JP4335735B2 - Sulfuric acid decomposer and hydrogen production apparatus using the same - Google Patents

Description

  The present invention relates to a sulfuric acid decomposer and hydrogen production using the same.

  For example, FIG. 11 shows a conventional hydrogen production apparatus that thermochemically produces hydrogen from water using iodine and sulfur dioxide.

As shown in FIG. 11, iodine (I ₂ ), sulfur dioxide (SO ₂ ), and water (H ₂ O) are reacted with Bunsen to produce sulfuric acid (H ₂ SO ₄ ) and hydrogen iodide (HI). The separator 10 communicates with the vessel 10 to separate the sulfuric acid aqueous solution and the hydrogen iodide aqueous solution generated by the reaction by specific gravity difference. A hydrogen iodide concentrator 30 for concentrating the hydrogen iodide aqueous solution communicates with the lower side of the separator 20. The sulfuric acid concentrator 60 for concentrating the sulfuric acid aqueous solution communicates with the upper side of the separator 20.

The hydrogen iodide concentrator 30 communicates with a hydrogen iodide decomposer 40 that heats the concentrated hydrogen iodide and decomposes it into iodine (I ₂ ) gas and hydrogen (H ₂ ) gas. Yes. The hydrogen iodide decomposer 40 cools iodine gas and hydrogen gas generated by decomposition to liquefy iodine, thereby separating iodine and hydrogen gas and isolating the hydrogen gas into the hydrogen recovery container 1. On the other hand, a cooling separator 50 for supplying liquefied iodine to the reactor 10 communicates.

On the other hand, the sulfuric acid concentrator 60 communicates with a sulfuric acid decomposer 70 that heats the concentrated sulfuric acid to decompose it into sulfur dioxide gas, oxygen (O ₂ ) gas, and water vapor. The sulfuric acid decomposing unit 70 supplies water to the reactor 10 by separating the water, sulfur dioxide gas and oxygen gas by cooling the gas generated by decomposition and liquefying water vapor, while supplying the gas to the reactor 10. A cooling separator 80 that communicates water (including residual sulfuric acid) to the concentrator 60 communicates. In addition, the oxygen recovery container 2 communicates with the reactor 10.

  As shown in FIG. 12, the decomposer 70 forms a plurality of flow passages 71a communicating with one surface and the other surface in a block-shaped main body 71 made of ceramics and the like. A block type structure having a structure in which a plurality of flow passages 71b communicating between one surface in a direction orthogonal to the axial direction of the passage 71a and the other surface facing each other is formed, and in one of the flow passages 71a By circulating a heated gas (for example, helium gas) and circulating sulfuric acid concentrated in the other flow passage 71b, the sulfuric acid can be heated and decomposed into sulfur dioxide gas, oxygen gas, and water vapor. It is like that.

  Next, a hydrogen production method using such a conventional hydrogen production apparatus will be described.

  When water is supplied into the reactor 10 and iodine and sulfur dioxide are supplied and reacted, an exothermic reaction (about 100 ° C.) shown in the following formula (1) is generated by the Bunsen reaction, and an aqueous sulfuric acid solution and iodine An aqueous hydrogen fluoride solution is formed.

2H ₂ O (L) + I ₂ (L) + SO ₂ (G) → H ₂ SO ₄ (aq) + 2HI (aq) (1)

  The liquid produced by the above reaction (sulfuric acid aqueous solution and hydrogen iodide aqueous solution) is fed from the reactor 10 to the separator 20, and the hydrogen iodide aqueous solution located below is fed to the concentrator 30. The sulfuric acid aqueous solution located in is fed to the concentrator 60.

  The aqueous hydrogen iodide solution is heated by the concentrator 30 (about 100 to 250 ° C.) to evaporate and distill off the water, thereby concentrating the aqueous hydrogen iodide solution and then supplying the concentrated hydrogen iodide to the decomposer 40. To send. The distilled water is returned to the reactor 10 and reused as a raw material.

  When the concentrated hydrogen iodide is heated by the decomposer 40 (about 250 ° C.), hydrogen iodide is decomposed into iodine gas and hydrogen gas as shown in the following formula (2).

2HI (L) → H ₂ (G) + I ₂ (G) (2)

  The iodine gas and hydrogen gas generated by decomposition are supplied to the cooling separator 50 to be cooled (about 100 to 200 ° C.), and the hydrogen gas and iodine are separated by liquefying the iodine gas, and the hydrogen gas is recovered into hydrogen. Collect in container 1. The separated iodine is supplied again into the reactor 10 together with the accompanying moisture and reused.

  On the other hand, the sulfuric acid aqueous solution fed to the concentrator 60 is heated (about 100 to 450 ° C.) to evaporate and distill off the water, thereby concentrating the sulfuric acid aqueous solution and then sending the concentrated sulfuric acid to the decomposer 70. To pay. The distilled water is returned to the reactor 10 and reused as a raw material.

  When the concentrated sulfuric acid is heated by the decomposer 70 (about 450 to 850 ° C.), the sulfuric acid is decomposed into sulfur dioxide gas, oxygen gas and water vapor as shown in the following formula (3).

H ₂ SO ₄ (L) → SO ₃ (G) + H ₂ O (G)
→ SO ₂ (G) + 1 / 2O ₂ (G) + H ₂ O (G) (3)

  The gas generated by decomposition is supplied to the cooling separator 80 and cooled (about 100 ° C.) to liquefy water vapor, and then the gas is supplied into the reactor 10 to recycle sulfur dioxide. Then, water is fed to the concentrator 60 to re-decompose the remaining sulfuric acid. Since the oxygen gas supplied into the reactor 10 remains in the reactor 10 without being subjected to the reaction, the oxygen gas is recovered from the reactor 10 into the oxygen recovery container 2 after the reaction.

