WO2006046426A1 - 水蒸気改質装置及びそれを用いた水蒸気改質方法並びに工業炉 - Google Patents
水蒸気改質装置及びそれを用いた水蒸気改質方法並びに工業炉 Download PDFInfo
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- WO2006046426A1 WO2006046426A1 PCT/JP2005/019043 JP2005019043W WO2006046426A1 WO 2006046426 A1 WO2006046426 A1 WO 2006046426A1 JP 2005019043 W JP2005019043 W JP 2005019043W WO 2006046426 A1 WO2006046426 A1 WO 2006046426A1
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- hydrogen
- industrial furnace
- reforming
- combustion
- reaction tube
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
- H01M8/0618—Reforming processes, e.g. autothermal, partial oxidation or steam reforming
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
- B01J8/062—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes being installed in a furnace
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
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- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/384—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts the catalyst being continuously externally heated
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F27B9/06—Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity heated without contact between combustion gases and charge; electrically heated
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- F27D7/00—Forming, maintaining, or circulating atmospheres in heating chambers
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
- F28F21/04—Constructions of heat-exchange apparatus characterised by the selection of particular materials of ceramic; of concrete; of natural stone
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00002—Chemical plants
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Definitions
- the present invention relates to a steam reformer, a steam reforming method using the steam reformer, and an industrial furnace. More specifically, the combustion heat of the industrial furnace (exhaust heat) is adjusted to the temperature range.
- a steam reformer that performs steam reforming by using it efficiently, and uses that steam reformer to efficiently use part of the combustion heat (exhaust heat) of an industrial furnace according to its temperature range
- the present invention relates to a steam reforming method for performing steam reforming by doing so, and an industrial furnace equipped with the steam reforming apparatus.
- an industrial furnace has been used as an apparatus for heating an object to be heated in various industrial fields.
- the object to be heated by burning carbon-containing fuel is one that generates high-temperature combustion gas containing carbon dioxide and carbon dioxide simultaneously with heat generation.
- the generated combustion gas was discharged to the outside (hereinafter, the combustion gas discharged to the outside may be referred to as “combustion exhaust gas” or simply “exhaust gas”).
- combustion exhaust gas or simply “exhaust gas”.
- Patent Document 1 Japanese Patent Laid-Open No. 2002-340482
- the present invention has been made in view of such problems of the prior art, and efficiently uses part of the combustion heat (exhaust heat) of an industrial furnace in accordance with its temperature range.
- the present invention is characterized by providing a steam reformer capable of performing steam reforming, a steam reforming method using the steam reformer, and an industrial furnace equipped with the steam reformer.
- a steam reformer of the present invention a steam reforming method using the steam reformer, and an industrial furnace that solve the above-described problems are as follows.
- a metal reaction tube or ceramic reaction tube that is disposed in an industrial furnace and is filled with a reforming catalyst that promotes a steam reforming reaction using hydrocarbons and steam that flow into the interior as raw materials.
- a steam reformer comprising: a low temperature reforming section having a high temperature reforming section having a ceramic reaction tube for causing the steam reforming reaction therein.
- the low temperature reforming section is disposed at a position where the temperature is 600 ° C or higher and less than 1000 ° C
- the high temperature reforming section is disposed at a position where the temperature is 1000 ° C or higher and 1800 ° C or lower.
- the material for the ceramic reaction tube is at least one selected from the group force consisting of silicon nitride, silicon carbide, aluminum nitride, acid-aluminum and acid-zirconium forces [1] or [2] The steam reformer described in 1.
- the steam reformer according to any one of [1] to [3] is placed at a position where the temperature is 600 ° C. or higher and lower than 1000 ° C. due to combustion heat of the industrial furnace.
- the steam reforming reaction is carried out by arranging in the industrial furnace such that the high temperature reforming part is arranged at a position where the temperature is 1000 ° C or higher and 1800 ° C or lower due to the combustion heat of the industrial furnace. Steam reforming method to be generated.
- a combustion apparatus that burns a fuel containing inflowing hydrocarbons to generate combustion gas, and heats and burns or burns an object to be fired or a material to be burned therein.
- an industrial furnace comprising an industrial furnace body that discharges combustion gas after combustion to the outside, and an exhaust gas discharge section that serves as a flow path for the combustion gas discharged from the industrial furnace body, [1] to [ 3], the low temperature reforming section is disposed at a position where the steam reforming apparatus according to any one of the above is 600 ° C. or more and less than 1000 ° C. due to the combustion heat of the industrial furnace.
- the high temperature reforming section should be placed at a position where the temperature is 1000 ° C or higher and 1800 ° C or lower.
- An industrial furnace further provided in the industrial furnace main body and z or in the exhaust gas discharge part.
- a part of the combustion heat is a heat received by the metal reaction tube and the ceramic reaction tube when the combustion gas directly contacts the metal reaction tube and the ceramic reaction tube, and
- a fuel cell that further generates electric power by a reaction between hydrogen and oxygen, or a reaction between hydrogen and oxygen and a reaction between hydrogen and carbon dioxide, and a part of the hydrogen contained in the reformed gas Alternatively, the industrial furnace according to [5] or [6], wherein the whole is hydrogen for a fuel cell and is used for a reaction with oxygen or oxygen and carbon dioxide in the fuel cell.
- the reformed gas generated in the steam reformer is allowed to flow into the interior to selectively separate the hydrogen in the reformed gas, and hydrogen fuel containing hydrogen as a main component.
- the industrial furnace according to any one of [5] to [7], further comprising a hydrogen separator that separates the residual gas containing oxygenated carbon.
- the industrial furnace is a firing furnace, and the industrial furnace (firing furnace) main body continuously carries the fired body into the fired body and continuously heats the fired body.
- the industrial furnace according to any one of [5] to [9], wherein the main body is a continuous firing furnace body that is carried out to the outside.
- a low temperature reforming section having a metal reaction tube or a ceramic reaction tube filled with a reforming catalyst, and a high temperature reforming section having a ceramic reaction tube Therefore, steam reforming is provided by arranging a low temperature reforming section in the low temperature region (less than 1000 ° C) of the industrial furnace and a high temperature reforming section in the high temperature region (over 1000 ° C).
- the reforming catalyst acts effectively and the steam reforming reaction proceeds efficiently.
- the steam reforming reaction proceeds efficiently even in the absence of a reforming catalyst.
- the low temperature reforming section is heated at a position of 600 ° C. or more and less than 1000 ° C. of the industrial furnace using the steam reforming apparatus of the present invention.
- the steam reforming apparatus of the present invention has a low temperature reforming portion disposed at a position where the heat of combustion of the industrial furnace is 600 ° C or higher and lower than 1000 ° C.
- a steam reforming reaction is provided in order to further provide the high-temperature reforming section in the industrial furnace main body and Z or exhaust gas discharge section at a position where the temperature is 1000 ° C or higher and 1800 ° C or lower due to the combustion heat of the industrial furnace.
