JP2008013397A - Hydrogen production apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrogen production apparatus of a simplified structure capable of improving energy utilization efficiency by using an exhaust gas from an existing iron-manufacturing plant as a heat source. <P>SOLUTION: The hydrogen production apparatus 3 comprises a raw material supply system 6 for generating a mixed steam of a fuel containing hydrogen and water, a reaction tube 4 containing a catalyst for producing hydrogen from the mixed steam from the raw material supply system 6, and a recovery system 7 for recovering hydrogen produced in the reaction tube 4. The reaction tube 4 is installed in the inside of an exhaust gas flow duct 2 in which an exhaust gas from an iron-manufacturing furnace 1 in an iron-manufacturing plant flows. The reaction tube 4 is heated by the exhaust gas in the inside of the exhaust gas flow duct 2 and produces hydrogen by reacting the mixed steam from the raw material supply system 6 in the presence of a catalyst. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a hydrogen production apparatus that uses exhaust gas from an existing steel manufacturing plant as a heating source, and in particular, can improve energy utilization efficiency and does not require heat medium oil piping and a circulation device. Relates to a simplified hydrogen production apparatus.

In recent years, in the electric power industry, technologies for diversifying fuels have been researched and developed for reasons such as energy saving against the depletion of fossil fuels and environmental conservation associated with increasing concentrations of CO ₂ and NO _x. One of them is the technology of using hydrogen gas.

For example, there are a fuel cell power plant and a hydrogen combustion power plant as such hydrogen gas utilization technology. The former directly generates electric energy by an electrochemical reaction between a fuel such as hydrogen and an oxidant typified by oxygen. For example, many inventions such as JP-A-6-140065 have been disclosed. In the latter, high-pressure hydrogen gas and pure oxygen gas are burned to generate high-temperature water vapor, and the generated high-temperature water vapor is expanded by a turbine, and the generator is driven by the power generated at this time. The power generation is performed, and for example, many inventions such as JP-A-11-36820 are disclosed. Both of these former and latter hydrogen gas utilization technologies do not generate environmental pollutants such as NO _x , SO _x , and CO ₂ and warming effect gas, and use extremely clean energy. The results of research and development are attracting attention as part of the energy promotion policy.

  By the way, it has been proposed that hydrogen supplied as fuel to such a fuel cell power plant or hydrogen combustion power plant is produced by electrolyzing water. In such a method for producing hydrogen that electrolyzes water, most of the cost required for producing hydrogen is derived from electric power.

  That is, in current nuclear power plants and thermal power plants, only about 50% of the fission energy exchanged for heat and fuel energy such as oil and natural gas is converted into electric power. In particular, the heat utilization efficiency in a nuclear power plant is about 30%. For this reason, when hydrogen is produced by electrolysis of water, there are inconveniences and inconveniences that the energy utilization efficiency is extremely poor and the cost for producing hydrogen is high.

On the other hand, oxygen-containing hydrocarbons such as methanol and dimethyl ether are advantageous in terms of cost when producing hydrogen because they can be steam reformed at low temperatures. Methanol, dimethyl ether, ethanol, and the like are relatively large in amount because they are obtained from methane in small and medium gas fields or gas fields with a high carbon dioxide CO ₂ content. The following patent document 1 exists in what was proposed paying attention to such a point. On the other hand, there is Patent Document 2 below as an energy recovery means in an ironworks.

  Among these, the technique described in Patent Document 1 is a methanol reforming reaction apparatus that performs a reaction while heating a mixed vapor of methanol and water with a heat medium oil in the presence of a catalyst. In other words, it is a small reformer, a U-shaped reaction tube is installed, heat medium oil is supplied to the upper part of the barrel side, extracted from the lower part, and the heat medium oil heated by an external heater is pumped This is a technology for an apparatus that heats a reaction tube while circulating it in a tank. The technology described as another example is a technology in which a raw material evaporator, a reforming reactor, an electric heating heater, a catalyst combustor and a stirrer are placed in the same heat medium oil tank and heated while stirring with a stirrer. It is.

Moreover, the technique described in Patent Document 2 relates to an energy recovery technique for gas discharged from a reduction furnace or the like of a steel mill. The exhaust gas is burned to generate a high-temperature gas, and the high-temperature gas is used as a gas. This technology generates electricity by driving a turbine.
Japanese Patent No. 2817236 JP-A-4-31632

The known technique described above has the following problems. That is, in Patent Document 1, a heating medium oil heating device, a circulation pump, piping, and the like are required outside, which may increase the number of facilities and increase the installation space for the facilities. On the other hand, in Patent Document 1, in order to omit the circulation pump and the piping, the raw material evaporator, the reforming reactor, the electric heating heater, the catalytic combustor, and the stirrer are placed in the same heat medium oil tank and stirred with the stirrer. A technique of heating while being proposed has also been proposed. However, even in this case, a heating device such as a heater or a catalytic combustor and a circulation device such as a stirrer are required.
On the other hand, if the exhaust gas energy at the steel works is further effectively used, the energy utilization efficiency can be improved and the environmental load can be reduced.

  The present invention has been made in consideration of the above points, and does not provide an independent heating source for the hydrogen production apparatus, and uses the exhaust gas from an existing steel manufacturing plant as a heating source, thereby improving energy utilization efficiency. It is an object of the present invention to provide a hydrogen production apparatus with a simplified structure, which can improve facilities, can simplify equipment, and does not require a heat medium oil pipe and a circulation device.

  The present invention includes a raw material supply system that generates a mixed vapor of hydrogen-containing fuel and water, a reaction tube that includes a catalyst and generates hydrogen from the mixed vapor from the raw material supply system, and hydrogen generated in the reaction tube. The reaction tube is provided inside an exhaust gas passage duct through which exhaust gas from an iron making furnace of an iron manufacturing plant flows, and raw material is supplied in the presence of a catalyst by exhaust gas in the exhaust gas passage duct. A hydrogen production apparatus characterized in that a mixed vapor from a system is reacted while being heated to generate hydrogen.

  The present invention relates to a raw material supply system that generates a mixed steam of hydrogen-containing fuel and water, a reformer that includes a catalyst and has a reaction tube that generates hydrogen from the mixed steam from the raw material supply system, and a reformer The reformer includes a shell that covers the entire reaction tube, a heat medium oil that is stored in contact with the reaction tube in the shell, and a heat generator. The reformer gas pipe is provided so as to pass through the inside of the medium oil, and the exhaust gas from the iron making furnace of the ironmaking plant flows.The reformer reaction pipe is heated by the exhaust gas flowing in the reformer gas pipe. The hydrogen production apparatus is characterized in that it is heated by the heat medium oil and reacts with the mixed steam from the raw material supply system in the presence of a catalyst to generate hydrogen.

  According to the present invention, the reaction tube of the reformer has a tube shape with both ends open and the catalyst is filled in the center portion, and the mixed steam from the raw material supply system flows from the upper end opening of the reaction tube, The hydrogen producing apparatus is characterized in that it becomes hydrogen in the presence of the catalyst, and this hydrogen flows out from the lower end opening of the reaction tube toward the product gas recovery system.

  According to the present invention, the reaction tube of the reformer is inserted in the center of the outer tube whose upper end is open and whose lower end is closed, and the both ends are open to form an annular gap between the outer tube and the outer tube. The annular gap has a catalyst filling portion filled with the catalyst and a catalyst non-filling portion which is provided below the catalyst filling portion and is not filled with a catalyst, The mixed vapor from the system flows into the catalyst filling portion from above the annular gap of the reaction tube, and becomes hydrogen in the presence of the catalyst in the catalyst filling portion, and this hydrogen is passed through the catalyst non-filling portion of the reaction tube. This hydrogen production apparatus is characterized in that it flows into the lower end opening of the inner pipe and flows out from the upper end opening of the inner pipe toward the product gas recovery system.

  According to the present invention, the raw material supply system includes a heat medium oil storage tank in which heat medium oil is stored, a fuel evaporator, a water evaporator and a mixing unit disposed in the heat medium oil storage tank, and fuel as the fuel. A fuel supply mechanism that supplies water into the evaporator, a water supply that supplies the water into the water evaporator, and a heat medium oil in a heat medium oil storage tank are provided in the heat medium oil, and exhaust gas from the iron making furnace of the iron making plant The mixing section is connected to the fuel evaporator and the water evaporator, and mixes the fuel vapor from the fuel evaporator and the water vapor from the water evaporator to generate the mixed steam. And the fuel evaporator, the water evaporator, and the mixing unit are heated by heating the heat medium oil in the heat medium oil storage tank by the exhaust gas in the gas pipe for fuel heating. is there.