  Therefore, according to the hydrogen production apparatus as described above, hydrogen can be produced using only water as a raw material by using iodine and sulfur dioxide.

JP-A-63-248701

  In the hydrogen production apparatus using iodine and sulfur dioxide as described above, it is required to use thermal energy as effectively as possible, and in particular, improvement in the efficiency of sulfuric acid gasification by the decomposer 70 is strongly required. It was.

  In view of the above, an object of the present invention is to provide a sulfuric acid decomposer with high efficiency of sulfuric acid gasification and a hydrogen production apparatus using the sulfuric acid decomposer.

  In order to solve the above-described problem, the sulfuric acid decomposer according to the first aspect of the present invention has a flow passage formed on one surface and penetrates between one surface and the other surface. A first flow plate formed with a communication hole that forms a pair communicating with the flow passage, a flow passage is formed on one surface, a communication groove that forms a pair communicating the flow passage and the outside, and further, The second flow plate formed with a communication hole communicating with the communication hole of the first flow plate is alternately arranged so that one surface of the one plate faces the other surface of the other plate. And a supply manifold that communicates with one of the connection holes of the plate is disposed on one side of the plate in the stacking direction, and the other of the connection holes of the plate is disposed on the other side of the plate in the stacking direction. Sending machine communicating with A main body portion provided with a hold, wherein either one of sulfuric acid or a heat medium is supplied into the supply manifold, and either the sulfuric acid or the heat medium is inserted into the communication groove of the second flow plate. Is provided.

  A sulfuric acid decomposer according to a second invention is the sulfuric acid decomposer according to the first invention, wherein a plurality of the main body portions are connected in series, and at least one of the supply manifold and the delivery manifold is a circulating sulfuric acid or heat medium. It has a mixing space portion that makes the temperature distribution uniform, and also makes the temperature distribution of the sulfuric acid or heat medium flowing between the communication grooves of the second flow plate of the adjacent main body portions connected in series uniform. It has a mixing space part.

  In the sulfuric acid decomposer according to a third aspect, in the first aspect, the flow path of the plate through which the heat medium flows corresponds to a back surface portion of the flow path of the plate through which sulfuric acid decomposition gas flows. It is set so as not to face the other surface.

  The sulfuric acid decomposer according to a fourth invention is the sulfuric acid decomposer according to the first invention, having a supply port to which liquid sulfuric acid is supplied on the lower side and a delivery port on the upper side, wherein the main body is in sulfuric acid. An outer container disposed inside so as to be immersed in, a heat medium supply pipe for supplying a heat medium from the outside of the outer container to the supply manifold of the main body, and the outer side from the delivery manifold of the main body A heat medium delivery pipe for delivering the heat medium to the outside of the container is provided.

  A sulfuric acid decomposer according to a fifth invention is characterized in that, in the fourth invention, a sulfuric tank is connected to the delivery port of the outer container through a throttle member.

A sulfuric acid decomposer according to a sixth aspect of the present invention includes a cylindrical shell having a supply port to which liquid sulfuric acid is supplied on the lower side and a delivery port on the upper side, and is disposed inside the shell. A shell and tube type main body having a tube through which a heat medium flows is provided.

  A sulfuric acid decomposer according to a seventh aspect of the invention comprises a flash tank that vaporizes liquid sulfuric acid by ejecting it from a throttle member, and a heating means that heats the gas collected in the flash tank. And

In addition, the hydrogen production apparatus according to the eighth invention for solving the above-mentioned problem is a reaction in which a halogen of iodine or bromine, sulfur dioxide, and water are reacted to produce a sulfuric acid aqueous solution and a hydrogen halide aqueous solution. Means, separation means for separating sulfuric acid aqueous solution and hydrogen halide aqueous solution by specific gravity difference, hydrogen halide concentration means for concentrating the separated hydrogen halide aqueous solution, and decomposing the concentrated hydrogen halide into halogen and hydrogen A hydrohalide decomposition means, a halogen recycle means for isolating the decomposed hydrogen to the reaction means, a sulfuric acid concentration means for concentrating the separated sulfuric acid aqueous solution, and a concentrated sulfuric acid Sulfuric acid decomposition means that decomposes into sulfur dioxide, oxygen, and water, and at least sulfur dioxide among the decomposed sulfur dioxide, oxygen, and water In the hydrogen production apparatus and a sulfur dioxide recycling means for supplying to the stage, the sulfuric acid decomposition unit, characterized in that the first th is any of sulfuric acid decomposer of the seventh aspect of the invention.

  According to the sulfuric acid decomposer according to the first invention, since the plate laminating type is used, it is possible to improve the gasification energy efficiency of sulfuric acid as compared with the conventional block type. Energy efficiency can be improved.

  According to the sulfuric acid decomposer according to the second aspect of the present invention, the main body portion has a mixing space portion that makes the temperature distribution of the sulfuric acid or the heat medium uniform between the main body portions connected in series. The thermal stress generated in the body can be suppressed as much as possible, and the life of the main body can be extended.

