JP7369053B2 - Hydrogen production method and hydrogen production device - Google Patents

Description

The present invention relates to a hydrogen production method and a hydrogen production apparatus.

As a technique for gasifying biomass raw materials, a technique using a three-column fluidized bed is conventionally known.

For example, the technology described in Patent Document 1 involves partial combustion by circulating a heat medium and calcium oxide (CaO), which functions as a CO ₂ absorbing material, through a pyrolysis tower and a reforming tower where an endothermic reaction occurs. This is a fluidized gasifier that is thermally independent without the need for

The fluidized gasifier includes a combustion tower, a reforming tower, and a pyrolysis tower. Calcium oxide moves through the fluidized gasifier in the following order: a combustion tower, then a reforming tower, and finally a pyrolysis tower. Calcium oxide in the pyrolysis tower is sent to the combustion tower again and is repeatedly circulated in the fluidized gasifier.

In order for the pyrolysis tower and the reforming tower to maintain a balance at the desired temperature, the heat balance of "reaction heat amount (absorption amount) = supply heat amount (CaO sensible heat)" is required in each of the pyrolysis tower and reforming tower. needs to hold true.

In the prior art, in order to establish the above-mentioned heat balance, it was necessary to lower the temperature of the pyrolysis tower by intralayer heat exchange, water spraying, or the like.

Japanese Patent Application Publication No. 2014-240472

However, the above-mentioned conventional techniques have a problem in that the energy (latent heat of vaporization) removed in the pyrolysis tower cannot be effectively used in the process.

One aspect of the present invention aims to realize a hydrogen production method and a hydrogen production apparatus that do not require heat removal in a pyrolysis tower and can effectively utilize energy within the process.

The present inventors supplied a part of the calcium oxide used in the modification process to the raw material to be thermally decomposed in the pyrolysis process, and also supplied a part of the calcium oxide used in the modification process. The present invention was completed based on the idea that if the thermal decomposition products burned in the combustion process were also supplied, the heat balance of "reaction heat amount (absorbed heat amount) = supplied heat amount (sensible heat of CaO)" could be established. I let it happen.

A hydrogen production method according to one aspect of the present invention is a hydrogen production method for producing hydrogen from phosphorus-containing biomass, in which a raw material containing the phosphorus-containing biomass is pyrolyzed in the presence of steam or superheated steam to generate heat. a pyrolysis step for obtaining a decomposition product and a combustible gas; a combustion step for obtaining a combustion product by burning the pyrolysis product; and a pyrolysis step for obtaining a combustion product from the flammable gas by steam reforming using calcium oxide a reforming step for producing a fuel gas with a higher hydrogen concentration than the hydrogen gas, and supplying a part of the calcium oxide used in the reforming step to the raw material to be thermally decomposed in the thermal decomposition step. and a calcium oxide supplying step of supplying a part of the calcium oxide used in the reforming step to the pyrolysis product to be burned in the combustion step.

A hydrogen production device according to one aspect of the present invention is a hydrogen production device that produces hydrogen from phosphorus-containing biomass, and the hydrogen production device pyrolyzes a raw material containing the phosphorus-containing biomass in the presence of steam or superheated steam to generate heat. a pyrolysis device for obtaining a decomposition product and a combustible gas; a combustion device for combusting the pyrolysis product to obtain a combustion product; a reforming device that produces a fuel gas with a higher hydrogen concentration than that of the hydrogen gas, and supplying a portion of the calcium oxide used in the reforming device to the raw material to be thermally decomposed in the thermal decomposition device. and a supply path for supplying a part of the calcium oxide used in the reformer to the pyrolysis product to be burned in the combustion device. , is equipped with.

According to one aspect of the present invention, it is not necessary to remove heat in a pyrolysis apparatus, and energy can be effectively used in the process.

For example, according to one aspect of the present invention, the amount of fuel required to operate the combustion device can be reduced by sending heat that was removed in the pyrolysis device in the prior art to the combustion device.

For example, according to one aspect of the invention, the amount of hydrogen produced can be increased.

1 is a diagram schematically showing the configuration of a hydrogen production apparatus according to an embodiment of the present invention. 1 is a diagram schematically showing the configuration of a hydrogen production apparatus according to an embodiment of the present invention. FIG. 2 is a diagram showing a process flow of a hydrogen production method according to an embodiment of the present invention. 1 is a diagram schematically showing the configuration of a cooling system provided in a conventional hydrogen production device.

Hereinafter, an example of an embodiment of the present invention will be described in detail, but the present invention is not limited thereto. The contents described in each item below can be used in other items as appropriate. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the claims. Therefore, embodiments obtained by appropriately combining technical means disclosed in different embodiments are also included in the technical scope of the present invention.

Unless otherwise specified herein, the numerical range "A to B" means "A or more and B or less". All academic and patent documents mentioned herein are incorporated herein by reference.

[Hydrogen production equipment]
A hydrogen production device according to an embodiment of the present invention is a hydrogen production device that produces hydrogen from phosphorus-containing biomass, and includes thermally decomposing a raw material containing the phosphorus-containing biomass in the presence of steam or superheated steam. a pyrolysis device for obtaining a pyrolysis product and a combustible gas; a combustion device for combusting the pyrolysis product to obtain a combustion product; A reformer that produces a fuel gas with a higher hydrogen concentration than the combustible gas, and a part of the calcium oxide used in the reformer is supplied to the raw material to be thermally decomposed in the thermal cracker. a supply path for supplying a portion of the calcium oxide used in the reformer to the pyrolysis product to be burned in the combustion device; It is equipped with.

Examples of the phosphorus-containing biomass include phosphorus-containing biomass such as sewage sludge generated in sewage treatment plants, human waste sludge generated in human waste treatment plants, meat and bone meal, and livestock manure. Examples of the form of phosphorus contained in the phosphorus-containing biomass include organic phosphorus derived from living organisms, phosphate phosphorus, and the like. However, the phosphorus-containing biomass is not limited to the above-mentioned phosphorus-containing biomass. In the following description, sludge slurry such as sewage sludge or human waste sludge will be used as an example of the phosphorus-containing biomass.