  According to the present invention, a reformer gas pipe of a reformer includes a first reformer gas pipe portion disposed in the vicinity of a reaction tube, a space portion in a shell below the first reformer gas pipe portion. And a second reformer gas pipe disposed in the lower layer of the heat medium oil stored in the hydrogen production apparatus.

  According to the present invention, plate fins for promoting heat transfer between the first reformer gas pipe section and the reaction pipe are attached to the first reformer gas pipe section and the reaction pipe of the reformer. This is a hydrogen production apparatus.

  The present invention is the hydrogen production apparatus characterized in that a flow path hole or a notch for promoting convection of the heat transfer oil is formed in the plate fin of the reformer.

  According to the present invention, heat energy of exhaust gas generated from an iron making furnace of an iron manufacturing plant can be used for a hydrogen production apparatus, so that most of energy necessary for producing hydrogen can be efficiently obtained, and energy of an iron manufacturing plant. Efficiency can be further improved.

  Further, according to the present invention, the reaction tube of the hydrogen production apparatus is directly inserted into the high-temperature exhaust gas passage duct and heated, so that the heat exchange amount of the reaction tube can be increased. For this reason, the heat transfer area of the reaction tube can be reduced, and the shape of the reaction tube can be made compact.

  Furthermore, according to the present invention, since the exhaust gas is returned to the steelmaking exhaust gas energy recovery device after being used, the exhaust gas can be effectively used without waste, and the energy efficiency of the steelmaking plant can be further improved.

  Furthermore, according to the present invention, since the heat medium oil is used for heating the reaction tube of the reformer, the reaction tube can be efficiently and stably heated.

  Furthermore, according to the present invention, since the high-pressure exhaust gas used in the steelmaking exhaust gas energy recovery device is guided into the reformer shell via the gas extraction pipe, there is a portion having a high pressure other than the gas extraction pipe. It does not exist, and the safety of the reformer can be increased.

  Furthermore, according to the present invention, high-pressure exhaust gas is not supplied directly into the reformer, and there is no need to make the shell have a high-pressure specification. Can do. Thereby, the metal resource used for a shell can be decreased.

  Furthermore, according to the present invention, the reformer gas pipe of the reformer is composed of the first reformer gas pipe part and the second reformer gas pipe part. At the same time as the medium oil is heated, a flow of the heat medium oil can be generated by natural circulation. Thereby, the temperature distribution in the heat medium oil can be made uniform. In addition, since a circulation device such as a circulation pump for circulating the heat medium oil can be dispensed with, the hydrogen production device can be simplified and the safety can be increased.

  Furthermore, according to the present invention, since the heat transfer promoting plate fin is attached to the first reformer gas pipe section and the reaction tube, the heat transfer performance of the reformer can be improved, The hydrogen production efficiency of the hydrogen production apparatus can be increased.

  Furthermore, according to the present invention, since the channel holes or notches are formed in the plate fins, natural convection of the heat medium oil can be promoted.

  Furthermore, according to the present invention, the catalyst filling part is heated from the outside by the heat medium oil, and also heated from the inside of the catalyst filling part by the product gas reheated in the catalyst non-filling part. The heat exchange efficiency of the vessel can be improved, and the hydrogen generation efficiency of the hydrogen production apparatus can be increased.

  Furthermore, according to the present invention, in the raw material supply system, the fuel evaporator, the water evaporator, and the mixing unit that require a heat source are arranged in the heat medium oil in the heat medium oil storage tank, and the iron making exhaust gas energy Since it heats collectively with the exhaust gas from a collection | recovery apparatus, the thermal efficiency in the case of a heating can be improved.

First Embodiment Hereinafter, a first embodiment of the present invention will be described with reference to FIG.
Here, FIG. 1 is a schematic structural diagram showing the first embodiment of the present invention.

First, the outline of the hydrogen production apparatus according to the present embodiment will be described with reference to FIG.
As shown in FIG. 1, the hydrogen production apparatus 3 includes a raw material supply system 6 that generates a mixed vapor of hydrogen-containing fuel and water, and a reaction that includes a catalyst and generates hydrogen from the mixed vapor from the raw material supply system 6. A tube 4 and a product gas recovery system 7 that recovers hydrogen generated in the reaction tube 4 are provided.
Among these, the reaction tube 4 is provided inside the exhaust gas passage duct 2 through which the high-temperature exhaust gas from the iron making furnace 1 of the steel manufacturing plant flows, and in the presence of the catalyst by the high-temperature exhaust gas inside the exhaust gas passage duct 2. The mixed vapor from the raw material supply system 6 is reacted while being heated to generate hydrogen.

  In other words, in the present embodiment, the hydrogen production apparatus 3 is connected to the exhaust gas flow channel duct 2 through which the exhaust gas discharged from the iron making furnace 1 of the iron making plant flows. This hydrogen production apparatus 3 uses the thermal energy of the exhaust gas from the iron making furnace 1 of the steel production plant to produce hydrogen by steam reforming a fuel containing hydrogen. Further, the exhaust gas flow channel duct 2 provided with the reaction tube 4 of the hydrogen production device 3 is connected to an iron-manufactured exhaust gas energy recovery device 5. This iron-manufactured exhaust gas energy recovery device 5 is composed of, for example, a facility for generating power by driving a gas turbine with exhaust gas, as shown in Patent Document 2, for example.

The raw material supply system 6 of the hydrogen production apparatus 3 includes a fuel supply device 8, a water vapor supply device 9, and a mixing unit 10 connected to the fuel supply device 8 and the water vapor supply device 9.
Among these, the fuel supply device 8 includes a fuel tank filled with fuel such as ethanol and dimethyl ether, a preheater for converting such fuel into fuel gas and preheating it.

  The water vapor supply device 9 is a device for supplying raw water to the mixing unit 10 as water vapor, and includes a water tank, a pump, a water evaporator, and the like. Further, the mixing unit 10 supplies a mixed vapor generated by mixing the fuel gas from the fuel supply device 8 and the water vapor from the water vapor supply device 9 toward the reaction tube 4.

  The reaction tube 4 is inserted into the exhaust gas flow duct 2 and is heated by the high temperature exhaust gas from the iron making furnace 1 of the iron making plant flowing in the exhaust gas flow duct 2. The reaction tube 4 has, for example, a U-shaped or bayonet shape, and a catalyst is accommodated therein.

  The product gas recovery system 7 has a device for separating and recovering hydrogen and other product gas generated by reforming the mixed steam, a device for purifying hydrogen, and the like.

Next, the operation of the present embodiment having such a configuration will be described.
In FIG. 1, the exhaust gas from the iron making furnace 1 of the iron making plant passes through the exhaust gas flow duct 2 and reaches the iron making exhaust gas energy recovery device 5. During this time, the reaction tube 4 provided in the exhaust gas passage duct 2 is heated by the exhaust gas. Since the exhaust gas is made of a high-temperature gas of about 1000 ° C., for example, the reaction tube 4 is made of a heat-resistant metal or ceramic that can withstand high temperatures.

On the other hand, in the fuel supply device 8 of the raw material supply system 6, for example, fuel composed of oxygen-containing hydrocarbons such as ethanol and dimethyl ether is gasified into fuel gas.
Further, in the water vapor supply device 9 of the raw material supply system 6, water is vaporized to become water vapor.

  The fuel gas such as ethanol or dimethyl ether from the fuel supply device 8 and the water vapor from the water vapor supply device 9 are mixed in the mixing unit 10 to be mixed vapor and supplied into the reaction tube 4. This mixed steam undergoes a reforming reaction while it passes through the voids of the catalyst packed bed filled with the catalyst in the reaction tube 4 and becomes hydrogen. For example, when the fuel is dimethyl ether, the reforming reaction is performed in the reaction tube 4 by the water vapor as shown in the following equation (1) to generate a product gas containing hydrogen.