  According to the sulfuric acid decomposer of the third invention, the flow path of the plate through which the heat medium flows does not face the other surface corresponding to the back surface portion of the flow path of the plate through which the decomposition gas of sulfuric acid flows. Since the thermal shock caused by the gas generated by heating coming into contact with the other surface of the second flow plate can be greatly reduced, the life of the main body can be extended. Can do.

  According to the sulfuric acid decomposer according to the fourth aspect of the invention, the plate of the main body always comes into contact with liquid sulfuric acid over the entire surface, so that the thermal shock applied to the plate due to the contact of the generated gas is greatly reduced. Therefore, the life of the main body can be extended, and furthermore, the liquid level position of sulfuric acid can be easily managed, and the operation control can be facilitated.

  According to the sulfuric acid decomposer according to the fifth aspect of the present invention, since the flush tank connected to the delivery port of the outer container via the throttle member is provided, the liquid level of sulfuric acid is always located at the throttle member portion. Therefore, the liquid level position of sulfuric acid can be easily managed, and the operation control can be facilitated.

  According to the sulfuric acid decomposer according to the sixth aspect of the invention, since it is of a shell and tube type, the liquid level position of sulfuric acid can be easily managed, and the operation control can be facilitated.

  According to the sulfuric acid decomposer according to the seventh aspect of the present invention, it is provided with a flash tank that vaporizes liquid sulfuric acid by ejecting it from the throttle member, and a heating means that heats the gas collected in the flash tank. From the above, sulfuric acid can be thermally decomposed by applying a general heater using a corrosion-resistant metal material such as high Cr steel, Ni base steel, Co base steel, etc., and ceramics such as SiC and Si-SiC The use of materials with high corrosion resistance, such as the flash tank part, can be done only, so the number of places where high corrosion resistance materials such as ceramics such as SiC and Si-SiC can be used can be reduced, making production easier. In addition, the manufacturing cost can be reduced.

  According to the hydrogen production apparatus according to the eighth aspect of the present invention, since the sulfuric acid decomposer according to any one of the first to seventh aspects of the invention is provided, the thermal efficiency related to the hydrogen production can be increased, and the hydrogen production The cost concerning can be reduced.

  Embodiments of a sulfuric acid decomposer and a hydrogen production apparatus using the same according to the present invention will be described below with reference to the drawings. However, the present invention is not limited to these embodiments.

[First embodiment]
A first embodiment of a sulfuric acid decomposer according to the present invention and a hydrogen production apparatus using the sulfuric acid decomposer will be described with reference to FIGS. FIG. 1 is a schematic configuration diagram of a hydrogen production apparatus, FIG. 2 is an overall schematic configuration diagram of a sulfuric acid decomposer, and FIG. 3 is a configuration diagram of main components of the sulfuric acid decomposer of FIG.

As shown in FIG. 1, iodine (I ₂ ), sulfur dioxide (SO ₂ ), and water (H ₂ O) are subjected to a Bunsen reaction to produce sulfuric acid (H ₂ SO ₄ ) and hydrogen iodide (HI). The reactor 110 which is a means communicates with a separator 120 which is a separation means for separating the sulfuric acid aqueous solution and the hydrogen iodide aqueous solution generated by the reaction by a specific gravity difference. A hydrogen iodide concentrator 130, which is a hydrogen halide concentrating means for concentrating the hydrogen iodide aqueous solution, communicates with the lower side of the separator 120. A sulfuric acid concentrator 160 that is a sulfuric acid concentrating means for concentrating the sulfuric acid aqueous solution communicates with the upper side of the separator 120.

The hydrogen iodide concentrator 130 is for hydrogen iodide, which is a hydrogen halide decomposition means for heating the concentrated hydrogen iodide to decompose it into iodine (I ₂ ) gas and hydrogen (H ₂ ) gas. The decomposer 140 is in communication. The hydrogen iodide decomposer 140 cools iodine gas and hydrogen gas generated by decomposition to liquefy iodine, thereby separating iodine and hydrogen gas and isolating the hydrogen gas into the hydrogen recovery container 101. On the other hand, a cooling separator 150 which is a halogen recycling means for supplying liquefied iodine to the reactor 110 communicates.

On the other hand, the sulfuric acid concentrator 160 communicates with a sulfuric acid decomposing unit 170 which is a sulfuric acid decomposing means for heating the concentrated sulfuric acid to decompose it into sulfur dioxide gas, oxygen (O ₂ ) gas and water vapor. Yes. The sulfuric acid decomposing unit 170 supplies water to the reactor 110 while separating the water, sulfur dioxide gas and oxygen gas by cooling the gas generated by decomposition and liquefying water vapor, while supplying the gas to the reactor 110. A cooling separator 180, which is a sulfur dioxide recycling means for feeding water (including residual sulfuric acid) to the concentrator 160, communicates. The reactor 110 is in communication with an oxygen recovery container 102.

  As shown in FIG. 2, the decomposer 170 alternately stacks a plurality of first flow plates 171 and second flow plates 172 made of highly corrosion-resistant materials such as ceramics such as SiC and Si—SiC. 172, a supply manifold 173 made of a highly corrosion-resistant material such as ceramics such as SiC or Si-SiC is disposed at one end in the stacking direction, and SiC is disposed at the other end in the stacking direction of the plates 171 and 172. Or a plate laminate type having a main body 170A provided with a delivery manifold 174 made of a highly corrosion-resistant material such as ceramics such as Si-SiC.