As shown in FIG. 1, a hydrogen production device in an embodiment of the present invention includes a dehydration device 1, a drying device 2, a pyrolysis device 3, a reforming device 4, a combustion device 5, and an ash separation device 6. . Note that the dehydration device 1, the drying device 2, and the ash separation device 6 are arbitrary structures for the hydrogen production device of the present invention. Each device is connected to each other by a device (not shown) having a conveying function so that phosphorus can be recovered continuously. That is, the hydrogen production apparatus is comprised of a plurality of fluidized bed apparatuses so that phosphorus can be recovered continuously. However, the hydrogen production apparatus of the present invention is not limited to a fluidized bed type recovery apparatus.

Hereinafter, each device constituting a hydrogen production device in an embodiment of the present invention will be described with reference to FIGS. 1 and 2.

<Dehydration device 1>
The dewatering device 1 removes a water-containing separated liquid from the sludge slurry (phosphorus-containing biomass) supplied through the sludge slurry supply path 21 to obtain dehydrated sludge, and then converts at least a portion of the obtained dehydrated sludge into dehydrated sludge. It is supplied to the drying device 2 through the supply path 22. The dewatering device 1 can also supply a portion of the dewatered sludge to the pyrolysis device 3 through a dryer bypass (not shown). Further, the dehydrator 1 can also discharge the separated liquid containing water to the outside through a separated liquid discharge path (not shown).

The dewatering device 1 may be any device that can remove a separated liquid containing water from the sludge slurry, and examples thereof include a pressure type dehydrator such as a belt press, or a mechanical dehydrator such as a centrifugal dehydrator. .

The dewatering device 1 preferably has the function of a mixing device that mixes the sludge slurry with an inorganic calcium compound supplied from an inorganic calcium compound supply path (not shown). Therefore, the dewatered sludge supplied to the drying device 2 may be a mixture of dewatered sludge and an inorganic calcium compound.

The inorganic calcium compound may be mixed into the sludge slurry before the separated liquid is removed from the sludge slurry, or during the removal of the separated liquid from the sludge slurry, or after the separated liquid is removed from the sludge slurry. It may be later, or a plurality of these periods may be combined. However, as shown below, since the inorganic calcium compound acts as a dehydration aid, it is more preferable to mix the inorganic calcium compound into the sludge slurry before removing the separated liquid.

(Inorganic calcium compound)
The inorganic calcium compound serves as a calcium source for tricalcium phosphate "Ca ₃ (PO ₄ ) ₂ " and also acts as a dewatering aid to promote dewatering of the sludge slurry. Therefore, by adding an inorganic calcium compound to the sludge slurry, the dewatering performance can be improved more than in a normal dewatering method.

The inorganic calcium compound is at least one selected from the group consisting of calcium carbonate "CaCO ₃ ", slaked lime "Ca(OH) ₂ ", quicklime "CaO", and dolomite "Ca.Mg(CO ₃ ) ₂ ". It is preferable. The particle size of the inorganic calcium compound is preferably 200 μm to 500 μm.

In addition to acting as a dehydration aid, inorganic calcium compounds play multiple roles such as a fluidizing medium, a carbon dioxide absorption medium, a heat source for the gasification process (sensible heat medium and carbon dioxide absorption reaction heat), and a phosphorus melting inhibitor. . Furthermore, inorganic calcium compounds also have the secondary function of contributing to the production of highly concentrated hydrogen.

The entire amount of the inorganic calcium compound supplied to the hydrogen production device may be supplied to the dehydration device 1, and a portion of the inorganic calcium compound may be supplied to any of the pyrolysis device 3, the reformer 4, and the combustion device 5, as described later. may be supplied.

The amount W (mol/kg-dry weight (DS)) of the inorganic calcium compound to be added to the sludge slurry is stoichiometrically as shown in the following formula (1). That is, the addition amount W may be at least the amount that allows the phosphorus and sulfur content in the sludge slurry to be recovered as tricalcium phosphate "Ca ₃ (PO ₄ ) ₂ " and gypsum "CaSO ₄ ".

W (mol/kg-DS) ≧ (3/2) x P (mol/kg-DS) + S (mol/kg-DS)...(1)
Therefore, the amount of the inorganic calcium compound added to the sludge slurry is not particularly limited as long as it satisfies formula (1). Specifically, 0.06 kg to 0.8 kg, more preferably 0.1 kg to 0.5 kg of the inorganic calcium compound may be mixed per 1 kg of dry weight of the sludge slurry (phosphorus-containing biomass). In particular, by mixing an excessive amount of an inorganic calcium compound with the sludge slurry, it is possible to more effectively prevent the melting of phosphorus compounds from adhering to the incinerator and the resulting clogging of the incinerator.

<Drying device 2>
The drying device 2 heats the dehydrated sludge supplied from the dehydrating device 1 to evaporate water to obtain dried sludge. The drying device 2 can supply the evaporated water as dry steam to the heat exchanger 10 through the steam supply path 23. In the heat exchanger 10, the temperature of the dry steam is adjusted to a desired temperature, and superheated steam is generated. Note that the specific temperature of the superheated steam is 150°C to 300°C.

A part of the superheated steam generated in the heat exchanger 10 can be supplied to the pyrolysis device 3 via the superheated steam supply path 24 and the superheated steam supply path 25. Further, a part of the superheated steam generated in the heat exchanger 10 can be supplied to the drying device 2 via the superheated steam supply path 24 and the superheated steam supply path 26. Thereby, heat can be used effectively. Note that at least one selected from the group consisting of the superheated steam supply path 24, the superheated steam supply path 25, and the superheated steam supply path 26 may be provided with the steam circulation fan 7. A steam circulation fan 7 allows superheated steam to be supplied to the intended arrangement.

A part of the superheated steam generated in the heat exchanger 10 can be supplied to the condenser 8 via the superheated steam supply path 27. The superheated steam supplied to the condenser 8 is cooled and condensed by the condenser 8, and can be discharged as removed water through the removed water discharge path 28.

The drying device 2 supplies the dried sludge from which water has been removed to the pyrolysis device 3 through the dried sludge supply path 29. Further, the drying device 2 supplies a part of the dried sludge to the combustion device 5 through the heat source dry sludge supply path 30 as necessary. The dried sludge supplied to the combustion device 5 can be burned as a heat source.

The drying device 2 may be any device that can dry dried sludge, and its method is not particularly limited. Note that FIG. 1 exemplifies a configuration that employs a direct heating type dryer in which dry steam is recycled as superheated steam by a heat exchanger 10. However, the hydrogen production device in one embodiment of the present invention is not limited to this configuration, and is a steam indirect heating type drying device that discharges dry steam outside the system and uses the steam as a heat medium in circulation as the drying device 2. It is also possible to use a machine.

