JPH07144901A - Hydrogen generation facility - Google Patents

Abstract

PURPOSE:To provide a highly efficient hydrogen generation facility by reducing an iron oxide with a reduction device provided with a cooler and bringing the product into contact with steam in a hydrogen generating equipment having a heater. CONSTITUTION:An iron oxide M (e.g. Fe3O4) is introduced into a reduction device A provided with a cooling heat exchanges AX and AX', cooled, if necessary, and then reduced to form an oxygen-deficient active oxide AM or metallic iron. The formed active oxide AM or metallic iron is supplied to a hydrogen generating device H furnished with heating heat exchangers HX and HX', heated and brought into contact with steam (m) to generate hydrogen. The active oxide AM is oxidized at the same time to the iron oxide M, the iron oxide M is again introduced into the reduction device A, heat-exchanged with a cooling medium, cooled and the reduced. The process is repeated to produce hydrogen.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a hydrogen generating facility. More specifically, the present invention reduces the iron-based oxide to generate oxygen-deficient active oxide or metallic iron, and brings the active oxide or metallic iron into contact with steam to form the iron-based oxide. It is related to a hydrogen generation facility that generates hydrogen while returning it.

[0002] The hydrogen generating equipment of the present invention is also used in a gas turbine or a combined power generation plant or installed in a nuclear power generation plant.

[0003]

2. Description of the Related Art Production of hydrogen (H ₂ ) on a commercial scale is performed by electrolysis of pure water. FIG. 15 shows a conventional water electrolysis device. In the electrolyzer, pure water is electrolyzed into hydrogen gas and oxygen gas by a direct current and taken out separately.

On the other hand, in a gas turbine or a combined power generation plant, the heat retained in the exhaust gas from the gas turbine is converted into steam by an exhaust heat recovery boiler HRSG. FIG. 16 shows a conventional combined power generation plant. HRSG typically consists of feed water heater ECO, evaporator EVA, superheater SH, SH and
The steam from the EVA is sent to the steam turbine ST to generate electricity, and the steam discharged from the steam is condensed by the condenser COND.
It is circulated and used for water supply.

In the gas turbine GT, after the atmospheric pressure (a) is boosted by the compressor C, it is used for combustion of the fuel (f) in the combustor CC, and is recovered as power by the turbine T, and the compressor is used from the power. The part with the load reduced is taken out from the generator GEN as electric power. Exhaust gas (e) discharged from the turbine is HR
Heat is recovered by SG and then released from the stack STCK. In addition,
In the exhaust heat recovery boiler shown in Fig. 16, the high pressure evaporator EVA (H
High pressure steam is generated in P) and low pressure steam is generated in the low pressure evaporator EVA (LP). High pressure steam can be mixed at the head of the steam turbine ST and low pressure steam can be mixed at the intermediate stage to generate electricity. If the steam turbine is a condensing turbine, condensate COND is also used to use condensate for HRSG water supply.

[0006] When using H ₂ as a fuel in a gas turbine or a combined power generation plant or when mixing H ₂ for calorie up of gas fuel, at present, either a H ₂ gas tank or a liquefied H ₂ tank is used. Must be attached. Alternatively, as shown in FIG. 17, a part of the generated power must be used to produce H ₂ onsite.

In this case, the pure water prepared by the pure water device D is stored in the pure water tank TK, and then the pure water is supplied to the electrolytic device R and the system power is converted into direct current by the AC / DC converter AC / DC. Then, R is operated to generate H ₂ gas.

[0008]

[Problems to be Solved by the Invention] An H ₂ production facility is installed side by side with a gas turbine or a combined power generation plant.
_In order to produce ₂ gas, it is necessary to consume valuable electric power obtained from a power plant. In this case, the efficiency of electrolysis of water is about 66% in power energy conversion efficiency, and only 60 to 70% of input power is converted to H ₂ energy.
If the fuel energy is 100%, 1/3 to 1/4 of the energy becomes H ₂ .

[0009] Further, the efficiency of electrolysis of water when using the electric power generated by nuclear power generation depends on the nuclear energy (heat).
At 100%, only 1/4 of the energy becomes H ₂ .

Further, since a large amount of pure water is consumed by electrolysis, a pure water device is necessary.

[0011]

The inventor has reduced the iron-based oxide to generate an oxygen-deficient active oxide or metallic iron, and contacting the active oxide or metallic iron with steam to produce the iron-based oxide. The present invention has been accomplished by finding a new hydrogen generation system that generates hydrogen while returning to oxides.