  More specifically, as shown in FIG. 3, the first flow plate 171 has a flow path 171 a having a concave shape formed on one surface, and faces one side and the one side. A plurality of communication holes 171b and 171c that penetrate between the one surface and the other surface and communicate with the flow passage 171a are formed on the side to be connected. The second flow plate 172 has a meandering groove-shaped flow passage 172a formed on one surface, and one side and a side opposite to the one side of the flow passage 172a. Communication grooves 172b and 172c for communicating each end side and the outside are formed, respectively, and further communicated with the communication holes 171b and 171c of the first flow plate 171 when stacked with the first flow plate 171. In this way, communication holes 172d and 172e penetrating between one surface and the other surface are formed.

  As shown in FIG. 2, the supply manifold 173 communicates with one of the communication holes 171b and 172d of the plates 171 and 172. The delivery manifold 174 communicates with the other communication holes 171c and 172e of the plates 171 and 172.

  That is, the decomposer 170 is supplied with concentrated sulfuric acid into the supply manifold 173 of the main body 170A, and is a heat medium such as helium in the communication groove 172b of each second flow plate 172 of the main body 170A. When heated gas is supplied, concentrated sulfuric acid flows into the connection holes 171b and 172d of the plates 171 and 172, and flows through the flow passages 171a of the first flow plates 171 while the heated gas flows into the communication holes 171a and 172d. By circulating in the flow passage 172a of the second flow plate 172, the concentrated sulfuric acid is heated by heat exchange with the heated gas to be decomposed gas, and the above-described plates 171 and 172 have the communication holes 171c and 172e through the communication holes 171c and 172e. The gas flows out to the delivery manifold 174, and the gas can be sent to the next process from the main body 170A. .

  The heated gas flowing through the flow passage 172a of each second flow plate 172 is sent out of the communication groove 172c to the outside of the main body portion A and heated, and then heated to each second flow plate of the main body portion 170A. 172 is supplied again to the communication groove 172b.

  Next, a hydrogen production method using such a hydrogen production apparatus according to this embodiment will be described.

  When water is supplied into the reactor 110 and iodine and sulfur dioxide are supplied and reacted, an exothermic reaction (about 100 ° C.) shown in the following formula (1) is caused by the Bunsen reaction to produce an aqueous sulfuric acid solution and iodine. An aqueous hydrogen fluoride solution is formed.

2H ₂ O (L) + I ₂ (L) + SO ₂ (G) → H ₂ SO ₄ (aq) + 2HI (aq) (1)

  The liquid produced by the above reaction (sulfuric acid aqueous solution and hydrogen iodide aqueous solution) is fed from the reactor 110 to the separator 120, and the hydrogen iodide aqueous solution located below is fed to the concentrator 130. The sulfuric acid aqueous solution located in the position is fed to the concentrator 160.

  The aqueous hydrogen iodide solution is heated by the concentrator 130 (about 100 to 250 ° C.) to evaporate and distill off the water, thereby concentrating the aqueous hydrogen iodide solution and then supplying the concentrated hydrogen iodide to the decomposer 140. To send. The distilled water is returned to the reactor 110 and reused as a raw material.

  When concentrated hydrogen iodide is heated by the decomposer 140 (about 250 ° C.), hydrogen iodide is decomposed into iodine gas and hydrogen gas as shown in the following formula (2).

2HI (L) → H ₂ (G) + I ₂ (G) (2)

  The iodine gas and hydrogen gas generated by decomposition are supplied to the cooling separator 150 and cooled (about 100 to 200 ° C.), and the iodine gas is liquefied to separate the hydrogen gas and iodine, and the hydrogen gas is recovered into hydrogen. Collect in the container 101. The separated iodine is supplied again into the reactor 110 together with the accompanying water and reused.

  On the other hand, the sulfuric acid aqueous solution fed to the concentrator 160 is heated (about 100 to 450 ° C.) to evaporate and distill off the water, thereby concentrating the sulfuric acid aqueous solution, and then sending the concentrated sulfuric acid to the decomposer 170. To pay. The distilled water is returned to the reactor 110 and reused as a raw material.

  When the concentrated sulfuric acid is supplied to the cracker 170, the sulfuric acid is gasified by being heated as described above, as shown in the following formula (3), and sulfur dioxide gas and oxygen Decomposes into gas and water vapor (about 450-850 ° C.).

H ₂ SO ₄ (L) → SO ₃ (G) + H ₂ O (G)
→ SO ₂ (G) + 1 / 2O ₂ (G) + H ₂ O (G) (3)

  The gas generated by decomposition is supplied to the cooling separator 180 for cooling (about 100 ° C.) to liquefy water vapor, and then the gas is supplied into the reactor 110 to recycle sulfur dioxide. Then, water is supplied to the concentrator 160 to re-decompose the remaining sulfuric acid. Since the oxygen gas supplied into the reactor 110 remains in the reactor 110 without being subjected to the reaction, it is recovered from the reactor 110 into the oxygen recovery container 102 after the reaction.

  Thus, hydrogen is produced using only water as a raw material using iodine and sulfur dioxide.

  That is, in the present embodiment, the concentrated sulfuric acid is decomposed and gasified by the plate stacking type decomposer 170.

  For this reason, in this embodiment, the gasification energy efficiency of a sulfuric acid can be improved rather than the case where concentrated sulfuric acid is decomposed | disassembled and gasified with the block-type cracker 70 like the past.

  Therefore, according to this embodiment, thermal energy efficiency can be improved.