<Pyrolysis device 3>
The pyrolysis device 3 heats the dried sludge supplied from the drying device 2 at 400° C. to 900° C., more preferably 600° C. to 800° C., more preferably about 700° C. in the presence of steam or superheated steam. , 0.1 hour to 2 hours, more preferably 0.5 hour to 1 hour, to thermally decompose. The pyrolysis results in pyrolysis products and combustible gases. In addition, when the heating temperature in the pyrolysis device 3 exceeds 750 ° C., as the pyrolysis temperature increases, the absorption reaction of carbon dioxide by calcium oxide tends to become difficult to occur, and the hydrogen concentration of the combustible gas decreases. Show trends. Therefore, from the viewpoint of increasing the concentration of hydrogen contained in the combustible gas, the thermal decomposition temperature in the thermal decomposition device 3 is preferably the above-mentioned temperature.

The pyrolysis device 3 supplies pyrolysis solid products among the pyrolysis products obtained by pyrolysis to the combustion device 5 through a pyrolysis solid product supply path 31 . On the other hand, the pyrolysis device 3 supplies combustible gas, which is a pyrolysis gas, to the reformer 4 through the combustible gas supply path 32 out of the pyrolysis products obtained by pyrolysis. In addition, calcium oxide "CaO" is supplied (circulated) from the reformer 4 to the pyrolysis device 3 through the supply path 33, and a portion of a new inorganic calcium compound is also supplied as necessary. . Details of the circulation of calcium oxide through the supply path 33 will be described later.

The thermal decomposition device 3 may be any device that can thermally decompose dried sludge, and its configuration is not particularly limited.

In the thermal decomposition device 3, thermal decomposition is performed by the following reaction, and flammable gas is generated. That is, the dried sludge is thermally decomposed in the presence of water vapor or superheated steam by the reaction shown in the following formula (2), and converted into pyrolysis gas and pyrolysis solid products. Thermal decomposition gases include hydrogen " _H2 ", carbon monoxide "CO", carbon dioxide " _CO2 ", hydrogen sulfide " _H2S " and ammonia " _NH3 ", as well as methane " _CH4 ", and hydrocarbons. The main component is a hydrocarbon gas "C _m H _n " containing gas and tar components. Pyrolysis solid products include charcoal and ash.

Dry sludge (C, H, O, N, S) + H ₂ O → Pyrolysis gas (H ₂ , CO, CO ₂ , C _m H _n , H ₂ S, NH ₃ ) + C (charcoal) + ash... (2)
Here, ash is a compound containing P, Si, Al, Fe, Mg, Ca, Na, K, etc.

Further, a part of the charcoal reacts with water vapor or superheated steam and is converted into carbon dioxide and hydrogen as shown in the following formula (3).

C (charcoal) + 2H ₂ O → CO ₂ + 2H ₂ ... (3)
Further, carbon monoxide contained in the pyrolysis gas reacts with water vapor or superheated steam and is converted to carbon dioxide as shown in the following formula (4).

CO + H ₂ O → CO ₂ + H ₂ …(4)
Most of the hydrogen sulfide contained in the pyrolysis gas reacts with inorganic calcium compounds in the dried sludge and calcium oxide mainly generated by heating, and becomes calcium sulfide, as shown in formula (5) below, and is fixed. be converted into In this way, most of the hydrogen sulfide contained in the pyrolysis gas becomes calcium sulfide and is fixed, resulting in an increase in the hydrogen concentration in the pyrolysis gas.

CaO + H ₂ S → CaS + H ₂ O…(5)
Then, the carbon dioxide generated by the reactions shown in formulas (2) to (4) above reacts with calcium oxide to become calcium carbonate "CaCO ₃ " and is fixed as shown in formula (6) below. Because only carbon dioxide is absorbed by calcium oxide and extracted from the pyrolysis gas by the reaction shown in equation (6), a rightward equilibrium shift occurs in the reactions shown in equations (2) to (4), resulting in a high A flammable gas containing a concentration of hydrogen is produced.

CaO + _CO2 → _CaCO3 ...(6)
On the other hand, phosphorus contained in the ash of the pyrolysis solid product reacts with an inorganic calcium compound in the pyrolysis device 3 to become tricalcium phosphate "Ca ₃ (PO ₄ ) ₂ ". In this embodiment, the amount of inorganic calcium compound added to the sludge slurry is extremely large, and more calcium is present in the pyrolysis device 3 (reaction field). Therefore, phosphorus can be converted to tricalcium phosphate, a high-melting phosphorus compound with a melting point of 1390°C.

Therefore, by thermal decomposition in the thermal decomposition device 3, solid components including tricalcium phosphate, calcium sulfide, charcoal, calcium carbonate, unreacted inorganic calcium compounds, and ash are decomposed from the dry sludge. A solid product is obtained.

Since the tricalcium phosphate is a main component of phosphate rock resources, it can be reused as an ore resource. Further, since the melting point of tricalcium phosphate is as high as 1390° C., it is possible to prevent the phosphorus compound from melting and adhering to the incinerator in the thermal decomposition device 3 and the combustion device 5, and thereby preventing the incinerator from clogging. Therefore, it becomes possible to operate the hydrogen production device more stably and continuously.

<Reformer 4>
The reformer 4 transforms the combustible gas supplied from the pyrolysis device 3 into a second combustible gas with a higher hydrogen concentration than the combustible gas by performing steam reforming using calcium oxide. The second combustible gas is discharged through the combustible gas discharge passage 35. The discharged second combustible gas is cooled by the heat exchanger 9 and recovered as a gas containing high concentration hydrogen. The heat recovered by the heat exchanger 9 can be supplied to the combustion device 5 via the combustion air supply path 39. Thereby, heat can be used effectively.

The reformer 4 heats the combustible gas supplied from the pyrolysis device 3 at a temperature of 800°C to 1100°C, more preferably 850°C to 1000°C, and even more preferably 950°C, for 0.5 seconds to 1000°C. Steam reforming is performed by retaining for 3.0 seconds, more preferably 1.0 seconds to 2.5 seconds.

In addition, calcium oxide "CaO" is supplied (circulated) from the ash separator 6 to the reformer 4 through the circulating calcium oxide supply path 37, and a new inorganic calcium compound is supplied as needed. . Furthermore, the reformer 4 supplies (circulates) calcium oxide to the pyrolysis device 3 through the supply path 33, and also supplies (circulates) calcium oxide to the combustion device 5, which will be described later, through the bypass supply path 34. Details of the circulation of calcium oxide through the supply path 33 and the bypass supply path 34 will be described later.