Therefore, an object of the present invention is to reduce an iron-based oxide to produce an oxygen-deficient active oxide or metallic iron, and contact the active oxide or metallic iron with steam to produce the iron-based oxide. In addition to the above, in a hydrogen generation facility for generating hydrogen, a reduction device for reducing the iron-based oxide, and a hydrogen generation device for generating hydrogen by contacting the active oxide or metallic iron with steam are included. In the hydrogen generating equipment, the reducing device is provided with a cooling device and the hydrogen generating device is provided with a heating device.

[0013]

The basic operation of the iron oxide used in the hydrogen generating equipment according to the present invention is shown in FIG. (1) First, reduction is performed to produce an oxygen-deficient active oxide or metallic iron that easily absorbs oxygen (operation I). The active oxide has an arbitrary composition between Fe ₃ O _4-δ (δ indicates the oxygen deficiency state) to Fe. Both can exhibit the following basic performance.
As a method of reduction, various general methods can be applied,
For example, in addition to the simplest use of H ₂ (at high temperature), heating in an oxygen-free gas / vacuum, high-voltage treatment at high temperature, electron charging, static electricity, nitrogen ion charging and the like are included. (2) Next, steam is made to act on this active oxide to generate H ₂ O.
H ₂ is produced by recovering O in the iron-based oxide (operation II). (3) thermal status of the system in operation I, the heat accompanying the reduction with a reducing means of the metal (when H ₂ reduction H ₂ + O → H ₂ O heat generation) of the exothermic reaction ~ endothermic reaction by excess or deficiency of the The degree varies. (4) In the hydrogen generation of the operation II, steam (H ₂ O) is changed to H ₂ and the energy level is improved. Since this reaction is an endothermic reaction, H ₂ is generated in proportion to the total amount of heat input from the outside and heat of metal oxidation.

FIG. 2 shows each function of the equipment constituting the hydrogen generating equipment according to the present invention.

For convenience of explanation, it is assumed that the hydrogen generator H and the reducer A are divided, and the active oxide (AM) and the iron-based oxide (including metallic iron) (M) move between them. ,
Achieves the reaction cycle shown in Fig. 2, including the case where H and A are integrated and AM and M are built in as a fixed bed (heating heat exchanger (HX) and cooling heat exchanger (AX) are also built in) Everything that you do is subject to this technology. (1) The AM reduced by A is supplied to H and brought into contact with water vapor (m). (2) m becomes H ₂ gas and is taken out of the system, but for this endothermic reaction, heating fluid is put into HX for heating. (3) At this time, since AM is oxidized and returns to M, it is transferred to A again and reduced. When cooling is required at A, the cooling fluid is added at AX to cool it. (4) If the cooling in A and the heating in H are balanced in calorific value and temperature, heat is generated between the heating heat exchanger and the cooling heat exchanger (HX'-AX '). The medium (d) can be circulated, and effective use of heat can be achieved. In some cases,
Heat pipes can also be used. The use of this AX'-HX 'is particularly effective when the heat exchange with the outside of the system is small or impossible. (5) Although any of the above-mentioned methods can be adopted as the reduction method carried out in A, when a separate gas (H ₂ , inert gas, etc.) is used, a reducing gas (v) is added to contain oxygen. Gas and residual reducing gas (v ') are discharged. For example, when v is H ₂ , H ₂ O is included in v ′, and when it is an inert gas, O ₂ is included in v ′, and O removed from M is discharged as some compound or O ₂ .

FIG. 2 illustrates the functions. As a concrete device, there are a divided structure (system) having a moving function of AM and M, and a device which is integrally formed and does not move the metal oxide. is there.

The action of the iron-based oxide will be described by taking Fe ₃ O ₄ as an example. Although Fe ₃ O ₄ is currently the most influential one, the system of the present invention can be applied to ferrite alloys (nickel / ferrite, etc.) that can exhibit similar ability. It holds. Reaction system 1 is a case where an iron-based oxide is reduced to pure iron before use, and the reaction is the simplest. The chemical equation is H ₂
Although it displayed in reduced, using a reducing method other than H ₂ H ₂
Four molecules (per mole of magnetite) can be produced. The reaction system 2 is a case where an iron-based oxide is partially reduced (activated) and used, and is characterized in that CO ₂ is fixed on the surface and goes through a carbon deposition state. Although this series of chemical reaction formulas is also represented by H ₂ reduction, hydrogen can be produced by using reduction methods other than H _2.
/ 12δ mol (per mol magnetite) can be produced. Here, since δ can take any value, the optimum value is used.