CH ₃ OCH ₃ + 3H ₂ O → 6H ₂ + 2CO ₂ (1)

The product gas generated in the reaction tube 4 in this way contains carbon dioxide CO ₂ in addition to hydrogen. This carbon dioxide is separated and purified by the product gas recovery system 7 and recovered.

  By the way, the reforming reaction shown in the above-described formula (1) is an endothermic reaction, and it is necessary to continuously apply a predetermined amount of heat in order to continue such a reforming reaction. For this reason, the reaction tube 4 is continuously heated by the exhaust gas from the iron making furnace 1.

  In the hydrogen production device 3 shown in FIG. 1, the reaction tube 4 is disposed in the exhaust gas flow duct 2 between the iron making furnace 1 and the iron production exhaust gas energy recovery device 5. However, the position of the reaction tube 4 may be in a temperature range in which sufficient heat necessary for the above-described reforming reaction can be obtained, and the position of the reaction tube 4 is not limited to that shown in FIG. That is, the reaction tube 4 may be disposed in an exhaust gas flow channel duct that flows after the exhaust gas passes through the steelmaking exhaust gas energy recovery device 5.

  As described above, according to the present embodiment, the thermal energy of the exhaust gas generated from the iron making furnace 1 of the steel plant can be supplied to the reaction tube 4 of the hydrogen production apparatus 3 and used for the reforming reaction in the reaction tube 4. In addition, most of the energy required for the production of hydrogen can be efficiently obtained, and the energy efficiency of the steelmaking plant can be further improved.

  That is, in many steel manufacturing plants, the exhaust gas generated in the iron making furnace 1 is recovered by the energy recovery device 5, and the thermal energy is effectively used. According to the present embodiment, the provision of the hydrogen production apparatus 3 as described above makes it possible to further effectively use energy.

  Further, according to the present embodiment, since the reaction tube 4 of the hydrogen production apparatus 3 is directly inserted into the high-temperature exhaust gas flow duct 2 and heated, the heat exchange amount of the reaction tube 4 can be increased. . For this reason, the heat transfer area of the reaction tube 4 can be reduced, and the shape of the reaction tube 4 can be made compact.

Second Embodiment Next, a second embodiment of the present invention will be described with reference to FIG.
Here, FIG. 2 is a schematic structural diagram showing a second embodiment of the present invention.

First, the outline of the hydrogen production apparatus according to the present embodiment will be described with reference to FIG.
As shown in FIG. 2, the hydrogen production apparatus 102 includes a raw material supply system 104 that generates a mixed steam of hydrogen-containing fuel and water, and a catalyst 115, and generates hydrogen from the mixed steam from the raw material supply system 104. A reformer 103 having a plurality of reaction tubes 111 and a product gas recovery system 105 that collects and collects hydrogen generated in the plurality of reaction tubes 111 of the reformer 103 are provided.

  Among these, the reformer 103 is provided so as to pass through the shell 112 covering the entire reaction tube 111, the heat medium oil 113 stored in contact with the reaction tube 111 in the shell 112, and the inside of the heat medium oil 113. And a reformer gas pipe 114 through which the exhaust gas supplied from the iron making furnace of the iron making plant through the energy recovery device 5 flows.

  Among these, the reaction tube 111 is heated by the heat medium oil 113 heated by the exhaust gas flowing in the reformer gas tube 114, and reacts with the mixed steam from the raw material supply system 104 in the presence of the catalyst to generate hydrogen. It is like that.

  That is, in FIG. 2, the hydrogen production apparatus 102 is an apparatus that generates hydrogen by steam reforming the fuel using the thermal energy generated by the exhaust gas from the steelmaking exhaust gas energy recovery device 5. This iron-manufactured exhaust gas energy recovery device 5 is composed of, for example, a facility for generating power by driving a gas turbine with exhaust gas, as shown in Patent Document 2, for example. In the present embodiment, the hydrogen production apparatus 102 extracts and uses the exhaust gas from the iron making furnace that has been used in the iron production exhaust gas energy recovery apparatus 5 and has a relatively low temperature.

The raw material supply system 104 of the hydrogen production apparatus 102 includes a fuel supply device 106, a water vapor supply device 107, and a mixing unit 108 connected to the fuel supply device 106 and the water vapor supply device 107.
Of these, the fuel supply device 106 includes a fuel tank filled with fuel such as ethanol and dimethyl ether, a preheater that preheats such fuel by converting it into fuel gas. The water vapor supply device 107 is a device for supplying raw material water vapor to the mixing unit 108 and includes a water tank, a pump, a water evaporator, and the like. Further, the mixing unit 108 supplies the mixed steam generated by mixing the fuel gas from the fuel supply device 106 and the steam from the steam supply device 107 toward the reaction tube 111 of the reformer 103.

  The product gas recovery system 105 includes a device for separating and recovering hydrogen and other product gas generated by reforming the mixed steam, a device for purifying hydrogen, and the like.

  Further, the reformer 103 includes a gas extraction pipe 109 for flowing the exhaust gas from the iron-manufactured exhaust gas energy recovery device 5 into the reformer gas pipe 114, and the exhaust gas from the reformer 103 to the reformer gas pipe 114. Is connected to a gas return pipe 110 that returns to the steelmaking exhaust gas energy recovery device 5.

  The reaction tube 111 of the reformer 103 has a tube shape with both ends open, and a central portion is filled with a catalyst 115 made of, for example, synthesized Cu—Zn.

  The heat medium oil 113 of the reformer 103 is made of a high boiling point high temperature heat medium oil such as Barrel Therm 400 (trade name), and can be used even at a temperature of 300 ° C. or higher.

  Here, the mixed vapor from the mixing unit 108 of the raw material supply system 104 flows from the upper end opening of the reaction tube 111 and becomes hydrogen in the reaction tube 111 in the presence of the catalyst 115. Next, the hydrogen flows out from the lower end opening of the reaction tube 111 toward the product gas recovery system 105.

Next, the operation of the present embodiment having such a configuration will be described.
In FIG. 2, the exhaust gas branched and extracted from the iron-manufactured exhaust gas energy recovery device 5 is supplied to the reformer gas pipe 114 of the reformer 103 through the gas extraction pipe 109 and passes through the reformer gas pipe 114. While passing, heat exchange with the heat medium oil 113 stored in the shell 112 is performed to heat the heat medium oil 113. Next, the exhaust gas that has passed through the reformer gas pipe 114 is returned to the steelmaking exhaust gas energy recovery device 5 through the gas return pipe 110.

  On the other hand, fuel supplied from the fuel supply device 106 of the raw material supply system 104, for example, oxygen-containing hydrocarbons such as ethanol and dimethyl ether, is gasified by the fuel supply device 106 to become fuel gas. Further, the water supplied from the water vapor supply device 107 of the raw material supply system 104 is vaporized by the water vapor supply device 107 to become water vapor. Thereafter, the fuel gas such as ethanol or dimethyl ether from the fuel supply device 106 and the water vapor from the water vapor supply device 107 are mixed in the mixing unit 108 to be mixed vapor and supplied into the reaction tube 111 of the reformer 103.

  This mixed vapor undergoes a reforming reaction while passing through the voids of the packed bed of the catalyst 115 in the reaction tube 111 to generate hydrogen. For example, when the fuel is made of dimethyl ether, the reforming reaction is performed in the reaction tube 111 by the water vapor as in the above-described equation (1) to generate a product gas containing hydrogen.

Thus, the product gas generated in the reaction tube 111 contains carbon dioxide CO ₂ in addition to hydrogen. This carbon dioxide is separated and purified by the product gas recovery system 105 and recovered.

  The above-described reforming reaction represented by the formula (1) is an endothermic reaction, and in order to continue such a reforming reaction, it is necessary to continuously apply a predetermined amount of heat. For this reason, the catalyst 115 and the mixed steam in the reaction tube 111 are heated by the heat medium oil 113 heated by the exhaust gas from the iron-manufactured exhaust gas energy recovery device 5.

  As described above, since the heat medium oil 113 is made of a high boiling point high temperature heat medium oil such as Barrel Therm 400 (trade name), the reaction tube 111 can be heated to 300 ° C. or higher. Further, the heat medium oil 113 has good thermal conductivity, a large specific heat, and a gradual change in temperature, so that the reaction tube 111 can be efficiently and stably heated.