The reformer 4 may be any device capable of steam reforming the combustible gas, and its configuration is not particularly limited.

In the reformer 4, steam reforming of the combustible gas is performed by the following reaction, and highly concentrated hydrogen is produced. That is, the combustible gas includes hydrogen and carbon monoxide, as well as methane "CH ₄ ", a hydrocarbon gas "C _m H _n " containing a hydrocarbon gas, and a tar component. The hydrocarbon gas contained in the combustible gas is reformed into hydrogen and carbon dioxide by steam reforming using calcium oxide as a catalyst, as shown in the above equation (4) and the following equation (7).

C _m H _n + H ₂ O → H ₂ + CO ₂ …(7)
The generated carbon dioxide is absorbed by calcium oxide, as shown in the above formula (6). As a result, a second combustible gas in which the concentration of hydrogen is further increased, that is, a gas containing a high concentration of hydrogen, is obtained from the combustible gas. The second combustible gas is composed of highly concentrated hydrogen, CO ₂ , and C _m H _n remaining unreacted in the above formula (7). A part of the second combustible gas may be used as a combustion gas as it is, or CO ₂ and C _m H _n after only high concentration hydrogen is separated using a gas separation device such as PSA. An off-gas containing as a main component may be used as the combustion gas. Thereby, the amount of combustion gas supplied from the outside can be reduced.

<Combustion device 5>
The combustion device 5 burns the pyrolysis solid product (pyrolysis product) supplied from the pyrolysis device 3 . The combustion device 5 supplies combustion solid products among the combustion products obtained by combustion to the ash separator 6 through the combustion solid product supply path 38 . Heated air or oxygen-containing gas is supplied to the combustion device 5 from a combustion air supply path 39 via a heat exchanger 9 . The combustion gas serving as a heat source may be supplied from the outside through the combustion gas supply path 36, or a portion of the second combustible gas or the off-gas may be supplied. Moreover, a new inorganic calcium compound can be supplied to the combustion device 5 as necessary.

The combustion device 5 heats the pyrolyzed solid product supplied from the pyrolysis device 3 at 850° C. to 1200° C., more preferably 900° C. to 1150° C., and still more preferably about 1100° C. for 0.1 hour. Burning is achieved by residence for ˜2.0 hours, more preferably 0.5 hours to 1.0 hours.

Furthermore, dry sludge can be supplied to the combustion device 5 from the drying device 2 through the dry sludge supply path 30 for heat source, if necessary. The dried sludge can be combusted as a heat source when it is difficult to combust the pyrolysis solid products using only the amount of heat generated by combustion of the combustion gas in the combustion device 5. By burning the dried sludge, the amount of combustion gas supplied from the outside can be reduced, so the amount of energy used can be reduced.

The combustion device 5 may be any device that can combust the pyrolysis solid product, and its configuration is not particularly limited.

In the combustion device 5, combustion solid products and combustion gas are produced by the following reaction. That is, as shown in equation (8) below, charcoal contained in the pyrolysis solid product is combusted into carbon dioxide by air or oxygen-containing gas. Moreover, as shown in the following formula (9), calcium carbonate contained in the thermal decomposition solid product is regenerated by becoming calcium oxide. Moreover, as shown in the following formula (10), calcium sulfide contained in the pyrolysis solid product is converted to gypsum (calcium sulfate) "CaSO ₄ " by air or oxygen-containing gas.

C (charcoal) + _O2 → _CO2 ...(8)
_CaCO3 → CaO + _CO2 ...(9)
CaS + 2O ₂ → CaSO ₄ ... (10)
The reactions shown in formulas (8) and (10) above are exothermic reactions, and the reaction heat generated in the reactions becomes sensible heat of the circulating calcium oxide, and is transferred to the thermal decomposition device 3, reformer 4, and It can be used as a heat source for the combustion device 5.

In the combustion device 5, calcium oxide, tricalcium phosphate, gypsum, ash, etc. are produced by the reactions shown in equations (8) to (10) and, if necessary, by combustion of the dried sludge supplied from the drying device 2. A combustion solid product is obtained which is a solid component containing. Further, together with the combustion solid products, combustion gas containing a high concentration of carbon dioxide is obtained. The combustion device 5 can discharge combustion gas out of the combustion products obtained by combustion through the combustion gas discharge path 40.

<Ash separation device 6>
The ash separator 6 separates phosphorus-containing ash from the combustion products obtained by the combustion device 5. For example, the ash separator 6 extracts particles containing calcium oxide as a main component and phosphorus-containing ash (a solid component containing tricalcium phosphate, gypsum, ash, etc.) from the combustion solid product supplied from the combustion device 5. combustion solid products other than calcium oxide). Then, the ash separator 6 can discharge the phosphorus-containing ash through the phosphorus-containing ash discharge path 41. The phosphorus-containing ash contains, as calcium phosphate compounds, tricalcium phosphate "Ca ₃ (PO ₄ ) ₂ " as well as P ₂ O ₅ , CaPO ₄ , Ca(PO ₃ ) ₂ , Ca ₂ P ₂ O ₇ , Contains _CaHPO4 etc. Note that the phosphorus-containing ash has a smaller particle size than particles containing calcium oxide as a main component.

On the other hand, the ash separator 6 supplies particles containing calcium oxide as a main component to the reformer 4 through the circulating calcium oxide supply path 37. Thereby, the calcium oxide circulates through the reformer 4, the pyrolysis device 3, the combustion device 5, and the ash separation device 6, and is repeatedly used to fulfill the plurality of roles described above.

The ash separation device 6 may be any device that can separate combustion solid products into particles containing calcium oxide as a main component and other combustion solid products, such as a cyclone. The configuration is not particularly limited.

The hydrogen production device according to this embodiment may collect phosphorus-containing ash containing tricalcium phosphate. Therefore, the hydrogen production device according to the present embodiment adds an acid to the phosphorus-containing ash containing tricalcium phosphate, which is supplied from the phosphorus-containing ash discharge path 41, and causes the acid to react with the tricalcium phosphate. The apparatus may further include a phosphoric acid production device (not shown) for producing a soluble phosphoric acid compound such as calcium dihydrogen phosphate.