When H ₂ reduction is also used as in these equations, it is necessary to dehumidify the produced H ₂ O (moisture separation). The reaction temperature range can be, for example, in the range of 300 to 400 ° C., but a lower temperature range can be expected depending on the ferrite alloy.

[0019]

EXAMPLE The basic structure of the hydrogen generating equipment of the present invention has been described with reference to FIG. 2, of which the hydrogen generating apparatus H will be described in detail with reference to FIG.

FIG. 3 (A) shows an apparatus used for carrying out the hydrogen generation reaction of the above reaction system I, which is an active oxide (AM).
Comes into contact with water vapor (m) to form H ₂ gas. As a method of contacting AM with m, a method of a general chemical engineering machine can be used, and for example, a fluidized bed (for example, AM is fluidized by m), a packed bed (for example, m flows in the AM layer), or the like is used.

Meanwhile, FIG. 3 (B), an apparatus that separately ingredient hydrogen generation reaction in the reaction system 2 is used when the involved gas contact device prior to contact with the steam (m) T _H
Since the active oxide (AM) is previously reacted with the adjusting gas (q) in (1), the produced gas is a mixed gas of H ₂ and other components.

No treatment is required even if the mixed gas does not interfere with the subsequent use, but when pure H ₂ is required, other components are separated by the gas separator S _H. In that case, the separation gas (p) can be reused as the adjustment gas (q). In the reaction system 2, CO ₂ gas is circulated and used.

The basic configuration of FIG. 2 describes the connections between the elements, but it can be performed either by making each element as a device or configuring it as a system or by integrating the elements of this figure as a device. Performance is the same.

The reducing device A and the hydrogen generating device H of FIG. 2 are operated at the same time. That is, the reduction operation and the hydrogen generation operation are simultaneously performed, and the movement of the active oxide (AM) and the iron-based oxide (M) is constantly circulated, or the movement is completed in a batch in a short time. good.

FIG. 4 shows an example of the integrated device.

The partition W divides the reducing apparatus A and the hydrogen generating apparatus H, and a heat pump circulating (AX 'to HX') a heat medium (d) exemplifies both.

The liquid heat medium (d ₁ ) is vaporized by heat absorption in the cooling heat exchanger AX 'of the reduction device, and is radiated to the hydrogen generator H in the heating heat exchanger HX' to release the gaseous heat medium (d ₁ ). ₂ ) condenses and circulates.

On the other hand, in order to circulate the heat medium with a pump,
A general configuration in which the pipe ends of HX 'and AX' are out of the system is also possible.

The method of moving AM and M and simultaneously using A and H is the same as in FIG. In addition, T _H and S _H can be installed together if necessary.

Although the method of moving AM and M has been described above, FIGS. 5 and 6 show a specific example of a method in which the reaction of AM⇔M is carried out in a fixed bed and the reaction is not carried out. The former is a type in which a metal oxide is also filled around the heat exchanger, and the latter is a type in which a space is secured around the heat exchanger. The features common to both are as follows. (1) Heat exchangers HX and AX are installed together. (2) Gas is allowed to pass through, and partition walls Wo (perforated plate, etc.) are used to hold the metal. One side is filled with an iron-based oxide, and a reducing gas (v) and an adjusting gas (q), if necessary, are introduced from the space. (3) When separating the mixed gas separately, gas separation device _SH
Be installed.

When a method other than the reduction with the gas (v) is adopted, the equipment required for the iron-based oxide filling section is appropriately installed.

For continuous operation of the system, a plurality of these units are arranged in parallel, and the reduction operation is performed one by one.

Although the apparatus shown in FIG. 5 is compact, the filling metal must be discharged when inspecting the heat transfer tube.

On the other hand, in the apparatus shown in FIG. 6, the filling metal and the heat transfer tube are separated for each block. In this case, although the apparatus is large, the heat transfer tubes can be easily inspected, and the fluid is uniformly mixed in the space of the heat transfer tube group, so that the reaction can be made uniform. When the fluid (v) is used, it is put into the HX section (v ₁ ), the flow is made uniform, and then it is passed through the metal block (v ₂ ) and discharged (v ₃ ). In this case, HX is used when heating is required and AX is used when cooling is required.