  In FIG. 2, a valve for adjusting the flow rate or closing the valve (not shown) is attached to the system outside the reformer 103.

  As described above, according to the present embodiment, the heat energy of the exhaust gas generated from the iron making furnace of the iron making plant can be used for the reaction tube 111 of the reformer 103 of the hydrogen production apparatus 102, so that the energy necessary for producing hydrogen is obtained. Can be obtained efficiently. Furthermore, since this exhaust gas is returned to the steelmaking exhaust gas energy recovery device 5 after being used, the exhaust gas can be used effectively without waste, and the energy efficiency of the steelmaking plant can be further improved.

  That is, in many steel manufacturing plants, the exhaust gas generated in the iron making furnace is recovered by the energy recovery device 5, and the thermal energy is effectively used. According to the present embodiment, since the hydrogen production apparatus 102 as described above is provided, the energy can be used more effectively.

  Further, according to the present embodiment, since the heat medium oil 113 is used for heating the reaction tube 111 of the reformer 103, the reaction tube 111 can be efficiently and stably heated.

  Furthermore, according to the present embodiment, the high-pressure exhaust gas used in the iron-manufactured exhaust gas energy recovery device 5 is guided into the shell 112 through the gas extraction pipe 109, so there is no high-pressure portion other than the pipe. The safety of the reformer 103 can be improved.

  Furthermore, according to the present embodiment, high-pressure exhaust gas is not directly supplied into the reformer 103, and the shell 112 does not need to have a high-pressure specification. Weight reduction can be achieved. Thereby, the metal resources used for the shell 112 can be reduced.

Third Embodiment Next, a third embodiment of the present invention will be described with reference to FIGS.
Here, FIG. 3 is a schematic structural diagram showing a third embodiment of the present invention, and FIG. 4 is a schematic structural diagram showing a modification of the present embodiment. Further, FIG. 5 is a schematic structural diagram inside the shell when the channel hole is formed in the plate fin, and FIG. 6 is a schematic structural diagram inside the shell when the notch is formed in the plate fin. It is.
The third embodiment shown in FIGS. 3 to 6 is different in the configuration of the reformer gas pipe 214, and the other configurations are substantially the same as those of the second embodiment described above. 3 to 6, the same parts as those of the second embodiment shown in FIG. 2 are denoted by the same reference numerals, and detailed description thereof is omitted.

First, the outline of the hydrogen production apparatus according to the present embodiment will be described with reference to FIG.
In FIG. 3, the reformer 203 passes through the shell 112 covering the entire reaction tube 111, the heat medium oil 113 stored in the shell 112 so as to be in contact with the reaction tube 111, and the heat medium oil 113. And a reformer gas pipe 214 through which an exhaust gas supplied from the iron making furnace of the iron making plant through the energy recovery device 5 flows.

  Among these, the reformer gas pipe 214 is disposed in the space inside the shell 112 below the first reformer gas pipe 214a disposed near the reaction tube 111 and the first reformer gas pipe 214a. It consists of a second reformer gas pipe 214b arranged in the lower layer of the stored heat medium oil 113.

  The first reformer gas pipe portion 214a and the second reformer gas pipe portion 214b of the reformer gas pipe 214 are respectively supplied with a gas extraction pipe 109 to which the exhaust gas from the steelmaking exhaust gas energy recovery device 5 is supplied; A gas return pipe 110 for returning the exhaust gas to the iron-manufactured exhaust gas energy recovery device 5 is branched and connected so that the exhaust gas for heating the heat medium oil 113 flows inside.

  As in the second embodiment, the reaction tube 111 is filled with a catalyst 115 synthesized, for example, Cu—Zn.

  The heat medium oil 113 is made of a high boiling point high temperature heat medium oil such as Barrel Therm 400 (trade name). The heat medium oil 113 can be used at a temperature of 300 ° C. or higher.

Next, the operation of the present embodiment having such a configuration will be described.
In FIG. 3, the exhaust gas branched and extracted from the iron-manufactured exhaust gas energy recovery device 5 is supplied to the reformer 103 through the gas extraction pipe 109, and the first reformer gas pipe portion of the reformer gas pipe 214. While passing through 214 a, heat exchange with the heat medium oil 113 stored in the shell 112 is performed to heat the heat medium oil 113. Next, the exhaust gas that has passed through the first reformer gas pipe portion 214 a is returned to the iron-making exhaust gas energy recovery device 5 through the gas return pipe 110.

  Similarly, the exhaust gas branched from the gas extraction pipe 109 is also supplied to the second reformer gas pipe portion 214 b of the reformer gas pipe 214. This exhaust gas heats the storage lower layer portion of the heat medium oil 113, and then merges with the gas return pipe 110 and is returned to the steelmaking exhaust gas energy recovery device 5.

On the other hand, a mixed vapor of fuel gas and water vapor made of ethanol or dimethyl ether from the raw material supply system 104 is supplied into the reaction tube 111 of the reformer 203. This mixed vapor undergoes a reforming reaction while passing through the voids of the packed bed of the catalyst 115 in the reaction tube 111 to generate a product gas containing hydrogen.
For example, when the fuel is dimethyl ether, the reforming reaction is performed by the water vapor as shown in the above formula (1), and a product gas containing hydrogen is generated.

Thus, the product gas generated in the reaction tube 111 contains carbon dioxide CO ₂ in addition to hydrogen. This carbon dioxide is separated and purified by the product gas recovery system 105 and recovered.

  The above-described reforming reaction represented by the formula (1) is an endothermic reaction, and in order to continue such a reforming reaction, it is necessary to continuously apply a predetermined amount of heat. For this reason, the catalyst 115 and the mixed steam in the reaction tube 111 are heated by receiving heat from the heat medium oil 113 heated by the exhaust gas from the steel exhaust gas energy recovery device 5.

On the other hand, if a low temperature stratification is formed in the lower layer of the reservoir layer of the heat medium oil 113 by heat exchange with the reaction tube 111, the efficiency of the reforming reaction in the reaction tube 111 may be reduced.
For this reason, the gas pipe part 214b for 2nd reformers is provided in this lower layer part, the exhaust gas from the iron-manufactured exhaust gas energy recovery device 5 is flowed, and this lower layer part is heated. As a result, the temperature of the lower layer rises and the specific gravity of the heat medium oil 113 becomes relatively light, natural convection occurs in the heat medium oil 113, and the temperature uniformity of the heat medium oil 113 is maintained.

  As described above, since the heat medium oil 113 is made of a high boiling point high temperature heat medium oil such as Barrel Therm 400 (trade name), the reaction tube 111 can be heated to 300 ° C. or higher. Further, the heat medium oil 113 has good thermal conductivity, a large specific heat, and a gradual change in temperature, so that the reaction tube 111 can be efficiently and stably heated.

  In FIG. 3, a valve for adjusting the flow rate or closing the valve (not shown) is attached to the system outside the reformer 103.

Modified Example Next, a modified example of the hydrogen production apparatus according to the present embodiment will be described with reference to FIGS.
In FIG. 4, a plurality of plate fins for promoting heat transfer between the first reformer gas pipe portion 214 a and the reaction tube 111 are provided in the first reformer gas pipe portion 214 a and the reaction tube 111 of the reformer 203. 316 is attached.
That is, the plate fin 316 is a plate-shaped heat transfer fin provided to improve the heat transfer performance from the heat medium oil 113 to the reaction tube 111.

  Thus, by attaching the plate fins 316 to the first reformer gas pipe 214a and the reaction tube 111 of the reformer 203, the heat transfer area of the reaction tube 111 is increased, thereby improving the heat transfer performance. improves. Further, heat transfer is performed by heat conduction from the first reformer gas pipe portion 214a to the reaction tube 111, thereby improving the heat transfer performance.

  Further, another heat transfer fin may be provided in the second reformer gas pipe portion 214b to further improve the heat transfer characteristics.

Further, as shown in FIG. 5, a channel hole 317 for promoting the convection of the heat medium oil 113 may be formed in the plate fin 316 of the reformer 203 described above.
Similarly, as shown in FIG. 6, notches 318 for promoting convection of the heat medium oil 113 may be formed in the plate fins 316 of the reformer 203.