<Calcium oxide supply path (supply path 33 and bypass supply path 34)>
The circulation of calcium oxide will be explained with reference to FIG. 2.

The ash separator 6 extracts particles containing calcium oxide as a main component and phosphorus-containing ash (calcium oxide), which is a solid component containing tricalcium phosphate, gypsum, ash, etc., from the combustion solid product supplied from the combustion device 5. solid products of combustion). Particles containing calcium oxide as a main component are supplied to the reformer 4 through the circulating calcium oxide supply path 37.

The reformer 4 supplies calcium oxide to the pyrolysis device 3 through a supply path 33 and also supplies calcium oxide to the combustion device 5 through a bypass supply path 34.

As shown in the examples described later, when the bypass supply path 34 does not exist, excessive heat is supplied to the pyrolysis device 3, and the temperature of the pyrolysis device 3 rises excessively. As a result, the absorption reaction of carbon dioxide by calcium oxide becomes difficult to occur, and the hydrogen concentration of the combustible gas decreases. On the other hand, since the hydrogen production device according to the embodiment of the present invention includes the bypass supply path 34, it is possible to prevent excessive heat from being supplied to the pyrolysis device 3. It is possible to prevent the temperature in step 3 from rising excessively. As a result, the hydrogen production apparatus in one embodiment of the present invention can increase the hydrogen concentration of the combustible gas. Furthermore, the hydrogen production device according to the embodiment of the present invention can operate the combustion device 5 at low cost by supplying surplus heat to the combustion device 5 through the bypass supply path 34.

The calcium oxide supply path of the hydrogen production device of this embodiment is configured to adjust the supply amount in order to adjust the amount of calcium oxide supplied to the combustion device 5 and the amount of calcium oxide supplied to the pyrolysis device 3. A device 50 may be included.

For example, in the bypass supply path 34, in order to adjust the amount of calcium oxide supplied to the combustion device 5 through the bypass supply path 34 and the amount of calcium oxide supplied to the pyrolysis device 3 through the supply path 33, A feed rate adjustment device 50 may be provided. In addition, in order to adjust the amount of calcium oxide supplied to the combustion device 5 through the bypass supply path 34 and the amount of calcium oxide supplied to the pyrolysis device 3 through the supply path 33, a supply amount is added to the supply path 33. An adjustment device 50 may be provided. The specific configuration of the supply amount adjusting device 50 is not limited, and for example, a known valve or damper can be used.

The hydrogen production device (more specifically, the thermal decomposition device 3) of the present embodiment may include a temperature measuring device 51 for measuring the temperature inside the thermal decomposition device 3 (thermal decomposition temperature). The temperature measurement device 51 may be any device that can measure the temperature inside the pyrolysis device 3, and its specific configuration is not limited. Temperature measuring device 51 may be a thermocouple, for example.

Information regarding the temperature inside the pyrolysis device 3 measured by the temperature measurement device 51 can be transmitted to the feed rate adjustment device 50 via the wiring 52. For example, when the temperature inside the pyrolysis device 3 is higher than a predetermined temperature, the supply amount adjusting device 50 provided in the bypass supply path 34 is opened and/or the supply amount adjustment device 50 provided in the supply path 33 is opened. The current feed rate regulator 50 can be closed. On the other hand, when the temperature inside the pyrolysis device 3 is lower than the predetermined temperature, the supply amount adjusting device 50 provided in the bypass supply path 34 is closed, and/or the supply amount adjustment device 50 provided in the supply path 33 is closed. The current feed rate regulator 50 can be opened.

Calcium oxide can be supplied to the combustion device 5 via a bypass supply path 34 and a pyrolysis solid product supply path 31 .

[Hydrogen production method]
A hydrogen production method according to an embodiment of the present invention is a hydrogen production method for producing hydrogen from phosphorus-containing biomass, which comprises thermally decomposing a raw material containing the phosphorus-containing biomass in the presence of steam or superheated steam. a pyrolysis step to obtain a pyrolysis product and a combustible gas; a combustion step to combust the pyrolysis product to obtain a combustion product; and a steam reforming process using calcium oxide from the combustible gas. A reforming step of producing a fuel gas with a higher hydrogen concentration than that of the combustible gas, and supplying a portion of the calcium oxide used in the reforming step to the raw material to be thermally decomposed in the thermal decomposition step. and a calcium oxide supplying step of supplying a part of the calcium oxide used in the reforming step to the thermal decomposition product to be burned in the combustion step.

In the hydrogen production method in one embodiment of the present invention, in addition to the steps described above, a temperature measurement step, a supply amount adjustment step, a dehydration step, a drying step, and an ash separation step are optionally selected. It may include at least one step.

A part of the calcium oxide supply process may be included in the thermal decomposition process, and a part of the process may be included in the modification process. For example, the calcium oxide supply step may include a temperature measurement step and a supply amount adjustment step, the temperature measurement step may be included in the thermal decomposition step, and the supply amount adjustment step may be included in the modification step.

Hereinafter, each step constituting the hydrogen production method according to an embodiment of the present invention will be described with reference to FIG. 3. However, regarding content that overlaps with the content explained in the above-mentioned hydrogen production apparatus, the explanation will be simplified or omitted.

<Dehydration step S1>
The dewatering step S1 is a step of removing a water-containing separated liquid from the phosphorus-containing biomass to produce dehydrated sludge.

In the dewatering step S1, the above-mentioned inorganic calcium compound may be mixed into the sludge slurry (phosphorus-containing biomass). Although the order of mixing the sludge slurry (phosphorus-containing biomass) with the inorganic calcium compound and removing the separated liquid from the phosphorus-containing biomass is not particularly limited, it is usually possible to It is possible to improve the dehydration performance compared to the dehydration method described above. The amount of the inorganic calcium compound added to the sludge slurry is as described above.

In the dewatering step S1, a mixture of sludge slurry and an inorganic calcium compound may be dehydrated. That is, the separated liquid containing water may be removed from the mixture of the sludge slurry and the inorganic calcium compound. The dehydrated sludge from which the separated liquid has been removed may be subjected to a drying step S2 or a thermal decomposition step S3, which will be described later.

Note that the specific mixing method for mixing the sludge slurry and the inorganic calcium compound and the specific dehydrating method for dewatering the mixture of the sludge slurry and the inorganic calcium compound are not particularly limited.