[Second Embodiment]
A second embodiment of the sulfuric acid decomposer according to the present invention and a hydrogen production apparatus using the sulfuric acid decomposer will be described with reference to FIG. FIG. 4 is an overall schematic configuration diagram of the sulfuric acid decomposer. In addition, about the part similar to the case of 1st embodiment mentioned above, by using the code | symbol similar to the code | symbol used in description of 1st embodiment mentioned above, 1st embodiment mentioned above is used. The description overlapping with the description in is omitted.

  As shown in FIG. 4, the sulfuric acid decomposer 270 according to the present embodiment includes a plurality of (three in the present embodiment) main body portions 270 </ b> A to 270 </ b> C having the same structure as that of the first embodiment described above in series. Concatenated.

  Specifically, the outlet of the delivery manifold 274 of the main body 270A is connected to the inlet of the supply manifold 273 of the main body 270B, and the outlet of the delivery manifold 274 of the main body 270B is received by the supply manifold 273 of the main body 270C. The communication groove 172c of the second flow plate 172 of the main body part 270C is connected to the communication groove 172b of the second flow plate 172 of the main body part 270B, so that the inlet of the second flow plate 172 of the main body part 270B is connected. The manifolds 273 and 274 of the main body portions 270A to 270C are overlapped and connected in series so that the flow groove 172c communicates with the flow groove 172b of the second flow plate 272 of the main body portion 270A.

  Further, the second flow plate 172 of the main body 270B and the second flow plate 172 of the main body 270B and the second flow plate 172 of the main body 270B and the second flow plate of the main body 270A are connected in series and adjacent to each other. A mixing space portion 270a that makes the temperature distribution of the circulating heated gas uniform is interposed between the two. Further, a mixing space portion 274a that makes the temperature distribution of the flowing sulfuric acid uniform is formed in the periphery of the delivery outlet of the delivery manifold 274 of the main body portions 270A and 270B.

  In the above decomposer 270 according to this embodiment, concentrated sulfuric acid is supplied into the supply manifold 273 of the main body 270A and also into the communication grooves 172b of the second flow plates 172 of the main body 270C. When a heating gas such as helium is supplied, concentrated sulfuric acid flows through the main body portions 270A, 270B, and 270C in the same order as in the first embodiment described above, while the heating gas flows as described above. In the same manner as in the first embodiment, the main body portions 270C, 270B, and 270A are circulated through the inside of the main body portions 270C, 270A, and the concentrated sulfuric acid is heated by heat exchange with the heated gas to be decomposed gas. The gas is sent from the delivery manifold 274 to the next process, and the heated gas is sent from the main body 270A and heated, and then the main body 270 is heated. It is supplied again to.

  At this time, the heated gas sent from the communication groove 172c of each of the second flow plates 172 of the main body portions 270C and 270B is once mixed in the mixing space portion 270a, and then the second flow plates of the main body portions 270B and 270A. 172 flows into the communication groove 172b, so even if temperature unevenness occurs in each of the second flow plates 172 flowing in the main body portions 270C and 270B, the temperature distribution is uniformed by mixing in the mixing space portion 270a. And then supplied to the next main body 270B, 270A.

  Further, since the sulfuric acid flowing into the supply manifold 273 of the main body portions 270B and 270C is once mixed in the mixing space portion 274a, the sulfuric acid has a temperature for each of the first flow plates 171 distributed in the main body portions 270A and 270B. Even if unevenness occurs, the mixture is mixed in the mixing space portion 274a and then supplied to the next main body portions 270B and 270C.

  That is, in the first embodiment described above, the decomposer 170 including the single main body 170 is used, but in the present embodiment, the plurality of main bodies 270A to 270C are connected in series, in other words, The main body portions 270A to 270C are divided into a plurality of parts, and sulfuric acid and heated gas that diverges and flows through the main body portions 270A to 270C are mixed in the mixing space portions 270a and 274a between the main body portions 270A to 270C. Once assembled and mixed, the temperature unevenness of sulfuric acid and heated gas was reduced as much as possible.

  For this reason, in the decomposer 270, the temperature difference generated in each of the main body portions 270A to 270C can be suppressed to be extremely small, and the thermal distortion generated in each of the main body portions 270A to 270C can be suppressed as much as possible.

  Therefore, according to the present embodiment, the thermal stress generated in the decomposer 270 can be suppressed as much as possible as well as the same effect as in the case of the first embodiment described above. The life of the 270 can be extended.

  In the present embodiment, the mixing space portion 274a is formed in the peripheral portion of the delivery outlet of the delivery manifold 274 of the main body portions 270A and 270B. Instead, the peripheral portion of the reception inlet of the supply manifold 273 of the main body portions 270B and 270C. It is also possible to form a mixing space portion, and it is also possible to form a mixing space portion in both the delivery manifold 274 and the supply manifold 273.

  In the present embodiment, the three main body portions 270A to 270C are connected. However, depending on various conditions, the two main body portions are connected or four or more main body portions are connected. It is also possible.

[Third embodiment]
A third embodiment of the sulfuric acid decomposer and the hydrogen production apparatus using the same according to the present invention will be described with reference to FIGS. FIG. 5 is an overall schematic configuration diagram of the sulfuric acid decomposer, and FIG. 6 is a configuration diagram of the main components of the sulfuric acid decomposer of FIG. In addition, about the part similar to the case of 1st, 2nd embodiment mentioned above, by using the code | symbol similar to the code | symbol used in description of 1st, 2nd embodiment mentioned above, the 1st mentioned above. The description overlapping with the description in the second embodiment is omitted.