The reduced exhaust gas is discharged at v ', but when there are other components (for example, H ₂ O) and condensate, they are discharged as reduced exhaust gas (y) (FIG. 5). In FIG. 6 as well, the space under Wo and y are used together if necessary.

The iron-based oxide may have any shape. For example, powdery, granular, pellet (cylindrical),
Honeycombs, brick blocks, etc. can be used, but AM
It is suitable to use powders / granules / pellets for moving M to M, and honeycombs / blocks for uniform filling when not moving.

The specific example of the hydrogen generating equipment according to the present invention has been described in detail above. Next, an application example in which the hydrogen generating equipment is incorporated into a gas turbine combined power generation system and a nuclear power generation system will be described.

FIG. 7 shows an example in which the hydrogen generating equipment according to the present invention is incorporated in a gas turbine combined power generation system (see FIG. 16). However, the present technology has high general applicability if there is a heat source / cooling source / source steam.

In FIG. 7, the hydrogen generating equipment according to the present invention is incorporated in a conventional gas turbine combined power generation system, and the steam system of the exhaust heat recovery boiler HRSG and the hydrogen generator H are connected. More specifically, the evaporator EVA (HP) of the exhaust heat recovery boiler and the heating heat exchanger HX of the hydrogen generator are connected via the heat source steam header HD and the EV
Separated from the A to HD conduit, this conduit is connected to H.

Further, the hydrogen generator H and the hydrogen storage facility HT
A hydrogen cooler HTR is installed between and to indirectly exchange heat with the water supply system from the condenser COND of the steam turbine ST to the water supply preheater PRE of the exhaust heat recovery boiler.

After the H ₂ gas generated by the hydrogen generator H is cooled by the hydrogen cooler HTR to recover heat, the hydrogen storage facility H
Store at T. From here, the H ₂ gas is supplied to the fuel mixer MX, mixed with the fuel (f), and then combustor CC of the gas turbine.
To be used for burning in. Due to the balance between the generation and consumption of H ₂ gas, surplus will be paid out to the market (MT) and shortage will be replenished from the market.

The features of this system are as follows. (1) The high-pressure steam of the exhaust heat recovery boiler is used as the heat source steam of the heat exchanger HX for heating the hydrogen generator, and is also used as the raw material steam (H ₂ O → H ₂ ) (m) in the hydrogen generator H. . High-pressure steam is injected into HX via steam header HD. If superheated steam is required, add steam from the superheater SH to the HD as appropriate. (2) Latent heat (and sensible heat) of high-pressure steam in the heat exchanger HX for heating
Is used to secure the maximum amount of heat used for a constant reaction temperature and amount of steam. (3) The drain (condensed water) from the heat exchanger HX for heating is fed again to the high-pressure evaporator EVA (HP). On the other hand, when the heat absorption in the cooling heat exchanger AX of the reduction device A is large, the drain is reused as steam by AX and again as heat source steam by the heat source steam header HD. (4) Cooling heat exchanger when cooling is required in the reduction device A
AX ″ is also installed side by side to cool by using the feed water from the condenser COND of the steam turbine ST. Also, the hydrogen gas from the hydrogen generator H has sensible heat (for example, 300 to 400 ° C). Store in HT after cooling with hydrogen cooler HTR.

Also in this case, since the feed water is used as the cooling water for the hydrogen cooler HTR and then fed to the feed water preheater PRE, heat exchange from the gas turbine exhaust to the feed water preheater PRE is reduced. (5) The hydrogen storage facility HT is a facility having a general storage capacity, and can utilize, for example, an H ₂ gas tank, a liquefaction facility and an L-H ₂ tank, and an H ₂ storage alloy. (6) Calories can be increased by mixing a part of the generated H ₂ gas with the fuel (f) in the fuel mixer MX. In addition, when the fuel is H ₂ , it can be saved. (7) When the amount of water in the GT exhaust increases due to the increase of H _{2 in} the fuel, the dehumidifier DEH is also used to prevent white smoke from the stack STCK (in winter). The recovered water of DEH is mixed with tap water and supplied to the system as make-up water (aw) to supplement the water consumed for H ₂ production. (8) optionally used gas contact device T _H and the gas separator S _H constituting the hydrogen generating apparatus H.