- the reforming catalyst works effectively and can efficiently recover exhaust heat by the steam reforming reaction. Is high 10 At positions above 00 ° C and below 1800 ° C, exhaust heat recovery by steam reforming reaction can be performed efficiently without the presence of a reforming catalyst. Further, the effect obtained from the use of the steam reforming apparatus of the present invention can be obtained.
- FIG. 1 is a side view schematically showing a firing furnace provided with an embodiment of a steam reformer of the present invention.
- FIG. 2 is a cross-sectional view taken along the line AA of the firing furnace shown in FIG.
- FIG. 3 is a block flow diagram schematically showing one embodiment of an industrial furnace (firing furnace) of the present invention.
- FIG. 4 is a graph showing the relationship between temperature and tensile strength of metal materials and ceramics.
- FIG. 5 is a graph showing the relationship between the reforming temperature and the conversion rate in the steam reforming reaction. Explanation of symbols
- dioic acid-carbon fixer 54 ... Fuel cells, 61 ... reformed gas, 62 ... hydrogen fuel, 63 ... residual gas, 64 ... hydrocarbon main fuel for mixing, 65 ... mixed fuel, 66 ... fuel containing hydrocarbons , 67 ... Fixing agent, 68 ... Waste liquid (Sodium carbonate-containing solution), 69 ... Reforming raw material, 70 ... Hydrogen for fuel cell, 71... Hydrogen fuel for mixing, 100, 200
- FIG. 1 schematically shows a firing furnace equipped with an embodiment of the steam reformer of the present invention.
- FIG. 2 is a side view
- FIG. 2 is a cross-sectional view of the firing furnace shown in FIG.
- the term “industrial furnace” refers to a furnace that is used industrially and that can be heated by putting a heated object inside (furnace), and includes a firing furnace, a combustion furnace, and the like.
- the reforming material inflow pipe 26 connected to the ceramic pipe 28 of the high temperature reforming section 22 is omitted.
- the arrows shown in FIGS. 1 and 2 indicate the direction in which the reforming raw material, the reformed gas, and the like move.
- the steam reformer 21 of this embodiment includes a low temperature reforming unit 23 and a high temperature reforming unit 22.
- the low temperature reforming section 23 has a metal reaction tube 25 filled with a reforming catalyst for promoting a steam reforming reaction
- the high temperature reforming section 22 has a ceramic reaction tube 24.
- the steam reformer 21 has a metal reaction tube 25 (FIG. 1) in the heat recovery part 5 formed so as to protrude outward from the side surface of the firing furnace body 1 of the firing furnace 100.
- the ceramic reaction tube 24 is arranged so as to extend in the vertical direction.
- the metal reaction tube 25 see FIG.
- the ceramic reaction tube 24 are preferably arranged so as to extend in the vertical direction, but the present invention is not limited to this and can be arranged in any direction. .
- the heat recovery unit 5 is formed on both side surfaces of the firing furnace body 1, it may be formed only on one side surface.
- the low temperature reforming section 23 is disposed in the heat recovery section 5 of the low temperature cooling zone 4
- the high temperature reforming section 22 is disposed in the heat recovery section 5 of the high temperature cooling zone 3. Yes.
- the steam reformer 21 is disposed in the heat recovery unit 5, it may be disposed directly in the firing furnace body 1 without forming the heat recovery unit 5.
- the temperature of the low temperature cooling zone 4 is preferably 600 ° C. or more and less than 1000 ° C.
- the temperature of the high temperature cooling zone 3 is preferably 1000 ° C. or more and 1800 ° C. or less.
- the steam reformer 21 includes a metal reaction tube 25 and a ceramic reaction tube 24 in an exhaust gas discharge section 6 which is a flow path of combustion gas (combustion exhaust gas) discharged from one firing furnace body. It is arranged to extend in the vertical direction.
- the low temperature reforming section 23 is disposed in the discharge section low temperature region 8 of the exhaust gas discharge section 6, and the high temperature reforming section 22 is disposed in the discharge section high temperature area 7 of the exhaust gas discharge section 6.
- the temperature of the discharge part low temperature region 8 is preferably 600 ° C. or more and less than 1000 ° C.
- the temperature of the discharge part high temperature region 7 is preferably 1 000 ° C.
- the firing furnace 100 in which the steam reforming apparatus 21 of the present embodiment is disposed includes a combustion apparatus (not shown) that combusts fuel containing inflowing hydrocarbons to generate combustion gas, and combustion.
- a firing furnace body 1 that heats and sinters the object to be fired that has been carried into the interior, and discharges the combustion gas after firing to the outside, and a flow path for the combustion gas discharged from the firing furnace body 1
- the exhaust gas discharge section 6 is provided.
- the firing furnace 100 generates the combustion gas by burning a fuel containing hydrocarbons such as natural gas and methane gas by the combustion device in order to fire the object 12 (see FIG. 2) in the firing zone 2. At the same time, combustion heat is generated.
- the combustion gas moves in the high-temperature cooling zone 3 while being gradually cooled, and then moves to the low-temperature cooling zone 4 while being further cooled. Then, the combustion gas cooled in the low temperature cooling zone 4 is discharged from the firing furnace body 1 to the outside through a low temperature gas discharge portion (not shown) disposed in the low temperature cooling zone 4 as combustion exhaust gas.
- the low temperature cooling zone 4 is an area below 1000 ° C
- the high temperature cooling zone 3 is an area above 1000 ° C.
- the fired body 12 also moves in the direction of movement 11 of the fired body 12.
- the firing furnace 100 is provided with an exhaust gas discharge section 6 for exhausting high-temperature combustion gas from the high-temperature cooling zone 3 of the firing furnace body 1 in the high-temperature cooling zone 3. Part of the high-temperature combustion gas existing in the high-temperature cooling zone 3 is discharged to the outside of the firing furnace body 1 through the exhaust gas discharge part 6.
- the combustion exhaust gas combustion gas discharged to the outside of the firing furnace body 1 is cooled while passing through the internal cavity of the exhaust gas discharge section 6, and then discharged to the outside.
- the area where the temperature of the combustion exhaust gas moving inside that is located closer to the firing furnace body 1 is 1000 ° C or higher is the discharge section high temperature area 7, which is far from the firing furnace main body 1.
- the area where the flue gas temperature is less than 1000 ° C located on the side is the low temperature area 8 of the exhaust section.
- the steam reforming apparatus 21 of the present embodiment uses the part of the combustion heat to heat the metal reaction tube 25, and in the low temperature reforming portion 23, inside the metal reaction tube 25.
- a steam reforming reaction is generated that generates reformed gas containing hydrogen and carbon dioxide from the inflowing hydrocarbons and hydrogen as raw materials.
- the high temperature reforming unit 22 A steam reforming reaction is generated in which a reformed gas containing hydrogen and carbon dioxide is generated using hydrocarbons and steam flowing into the raw material as raw materials.