  As shown in FIGS. 5 and 6, the second flow plate 372 of the main body 370 </ b> A of the sulfuric acid decomposer 370 according to the present embodiment has a flow passage on one of the sides intersecting the side where the communication groove 172 c is formed. A communication groove 372b that connects the 372a and the outside is formed, and the flow passage 372a is formed only within a range that can be positioned between the communication grooves 372b and 172c.

  In such a decomposer 370 according to the present embodiment, concentrated sulfuric acid is supplied into the supply manifold 173 of the main body 370A and the main body 370A of the main body 370A, as in the case of the first embodiment described above. When heated gas is supplied into the communication groove 372b of each second flow plate 372, the concentrated sulfuric acid is heated and gasified by heat exchange with the heated gas.

  At this time, as shown in FIG. 6, the liquid level of sulfuric acid flowing in the flow passage 171a of the first flow plate 171 is located between the flow passage 372a of the second flow plate 372 and the communication hole 172e. In other words, the flow passage 372a of the second flow plate 372 does not face the other surface corresponding to the back surface portion of the flow passage 171a of the first flow plate 171 through which the sulfuric acid decomposition gas flows. Since it is set, the thermal shock caused by the gas generated by heating coming into contact with the other surface of the second flow plate 372 can be greatly reduced.

  Therefore, according to the present embodiment, the same effect as that of the first embodiment described above can be obtained, as well as the heat applied to the second flow plate 372 of the main body portion 370A of the decomposer 370. Since the impact can be suppressed as much as possible, the life of the main body 370A of the decomposer 370 can be extended.

[Fourth embodiment]
A fourth embodiment of a sulfuric acid decomposer and a hydrogen production apparatus using the sulfuric acid decomposer according to the present invention will be described with reference to FIG. FIG. 7 is an overall schematic configuration diagram of the sulfuric acid decomposer. In addition, about the part similar to the case of 1st-3rd embodiment mentioned above, by using the code | symbol similar to the code | symbol used in description of 1st-3rd embodiment mentioned above, the 1st mentioned above. The description overlapping with the description in the third embodiment is omitted.

  As shown in FIG. 7, the decomposer 470 according to the present embodiment has a supply port 475a to which liquid sulfuric acid is supplied on the lower side and a delivery port 475b on the upper side, and the main body 170A is made of sulfuric acid. An outer container 475 made of a highly corrosion-resistant material such as SiC or Si-SiC ceramics disposed inside so as to be immersed therein, and a heating gas from the outside of the outer container 475 to the supply manifold 173 of the main body 170A A heating medium supply pipe 476a made of highly corrosion-resistant material such as ceramics such as SiC or Si-SiC to be supplied, SiC, Si-SiC, etc. for sending a heating gas from the delivery manifold 174 of the main body 170A to the outside of the outer container 475, etc. And a heat medium delivery pipe 476b made of a highly corrosion resistant material such as ceramics.

  That is, in the first to third embodiments described above, sulfuric acid is circulated from the supply manifold 173 to the flow passage 171a of the first flow plate 171 and from the communication grooves 172b and 372b of the second flow plates 172 and 372, the flow passage 172a. In the present embodiment, the main body 170A is immersed in the liquid sulfuric acid in the outer container 475, so that the flow passage 172a from the communication groove 172b of the second flow plate 172 is circulated. Then, the sulfuric acid was circulated through the heating medium, and the heating gas was circulated from the heat medium supply pipe 476a to the flow passage 171a of the first flow plate 171 through the supply manifold 173.

  For this reason, in the decomposer 470 according to the present embodiment, the plates 171 and 172 of the main body 170 always come into contact with liquid sulfuric acid over the entire surface, so that the generated gas contacts the plates 171 and 172. Thermal shock can be greatly reduced.

  Therefore, according to this embodiment, it is possible to obtain the same effect as that of the first embodiment described above, as well as the case of the third embodiment described above. The thermal shock applied to the plates 171 and 172 of the main body 170A of the 470 can be suppressed as much as possible, the life of the main body 170A of the decomposer 470 can be extended, and the liquid level position of the sulfuric acid can be managed. This can be easily performed, and the operation control can be facilitated.

[Fifth embodiment]
A fifth embodiment of the sulfuric acid decomposer and the hydrogen production apparatus using the sulfuric acid decomposer according to the present invention will be described with reference to FIG. FIG. 8 is an overall schematic configuration diagram of the sulfuric acid decomposer. In addition, about the part similar to the case of the 1st-4th embodiment mentioned above, by using the code | symbol similar to the code | symbol used in description of the 1st-4th embodiment mentioned above, the 1st mentioned above. The description overlapping with the description in the fourth embodiment will be omitted.

  As shown in FIG. 8, the decomposer 570 according to the present embodiment has a supply port 571a to which liquid sulfuric acid is supplied on the lower side and ceramics such as SiC or Si-SiC having a delivery port 571b on the upper side. A shell 571 that is a cylindrical outer container made of a highly corrosion-resistant material such as, and a plurality of heats made of a highly corrosion-resistant material such as SiC or Si-SiC that is disposed inside the shell 571 and through which a heated gas flows. A tube 572 that is a medium circulation pipe, a supply manifold 573 that is disposed on one end side of the shell 571 and supplies heated gas to the tube 572, and a tube 572 that is disposed on the other end side of the shell 571 and flows through the tube 572. A main body 570A having a delivery manifold 574 for collecting the heated gas is provided.

