, this bio-derived methane gas (impurity such as water, sulfur CO ₂ , siloxane and the like has already been removed) is filled in the methane cylinder 3 and hydrogen is produced from the methane gas and water in the hydrogen generator 5 by steam reforming. Then, the CO concentration of the residual hydrogen is reduced to 1 ppm or less, hydrogen is supplied to the fuel cell stack to generate electricity.

This hydrogen can be pressurized to less than 1 MPa with a hydrogen filling machine and filled into the hydrogen filling container 161 and stored in a fuel cell bike, a fuel cell forklift, or a fuel cell emergency power supply. By sharing the hydrogen filling machine 131 in this way, it is possible to commonly fill hydrogen in various fuel cell devices, and since the filling pressure is less than 1 MP, there is no conflict with the high pressure gas method, A hydrogen stand can be made at a low price because there is no need for excessive infrastructure such as explosion proof, and because it uses bio-derived methane gas, it is a carbon neutral hydrogen stand even if it oxidizes CO and emits CO ₂ Play an effective role in

The present invention is not limited to the embodiments described above.
That is, those skilled in the art may make various modifications, combinations, subcombinations, and substitutions within the technical scope of the present invention or equivalent components thereof regarding the components of the embodiments described above.

In the embodiment described above, an electric heater is used to heat a pipe (heat beam) through which a mixed fluid of CH ₄ and H ₂ O flows, but this is replaced with a burner to burn bio-derived methane gas in the burner The heating beam may be heated.
In addition, the heating means of the present invention may use a heating means having a configuration different from that of the heating unit 31 described above.

  The present invention is applicable to a hydrogen generator and a hydrogen filling device.

DESCRIPTION OF SYMBOLS 1 ... hydrogen filling apparatus 3 ... methane cylinder 5 ... hydrogen generation apparatus 21 ... methane inflow part 23 ... water tank 25 ... water pump 28 ... heat insulation plate 29 ... inflow port 31 ... heating part 33 ... first reaction chamber 35 ... second Reaction chamber 37 ... Heat insulation catalyst reactor 41 ... CO2 removal unit 45 ... Heat exchanger 47 ... Hydrogen separation unit 49 ... Water tank 131 ... Hydrogen filling machine 161 ... Hydrogen filling vessel

Claims (5)

Heating means for mixing and heating CH ₄ and H ₂ O;
The first mixed fluid of CH ₄ and H ₂ O (steam) mixed and heated by the heating means is promoted by the first catalyst to be reformed and reformed into a second mixed fluid of 3H ₂ and CO A first reaction chamber to be generated,
A second reaction chamber for promoting CO of the second mixed fluid supplied from the first reaction chamber with a second catalyst to generate a third mixed fluid of CO ₂ and H ₂ ;
A hydrogen separation unit that removes CO ₂ from the second mixed fluid to obtain H ₂ ;
Have
The first catalyst is Ru, Ni / Al ₂ O ₃ , or Rh / Al ₂ O ₃ .
The second catalyst is an oxidation catalyst CuO / CeO ₂ in which CuO nanoparticles are deposited on ceria (CeO ₂ beads),
The oxidation catalyst CuO / CeO ₂ of the _second catalyst is OH ^- and H which cracked water adsorbed in a vacuum chamber by depositing Cu plasma on CeO ₂ beads without introducing oxygen. A hydrogen generator that uses CuO obtained by oxidizing Cu using ⁺ . The hydrogen generator according to claim 1, wherein a shape of CuO of the oxidation catalyst CuO / CeO ₂ of the _second catalyst is flat. The heating means is
A plurality of circumferential grooves are provided on the side of the column so as to surround the column,
A plurality of connection grooves for connecting the circumferential grooves are provided in each of the side surfaces of the pillars and between the circumferential grooves adjacent to each other,
Each of the plurality of connection grooves is disposed so that the position on the circumference of the circumferential groove does not overlap with another connection groove adjacent to the circumferential groove.
A fluid in which the CH ₄ and H ₂ O are mixed flows from the inlet to the outlet of the inner wall of the cylinder in which the column is in close contact and stored and the channel formed by the column flows from the connection groove The hydrogen generator according to claim 1 or 2, wherein the fluid collides with the inner wall of the circumferential groove to exchange heat between the column and the fluid. The heat insulation catalytic reaction furnace which is located in the latter part of the above-mentioned heating means, and is located before the above-mentioned hydrogen separation part, and accommodates the above-mentioned 1st reaction room and the 2nd reaction room. Hydrogen generator as described. The hydrogen generator according to any one of claims 1 to 4,
A hydrogen filling machine for filling the hydrogen-filled container with H ₂ generated by the hydrogen generation apparatus.