  That is, in the embodiment shown in FIG. 4, the plate fin 316 is attached to the first reformer gas pipe portion 214 a and the reaction pipe 111 of the reformer 203, so that the heat medium oil 113 in the reformer 203 is provided. Natural convection may be impaired, and the temperature in the heat medium oil 113 may not be uniform. For this reason, as shown in FIGS. 5 and 6, flow hole 317 or notch 318 is formed in plate fin 316, thereby promoting natural convection of heat medium oil 113.

  In the present embodiment, a partition plate or the like may be provided in the heat medium oil 113 so that the upward flow and the downward flow of the heat medium oil 113 do not interfere with each other to promote convection.

  Thus, according to the present embodiment, in addition to the effects of the second embodiment, the reformer gas pipe 214 of the reformer 203 is connected to the first reformer gas pipe section 214a and the second reformer. Since it comprises the gas pipe section 214b for equipment, the heat medium oil 113 can be heated in the reformer 203, and at the same time, the flow of the heat medium oil 113 can be generated by natural circulation. Thereby, the temperature distribution in the heat medium oil 113 can be made uniform. In addition, since a circulation device such as a circulation pump for circulating the heat medium oil 113 is not required, the hydrogen production apparatus 102 can be simplified and the safety can be improved.

  Further, according to the present embodiment, since the heat transfer promoting plate fins 316 are attached to the first reformer gas pipe portion 214 a and the reaction tube 111, the heat medium oil 113 in the reformer 203 is used. The heat transfer performance due to the hydrogen can be improved, and the hydrogen production efficiency of the hydrogen production apparatus 102 can be increased.

  Furthermore, according to the present embodiment, since the channel hole 317 or the notch 318 is formed in the plate fin 316, natural convection of the heat medium oil 113 can be promoted.

Fourth Embodiment Next, a fourth embodiment of the present invention will be described with reference to FIG.
Here, FIG. 7 is a schematic structural diagram showing the fourth embodiment of the present invention.
The fourth embodiment shown in FIG. 7 is different in the configuration of the reaction tube 411 of the reformer 403, and the other configurations are substantially the same as those of the second embodiment described above. In FIG. 7, the same parts as those of the second embodiment shown in FIG.

First, the outline of the hydrogen production apparatus according to the present embodiment will be described with reference to FIG.
As shown in FIG. 7, the hydrogen production apparatus 102 includes a raw material supply system 104 that generates a mixed steam of hydrogen-containing fuel and water, and a catalyst 415, and generates hydrogen from the mixed steam from the raw material supply system 104. A reformer 403 having a plurality of reaction tubes 411 and a product gas recovery system 105 that collectively collects hydrogen generated in the plurality of reaction tubes 411 of the reformer 403 are provided.

  Among these, the reformer 403 is provided so as to pass through the shell 412 covering the entire reaction tube 411, the heat medium oil 113 stored in contact with the reaction tube 411 in the shell 412, and the inside of the heat medium oil 113. And a reformer gas pipe 414 through which exhaust gas supplied from the iron making furnace of the iron making plant through the energy recovery device 5 flows.

  Among these, the reaction tube 411 is inserted in the center of the outer tube 411a whose upper end is open and whose lower end is closed, and the inner tube which is open at both ends and forms an annular gap 422 between the outer tube 411a. Tube 411b.

  Among these, in the annular gap 422, for example, a catalyst filling portion 411d filled with a catalyst 415 synthesized with Cu-Zn or the like, and a catalyst non-filling portion 411c provided below the catalyst filling portion 411d and not filled with the catalyst 415 are provided. It is made up of.

  By the way, the mixed steam from the raw material supply system 104 flows into the catalyst filling portion 411d from above the annular gap 422 of the reaction tube 411, and becomes hydrogen in the presence of the catalyst 415 in the catalyst filling portion 411d. It flows into the lower end opening 411e of the inner tube 411b via the catalyst non-filling portion 411c of the tube 411, and flows out from the upper end opening 411f of the inner tube 411b toward the product gas recovery system 105.

  Further, a gas extraction pipe 109 and a gas return pipe 110 are connected to the reformer gas pipe 414 so that the exhaust gas for heating supplied from the steelmaking exhaust gas energy recovery device 5 flows.

  The reaction tube 411 has a bayonet shape with a double tube configuration. The outer tube 411 a of the reaction tube 411 has a lower end closed and an upper end opened to be fixed to the tube plate 419. Both ends of the inner tube 411 b of the reaction tube 411 are open, and the upper end is fixed to the tube plate 420.

  Furthermore, the shell 412 is divided into three rooms 412a, 412b, and 412c by a tube plate 419 and a tube plate 420. Among these, the heat medium oil 113 is stored in the room 412 a, and the reformer gas pipe 414 is immersed in the heat medium oil 113. The chamber 412b is filled with mixed steam supplied from the raw material supply system 104, and serves as a mixed steam manifold for branching into the plurality of reaction tubes 411. The chamber 412c is a product gas manifold in which product gases such as hydrogen produced by the reforming reaction in the plurality of reaction tubes 411 are collected. In this way, the product gas collected in the room 412 c flows out into the product gas recovery system 105 and is separated and purified by the product gas recovery system 105.

  Furthermore, as described above, the catalyst filling portion 411d of the annular gap 422 of the reaction tube 411 is filled with the catalyst 415. The catalyst filling part 411d has a gap inside, and the mixed steam flows in this gap. Further, in order to provide the catalyst non-filling portion 411c below the catalyst filling portion 411d of the annular gap 422, a perforated receiving plate 421 having, for example, a mesh is installed below the catalyst filling portion 411d.

Next, the operation of the present embodiment having such a configuration will be described.
The exhaust gas that is branched and supplied from the iron-manufactured exhaust gas energy recovery device 5 is supplied into the reformer gas pipe 414 of the reformer 403 via the gas extraction pipe 109, and the heat medium oil 113 stored in the shell 412. The heat medium oil 113 is heated by exchanging heat. Next, the exhaust gas from the reformer gas pipe 414 is returned to the steelmaking exhaust gas energy recovery device 5 through the gas return pipe 110.

  On the other hand, for example, a mixed vapor of fuel and water vapor made of oxygen-containing hydrocarbon gas such as ethanol and dimethyl ether is supplied from the raw material supply system 104 into the room 412b. Next, the mixed steam thus supplied into the chamber 412 b is divided into the annular gaps 422 of the plurality of reaction tubes 411, and then passes through the gaps of the catalyst filling part 411 d filled with the catalyst 415. To do. At this time, the heating medium oil 113 is heated. For example, when the fuel is dimethyl ether, the reforming reaction represented by the above-described formula (1) is performed with water vapor to generate a product gas containing hydrogen and the like.

  This product gas makes a U-turn at the lower part of the reaction tube 411, travels upward in the inner tube 411b, reaches the room 412c, and then flows out to the product gas recovery system 105.

  Incidentally, an endothermic reaction is performed in the catalyst filling portion 411 d of the reaction tube 411, and the amount of heat necessary for this reaction is received from the heat medium oil 113. On the other hand, since the catalyst unfilled portion 411c where no endothermic reaction is performed is provided at the lower portion of the reaction tube 411, the product gas is reheated in the catalyst unfilled portion 411c. When the reheated product gas flows through the inner pipe 411b, heat exchange is performed, and the catalyst filling unit 411d is also heated from the inside of the catalyst filling unit 411d. Therefore, the catalyst filling unit 411d generates a larger amount of heat. Can receive.

Thus, the product gas produced in the reaction tube 411 contains carbon dioxide CO ₂ in addition to hydrogen. This carbon dioxide is separated and purified by the product gas recovery system 105 and recovered.

  By the way, since the heat medium oil 113 is made of heat medium oil for high boiling point and high temperature such as Barrel Therm 400 (trade name), the reaction tube 411 can be heated to 300 ° C. or higher. Further, since the heat medium oil 113 has good thermal conductivity, large specific heat, and moderate temperature fluctuation, the reaction tube 411 can be efficiently and stably heated.

  In FIG. 7, a flow rate adjusting valve or a closing valve (not shown) is attached to a system outside the reformer 403.

  As described above, according to the present embodiment, the heat energy of the exhaust gas generated from the iron making furnace of the iron making plant can be used for the reaction tube 411 of the reformer 403, so that most of the energy necessary for producing hydrogen can be efficiently used. Can get to. Furthermore, since this exhaust gas is returned to the steelmaking exhaust gas energy recovery device 5 after being used, the exhaust gas can be used effectively without waste, and the energy efficiency of the steelmaking plant can be further improved.