- a reforming raw material containing hydrocarbons and steam is heated by a part of the combustion heat, and a reforming catalyst is used in a low temperature part where reactivity is particularly low, to thereby convert hydrocarbons and steam.
- a reformed gas containing hydrogen and carbon dioxide is used as a heating mode when heating by a part of the combustion heat.
- a mode in which the object to be fired is directly heated by contact with combustion gas (including combustion exhaust gas) after firing, and a firing furnace main body by the combustion gas is used.
- the firing jig and the furnace wall, and the wall of the exhaust gas discharge part 6 are heated, and the radiant heat generated from the heated firing object, the firing jig, the furnace wall and the wall of the exhaust gas discharge part 6
- Radiation heat begins to be generated even at about 600 ° C, but almost no radiant heat is generated when the temperature is low, which is about one-tenth of convection heat.
- the ratio of radiant heat to the total heating is 60%, and above 1000 ° C, the ratio of radiant heat is 80%. In addition, the radiant heat becomes dominant as the temperature rises.
- the low temperature reforming section 23 having the metal reaction tube 25 filled with the reforming catalyst and the high temperature reforming unit having the ceramic reaction tube 24 is disposed in the low temperature region (low temperature cooling zone 4) of the firing furnace 100, and the high temperature reforming portion 22 is disposed in the high temperature region (high temperature cooling zone 3). Therefore, in the low temperature region where the reactivity of the steam reforming reaction is low, the reforming catalyst works effectively to efficiently recover exhaust heat, and in the high temperature region where the reactivity of the steam reforming reaction is high, Even if there is no reforming catalyst, exhaust heat can be recovered efficiently.
- the conventional metal reaction tube will be described.
- the metal reaction tube has been insufficient in heat resistance.
- the metal material undergoes a significant drop in strength in the temperature range above 800 ° C, and the strength at 1000 ° C is about lOOMPa.
- the actual steam reformer had to be operated with its operating temperature controlled to about 800-900 ° C.
- 1000 ° C is a usable temperature, and the continuous operation at 1000 ° C may lead to the strength reduction force of the metal reaction tube.
- Fig. 5 is a usable temperature, and the continuous operation at 1000 ° C may lead to the strength reduction force of the metal reaction tube.
- Fig. 4 is a graph showing the relationship between the temperature and strength of metal materials and ceramics
- Fig. 5 shows the relationship between the reforming temperature and the conversion rate (reaction rate of raw material methane) in the steam reforming reaction. It is a graph to show.
- the strength data for ceramics in Fig. 4 is from “Ceramics Engineering Nordbook, Ceramics Association (1989), P2018, P2080”, converted from bending strength to tensile strength.
- the high-temperature bending strength was converted to the high-temperature tensile strength using the ratio of bending strength and tensile strength at room temperature described in the same source.
- the tensile strength (strength) data of the metal in Fig. 4 are measured values for Fe-Ni-Cr-Nb-based austenitic alloys usually used in steam reforming tubes, and measured by a method based on JIS Z2241. Value.
- the strength characteristics of ceramics are those that gradually decrease in strength as the temperature rises at room temperature.
- ceramics 1 (carbide: SiC)
- the reforming catalyst is a form in which metallic Ni particles as a catalyst are dispersed on an alumina support. Above 1000 ° C, these Ni particles gradually sinter and coarsen.
- the coarsening of the Ni particles reduces the specific surface area of the Ni particles and reduces the reactivity, making it impossible to use a reforming catalyst at high temperatures.
- the power of the catalyst varies somewhat depending on the type.
- the heat-resistant temperature is about 1000 ° C
- the temperature range above 1000 ° C is the temperature range where the catalyst cannot be used. From the above, it can be seen that steam reforming is possible by using ceramic tubes even in a temperature range of 1000 ° C or higher, where metal reaction tubes and catalysts cannot be used.
- the ceramic reaction tube 24 having excellent heat resistance is used. Steam reforming reaction can be performed.
- the ceramic reaction tube 24 was not easily used as a reaction tube for the steam reforming reaction because it was easy to break, but it was buried in a heat-resistant layer made of heat-resistant carbon fiber alumina fibers or the like, or By wrapping with a heat-resistant cloth made of alumina fiber, and by forming a double structure by putting a metal tube in a ceramic tube, and by making a composite material with fibers such as fibers in ceramics, It can be used as a reaction tube for steam reforming reaction.
- the steam reforming reaction proceeds well without using a reforming catalyst in the high temperature region, the use of the reforming catalyst can be avoided, and as a result, carbon derived from hydrocarbon pyrolysis is introduced into the reaction tube. Since there is no precipitation, the reaction tube is blocked or the reforming catalyst is deactivated, and there is no need to replace the catalyst, so there is no loss of time due to catalyst replacement, such as cooling and reheating of the ceramic reaction tube during replacement. Operation is also unnecessary. Further, since the amount of the reforming catalyst used in the entire steam reforming apparatus 21 is reduced, the cost of the reforming catalyst itself is also reduced.
- a firing furnace is used as an industrial furnace, but when a combustion furnace that burns a heated object is used as an industrial furnace, a ceramic reaction tube is also used in the low temperature reforming section. It is preferable.
- various corrosive components may be contained in the industrial furnace or in the exhaust gas from the industrial furnace. These components are usually detoxified and released after leaving the furnace.
- metals even if the temperature is lower than the heat-resistant temperature (about 1000 ° C), depending on the environment in which it is used, it may not be usable due to corrosion, but in the case of ceramics, it may be usable.
- the heat-resistant temperature about 1000 ° C
- carbon carbide: SiC material can be used up to 870 ° C against SO gas
- nitride nitride Si N is compatible with C1 gas.
- O has corrosion resistance to HC1, S, SO (Ceramics Engineering Nord Book, Japan Association)
- a firing furnace it is preferable to use a metal reaction tube in the low temperature reforming portion as described above from the viewpoint of economy, but a ceramic reaction tube may be used. .
- a ceramic reaction tube in the low temperature reforming part when corrosion becomes a problem due to the atmosphere in the low temperature reforming part.
- the steam reforming apparatus 21 of the present embodiment may be any one of the forces disposed in both the firing furnace main body 1 and the exhaust gas discharge part 6. Further, the high temperature reforming section 22 may be disposed in one of the firing furnace main body 1 and the exhaust gas discharge section 6, and the low temperature reforming section 23 may be disposed in the remaining one.
- the low temperature reforming unit 23 and a plurality of metal reaction tubes 25 are arranged substantially in parallel. At both ends, the end portions of the plurality of metal reaction tubes arranged in a row are connected to the side surface of the metal tube 29 so that the inner portions thereof communicate with each other.
- a plurality of ceramic reaction tubes 24 are arranged substantially in parallel. At both ends, end forces of the plurality of ceramic reaction tubes 24 arranged in a row are connected to the side surfaces of the ceramic tubes 28 so that the respective internal spaces communicate with each other.