In the dewatering step S1, the sludge slurry is dehydrated so that the water content of the dehydrated sludge is preferably 70% to 80% by weight, more preferably 70% to 75% by weight. This makes it possible to reduce the amount of auxiliary fuel used.

<Drying step S2>
The drying step S2 is a step in which water is evaporated from the dehydrated sludge produced in the dehydration step S1 using water vapor or superheated steam to obtain dried sludge.

In the drying step S2, at least a portion of the dehydrated sludge obtained through the dewatering step S1 is taken out, and at least a portion of the water contained in the taken out dehydrated sludge is evaporated. A part of the evaporated moisture (dry steam) may be condensed by cooling and discharged as removed water. The remainder of the evaporated water (dry steam) can be used as a heat source in the drying step S2 and the pyrolysis step S3.

Note that the specific drying method for drying the raw material is not particularly limited. In the drying step S2, the moisture content of the dried sludge is preferably 3% to 30% by weight, more preferably 5% to 20% by weight, and even more preferably 10% to 15% by weight. preferable.

In the drying step S2, it is also possible to supply a part of the dried sludge from which moisture has been removed to the combustion step S5.

<Thermal decomposition step S3>
The thermal decomposition step S3 is a step of thermally decomposing dry sludge containing phosphorus-containing biomass in the presence of steam or superheated steam to obtain a thermal decomposition product and a combustible gas.

In the pyrolysis step S3, dry sludge containing phosphorus-containing biomass is heated at 400°C to 900°C, more preferably 600°C to 800°C, more preferably about 700°C in the presence of water vapor or superheated steam, while Thermal decomposition is carried out by residence for 1 to 2 hours, more preferably for 0.5 to 1 hour.

In the thermal decomposition step S3, thermal decomposition is performed by the above-mentioned reaction to produce a thermal decomposition solid product and a combustible gas which is a thermal decomposition gas. The pyrolysis solid product obtained by pyrolysis is subjected to a combustion step S5. On the other hand, the combustible gas obtained by thermal decomposition is subjected to a reforming step S4. In addition, in the thermal decomposition step S3, the calcium oxide "CaO" used in the modification step S4 is supplied (circulated), and a new inorganic calcium compound can be supplied as necessary.

Since the melting point of tricalcium phosphate contained in the pyrolysis solid product is as high as 1390°C, it prevents the melting of phosphorus compounds from adhering to the incinerator and the resulting clogging of the incinerator in the pyrolysis step S3 and combustion step S5. can do. Therefore, it becomes possible to operate the hydrogen production method more stably and continuously.

<Reforming step S4>
The reforming step S4 is a step of producing a fuel gas with a higher hydrogen concentration than the combustible gas by steam reforming the combustible gas using calcium oxide.

In the reforming step S4, the combustible gas obtained in the pyrolysis step S3 is subjected to the above-mentioned reaction by steam reforming using calcium oxide to produce a second gas having a higher hydrogen concentration than that of the combustible gas. of flammable gas. A part of the second combustible gas may be used as a combustion gas as it is, or it may be mainly CO ₂ and C _m H _n after separating only high concentration hydrogen using a gas separation device such as PSA. The component off-gas may be used as the combustion gas. Thereby, the amount of combustion gas supplied from the outside can be reduced. The produced second combustible gas may be cooled and recovered as a gas containing a high concentration of hydrogen. The heat recovered from the second combustible gas may be supplied to the combustion step S5.

In the reforming step S4, the combustible gas obtained through the thermal decomposition step S3 is heated for 0.5 seconds to 1100°C, more preferably 850°C to 1000°C, and even more preferably about 950°C. Steam reforming is performed by retaining for 3.0 seconds, more preferably 1.0 seconds to 2.5 seconds.

Further, in the reforming step S4, the calcium oxide “CaO” separated in the ash separation step S6 is supplied (circulated), and a new inorganic calcium compound can be supplied as necessary. Further, the calcium oxide used in the reforming step S4 is supplied (circulated) to the thermal decomposition step S3 and the combustion step S5. Details of the circulation of calcium oxide will be described later.

Note that the specific method of steam reforming the combustible gas is not particularly limited.

<Combustion step S5>
The combustion step S5 is a step of burning the thermal decomposition product to obtain a combustion product.

In the combustion step S5, the above-mentioned reaction is performed by burning the pyrolysis solid product obtained in the pyrolysis step S3, and a combustion solid product and a combustion gas are obtained as combustion products. The combustion solid products and combustion gases are fed to an ash separation step S6. The combustion gas contains a high concentration of carbon dioxide. In the combustion step S5, a combustion gas serving as a heat source may be supplied from the outside together with air or oxygen-containing gas, or a part of the second combustible gas or the off-gas may be supplied. Further, in the combustion step S5, a new inorganic calcium compound may be supplied as necessary.

In the combustion step S5, the pyrolysis solid product obtained through the pyrolysis step S3 is heated for 0.1 hour at a temperature of 850°C to 1200°C, more preferably 900°C to 1150°C, and even more preferably about 1100°C. Burning is achieved by residence for ˜2.0 hours, more preferably 0.5 hours to 1.0 hours.

Furthermore, in the combustion step S5, dry sludge from which water has been removed and dried may be supplied from the drying step S2, if necessary. The dried sludge may be combusted as a heat source when it is difficult to combust the pyrolysis solid product using only the amount of heat generated by combustion of the combustion gas in the combustion step S5. By burning the dried sludge, the amount of combustion gas supplied from the outside can be reduced, so the amount of energy used can be reduced.

Note that the specific combustion method for burning the pyrolysis solid product is not particularly limited.

<Ash separation step S6>
The ash separation step S6 is a step of separating phosphorus-containing ash from the combustion products obtained in the combustion step S5.

In the ash separation step S6, particles containing calcium oxide as a main component and phosphorus-containing ash (calcium oxide), which is a solid component containing tricalcium phosphate, gypsum, and ash, are separated from the combustion solid product obtained in the combustion step S5. combustion solid products).

Particles containing calcium oxide as a main component may be supplied to the modification step S4. Thereby, the calcium oxide circulates through the reforming step S4, the thermal decomposition step S3, the combustion step S5, and the ash separation step S6, and is repeatedly used to fulfill the plurality of roles described above.

Although the specific separation method for separating the combustion solid product into particles containing calcium oxide as a main component and other combustion solid products is not particularly limited, for example, a separation method using a cyclone is preferable. .