For example, in reaction system 1, both T _H and S _H are omitted, and in reaction system 2, both T _H and S _H are used to obtain high purity H.
Generates ₂ .

Furthermore, when it is used as an auxiliary gas turbine fuel and H ₂ of high purity is not required, only T _H can be used in the reaction system 2 and S _H can be omitted.

For convenience of description, the hydrogen generating equipment is shown as the hydrogen generating apparatus H and the reducing apparatus A being separated, but an integrated type shown in FIGS. 4-6 can be used, and the configuration and function are the same. Is.

Next, FIGS. 8-10 show some specific examples in which the hydrogen generating equipment of the present invention is incorporated in the main steam system of a nuclear reactor.

The features of these systems are as follows. (1) Hydrogen generator H is used for high pressure main steam (SS) of reactor AR
Is used as a heat source steam in the heating heat exchanger HX of FIG. 1 and the steam from the secondary system is used as a raw material steam (m) of the hydrogen generator H. High-pressure steam is introduced into the heating heat exchanger HX via the main steam pipe. When superheated steam is required, the optimum steam is put into the HX as appropriate. (2) The latent heat (and sensible heat) of the main steam is used in the heat exchanger HX for heating to secure the maximum usable heat quantity for a constant reaction temperature and steam quantity. (3) The drain (condensate) (ds) in the heating heat exchanger HX is charged again into the evaporator in the reactor (line I). On the other hand, when the heat absorption in the cooling heat exchanger AX of the reduction device A is large, the drain (ds) is used for cooling to make steam again, and the steam header HD is used as heat source steam again (Fig. 10). Steam is supplied to the secondary steam header HDR (Figs. 8 and 9). (4) When the condensed water (ds) needs to be cooled, the feed water heater HT
R1 and HTR2 are also installed to heat the water supply. Since the H ₂ gas from the hydrogen generator H has sensible heat (for example, 300 to 400 ° C.), it is cooled by the hydrogen cooler HTR and then the hydrogen storage facility H.
Store in T. The feed water of the adjacent power generation plant is used as the cooling water for this hydrogen cooler HTR, and steam is generated in the cooling heat exchanger AX of the reduction device A or the feed water preheater of the exhaust heat recovery boiler HRSG of the secondary gas turbine GT. Since it is put into the PRE, heat exchange from the GT exhaust to the PRE becomes small. (5) The hydrogen storage facility HT is the same as that in the combined power generation plant. (6) A part of the generated H ₂ (f *) is mixed with the fuel (f) of the gas turbine in the side-by-side power plant in the fuel mixer MX to increase calories. The fuel (f)
Can be saved when is H ₂ . (7) When water in the GT exhaust increases due to an increase in H ₂ in the fuel (f), the dehumidifier DEH also removes water in order to prevent white smoke from the stack STCK (in winter). The recovered water of DEH is mixed with clean water and supplied to the system as make-up water (aw) for the adjacent power plant to supplement the water consumed for H ₂ production. On the other hand, when configuring the closed cycle gas turbine GT of H ₂ O, the exhaust heat recovery boiler HRSG outlet is recirculated to the compressor inlet. (8) The raw material steam (m) used in the hydrogen generator H is taken out from the steam line of the secondary system isolated from the primary system. Low-pressure steam from the exhaust heat recovery boiler HRSG, and high-pressure steam as needed are input to the steam header HDR to control the conditions of the raw material steam (m). The generated steam (as) generated in the cooling heat exchanger AX of the reduction device (Figs. 8 and 9) and the process steam (ps) (Figs. 8, 9 and 10) from outside the system can also be collectively used in HDR. .
Further, the steam from the steam header HDR may be mixed with the steam turbine ST and used for power generation. (9) H ₂ gas (MT) is appropriately shipped from the hydrogen storage facility HT to the market. (10) In the specific example shown in FIG. 9, the steam generator SG is configured by the feed water heater HTR1 and the steam generator EVA1, and the steam generated here can be used in the steam header HDR (secondary system). (11) In the specific example shown in FIG. 10, the condensate (ds) from the heating heat exchanger HX of the hydrogen generator is cooled by the reducing device.
It is thrown into AX and reused as steam again with steam header HD. In this case, steam from the reactor AR will be used as a supplement to the steam balance at HD.

Further, another specific example in which the hydrogen generating equipment of the present invention is incorporated in a combined power generation system is shown in FIG.
Will be described with reference to. Such systems are intended to produce large amounts of hydrogen.