- the size and number of the metal reaction tubes and ceramic reaction tubes can be determined as appropriate depending on the size of the firing furnace, the amount of combustion gas, the temperature of the combustion gas, the location of the combustion tube, and the like.
- the reaction tube may be a simple cylinder, but by increasing the heat receiving area by attaching protrusions, blades, etc. to the outer surface, the amount of recovered heat per unit length of the reforming tube is increased. The tube length required for a predetermined reaction amount can be reduced.
- a reforming raw material inflow pipe 26 is further connected to a metal pipe 29 connected to one end side of the low temperature reforming section 23.
- the reformed gas outflow pipe 27 is further connected to the metal pipe 29 connected to the other end side.
- the reforming material inflow pipe 26 is further connected to the ceramic pipe 28 connected to one end side of the high temperature reforming section 22, and connected to the other end side.
- a reformed gas outflow pipe 27 is further connected to the ceramic pipe 28 formed.
- a reforming raw material obtained by mixing hydrocarbons and steam supplied from a hydrocarbon supply device (not shown) and a steam supply device (not shown) in a mixer (not shown) is reformed. It is preferable that the raw material is supplied through the inflow pipe 26.
- a hydrocarbon supply apparatus what is generally used can be used without being specifically limited.
- hydrocarbon raw materials such as LPG and kerosene can be supplied by installing pipes, or they can be supplied by local force pipes such as tanks and cylinders.
- a raw material in a liquid state it is supplied as a gas state by calorie heat or other means before flowing into the reforming pipe. It is also effective to increase the raw material gas pressure using a booster pump as necessary, which increases the amount of reaction.
- a generally used device can be used without being particularly limited. For example, a normal steam boiler, a furnace, or an exhaust heat boiler that uses exhaust heat from other heat sources can be used. Further, when a fuel cell is provided, steam can be generated and supplied using the exhaust heat of the fuel cell.
- the material of the ceramic reaction tube 24 is at least a group force selected from silicon nitride, silicon carbide, aluminum nitride, acid aluminum, and acid zirconium oxide.
- a group force selected from silicon nitride, silicon carbide, aluminum nitride, acid aluminum, and acid zirconium oxide is preferred.
- Examples of the material of the metal reaction tube 25 include SUS309, SUS310, SCH22CF (HK40), SCH24CF (HP), HA230, and the like.
- the ceramic reaction tube 24 has corrosion resistance, it may be corroded depending on the atmosphere in the firing furnace 100, and the metal reaction tube 25 may be corroded as well.
- the reaction tube is corroded by the atmosphere in the firing furnace 100, a hole through which the ceramic reaction tube 24 or the metal reaction tube 25 passes is made in the heat-resistant brick, and the ceramic reaction is made there.
- a tube 24 or a metal reaction tube 25 is preferably provided. As a result, part of the combustion heat is transferred to the ceramic reaction tube 24 or the metal reaction tube 25 by the heat conduction of the heat-resistant brick, while the atmospheric gas containing corrosive components is blocked by the heat-resistant brick. Tube 24 or metal reaction tube 25 is not corroded.
- a Synetix catalyst manufactured by Johnson Matthey can be suitably used as a nickel-containing catalyst.
- effective catalysts include Ni-based, Cu-based, transition metal-based, and platinum-based catalysts.
- ICI method methane (1 mol) and water (2 mol) are heated under a nickel-containing catalyst at a temperature of 700 to 950 (° C) and a pressure of 1 Suitable using a method that generates hydrogen (4 mol) and carbon dioxide (1 mol) by endothermic reaction under the conditions of 01 X 10 5 to 40.52 X 10 5 (N / m 2 ) Can be used for
- the reaction rate of hydrocarbons and water in the steam reformer 21 (ratio of the amount of hydrogen actually generated to the theoretical value of the amount of hydrogen to be generated) is preferably 50 (mol%) or more. Yes. If it is lower than 50 (mol%), the amount of fuel used may increase. Also, the higher the reaction rate of hydrocarbon and water, the better.
- the hydrogen content is preferably 10 to 80 mol%, and the diacid-carbon content is preferably 1 to 20 mol%. Preferably there is.
- examples of the hydrocarbon used as a raw material for the steam reforming reaction include methane, ethane, propane, and butane, and methane is preferable.
- the hydrocarbon and water are reacted under the conditions of 1000 ° C or higher and 180 ° C or lower to form hydrogen and carbon dioxide. Is preferably generated.
- the steam reforming method of the present embodiment uses the steam reformer of the present invention described above to recover part of the combustion heat in the firing furnace.
- the force described in the case where a firing furnace is used as an industrial furnace is not limited to this.
- a firing furnace provided with the steam reformer of the present invention is used.
- a low-temperature reforming part is placed at a position where the temperature is 600 ° C or higher and lower than 1000 ° C due to the heat of the exhaust gas (including heat from waste heat). Scrub to place the part.
- a steam reforming reaction is generated while heating the low temperature reforming part at a position of 600 ° C or higher and lower than 1000 ° C in the baking furnace, and a high temperature reforming is performed at a position of 1000 ° C or higher and 1800 ° C or lower in the baking furnace.
- a steam reforming reaction is generated while heating the mass part to recover a part of the combustion heat of the firing furnace.
- the configuration and conditions of use of the steam reformer are the same as those of the steam reformer of the present invention shown in FIG.
- the steam reformer 21 may be any one of the forces disposed in the calcining furnace main body 1 and the exhaust gas discharge section 6.
- the high temperature reforming section 22 may be disposed on one of the firing furnace main body 1 and the exhaust gas discharge section 6, and the low temperature reforming section 23 may be disposed on the remaining one.
- the low temperature reforming section is heated at a position of 600 ° C or higher and lower than 1000 ° C of the firing furnace using the steam reforming apparatus of the present invention.
- Water vapor reforming reaction is generated, and steam reforming reaction is generated while heating the high temperature reforming part at a temperature of 1000 ° C or higher and 1800 ° C or lower in the firing furnace, and a part of the combustion heat of the firing furnace.
- the steam reforming reaction has a low reactivity at a temperature of 600 ° C or higher and lower than 1000 ° C. Exhaust heat recovery can be performed efficiently even when there is no reforming catalyst at positions where the reactivity of the reaction is higher than 1000 ° C and lower than 1800 ° C. Further, the effects obtained by using the steam reformer of the present invention can be obtained.
- FIG. 3 is a block flow diagram schematically showing an embodiment of the industrial furnace of the present invention.
- a firing furnace is used as an engineering furnace.
- the present invention is not limited to this.
- the arrows shown in FIG. 3 indicate the state in which the reforming material, reformed gas, etc. move.
- the firing furnace 200 includes a firing furnace body 31 in which the steam reforming apparatus 41 of the present invention having the high temperature reforming section 42 and the low temperature reforming section 43 is disposed, and the above-described book.