  That is, in many steel manufacturing plants, the exhaust gas generated in the iron making furnace is recovered by the energy recovery device 5, and the thermal energy is effectively used. According to the present embodiment, the hydrogen production apparatus described above can further effectively use energy.

  Further, according to the present embodiment, since the heat medium oil 113 is used for heating the reaction tube 411 of the reformer 403, the reaction tube 411 can be efficiently and stably heated.

  Furthermore, according to the present embodiment, the high-pressure exhaust gas used in the iron-manufactured exhaust gas energy recovery device 5 is guided into the shell 412 through the gas extraction pipe 109, so there is no high-pressure portion other than the pipe. The safety of the reformer 403 can be improved.

  Furthermore, according to the present embodiment, high-pressure exhaust gas is not directly supplied into the reformer 403, and the shell 412 does not need to have a high-pressure specification. Weight reduction can be achieved. Thereby, the metal resources used for the shell 412 can be reduced.

  Furthermore, according to the present embodiment, the catalyst filling portion 411d is heated from the outside by the heat medium oil 113, and is also heated from the inside of the catalyst filling portion 411d by the product gas reheated by the catalyst non-filling portion 411c. Is done. Thereby, the heat exchange efficiency of the reformer 403 can be further improved, and the hydrogen generation efficiency of the hydrogen production apparatus can be increased.

Fifth Embodiment Next, a fifth embodiment of the present invention will be described with reference to FIGS.
Here, FIG. 8 is a schematic structural diagram showing a fifth embodiment of the present invention, and FIG. 9 is a schematic structural diagram showing a modification of the present embodiment. Further, FIG. 10 is a schematic structural diagram inside the shell when the channel hole is formed in the plate fin, and FIG. 11 is a schematic structural diagram inside the shell when the notch is formed in the plate fin. It is.
The fifth embodiment shown in FIGS. 8 to 11 is different in the configuration of the reformer gas pipe 414, and the other configurations are substantially the same as those of the above-described fourth embodiment. In FIG. 8, the same parts as those of the fourth embodiment shown in FIG.

First, the outline of the hydrogen production apparatus according to the present embodiment will be described with reference to FIG.
As shown in FIG. 8, the reformer 403 passes through the shell 412 covering the entire reaction tube 411, the heat medium oil 113 stored in the shell 412 so as to be in contact with the reaction tube 411, and the heat medium oil 113. And a reformer gas pipe 414 through which the exhaust gas supplied from the iron making furnace of the iron making plant through the energy recovery device 5 flows.

  Of these, the reformer gas pipe 414 includes a first reformer gas pipe 414 a disposed in the vicinity of the reaction tube 411, and a space below the first reformer gas pipe 414 a and in the space inside the shell 412. It consists of a second reformer gas pipe portion 414b disposed in the lower layer portion of the stored heat medium oil 413.

  The first reformer gas pipe portion 414a and the second reformer gas pipe portion 414b of the reformer gas pipe 414 are each supplied with a gas extraction pipe 109 to which the exhaust gas from the iron exhaust gas energy recovery device 5 is supplied, A gas return pipe 110 from which the exhaust gas is returned to the iron-manufactured exhaust gas energy recovery device 5 is branched and connected so that the exhaust gas for heating the heat medium oil 113 flows inside.

Next, the operation of the present embodiment having such a configuration will be described.
In FIG. 8, the exhaust gas branched and extracted from the iron-manufactured exhaust gas energy recovery device 5 is supplied into the reformer gas pipe 414 of the reformer 403 through the gas extraction pipe 109, and the first reformer gas pipe The heat medium oil 113 is heated by exchanging heat with the heat medium oil 113 stored in the shell 412 while passing through the portion 414a. Next, the exhaust gas that has passed through the first reformer gas pipe portion 414 a is returned to the steelmaking exhaust gas energy recovery device 5 through the gas return pipe 110.

  Similarly, the exhaust gas branched from the gas extraction pipe 109 is also supplied to the second reformer gas pipe portion 414 b arranged in the reservoir of the heat medium oil 113. After heating the part, it joins with the gas return pipe 110 and is returned to the iron-making exhaust gas energy recovery device 5.

On the other hand, a mixed vapor of fuel gas and water vapor made of ethanol or dimethyl ether from the raw material supply system 104 is supplied into the reaction tube 411 of the reformer 403. The mixed vapor undergoes a reforming reaction while passing through the voids of the packed bed of the catalyst 415 in the reaction tube 411, and a product gas containing hydrogen is generated.
For example, when the fuel is dimethyl ether, the reforming reaction is performed by the water vapor as shown in the above formula (1), and a product gas containing hydrogen is generated.

Thus, the product gas produced in the reaction tube 411 contains carbon dioxide CO ₂ in addition to hydrogen. This product gas makes a U-turn at the lower part of the reaction tube 411, passes through the inner tube 411 b, is collected in the room 412 c, then flows out to the product gas recovery system 105, and is separated and purified by the product gas recovery system 105 And recovered.

  As described above, since the heat medium oil 113 is made of a high boiling point high temperature heat medium oil such as Barrel Therm 400 (trade name), the reaction tube 411 can be heated to 300 ° C. or higher. Further, since the heat medium oil 113 has good thermal conductivity, large specific heat, and moderate temperature fluctuation, the reaction tube 411 can be efficiently and stably heated.

  On the other hand, if a low temperature stratification is formed in the lower layer of the reservoir layer of the heat medium oil 113 by heat exchange with the reaction tube 411, the efficiency of the reforming reaction in the reaction tube 411 may be reduced. For this reason, the gas pipe part 414b for 2nd reformers is provided in this lower layer part, the waste gas from the iron-making exhaust gas energy recovery apparatus 5 is flowed, and this lower layer part is heated. As a result, the temperature of the lower layer rises and the specific gravity of the heat medium oil 113 becomes relatively light, natural convection occurs in the heat medium oil 113, and the temperature uniformity of the heat medium oil 113 is maintained.

  In FIG. 8, a valve for adjusting the flow rate or closing the valve (not shown) is attached to the system outside the reformer 403.

Modified Example Next, a modified example of the hydrogen production apparatus according to the present embodiment will be described with reference to FIGS.
In FIG. 9, a plurality of plate fins for promoting heat transfer between the first reformer gas pipe 414 a and the reaction tube 411 are provided in the first reformer gas pipe 414 a and the reaction pipe 411 of the reformer 403. 616 is attached.
The plate fins 616 are plate-shaped heat transfer fins for improving the heat transfer performance from the heat medium oil 113 to the reaction tube 411.

  As described above, the heat transfer fins 616 are attached to the first reformer gas pipe portion 414a and the reaction pipe 411 of the reformer gas pipe 414, thereby increasing the heat transfer area of the reaction tube 411 and increasing the heat transfer performance. Will improve. In addition, heat transfer is performed by heat conduction from the first reformer gas pipe portion 414a to the reaction tube 411, thereby improving the heat transfer performance.

  Further, another heat transfer fin may be provided in the second reformer gas pipe portion 414b to further improve the heat transfer characteristics.

In addition, as shown in FIG. 10, a channel hole 617 for promoting convection of the heat medium oil 113 may be formed in the plate fin 616 of the reformer 403.
Similarly, as shown in FIG. 11, notches 618 for promoting convection of the heat medium oil 113 are formed in the plate fins 616 of the reformer 403.

  As described above, the heat transfer promoting plate fins 616 are attached to the first reformer gas pipe portion 414a and the reaction pipe 411, so that the heat transfer performance of the reformer 403 can be improved. The hydrogen generation efficiency of the production apparatus can be increased.

  In the present embodiment, a partition plate or the like may be provided in the heat medium oil 113 so that the upward flow and the downward flow of the heat medium oil 113 do not interfere with each other to promote convection.