This specific example is substantially the same as the example described with reference to FIG. 7, except that the exhaust heat recovery boiler HRSG is provided with a high pressure evaporator EVA (HP) (and a feed water heater ECO if necessary). (As a set) are arranged in series, and the vapor from each evaporator is collected by the vapor header SHD and supplied to the vapor header HD, which is then supplied to the hydrogen generator H and used as the raw material vapor (m) of H. And used as a heat source for the heating exchanger HX. Condensate generated by heat exchange in the HX is supplied to the feed water header WHD and recirculated to each feed water heater ECO. In addition, exhaust treatment equipment is installed downstream of a series of high-pressure evaporator EVA (HP).

The features of this system are as follows. (1) O ₂ remaining in the gas turbine GT exhaust (e) is reburned (fuel input) until it reaches 0% to extract the maximum amount of steam heat. (2) Although the energy converted to hydrogen is the heat recovered in (1) above, a large number of similar sets are used for heat utilization in the high-pressure evaporator EVA (HP) -feed water heater ECO.

In the EVA (HP) -ECO region of FIG. 12, T _E ′ → T _B
The exhaust gas whose temperature has been raised by the fuel injection is repeated up to T _F (T _F → T _B ) to recover heat (# 1 to #n).

Regarding the last stage (ie, evaporator #n) and thereafter, FIG. 11 shows the configurations of the low-pressure evaporator EVA (LP), feed water heater ECO, deaerator / evaporator DEA, and feed water preheater PRE, but it is optional. Can be configured.

In the specific example of FIG. 11, a plurality of sets of (EVA (H
The use destination of the steam obtained in (P) -ECO) is steam header SHD
After passing through, there are two main steam line of superheater SH and heating steam line to steam header HD.

A plurality of outlet lines of the heat exchanger HX for heating of the hydrogen generator H are connected to a plurality of sets of E via the feed water header WHD.
It is circulated and used at the entrance of CO. However, when the heat recovery AX of the reduction device is also expected to recover heat, a part of the condensate is used to obtain steam again, and the steam is circulated to the steam header HD. The steam from the steam header SHD on the HRSG side of the exhaust heat recovery boiler will make up for the lack of balance between the hydrogen generator and the reducer. For heat control in HD
The use of SH outlet steam is the same as in the example of FIG. 7. (3) Exhaust treatment equipment RCO is a general equipment such as denitration equipment, CO ₂ recovery equipment, etc., and is installed downstream of a series of high-pressure evaporator EVA (HP) (with feed water heater ECO if necessary). . For example, an exhaust gas CO ₂ recovery device is provided on the downstream side of EVA (HP) -ECO # n. Since the residual exhaust gas O ₂ ≈0%, it is optimal for an exhaust gas treatment system that does not like the coexistence of O ₂ . For example, active metal oxides have the ability to deposit and fix carbon solids on their surface when they come into contact with CO _2, and this exhaust treatment facility is utilized.

[0056]

The hydrogen generating equipment according to the present invention has the following effects. 1. H ₂ can be generated without using electric power and pure water. 2. H ₂ can be produced from a heat source at 300 to 400 ° C. or lower and steam. Further, its purity is extremely high, and H ₂ having a purity of 100% can be produced depending on the conditions, so that separation and purification are unnecessary.