- Exhaust gas discharge unit 36 in which the water steam reforming apparatus 41 of the invention is disposed, and fuel 66 containing inflowing hydrocarbons 66 And a combustion device 51 for generating combustion gas.
- the hydrocarbon contained in the fuel 66 containing hydrocarbon is preferably methane.
- the object to be fired carried inside is heated and burned by the combustion gas, and the burned combustion gas is discharged to the outside through the exhaust gas discharge unit 36 and the like.
- a combustion device 51 is disposed in the firing zone 32, and the furnace wall and the like of the firing furnace body 31 are heated by the combustion gas generated by the combustion device 51 and the combustion gas.
- the body to be fired is fired with radiant heat generated from the wall, etc., and then the combustion gas is gradually cooled and moves to the high temperature cooling zone 33, and further cooled to the low temperature cooling zone 34.
- the combustion gas that has moved to the low-temperature cooling zone 34 and turned into a low-temperature gas is discharged outside as a low-temperature exhaust gas.
- the low temperature cooling zone 34 is a temperature region below 1 000 ° C
- the high temperature cooling zone 33 is a temperature region above 1000 ° C.
- the water vapor reforming apparatus 41 of the present invention described above is discharged to the outside from the firing furnace body 31 and Z or the firing furnace body 31. It is provided in the flow path (exhaust gas discharge part 36) of the combustion gas (combustion exhaust gas).
- the low-temperature reforming section 43 is disposed in the low-temperature cooling zone 34 that becomes 600 ° C or higher and lower than 1000 ° C by the combustion heat of the firing furnace 200, and 1000 ° C or higher and 1800 ° by the combustion heat of the firing furnace 200.
- the high temperature reforming section 42 is arranged in the high temperature cooling zone 33 that is C or less.
- FIG. 3 the state (configuration) in which the steam reformer 41 of the present invention is disposed in the firing furnace main body 31 and the exhaust gas discharge unit 36 is shown in FIG. This is the same as the state (configuration) arranged in 1.
- the steam reformer 41 may be any one of the forces disposed in the firing furnace main body 31 and the exhaust gas discharge unit 36.
- the high temperature reforming section 42 may be disposed in one of the firing furnace main body 31 and the exhaust gas discharge section 36, and the low temperature reforming section 43 may be disposed in the remaining one.
- the firing furnace 200 of the present embodiment includes the steam reforming apparatus 41 of the present invention in the firing furnace main body 31 and Z or in the exhaust gas discharge part 36, and the low temperature reforming part 43 and The high temperature reforming section 42 is arranged at a position where the combustion heat of the firing furnace 200 is 600 ° C. or higher and lower than 1000 ° C.
- the reforming catalyst is effective at positions above 600 ° C and below 1000 ° C where the reactivity of the steam reforming reaction is low Acting on the effect Exhaust heat can be recovered efficiently, and exhaust heat recovery can be performed efficiently even in the absence of a reforming catalyst at positions where the steam reforming reaction is highly reactive at temperatures above 1000 ° C and below 1800 ° C. Further, the same effect as that obtained by using the steam reforming apparatus 41 of the present invention described above can be obtained.
- the steam reformer 41 is heated by a part of the combustion heat to perform the steam reforming reaction, as in the case of the water steam reformer of the present invention.
- a part of the combustion heat means that the combustion gas is in direct contact with the metal reaction tube and the ceramic reaction tube and received by the metal reaction tube and the ceramic reaction tube, and the combustion gas is in the firing furnace 200.
- the furnace wall isotropic force heated by heating is also the heat received by the metal reaction tube and the ceramic reaction tube among the radiant heat generated in the firing furnace 200.
- the configuration and use conditions of the steam reformer 41 are the same as the configuration and use conditions of the steam reformer of the present invention described above.
- a combustion furnace is used as an industrial furnace, it is preferable to use a ceramic reaction tube in the low temperature reforming section as in the case of the steam reforming apparatus of the present invention described above.
- the firing furnace 200 of the present embodiment selectively introduces hydrogen in the reformed gas 61 by flowing the reformed gas 61 generated by the steam reformer 41 into the interior.
- the hydrogen separator 52 is separated into a hydrogen fuel 62 containing hydrogen as a main component and a residual gas 63 containing carbon dioxide, and the carbon dioxide in the residual gas 63 separated by the hydrogen separator 52 is gasified.
- a fuel cell that generates electricity by a reaction between hydrogen and oxygen, or a reaction between hydrogen and oxygen and a reaction between hydrogen and carbon dioxide. I prefer to have 54 more.
- the firing furnace 200 of the present embodiment includes a combustion apparatus 51, and a mixed fuel 65 composed of a mixed hydrocarbon main fuel 64 containing hydrocarbons and a hydrogen fuel 62 separated by a hydrogen separator 52. It is preferable to reduce the carbon dioxide content in the combustion gas by burning the gas to generate combustion gas. That is, it is preferable to use the mixed fuel 65 as the fuel 66 containing hydrocarbons. As a result, when the combustion gas is discharged to the outside as exhaust gas, the emission amount of carbon dioxide and carbon dioxide to the outside is reduced.
- the hydrocarbon contained in the hydrocarbon main fuel 64 for mixing is preferably methane.
- the carbon dioxide fixing device 53 Then, sodium hydroxide sodium was introduced as a fixing agent 67 for fixing carbon dioxide and carbon inside, and the fixing agent 67 and the residual gas 63 were brought into contact with each other. It is formed so that carbon dioxide contained in 63 is absorbed to produce sodium carbonate, and waste liquid 68 containing sodium carbonate is discharged to the outside.
- the hydrocarbon main fuel 64 containing hydrocarbons has a hydrocarbon content of 80 (volume%) or more.
- the immobilizing agent 67 include NaOH and Mg (OH) which are not particularly limited as long as they can react with carbon dioxide or absorb carbon dioxide.
- each device is connected by a predetermined pipe, and each fuel etc. flows and moves in the pipe.
- the hydrocarbon main fuel 64 for mixing and the hydrogen fuel 62 are mixed as the fuel 66 containing hydrocarbons burned by the combustion device 51. Since the mixed fuel 65 is used, even if the mixed fuel 65 is burned, carbon dioxide is not generated! Carbon dioxide generation is reduced by the amount of hydrogen (hydrogen fuel 62). Can. At this time, the content of hydrogen contained in the mixed fuel 65 (hydrogen / mixed fuel) is preferably 5 to 95 (volume%), and more preferably 25 to 75 (volume%). If it is less than 5 (volume%), the carbon dioxide reduction effect may not be sufficient. If it is more than 95 (volume%), only a part of the combustion heat is required when performing the water vapor reforming reaction.
- a heat source may be required.
- carbon dioxide produced when the reforming raw material 69 is reacted with the reforming catalyst is fixed by the diacid-carbon fixing device 53, the carbon dioxide produced from the reforming raw material 69 is reduced. It is not released to the outside in the state of gas.