  That is, in the first to fourth embodiments described above, the decomposers 170, 270, 370, and 470 including the plate-stacked main body portions 170A, 270A to 270C, and 370A are applied. The decomposer 570 provided with the and tube type main body 570A is applied.

  Therefore, according to this embodiment, it is possible to obtain the same effect as that of the first embodiment described above, as well as the case of the fourth embodiment described above. The liquid level position can be easily managed, and the operation control can be facilitated.

[Sixth embodiment]
A sixth embodiment of the sulfuric acid decomposer and the hydrogen production apparatus using the sulfuric acid decomposer according to the present invention will be described with reference to FIG. FIG. 9 is an overall schematic configuration diagram of the sulfuric acid decomposer. In addition, about the part similar to the case of 1st-5th embodiment mentioned above, by using the code | symbol similar to the code | symbol used in description of 1st-5th embodiment mentioned above, the 1st mentioned above. The description overlapping with the description in the fifth embodiment will be omitted.

  As shown in FIG. 9, the decomposer 670 according to the present embodiment is similar to the decomposer 470 according to the fourth embodiment described above, via a throttle member 677 a such as an orifice at the delivery port 475 b of the external container 475. A flash tank 677 made of a highly corrosion resistant material such as SiC or Si-SiC ceramics is connected, and the liquid sulfuric acid heated by the main body 470A is vaporized by being ejected from the throttle member 677a. It can be done. In FIG. 9, reference numeral 679 denotes a pressure pump.

  In such a decomposer 670, liquid sulfuric acid is pressurized and supplied to the inside of the outer container 475 (about 4 MPa) by the pressure pump 679, and the same as in the case of the fourth embodiment described above. When the liquid sulfuric acid is heated by the main body 170A, the heated and pressurized liquid sulfuric acid is jetted into the flash tank 677 through the throttle member 677a and gasified by a pressure drop (about 2 MPa).

  For this reason, in the decomposer 670, the liquid level of sulfuric acid can always be positioned at the portion of the throttle member 677a.

  Therefore, according to this embodiment, it is possible to obtain the same effect as that of the first embodiment described above, as well as the case of the fourth embodiment described above. The liquid level position can be easily managed, and the operation control can be facilitated.

[Seventh embodiment]
A seventh embodiment of the sulfuric acid decomposer and the hydrogen production apparatus using the same according to the present invention will be described with reference to FIG. FIG. 10 is an overall schematic configuration diagram of the sulfuric acid decomposer. In addition, about the part similar to the case of 1st-6th embodiment mentioned above, by using the code | symbol similar to the code | symbol used in description of 1st-6th embodiment mentioned above, the 1st mentioned above. The description overlapping with the description in the sixth embodiment is omitted.

  As shown in FIG. 10, the decomposer 770 according to this embodiment heats a flash tank 677 that vaporizes liquid sulfuric acid by ejecting liquid sulfuric acid from a throttle member 677 a such as an orifice, and gas collected in the flash tank 677. And a heater 778 which is a heating means. In FIG. 10, 779 is a compressor.

  In such a decomposer 770, liquid sulfuric acid in a pressure state (2 MPa) in the system is injected into the flash tank 677 from the throttle member 677a and gasified by depressurization (1 to 1.5 MPa). Then, after the gas is heated and decomposed by the heater 778, the gas can be pressurized and sent to the pressure state in the system by the compressor 779.

  That is, in the sixth embodiment described above, the liquid sulfuric acid is heated to a required temperature (550 to 850 ° C.) and higher than the pressure (2 MPa) in the system (4 MPa). In this embodiment, liquid sulfuric acid is reduced to a pressure in the system (2 MPa) in the flash tank 677 in a pressure state (2 MPa). By jetting, the pressure is reduced to a pressure state (1 to 1.5 MPa) lower than the pressure in the system and gasified, and then the gas is brought to a necessary temperature (550 to 850 ° C.) with a heater 778. The gas was heated to a pressure in the system (2 MPa) by the compressor 779 and then sent out.

  For this reason, in this embodiment, a general heater 778 using a corrosion-resistant metal material such as high Cr steel, Ni base steel, Co base steel or the like can be applied, such as SiC or Si-SiC. The use of a material having high corrosion resistance such as ceramics can be performed only in the flash tank 677 portion.

  Therefore, according to the present embodiment, it is possible to obtain the same effects as those of the first and sixth embodiments described above, as well as high corrosion resistance of ceramics such as SiC and Si-SiC. Since the number of locations where the material is used can be reduced, the manufacturing can be facilitated and the manufacturing cost can be reduced.

[Other Embodiments]
In the first to seventh embodiments described above, the case where the present invention is applied to a hydrogen production apparatus that produces hydrogen using iodine has been described. However, in the hydrogen production apparatus that produces hydrogen using bromine instead of iodine. Even if it exists, it can apply like the case of the 1st-7th embodiment mentioned above.

  Furthermore, in the first to seventh embodiments described above, the case where the present invention is applied to a hydrogen production apparatus has been described. However, the present invention is not limited to this, and the present invention can be applied without any problem as long as sulfuric acid is decomposed.

  The sulfuric acid decomposer according to the present invention and the hydrogen production apparatus using the same can improve the thermal efficiency related to sulfuric acid decomposition, and can produce hydrogen at a low cost. Can do.