In addition to the above effects, the following effects can be obtained in the concrete example shown in FIG. 1. Since the generated H ₂ is mixed with the fuel to increase calories, the fuel can be saved. Moreover, in the case of a hydrogen combustion gas turbine, the consumption of liquid hydrogen can be similarly saved. 2. The hydrogen generation reaction is 300-500 ℃ at the gas turbine exhaust temperature.
It is a chemical endothermic system that can be used in the region. (1) As a famous chemical endothermic system, there is a methanol reforming system represented by the following reaction formula, but since the product is a mixed gas, separation of H ₂ is required (to use as it is, to a gas turbine) There is only direct input). Steam reforming CH ₃ OH + H ₂ O → CO ₂ + 3H ₂ decomposition CH ₃ OH → CO + 2H ₂ On the other hand, in the case of the present invention, high purity H ₂ is obtained, and even if separation is required, it is extremely high. Small size is all right, and even if it is put into the gas turbine as it is, the effect of increasing calories is great. From the viewpoint of H ₂ purification, the system of the present invention is excellent. (2) In addition, since only the fuel consumed by the gas turbine is handled in the methanol treatment, only about 50% of the heat retained in the gas turbine exhaust can be utilized quantitatively. Therefore, from the remaining 50% of the heat quantity, steam turbine drive using steam, that is, combined use, or steam injection to the gas turbine will be used together. However, in the case of combined use, the warm waste water of the steam turbine condenser and in the case of steam injection, H ₂ O in the exhaust becomes a system loss, and the overall efficiency of the system decreases. On the other hand, in the system of the present invention, since most of the recovered steam of the gas turbine exhaust can be converted into H ₂ , the above system loss can be further reduced and the efficiency of the entire plant can be improved. 3. In addition to using the generated H ₂ in the plant, it can be sold to the market, which is advantageous for reducing plant operating costs and amortizing construction costs (highly economical). In other words, in addition to the system of the present invention, all the generated power is H ₂ production (water electrolysis).
It is possible to build an H ₂ manufacturing plant (cogeneration system) that is suitable for this. 4. When evaluated as a hydrogen production plant, energy conversion efficiency is improved. (1) Conventional CC plant; 24-35% of fuel is converted to H ₂ energy (water electrolysis at total power generation). (2) Plant of the present invention; 54% of the fuel is converted to H ₂ energy (H ₂ 26% by chemical endotherm + water electrolysis H ₂ 28% at total power generation). 5. Utilizing the generated H ₂ to save gas turbine fuel,
For improving plant power generation efficiency, for example, about 30%
Fuel consumption can be saved and significant improvements can be made. (1) CC power generation efficiency: 50% (conventional) (2) CC power generation efficiency in the plant of the present invention: 60% 6. In the reduction operation of metal oxides and the hydrogen generation operation, the heat due to the change of the metal oxide itself and the heat on the gas phase reaction side often reverse the absorption and heat generation. The heating amount and cooling amount are reduced as compared with the case of paying attention to the gas phase reaction. The degree of improvement in each of the above 4 and 5 has room for further improvement because it focuses on the gas phase reaction (Fig. 13). 7. When operating the reducing device and the hydrogen generator at the same time,
The reduction heat difference Q _A can be transferred to the hydrogen production heat difference Q _H for use. It is also possible to generate steam in Q _A and recycle it to steam Heder HD (Fig. 14). Under the conditions illustrated in Fig. 13, Q
_Although it is almost reversible when _A = Q _H , the characteristic of the system of the present invention is that (i) the reduction operation is performed other than H ₂ , and (ii) H ₂ is obtained in the hydrogen generation operation. _A and Q _H
A slight difference in balance occurs, and the heat is transferred to and from the steam header HD to balance the difference. The degree of the improvement in the 4 and 5, since the evaluation as to cover the Q _H only heat input to the steam Heda HD from the plant side, if you can utilize Q _A, in correspondingly to the HD Heat input can be saved and there is room for further improvement. 8. Next, when the reduction operation is performed by a means other than H ₂ , it is expected that the heat absorption amount H _B on the metal side will be dominant and that a factor of temperature increase (electromagnetic force, etc.) will be added (see FIG. 13). (I) When Q _A <0 in the reduction operation). In that case, the reduction device A
The cooling heat exchanger AX in Fig. 13 is configured as a heating heat exchanger as in the hydrogen production operation (ii) in Fig. 13. The heating source and the transfer destination of the condensate are arbitrary, but may be unified with the H side as shown in the figure.

The peculiar effects of the specific example shown in FIGS. 8-10 are as follows. 1. When evaluated as a hydrogen production plant, energy conversion efficiency is improved. (1) Combined conventional nuclear power plant and water electrolysis plant; 23% of nuclear reactor heat is converted to H ₂ energy (water electrolysis with total power generation). (2) The plant of the present invention; Almost 100% of the reactor heat is converted to H ₂ energy (because the thermal energy is used directly without using electric power). 2. The reactor can be of the conventional power generation grade, with a main steam temperature of 300.
A temperature of ~ 400 ° C is enough. Therefore, 900 ℃ like high temperature gas furnace
No class heat source is required and could be the first plant to utilize reactor heat for chemical purposes.