- a part of the combustion heat discharged from the calcining furnace body 31 is used as the amount of heat necessary for the endothermic reaction when the reforming raw material 69 is reacted with the reforming catalyst, a part of the exhaust heat is used as the fuel. It can be effectively recovered as combustion heat, which can reduce the total amount of fuel used.
- the hydrogen fuel 62 obtained by separation in the hydrogen separator 52 is branched as hydrogen 70 for a fuel cell, and this is used for the fuel cell 54 to generate electric power.
- the reformed gas 61 discharged from the steam reformer 41 may be used directly in the fuel cell 54 without passing through the hydrogen separator 52. Since the hydrogen fuel 62 obtained by separation in the hydrogen separator 52 has a high purity of hydrogen contained therein, the fuel cell 54 can efficiently generate power. example For example, the power efficiency of about 40% when generating power from a fuel cell using normal hydrogen In the fuel cell 54 used in this embodiment, the power efficiency is drastically 60-70%. To be high.
- the hydrogen in the reformed gas 61 is used for power generation.
- the remaining gas is discharged from 54 fuel cells.
- This residual gas is preferably mixed with fuel and burned in a combustion device.
- the residual gas is discharged from the fuel cell 54, so that this residual gas is also mixed with the fuel. It is preferable to burn with the combustion device 51 U ⁇
- the residual gas discharged from the fuel cell cartridge is converted into carbon dioxide and carbon dioxide. It is preferable to remove the carbon dioxide by passing through a fixing device, and then mix it with fuel and burn it with a combustion device.
- the entire amount of the hydrogen fuel 62 may be used as the mixing hydrogen fuel 71, or may be divided into the mixing hydrogen fuel 71 and the fuel cell hydrogen 70.
- the ratio when dividing hydrogen fuel for mixing 71 and hydrogen for fuel cell 70 is not particularly limited, and the carbon dioxide emissions and power generation amount should be balanced to an appropriate value as appropriate. !
- the firing furnace main body 31 is not particularly limited, and ceramic or the like is carried into the body as a body to be fired, and carbonized by the combustion device 51.
- a fired body such as ceramic is fired by a combustion gas generated by burning fuel 66 containing hydrogen.
- a ceramic house structure can be suitably fired.
- the ceramic hard structure is a ceramic made of a ceramic having a plurality of cells serving as fluid flow paths partitioned by partition walls. It is a structure of a system structure.
- the firing furnace main body 31 may be a batch type in which a predetermined amount of a body to be fired is fired as a unit for one firing, and is fired intermittently once.
- the continuous firing furnace main body 31 is preferable in which the fired body is continuously carried into the interior, the fired body is heated and fired inside, and then continuously carried out to the outside.
- the firing furnace body 31 can generate combustion heat stably and stably, so in the steam reformer 41, the methane reforming reaction is stabilized by part of the combustion heat.
- the hydrogen fuel 62 can be supplied stably, and the mixed fuel 65 obtained by mixing the hydrogen fuel 62 and the hydrocarbon main fuel 64 for mixing can be stably burned.
- Device 51 can be supplied.
- the combustion device 51 is not particularly limited as long as it can efficiently burn the fuel 66 containing hydrocarbons.
- the combustion device 51 is disposed outside the firing furnace body 31 so that the combustion gas flows into the firing furnace body 31 through piping, but is disposed inside the firing furnace body 31. ! / Further, only one combustion device 51 or a plurality of combustion devices 51 may be provided in the firing furnace main body 31 depending on the capacity, the size of the combustion furnace main body 31, and the like.
- the combustion device 51 is not particularly limited as long as it is a burner having a line for introducing air and fuel gas. A regenerative burner or the like that preheats combustion air can also be suitably used.
- the hydrogen separator 52 flows into the interior a reformed gas 61 containing hydrogen generated by the steam reformer 41 and carbon dioxide and carbon dioxide.
- hydrogen in the reformed gas 61 is selectively separated into hydrogen fuel 62 mainly containing hydrogen and residual gas 63 containing carbon dioxide.
- the hydrogen separator 52 is not particularly limited as long as it can selectively separate hydrogen containing hydrogen.
- an alloy containing no ⁇ radium or palladium is formed into a film ( (Hydrogen separation membrane) is formed in a cylindrical shape, and the hydrogen separation membrane is disposed in a cylindrical container made of stainless steel or the like so that the space on the inner side of the cylinder of the hydrogen separation membrane is connected to the outer space.
- the mixed gas containing hydrogen is introduced into the cylindrical container, and introduced into the inside of the cylinder of the hydrogen separation membrane, and only hydrogen is selectively perimeter from the inner side of the hydrogen separation membrane. Transparent to the side
- the hydrogen flowing out to the outer peripheral side of the hydrogen separation membrane cylinder is discharged as hydrogen fuel 62 to the outside of the cylindrical container, and the other gases are passed through the cylinder of the hydrogen separation membrane as residual gas 63.
- the mixed gas containing hydrogen may be introduced outside the cylinder of the hydrogen separation membrane so that the hydrogen flows out to the inside of the cylinder of the hydrogen separation membrane.
- the separated hydrogen is used as hydrogen fuel 62 mainly composed of hydrogen, and the remaining gas 63 containing other carbon dioxide is sent to the diacid-carbon anchor 53.
- the “hydrogen-based” of the hydrogen fuel 62 mainly containing hydrogen means that the hydrogen content is 50 (volume%) or more.
- the cylindrical container need not be cylindrical, and may have a box shape or the like as long as it has a space inside.
- the hydrogen separation membrane may be formed so as to be disposed on the surface or inside of a porous body that also has a ceramic isotropic force. Further, the hydrogen separation membrane may have a flat shape or any other shape that does not need to be cylindrical.
- the hydrogen separator 52 is formed integrally with the steam reformer 41, and hydrogen generated in the steam reformer 41 is converted into a hydrogen separator 41 provided in the steam reformer 41.
- the hydrogen may be selectively separated by using the steam reformer 41 and the hydrogen may be used as the hydrogen fuel 62.
- a hydrogen separation membrane formed in a cylindrical shape is disposed in the steam reformer 41, and a reforming catalyst is placed inside the cylinder. It can be arranged.
- the hydrogen separation membrane functions as the hydrogen separator 52, and the hydrogen separator 52 is disposed in the steam reformer 41.
- the reforming raw material 69 is introduced into the cylinder of the hydrogen separation membrane, hydrogen is generated by the reforming catalyst disposed inside the cylinder of the hydrogen separation membrane, and the generated hydrogen is removed from the hydrogen separation membrane. It can flow out to the outer periphery of the cylinder.
- the outflowed hydrogen is used as hydrogen fuel 62.