The hydrogen production method according to the present embodiment may collect phosphorus-containing ash containing tricalcium phosphate. Therefore, in the hydrogen production method according to the present embodiment, an acid is added to the phosphorus-containing ash containing tricalcium phosphate obtained in the ash separation step S6, and the acid and tricalcium phosphate are reacted. The method may further include a phosphoric acid production step of producing an acid and a soluble phosphoric acid compound such as calcium dihydrogen phosphate.

<Calcium oxide supply process>
The calcium oxide supply step supplies a part of the calcium oxide used in the modification step S4 to the raw material to be thermally decomposed in the thermal decomposition step S3, and also supplies part of the calcium oxide used in the modification step S4. This is a step of supplying a portion to the thermal decomposition products to be burned in the combustion step S5.

The calcium oxide supply step includes (i) a temperature measurement step of measuring the thermal decomposition temperature in the thermal decomposition step, and (ii) an oxidation step of supplying the raw material to be thermally decomposed in the thermal decomposition step S3 based on the thermal decomposition temperature. The method may include a supply amount adjustment step of adjusting the amount of calcium and the amount of calcium oxide supplied to the pyrolysis product to be combusted in the combustion step S5.

A part of the calcium oxide supply process may be included in the thermal decomposition process S3, and a part of the process may be included in the modification process S4. For example, the temperature measurement step may be included in the thermal decomposition step S3, and the supply amount adjustment step may be included in the reforming step S4.

Information regarding the pyrolysis temperature in the pyrolysis step measured by the temperature measurement step can be used in the supply amount adjustment step. For example, if the pyrolysis temperature is higher than a predetermined temperature, the amount of calcium oxide supplied to the raw material to be pyrolyzed in the pyrolysis step S3 is reduced in the supply amount adjustment step, and the amount of calcium oxide supplied to the raw material to be pyrolyzed in the pyrolysis step S3 is reduced, and the The amount of calcium oxide fed to the pyrolysis products that are combusted can be increased. On the other hand, if the pyrolysis temperature is lower than the predetermined temperature, the amount of calcium oxide supplied to the raw material to be pyrolyzed in the pyrolysis step S3 is increased in the supply amount adjustment step, and the amount of calcium oxide to be supplied to the raw material to be pyrolyzed in the pyrolysis step S3 is increased, and the The amount of calcium oxide fed to the pyrolysis products that are combusted can be reduced.

As shown in the examples described later, when the calcium oxide supply step does not exist, excessive heat is supplied to the thermal decomposition step S3, and the thermal decomposition temperature of the thermal decomposition step S3 rises excessively. As a result, the absorption reaction of carbon dioxide by calcium oxide becomes difficult to occur, and the hydrogen concentration of the combustible gas decreases. On the other hand, since the hydrogen production method in one embodiment of the present invention includes the calcium oxide supply step, it is possible to prevent excessive heat from being supplied to the thermal decomposition step S3. It is possible to prevent the thermal decomposition temperature from rising excessively. As a result, the hydrogen production method in one embodiment of the present invention can increase the hydrogen concentration of the combustible gas. Furthermore, in the hydrogen production method in one embodiment of the present invention, the combustion step S5 can be performed at low cost by supplying surplus heat to the combustion step S5.

〔Example〕
<Overview of hydrogen production equipment>
In Example 1, the thermal decomposition temperature in the thermal decomposition device and the amount of H ₂ -rich gas generated were estimated for a hydrogen production device (corresponding to the present invention) equipped with a bypass supply path.

On the other hand, in Comparative Example 1, a hydrogen production apparatus (corresponding to the prior art) that does not have a bypass supply path and is equipped with a pyrolysis apparatus having a cooling system as shown in FIG. The thermal decomposition temperature and the amount of H ₂ -rich gas generated were estimated. Specifically, the pyrolysis apparatus 100 has calcium oxide 102 and a cooling water supply path 101 arranged therein. By passing water through the cooling water supply path 101, the inside of the pyrolysis apparatus 100 can be cooled.

<Estimation conditions>
The trial calculation conditions are shown in Tables 1 and 2.

Specifically, the dehydrated sludge slurry was dehydrated using a dehydrator to obtain the dehydrated sludge shown in Table 1. The lower calorific value shown in Table 1 was calculated according to a method according to JIS M 8814. The elemental analysis values shown in Table 1 were calculated according to a method using a CHN elemental analyzer.

The dehydrated sludge was dried using a direct heating dryer to obtain dried sludge shown in Table 1. The dried sludge was supplied in the amounts listed in Table 2 to a reformer and combustion device operating at the temperatures listed in Table 1.

As shown in Table 2, in Example 1, 78 t/d of calcium oxide was circulated within the hydrogen production device, and 56 t/d of this calcium oxide was supplied from the reformer to the combustion device via the bypass supply path. . On the other hand, in Comparative Example 1, 63 t/d of calcium oxide was circulated within the hydrogen production device.

<Estimate results>
In the hydrogen production device of Example 1 equipped with a bypass supply path, the temperature of the pyrolysis device stabilized at 739° C. and a large amount of H ₂ -rich gas was generated.

On the other hand, in the hydrogen production device of Comparative Example 1, which is not equipped with a bypass supply path, when the cooling system is operated, the temperature of the pyrolysis device stabilizes at 700°C, and only a small amount of H ₂ -rich gas is generated. Ta.

When the cooling system was stopped in the hydrogen production device of Comparative Example 1, which was not equipped with a bypass supply path, the temperature of the pyrolysis device stabilized at 810° C., and only a small amount of H ₂ -rich gas was generated. . When the heating temperature in the pyrolysis device exceeds 750° C., the higher the heating temperature, the more difficult the absorption reaction of carbon dioxide by calcium oxide tends to occur. Therefore, it is considered that when the cooling system was stopped in the hydrogen production apparatus of Comparative Example 1 which was not equipped with a bypass supply path, only a small amount of H ₂ -rich gas was generated.