Further, the peculiar effects of the specific example shown in FIG. 11 are as follows. 1. In the exhaust heat recovery boiler, an exhaust gas treatment system (generally all) that does not like residual O ₂ such as a system that fixes CO ₂ from the exhaust gas and recovers CO ₂ by carbon deposition can be applied. 2. Exhaust heat recovery boiler performs multistage reburn (or auxiliary combustion),
Since the fuel is fed until O ₂ in the exhaust gas becomes 0%, the maximum steam generation can be obtained. 3. The maximum hydrogen production capacity can be obtained by utilizing this large amount of high-pressure steam for hydrogen conversion. Almost 100% of the reburning (or supporting) fuel energy can be effectively converted to hydrogen energy. This is because as shown in Fig. 12, the high-temperature condensate that used latent heat in the heating heat exchanger HX of the hydrogen generator is circulated again to the exhaust heat recovery boiler HRSG, and this condensate is used without cooling. (Exhaust T _B → T _F
Repeated heat recovery).

[Brief description of drawings]

FIG. 1 is a diagram showing a basic operation of hydrogen generation according to the present invention.

FIG. 2 is a diagram showing each function of the constituent equipment of the hydrogen generation equipment according to the present invention.

FIG. 3 is a diagram showing one specific example of a hydrogen generation apparatus that constitutes hydrogen generation equipment according to the present invention.

FIG. 4 is a diagram showing one specific example of the hydrogen generation equipment according to the present invention.

FIG. 5 is a diagram showing another specific example of the hydrogen generation equipment according to the present invention.

FIG. 6 is a diagram showing another specific example of the hydrogen generation facility according to the present invention.

FIG. 7 is a diagram showing a specific example in which the hydrogen generation facility according to the present invention is used in a combined power generation plant.

FIG. 8 is a diagram showing a specific example in which the hydrogen generation equipment of the present invention is used in a nuclear power plant.

FIG. 9 is a diagram showing another specific example in which the hydrogen generating equipment of the present invention is used in a nuclear power plant.

FIG. 10 is a diagram showing another specific example in which the hydrogen generation equipment of the present invention is used in a nuclear power plant.

FIG. 11 is a diagram showing another specific example in which the hydrogen generation facility according to the present invention is used in a combined power generation plant.

12 is a graph showing heat exchange of the exhaust heat recovery boiler in the specific example shown in FIG.

FIG. 13 is a diagram showing a heat transfer state of a reduction operation-hydrogen generation operation according to the present invention.

FIG. 14 is a diagram showing a heat transfer state of a reduction operation-hydrogen generation operation according to the present invention.

FIG. 15 is a diagram showing a conventional hydrogen production device.

FIG. 16 is a diagram showing a conventional combined power generation plant.

FIG. 17 is a system diagram of a hydrogen production power plant according to a combination of conventional techniques.

[Explanation of Codes] A reduction device H hydrogen generation device AM active oxide M iron oxide HX, HX 'heating heat exchanger AX, AX' cooling heat exchanger

Claims (3)

[Claims] 1. An iron-based oxide is reduced to produce an oxygen-deficient active oxide or metallic iron, and the active oxide or metallic iron is brought into contact with steam to be returned to the iron-based oxide, and hydrogen is also removed. In a hydrogen generating facility for generating, a reducing device for reducing the iron-based oxide and a hydrogen generating device for generating hydrogen by bringing the active oxide or metallic iron into contact with steam are included, and the reducing device is cooled. Hydrogen generating equipment, characterized in that a heating device is provided in the hydrogen generating device in addition to the device. 2. The hydrogen generating facility according to claim 1, which is used in a gas turbine power plant or a combined power plant, wherein a hydrogen generator is connected to a steam system of a boiler in the gas turbine power plant or the combined power plant. The steam of the boiler is used as the raw material steam source of the hydrogen generator and the heating source of the heating device, and a hydrogen cooler is provided in the hydrogen discharge system of the hydrogen generator, and the hydrogen cooler is provided in the gas turbine power plant. And a hydrogen generating facility connected to a water supply system of a combined power generation plant and used as a cooling source of the hydrogen cooler. 3. A method for use in a nuclear power plant.
In the hydrogen generation facility described, the hydrogen generator is connected to the steam system from the nuclear reactor of the nuclear power plant, is used as a heating source of the heating device, and the condensate is returned to the steam system of the reactor at a high temperature. At the same time, a hydrogen cooler is provided in the hydrogen discharge system of the hydrogen generator, and the hydrogen cooler is connected to the water supply system of the auxiliary power plant to be used as a cooling source of the hydrogen cooler. A hydrogen generating facility.