It is a schematic block diagram of 1st embodiment of the hydrogen production apparatus which concerns on this invention. 1 is an overall schematic configuration diagram of a first embodiment of a sulfuric acid decomposer according to the present invention. It is a block diagram of the principal part of the sulfuric acid decomposer of FIG. It is a whole schematic block diagram of 2nd embodiment of the sulfuric acid decomposer which concerns on this invention. It is a whole schematic block diagram of 3rd embodiment of the sulfuric acid decomposer which concerns on this invention. It is a block diagram of the member of the principal part of the sulfuric acid decomposer of FIG. It is a whole schematic block diagram of 4th embodiment of the sulfuric acid decomposer which concerns on this invention. It is a whole schematic block diagram of 5th embodiment of the sulfuric acid decomposer which concerns on this invention. It is a whole schematic block diagram of 6th embodiment of the sulfuric acid decomposer which concerns on this invention. It is a whole schematic block diagram of 7th embodiment of the sulfuric acid decomposer which concerns on this invention. It is a whole schematic block diagram of an example of the conventional hydrogen production apparatus. It is a whole schematic block diagram of an example of the conventional sulfuric acid decomposer.

Explanation of symbols

DESCRIPTION OF SYMBOLS 101 Hydrogen recovery container 102 Oxygen recovery container 110 Reaction container 120 Separator 121 Switching valve 130 Concentrator 140 Decomposer 150 Cooling separator 160 Concentrator 180 Cooling separator 170,270,370,470,570,670,770 Decomposer 170A , 270A to 270C, 370A, 570A body 171 first flow plate 171a flow passage 171b, 171c communication hole 172, 372 second flow plate 172a, 372a flow passage 172b, 172c, 372b communication groove 172d, 172e communication hole 173, 273 Supply manifold 174, 274 Delivery manifold 270a Mixing space 274a Mixing space 475 External container 475a Supply port 475b Outlet 476a Heat medium supply pipe 476b Heat medium supply pipe 571 Shell 572 Over Bed 573 supply manifold 574 sends manifold 677 flash tank 677a diaphragm member 679 pressurizing pump 778 heater 779 compressor

Claims (8)

A flow path is formed on one surface, and a first flow plate formed with a pair of communication holes penetrating between the one surface and the other surface and communicating with the flow path;
A flow passage is formed on one surface, a communication groove that forms a pair that connects the flow passage and the outside is formed, and a communication hole that communicates with the communication hole of the first flow plate is formed. The second distribution plate,
A plurality of layers are alternately stacked such that one surface of one plate faces the other surface of the other plate,
A supply manifold that communicates with one of the connection holes of the plate is disposed on one side in the stacking direction of the plates,
On the other side in the laminating direction of the plate, a main body portion is provided that is provided with a delivery manifold that communicates with the other of the communication holes of the plate.
Either one of sulfuric acid or a heat medium is supplied into the supply manifold, and either the sulfuric acid or the heat medium is supplied into the communication groove of the second flow plate. . In claim 1,
A plurality of the main body portions are connected in series,
At least one of the supply manifold and the delivery manifold has a mixing space that makes the temperature distribution of the flowing sulfuric acid or heating medium uniform,
Between the communicating grooves of the second circulation plate of the main body parts that are connected in series and adjacent to each other, a mixing space part that makes the temperature distribution of the circulating sulfuric acid or the heat medium uniform is provided. Sulfuric acid decomposer. In claim 1,
The sulfuric acid is characterized in that the flow passage of the plate through which the heat medium flows is set so as not to face the other surface corresponding to the back surface portion of the flow passage of the plate through which the decomposition gas of sulfuric acid flows. Decomposer. In claim 1,
An external container having a supply port to which liquid sulfuric acid is supplied on the lower side, a delivery port on the upper side, and being disposed inside so that the main body is immersed in sulfuric acid;
A heat medium supply pipe for supplying a heat medium to the supply manifold of the main body from the outside of the external container;
A sulfuric acid decomposer comprising: a heat medium delivery pipe for delivering a heat medium from the delivery manifold of the main body to the outside of the outer container. In claim 4,
A sulfuric acid decomposer, comprising: a flash tank connected to the delivery port of the outer container via a throttle member. A cylindrical shell having a supply port to which liquid sulfuric acid is supplied on the lower side and a delivery port on the upper side;
A sulfuric acid decomposer comprising: a shell and tube type main body having a tube disposed inside the shell and through which a heat medium flows. A flash tank that vaporizes liquid sulfuric acid by ejecting it from the throttle member;
And a heating means for heating the gas collected in the flash tank. A reaction means for reacting a halogen of iodine or bromine with sulfur dioxide and water to produce an aqueous sulfuric acid solution and an aqueous hydrogen halide solution;
Separation means for separating the sulfuric acid aqueous solution and the hydrogen halide aqueous solution by the specific gravity difference;
A hydrogen halide concentrating means for concentrating the separated aqueous hydrogen halide solution,
Hydrogen halide decomposition means for decomposing the concentrated hydrogen halide into halogen and hydrogen;
A halogen recycling means for isolating the hydrogen produced by decomposition, and supplying the halogen produced by decomposition to the reaction means;
Sulfuric acid concentration means for concentrating the separated sulfuric acid aqueous solution;
A sulfuric acid decomposition means for decomposing the concentrated sulfuric acid into sulfur dioxide, oxygen and water;
In the hydrogen production apparatus, comprising sulfur dioxide recycling means for supplying at least sulfur dioxide to the reaction means among the decomposed sulfur dioxide, oxygen, and water,
The sulfuric acid decomposition means
The hydrogen production apparatus according to claim 1, wherein the sulfuric acid decomposer is any one of claims 1 to 7.

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