  As described above, according to the present embodiment, in addition to the effects of the fourth embodiment, the reformer gas pipe 414 of the reformer 403 includes the first reformer gas pipe portion 414a and the second reformer use. Since it consists of the gas pipe portion 414b, the heat medium oil 113 can be heated in the reformer 403 and at the same time the flow of the heat medium oil 113 can be generated by natural circulation. Thereby, the temperature distribution in the heat medium oil 113 can be made uniform. Further, since a circulation device such as a circulation pump for circulating the heat medium oil 113 can be made unnecessary, the hydrogen production device can be simplified and the safety can be enhanced.

Sixth Embodiment Next, a sixth embodiment of the present invention will be described with reference to FIG.
Here, FIG. 12 is a schematic configuration diagram showing a sixth embodiment of the present invention.

First, the outline of the hydrogen production apparatus according to the present embodiment will be described with reference to FIG.
As shown in FIG. 12, the hydrogen production apparatus 702 includes a raw material supply system 704 that generates a mixed steam of hydrogen-containing fuel and water, and a reformer 103 that generates hydrogen from the mixed steam from the raw material supply system 704. And a product gas recovery system 105 including a device for separating and recovering hydrogen and other product gas generated by reforming the mixed steam in the reformer 103 and purifying the hydrogen gas.

  Among these, the raw material supply system 704 includes a heat medium oil storage tank 727 in which the heat medium oil 713 is stored, and a fuel evaporator 723, a water evaporator 725, and a mixing unit 726 disposed in the heat medium oil storage tank 727. Have.

  The fuel evaporator 723 gasifies and preheats fuel such as ethanol and dimethyl ether, for example, and the fuel evaporator 723 includes a fuel supply mechanism 722 including a fuel tank that supplies fuel into the fuel evaporator 723. Is connected.

  The water evaporator 725 converts raw water into steam, and a water supply 724 including a raw water tank and a water supply pump for supplying water into the water evaporator 725 is connected to the water evaporator 725. Has been.

  Furthermore, a fuel heating gas pipe 728 is supplied into the heat medium oil 713 of the heat medium oil storage tank 727 from the iron making furnace of the iron making plant and the exhaust gas having a relatively low temperature flows through the iron making exhaust gas energy recovery device 5. Is provided. This iron-manufactured exhaust gas energy recovery device 5 is composed of, for example, a facility for generating power by driving a gas turbine with exhaust gas, as shown in Patent Document 2, for example.

  In addition, since the heat medium oil 713 is made of a high boiling point high temperature heat medium oil such as Barrel Therm 400 (trade name), the inside of the reformer 103 can be heated to 300 ° C. or higher. The heat medium oil 713 has good heat conductivity, a large specific heat, and a gradual change in temperature. Therefore, the heat medium oil 713 can be efficiently and stably heated.

  By the way, the mixing unit 726 is connected to the fuel evaporator 723 and the water evaporator 725, and mixes the fuel vapor from the fuel evaporator 723 and the water vapor from the water evaporator 725 to generate a mixed vapor. Yes. Further, the heat medium oil 713 of the heat medium oil storage tank 727 is heated by the exhaust gas in the fuel heating gas pipe 728 so that the fuel evaporator 723, the water evaporator 725, and the mixing unit 726 are heated. It has become.

  Moreover, in order to heat the heat medium oil 713 in the reformer 103 and the heat medium oil storage tank 727 by extracting a part of the exhaust gas from the iron manufacture exhaust gas energy recovery apparatus 5, the iron manufacture exhaust gas energy recovery apparatus 5 and the reformer 103 are heated. And the gas extraction pipe 109 and the gas return pipe 110 are connected between the steelmaking exhaust gas energy recovery device 5 and the heat medium oil storage tank 727.

  The reformer 103 has the same configuration as that of the embodiment shown in FIG.

Next, the operation of the present embodiment having such a configuration will be described.
The exhaust gas branched and extracted from the iron-manufactured exhaust gas energy recovery device 5 is branched and passed through the gas extraction pipe 109 to the reformer 103 side and the heat medium oil storage tank 727 side.

  First, the exhaust gas flowed from the iron-manufactured exhaust gas energy recovery device 5 to the heat medium oil storage tank 727 side passes through the fuel heating gas pipe 728 to heat the heat medium oil 713 and then passes through the gas return pipe 110. Returned to the steelmaking exhaust gas energy recovery device 5.

During this time, in the heat medium oil storage tank 727, the heat medium oil 713 heated by the exhaust gas passing through the fuel heating gas pipe 728 heats the fuel evaporator 723, thereby causing fuel in the fuel evaporator 723. Is heated to produce fuel vapor.
Further, the heat medium oil 713 heated by the exhaust gas passing through the fuel heating gas pipe 728 heats the water evaporator 725, thereby generating water vapor.

  Next, the fuel gas from the fuel evaporator 723 and the water vapor from the water evaporator 725 are mixed in the mixing unit 726 and heated by the heat medium oil 713 heated by the exhaust gas passing through the fuel heating gas pipe 728. Heated to produce mixed steam. Next, the mixed steam is supplied to the reformer 103 and reformed in the reformer 103 to generate hydrogen.

  In this manner, the heat medium oil 713 is circulated by natural convection in the heat medium oil storage tank 727 and is heat-exchanged with the exhaust gas flowing in the fuel heating gas pipe 728.

  The exhaust gas supplied to the reformer 103 heats the reformer 103 by the same action as described in the second embodiment, and thereby hydrogen is generated in the reformer 103. Detailed description will be omitted.

  In FIG. 12, a valve for adjusting the flow rate or closing the valve (not shown) is attached to the system outside the reformer 103.

  In FIG. 12, the reformer 103 may be replaced with the reformer 203 shown in the embodiment of FIGS.

  As described above, according to the present embodiment, the heat energy of the exhaust gas generated from the iron making furnace of the iron making plant can be used for the reformer 103 of the hydrogen production apparatus 702, so that most of the energy necessary for producing hydrogen is efficiently used. Can be obtained. Furthermore, since this exhaust gas is returned to the steelmaking exhaust gas energy recovery device 5 after being used, the exhaust gas can be used effectively without waste, and the energy efficiency of the steelmaking plant can be further improved.

  That is, in many steel manufacturing plants, the exhaust gas generated in the iron making furnace is recovered by the energy recovery device 5, and the thermal energy is effectively used. According to the present embodiment, since the hydrogen production apparatus 702 as described above is provided, it is possible to further effectively use energy.

  Further, according to the present embodiment, since the heat medium oil 713 is used for heating the reformer 103, the reformer 103 can be efficiently and stably heated.

  Furthermore, according to the present embodiment, the high-pressure exhaust gas used in the iron-manufactured exhaust gas energy recovery device 5 is guided into the reformer 103 through the gas extraction pipe 109, so that there is a high-pressure portion other than the pipe. Without this, the safety of the reformer 103 can be improved.

  Furthermore, according to the present embodiment, in the raw material supply system 704, the fuel evaporator 723, the water evaporator 725, and the mixing unit 726 that require a heat source are connected to the heat medium oil 713 in the heat medium oil storage tank 727. Since it is immersed in and heated with the exhaust gas heated from the steelmaking exhaust gas energy recovery device 5, it is possible to improve the thermal efficiency during heating.

Seventh Embodiment Next, a seventh embodiment of the present invention will be described with reference to FIG.
Here, FIG. 13 is a schematic structural diagram showing a seventh embodiment of the present invention.
The seventh embodiment shown in FIG. 13 is different in the configuration of the reformer 403, and the other configurations are substantially the same as those in the sixth embodiment described above. In FIG. 13, the same parts as those in the sixth embodiment shown in FIG.

First, the outline of the hydrogen production apparatus according to the present embodiment will be described with reference to FIG.
As shown in FIG. 13, the hydrogen production apparatus 702 includes a raw material supply system 704 that generates a mixed steam of hydrogen-containing fuel and water, and a reformer 403 that generates hydrogen from the mixed steam from the raw material supply system 704. And a product gas recovery system 105 including a device for separating and recovering hydrogen and other product gas generated by reforming the mixed steam in the reformer 403 and purifying the hydrogen gas.

  Among these, the raw material supply system 704 includes a heat medium oil storage tank 727 in which the heat medium oil 713 is stored, and a fuel evaporator 723, a water evaporator 725, and a mixing unit 726 disposed in the heat medium oil storage tank 727. Have.

  Among these, the fuel supply mechanism 722 is connected to the fuel evaporator 723, and the water supply unit 724 is connected to the water evaporator 725.