- the hydrogen separation efficiency when hydrogen is separated from the reformed gas 61 by the hydrogen separator 52 is (amount of hydrogen contained in the reformed gas 61): (amount of separated hydrogen) is 50. : 50 to 1:99 (volume ratio) is preferable. If it is lower than 50:50 (volume ratio), fuel may not be used efficiently. The higher the separation efficiency, the better. However, 1:99 (volume ratio) is sufficient for the recovery efficiency of combustion hydrogen. To achieve higher separation efficiency, the cost may be higher. is there. [0067] In the firing furnace 200 of the present embodiment shown in FIG. 3, the diacid / carbon fixture 53 is a gas state of the diacid / carbon in the residual gas 63 separated by the hydrogen separator 52.
- the diacid-carbon fixer 53 fixes the diacid-carbon contained in the residual gas 63 and can prevent the diacid-carbon from being released to the outside in a gas state
- an aqueous solution of sodium hydroxide and sodium hydroxide as a fixing agent 67 for fixing carbon dioxide and carbon dioxide in a predetermined container is introduced, and residual gas 63 is introduced into the container and hydroxyaluminum is added.
- a method of immobilizing carbon dioxide by reacting carbon dioxide contained in residual gas 63 with sodium hydroxide to produce sodium carbonate while publishing an aqueous sodium solution with residual gas 63 is suitable.
- fixing carbon dioxide means that carbon dioxide is not released to the outside in the state of gas by reacting with other substances or absorbing them. To do so! Uh.
- the sodium carbonate in the diacid carbonate fixing device 53 is used. Therefore, the waste liquid 68 discharged from the diacid carbonate fixing device 53 can be used as a solution containing sodium carbonate, and the diacid carbonate fixing device 53 can be used as a sodium carbonate generator. can do.
- the case of using the sodium carbonate generator as an example will be described in more detail with respect to the carbon dioxide fixing device 53.
- the structure of the predetermined container constituting the diacid-carbon anchor 53 is that sodium hydroxide is placed in the container and reacted with diacid-carbon to produce sodium carbonate.
- a cylindrical container having at least one introduction pipe for introducing residual gas and sodium hydroxide, and a discharge part for discharging waste liquid (hereinafter sometimes referred to as “sodium carbonate-containing solution”) is provided.
- sodium carbonate-containing solution a waste liquid
- the shape of the container is not particularly limited, and may be a cylindrical shape, a polygonal cylinder (including a box shape) whose bottom shape is a square, or a cylinder (including a box shape) whose bottom shape is indefinite. be able to.
- the diacid / carbon dioxide fixing device 53 may be provided with a stirrer, a jacket or a coil for heating and cooling, if necessary. Furthermore, as the diacid-carbon anchor 53, one container is provided, and when almost all of the sodium hydroxide has reacted, the inflow of residual gas is stopped, After discharging the sodium carbonate-containing solution, it may be a batch type in which sodium hydroxide is put into the container and the inflow of residual gas is started again. When almost all of the sodium hydroxide has reacted in the container, the inflow of the residual gas is switched to the other container, and the production of sodium carbonate is started in the other container. As a semi-batch method, the solution containing sodium carbonate in a container in which almost all has reacted is discharged.
- a sodium hydroxide aqueous solution is used as the fixing agent 67, and the sodium hydroxide aqueous solution is circulated. Let the residual gas 63 flow into the circulating sodium hydroxide solution and mix it so that sodium hydroxide reacts with carbon dioxide! ⁇ .
- the sodium hydroxide aqueous solution is put in a container, and the container power is also discharged through a pipe. The aqueous solution can be pumped back into the container.
- sodium hydroxide is continuously fed into the circulation system of the aqueous solution containing sodium hydroxide and sodium carbonate produced by the reaction, and the aqueous solution containing sodium carbonate continuously circulated from this circulation system. May be extracted as a sodium carbonate-containing solution (waste liquid) 68, and the carbon dioxide fixing device 53 may be operated continuously.
- the hydrogen gas 52 contains the diacid / carbon content in the residual gas 63 after the hydrogen is separated from the reformed gas 61 by the hydrogen separator 52.
- the power is preferably 15-99.9% by mass, more preferably 60% by mass or more. If it is lower than 15% by mass, impurities in the residual gas 63 increase, so it is difficult to increase the purity of the sodium carbonate that is obtained by purifying the waste liquid (sodium carbonate-containing solution) 68 discharged from the carbon dioxide fixing device 53. Sometimes.
- the carbon dioxide content in the residual gas 63 is low or if you want to increase the carbon dioxide content in the residual gas 63, install a transformer (monoxide carbon converter). Also good. In this case, the residual gas 63 discharged from the hydrogen separator 52 is caused to flow into the transformer, and the residual gas 63 that has been transformed and has a high content of carbon dioxide is fed to the carbon dioxide fixer 53. Let it flow.
- a transformer monoxide carbon converter
- Carbon monoxide generated as a by-product in the steam reformer 41 in the residual gas 63 If a large amount of carbon is contained, a carbon monoxide converter may be installed, and the residual gas 63 may flow into the carbon monoxide converter.
- a suitable monoxide-carbon converter is one that transforms monoxide-carbon by bringing the residual gas 63 adjusted to 350 ° C to 360 ° C into contact with the Fe-Cr catalyst. Can be used for In this case, the carbon monoxide transformer generates carbon dioxide and hydrogen using carbon monoxide and water as raw materials. As a result, the carbon monoxide contained in the residual gas 63 is converted to carbon dioxide, and the content of carbon monoxide in the residual gas 63 can be reduced.
- the residual gas 63 having a reduced content of carbon monoxide can be flowed into the carbon dioxide anchor 53. Since the carbon monoxide converter generates hydrogen in addition to carbon dioxide, the hydrogen gas is separated by passing the residual gas 63 that has flowed out through the hydrogen separator, and the hydrogen is mixed with the fuel. May be mixed with 65. At this time, a new hydrogen separator may be installed to allow the entire amount of the residual gas 63 to flow in, or a part of the residual gas 63 may be extracted and flowed into the hydrogen separator 52 together with the reformed gas 61. Thus, a part of the residual gas 63 may be circulated.
- Residual gas 63 that has been transformed and has a high content of carbon dioxide (the residual gas 63 that has also flowed out of the hydrogen separator when it is passed through a hydrogen separator after transformation) is converted into a carbon dioxide fixator 53 Inflow.
- the residual gas 63 is transformed by the above-mentioned carbon monoxide converter, carbon monoxide still remains in the residual gas 63, or the residual gas 63 in which carbon monoxide remains is removed by the monoacid. If the carbon dioxide is not transformed, the residual gas 63 flows into the diacid-carbon fixer 53, and the exhaust gas after reacting the diacid-carbon is reacted (dioxide-carbon fixer exhaust gas). In addition, the carbon monoxide remaining in the residual gas 63 is contained.
- Dioxide-carbon fixer exhaust gas may contain sodium hydroxide and sodium hydroxide in the diacid-fixed carbon fixer 53.
- the fixer exhaust gas When the fixer exhaust gas is mixed into the mixed fuel 65, the contained sodium hydroxide and sodium hydroxide penetrates into the calcining furnace body 31, The firing furnace body 31 may be corroded. For this reason, it is preferable to remove sodium hydroxide and sodium before combustion when the exhaust gas of carbon dioxide and carbon dioxide is mixed with the mixed fuel 65 and burned.