〔summary〕
The present invention includes the following configurations.
<1>
A hydrogen production method for producing hydrogen from phosphorus-containing biomass,
A pyrolysis step of pyrolyzing the raw material containing the phosphorus-containing biomass in the presence of steam or superheated steam to obtain a pyrolysis product and a combustible gas;
a combustion step of burning the pyrolysis product to obtain a combustion product;
a reforming step of producing a fuel gas with a higher hydrogen concentration than the combustible gas by steam reforming using calcium oxide from the combustible gas;
A portion of the calcium oxide used in the modification step is supplied to the raw material to be thermally decomposed in the thermal decomposition step, and a portion of the calcium oxide used in the modification step is supplied to the raw material to be thermally decomposed in the thermal decomposition step. , a step of supplying calcium oxide to the thermal decomposition product combusted in the combustion step.
<2>
a temperature measurement step of measuring the pyrolysis temperature in the pyrolysis step;
Based on the pyrolysis temperature, determine the amount of calcium oxide to be supplied to the raw material to be pyrolyzed in the pyrolysis step and the amount of calcium oxide to be supplied to the pyrolysis product to be combusted in the combustion step. The hydrogen production method according to <1>, including a supply amount adjustment step of adjusting the amount.
<3>
The hydrogen production method according to <1> or <2>, including a dehydration step of removing a water-containing separated liquid from the phosphorus-containing biomass to produce the raw material.
<4>
The hydrogen production method according to any one of <1> to <3>, which includes a drying step of evaporating water from the raw material using steam or superheated steam between the dehydration step and the thermal decomposition step.
<5>
The hydrogen production method according to any one of <1> to <4>, including an ash separation step of separating phosphorus-containing ash from the combustion product obtained in the combustion step.
<6>
A hydrogen production device that produces hydrogen from phosphorus-containing biomass,
A pyrolysis device that pyrolyzes the raw material containing the phosphorus-containing biomass in the presence of steam or superheated steam to obtain a pyrolysis product and a combustible gas;
a combustion device that burns the pyrolysis product to obtain a combustion product;
a reformer that produces a fuel gas with a higher hydrogen concentration than the combustible gas by steam reforming the flammable gas using calcium oxide;
a supply path for supplying a portion of the calcium oxide used in the reformer to the raw material to be thermally decomposed in the pyrolysis device; A hydrogen production device comprising: a calcium oxide supply path having a portion of the supply path for supplying the thermal decomposition product to be burned in the combustion device.
<7>
a temperature measuring device that measures the pyrolysis temperature in the pyrolysis device;
Based on the pyrolysis temperature, the amount of calcium oxide to be supplied to the raw material to be pyrolyzed in the pyrolysis device, and the amount of calcium oxide to be supplied to the pyrolysis product to be combusted in the combustion device. The hydrogen production device according to <6>, further comprising a supply amount adjustment device that adjusts the supply amount.
<8>
The hydrogen production device according to <6> or <7>, comprising a dehydration device that removes a water-containing separated liquid from the phosphorus-containing biomass to produce the raw material.
<9>
The hydrogen production device according to any one of <6> to <8>, comprising a drying device that evaporates water from the raw material using steam or superheated steam.
<10>
The hydrogen production device according to any one of <6> to <9>, comprising an ash separation device that separates phosphorus-containing ash from the combustion product obtained by the combustion device.

The hydrogen production method and hydrogen production device according to an embodiment of the present invention use phosphorus-containing biomass such as sewage sludge generated at a sewage treatment plant, human waste sludge generated at a human waste treatment plant, meat and bone meal, and livestock dung as raw materials. It is suitably used in the production of hydrogen.

1 Dehydration device (mixing device)
2 Drying device 3 Pyrolysis device 4 Reforming device 5 Combustion device 6 Ash separation device

Claims (10)

A hydrogen production method for producing hydrogen from phosphorus-containing biomass,
A pyrolysis step of pyrolyzing the raw material containing the phosphorus-containing biomass in the presence of steam or superheated steam to obtain a pyrolysis product and a combustible gas;
a combustion step of burning the pyrolysis product to obtain a combustion product;
a reforming step of producing a fuel gas with a higher hydrogen concentration than the combustible gas by steam reforming using calcium oxide from the combustible gas;
A portion of the calcium oxide used in the modification step is supplied to the raw material to be thermally decomposed in the thermal decomposition step, and a portion of the calcium oxide used in the modification step is supplied to the raw material to be thermally decomposed in the thermal decomposition step. , a step of supplying calcium oxide to the thermal decomposition product combusted in the combustion step. a temperature measurement step of measuring the pyrolysis temperature in the pyrolysis step;
Based on the pyrolysis temperature, determine the amount of calcium oxide to be supplied to the raw material to be pyrolyzed in the pyrolysis step and the amount of calcium oxide to be supplied to the pyrolysis product to be combusted in the combustion step. The hydrogen production method according to claim 1, further comprising a supply amount adjustment step of adjusting the amount. The hydrogen production method according to claim 1 or 2, comprising a dehydration step of removing a water-containing separated liquid from the phosphorus-containing biomass to produce the raw material. The hydrogen production method according to claim 3 , further comprising a drying step of evaporating water from the raw material using steam or superheated steam between the dehydration step and the thermal decomposition step. The hydrogen production method according to any one of claims 1 to 4, comprising an ash separation step of separating phosphorus-containing ash from the combustion product obtained in the combustion step. A hydrogen production device that produces hydrogen from phosphorus-containing biomass,
A pyrolysis device that pyrolyzes the raw material containing the phosphorus-containing biomass in the presence of steam or superheated steam to obtain a pyrolysis product and a combustible gas;
a combustion device that burns the pyrolysis product to obtain a combustion product;
a reformer that produces a fuel gas with a higher hydrogen concentration than the combustible gas by steam reforming the flammable gas using calcium oxide;
a supply path for supplying a portion of the calcium oxide used in the reformer to the raw material to be thermally decomposed in the pyrolysis device; A hydrogen production device comprising: a calcium oxide supply path, a portion of which is supplied to the thermal decomposition product to be burned in the combustion device. a temperature measuring device that measures the pyrolysis temperature in the pyrolysis device;
Based on the pyrolysis temperature, the amount of calcium oxide to be supplied to the raw material to be pyrolyzed in the pyrolysis device, and the amount of calcium oxide to be supplied to the pyrolysis product to be combusted in the combustion device. The hydrogen production apparatus according to claim 6, further comprising a supply amount adjusting device that adjusts the amount of hydrogen. The hydrogen production device according to claim 6 or 7, further comprising a dehydration device that removes a water-containing separated liquid from the phosphorus-containing biomass to produce the raw material. The hydrogen production device according to any one of claims 6 to 8, comprising a drying device that evaporates moisture from the raw material using steam or superheated steam. The hydrogen production device according to any one of claims 6 to 9, comprising an ash separator that separates phosphorus-containing ash from the combustion product obtained by the combustion device.

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