  Also, a fuel heating gas pipe 728 is supplied into the heat medium oil 713 of the heat medium oil storage tank 727 and flows from the iron making furnace of the iron making plant and the exhaust gas having a relatively low temperature flows through the iron making exhaust gas energy recovery device 5. Is provided.

  By the way, the mixing unit 726 is connected to the fuel evaporator 723 and the water evaporator 725, and mixes the fuel vapor from the fuel evaporator 723 and the water vapor from the water evaporator 725 to generate a mixed vapor. Yes. Further, the heat medium oil 713 of the heat medium oil storage tank 727 is heated by the exhaust gas in the fuel heating gas pipe 728 so that the fuel evaporator 723, the water evaporator 725, and the mixing unit 726 are heated. It has become.

  Further, in order to heat the heat medium oil 713 in the reformer 403 and the heat medium oil storage tank 727 by extracting a part of the exhaust gas from the iron manufacture exhaust gas energy recovery apparatus 5, the iron manufacture exhaust gas energy recovery apparatus 5 and the reformer 403 are heated. And the gas extraction pipe 109 and the gas return pipe 110 are connected between the steelmaking exhaust gas energy recovery device 5 and the heat medium oil storage tank 727.

  The reformer 403 has the same configuration as that of the embodiment shown in FIG. 7, but may have the same configuration as that of the embodiment shown in FIGS.

  As described above, according to the present embodiment, in the raw material supply system 704, the fuel evaporator 723, the water evaporator 725, and the mixing unit 726 that require a heat source are connected to the heat medium oil in the heat medium oil storage tank 727. Since it is immersed in 713 and heated together with heated exhaust gas from the iron-manufactured exhaust gas energy recovery device 5, the thermal efficiency in heating required for these heating can be improved.

BRIEF DESCRIPTION OF THE DRAWINGS The schematic structure figure which shows 1st Embodiment of the hydrogen production apparatus by this invention. FIG. 3 is a schematic structural diagram showing a second embodiment of the hydrogen production apparatus according to the present invention. The schematic structure figure showing a 3rd embodiment of the hydrogen production device by the present invention. The schematic structure figure which shows the modification of 3rd Embodiment of the hydrogen production apparatus by this invention. The schematic structure figure inside a shell in case a channel hole is formed in a plate fin. The schematic structure figure inside a shell in case a notch is formed in a plate fin. FIG. 5 is a schematic structural diagram showing a fourth embodiment of a hydrogen production apparatus according to the present invention. FIG. 9 is a schematic structural diagram showing a fifth embodiment of a hydrogen production apparatus according to the present invention. The schematic structure figure which shows the modification of 5th Embodiment of the hydrogen production apparatus by this invention. The schematic structure figure inside a shell in case a channel hole is formed in a plate fin. The schematic structure figure inside a shell in case a notch is formed in a plate fin. FIG. 9 is a schematic structural diagram showing a sixth embodiment of a hydrogen production apparatus according to the present invention. The schematic structure figure showing a 7th embodiment of the hydrogen production device by the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Iron furnace 2 Exhaust gas flow duct 3 Hydrogen production apparatus 4 Reaction tube 5 Steel production exhaust gas energy recovery apparatus 6 Raw material supply system 7 Generated gas recovery system 8 Fuel supply apparatus 9 Steam supply apparatus 10 Mixing parts 102 and 702 Hydrogen production apparatuses 103 and 203 , 403 Reformer 104, 704 Raw material supply system 105 Product gas recovery system 106 Fuel supply device 107 Steam supply device 108 Mixing part 109 Gas extraction pipe 110 Gas return pipe 111, 411 Reaction pipe 112, 412 Shell 113, 713 Heat medium oil 114, 214, 414 Steam pipe 115, 415 Catalyst 214a, 414a Gas pipe part 214b for the first reformer 214b, 414b Gas pipe part 316, 616 for the second reformer Plate fins 317, 617 Channel holes 318, 618 Notch flow Path 411a Outer tube 411b Inner tube 411c Catalyst unfilled portion 411d Catalyst filled 411e bottom opening 411f top opening 412a, 412b, 412c room 422 annular gap 723 fuel evaporator 724 water supplying device 725 water evaporator 726 mixing portion 727 thermal oil storage tank 728 fuel heating gas pipe

Claims (8)

A raw material supply system for generating a mixed steam of hydrogen-containing fuel and water;
A reaction tube containing a catalyst and generating hydrogen from the mixed steam from the raw material supply system;
A product gas recovery system for recovering hydrogen generated in the reaction tube,
The reaction tube is provided inside the exhaust gas flow duct where the exhaust gas from the iron making furnace of the steel plant flows, and the reaction is performed while heating the mixed steam from the raw material supply system in the presence of the catalyst by the exhaust gas inside the exhaust gas flow duct. A hydrogen production apparatus characterized in that hydrogen is produced. A raw material supply system for generating a mixed steam of hydrogen-containing fuel and water;
A reformer having a reaction tube containing a catalyst and generating hydrogen from the mixed steam from the raw material supply system;
A product gas recovery system for recovering hydrogen generated in the reaction tube of the reformer,
The reformer is provided so as to pass through the shell covering the entire reaction tube, the heat medium oil stored in contact with the reaction tube in the shell, and the heat medium oil, and exhaust gas from the iron making furnace of the steel plant A gas pipe for a reformer through which
The reaction tube of the reformer is heated by the heat medium oil heated by the exhaust gas flowing in the gas tube for the reformer, and reacts with the mixed steam from the raw material supply system in the presence of the catalyst to generate hydrogen. Hydrogen production equipment. The reformer reaction tube has a tube shape with both ends open, and the catalyst is filled in the center portion,
The mixed steam from the raw material supply system flows in from the upper end opening of the reaction tube, becomes hydrogen in the presence of the catalyst, and this hydrogen flows out from the lower end opening of the reaction tube toward the product gas recovery system. The hydrogen production apparatus according to claim 2. The reaction tube of the reformer is
An outer tube whose upper end is open and whose lower end is closed, and an inner tube which is inserted into the center of the outer tube and which opens at both ends to form an annular gap between the outer tube,
The annular gap has a catalyst filling portion filled with the catalyst, and a catalyst non-filling portion which is provided below the catalyst filling portion and is not filled with a catalyst,
The mixed steam from the raw material supply system flows into the catalyst filling portion from above the annular gap of the reaction tube, and becomes hydrogen in the presence of the catalyst in this catalyst filling portion, and this hydrogen passes through the catalyst non-filling portion of the reaction tube. The hydrogen production apparatus according to claim 2, wherein the hydrogen production apparatus flows into the lower end opening of the inner tube of the reaction tube and flows out from the upper end opening of the inner tube toward the product gas recovery system. The raw material supply system is
A heat medium oil storage tank in which the heat medium oil is stored;
A fuel evaporator, a water evaporator and a mixing unit disposed in the heat medium oil storage tank;
A fuel supply mechanism for supplying the fuel into a fuel evaporator;
A water supply for supplying the water into the water evaporator;
Provided in the heat medium oil of the heat medium oil storage tank, and has a gas pipe for heating the fuel through which the exhaust gas from the iron making furnace of the steel plant flows.
The mixing unit is connected to the fuel evaporator and the water evaporator, mixes the fuel vapor from the fuel evaporator and the water vapor from the water evaporator to generate the mixed vapor, and is heated by the exhaust gas in the fuel heating gas pipe. The hydrogen production apparatus according to any one of claims 2 to 4, wherein the fuel evaporator, the water evaporator, and the mixing unit are heated by heating the heat medium oil in the medium oil storage tank.   The reformer gas pipe of the reformer was stored in the first reformer gas pipe portion disposed in the vicinity of the reaction tube and the space in the shell below the first reformer gas pipe portion. 6. The hydrogen production apparatus according to claim 2, comprising a gas pipe section for a second reformer disposed in a lower layer portion of the heat transfer oil.   A plate fin for promoting heat transfer between the first reformer gas pipe section and the reaction pipe is attached to the first reformer gas pipe section and the reaction pipe of the reformer. Item 7. The hydrogen production apparatus according to Item 6.   The hydrogen production apparatus according to claim 7, wherein a channel hole or a cutout for promoting convection of the heat transfer oil is formed in the plate fin of the reformer.

Images