- the sodium hydroxide sodium can be removed before or after the dicarbonate carbon fixer exhaust gas is mixed with the mixed fuel 65.
- the sodium hydroxide can be removed by passing it through a sodium hydroxide remover (not shown) before the dioxide-carbon fixer exhaust gas is mixed into the mixed fuel 65.
- a sodium hydroxide remover As the sodium hydroxide sodium remover, a trap filled with water or the like can be used, and it is preferably installed in the middle of the piping.
- the diacid-carbon in the residual gas 63 does not completely react in the diacid-carbon fixer 53, and unreacted diacid-carbon remains in the exhaust gas of the carbon dioxide fixator.
- another carbon dioxide fixing device may be provided, and the carbon dioxide fixing exhaust gas may be flowed into the second carbon dioxide fixing device to generate sodium carbonate. As a result, the remaining carbon dioxide can be further reduced.
- the sodium carbonate produced in the diacid carbonate fixing device 53 is discharged from the diacid carbonate fixing device 53 as a waste liquid (sodium carbonate-containing solution) 68, and then the sodium carbonate purification step (not shown) And purified as high-purity sodium carbonate. Therefore, the content of sodium carbonate contained in the sodium carbonate-containing solution 68 generated in the diacid carbonate fixing device 53 is 80 to 99. It is more preferable to set it to 9 mass%, and it is still more preferable to set it to 95 mass% or more. When it is lower than 80% by mass, the purity of sodium carbonate obtained by purification in the sodium carbonate purification step (not shown) is difficult to increase.
- the content power with respect to the fixing agent 67 as a whole is preferably 80 to 99.9% by mass, more preferably 95% by mass or more. If it is lower than 80% by mass, the purity of sodium carbonate obtained by purification may be difficult to increase.
- an aqueous solution of sodium hydroxide may be used as described above, or molten sodium hydroxide may be used.
- the content of sodium hydroxide relative to the entire aqueous solution is preferably 30 to 95% by mass. If the concentration is lower than 30% by mass, the concentration of sodium hydroxide and sodium will be low, and it will be difficult to react efficiently with carbon dioxide and carbon dioxide remaining in the exhaust gas of the carbon dioxide fixer. The rate may be high. On the other hand, if it is more than 95% by mass, the viscosity of the sodium hydroxide aqueous solution becomes high and the fluidity becomes poor, so that it may be difficult to efficiently react with carbon dioxide.
- the purity of sodium carbonate taken out by purifying the sodium carbonate-containing solution 68 discharged from the diacid-carbon anchor 53 in a purification step is 98 to 99.9% by mass. It is more preferable that the content is 99.0% by mass or more. By making it higher than 98% by mass, the obtained high-purity sodium carbonate can be used in fields requiring high-purity sodium carbonate such as optical glass and pharmaceuticals as raw materials. The higher the upper limit of the purity of sodium carbonate, the better. Further, the content of sodium carbonate in the entire sodium carbonate-containing solution 68 is preferably 60 to 95% by mass.
- the concentration of sodium carbonate is low, and it may be difficult to efficiently produce sodium carbonate crystals.
- the content is higher than 95% by mass, when sodium carbonate is crystallized by a crystallizer, the slurry concentration due to the sodium carbonate crystal becomes high, and the fluidity may deteriorate.
- a purification method for purifying the sodium carbonate-containing solution 68 discharged from the diacid-carbon anchor 53 sodium carbonate crystals are precipitated from the sodium carbonate-containing solution 68, and the precipitated sodium carbonate is separated from the mother liquor.
- a method of taking out the sodium carbonate crystals is preferable. This purification method precipitates sodium carbonate crystals from sodium carbonate-containing solution 68.
- a refining step comprising a crystallizer (not shown) to be separated and a filter (not shown) for separating the sodium carbonate crystals precipitated by the crystallizer from the mother liquor. ⁇ .
- a commercially available system can be used as the fuel cell 54.
- Any of a polymer type, a phosphoric acid type, a molten carbonate type, and a solid electrolyte type may be used, but a phosphoric acid type, a molten carbonate type, or a solid electrolyte type is preferable because exhaust heat is high.
- the amount of power that can be generated can be designed freely by adopting a method such as the parallel installation of 100KW to 2000KW per system based on the performance of current sales systems.
- hydrogen 70 for fuel cell reacts with air (oxygen in the air), or for fuel cell.
- Hydrogen 70 and oxygen, and fuel cell hydrogen 70 and carbon dioxide each react to generate electricity.
- the steam reformer of the present invention includes the combustion gas discharged in the industrial furnace and in the flow path of the Z or exhaust gas, particularly in the firing furnace for firing ceramics and the like in the ceramic industry and the Z or firing furnace main body. It can be used by being disposed in the exhaust gas discharge section, which becomes the flow path of this, and it becomes possible to efficiently recover a part of the combustion heat generated in the industrial furnace (firing furnace) . Furthermore, according to a preferred embodiment of the present invention, it is possible to reduce the amount of carbon dioxide contained in the combustion exhaust gas, to reduce the amount of carbon dioxide released into the atmosphere, and to further reduce the fuel cost. It becomes possible to reduce. In addition, it is possible to generate power with a fuel cell by recovering and using the thermal energy of the combustion exhaust gas.
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Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2005800368455A CN101048339B (zh) | 2004-10-26 | 2005-10-17 | 水蒸汽重整装置及使用它的水蒸汽重整方法以及工业炉 |
CA2585624A CA2585624C (en) | 2004-10-26 | 2005-10-17 | Steam reforming apparatus and method for steam reforming using the same, and industrial furnace |
EP05793493A EP1816101B1 (en) | 2004-10-26 | 2005-10-17 | Industrial furnace with steam reforming apparatus and method for steam reforming using the same |
PL05793493T PL1816101T3 (pl) | 2004-10-26 | 2005-10-17 | Piec przemysłowy z urządzeniem do reformingu parowego i stosujący go sposób reformingu parowego |
JP2006542971A JP4970949B2 (ja) | 2004-10-26 | 2005-10-17 | 水蒸気改質装置及びそれを用いた水蒸気改質方法並びに工業炉 |
US11/738,093 US20070186471A1 (en) | 2004-10-26 | 2007-04-20 | Steam reforming apparatus and method for steam reforming using the same, and industrial furnace |
Applications Claiming Priority (2)
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JP2004-310575 | 2004-10-26 | ||
JP2004310575 | 2004-10-26 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US11/738,093 Continuation US20070186471A1 (en) | 2004-10-26 | 2007-04-20 | Steam reforming apparatus and method for steam reforming using the same, and industrial furnace |
Publications (1)
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WO2006046426A1 true WO2006046426A1 (ja) | 2006-05-04 |
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ID=36227669
Family Applications (1)
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PCT/JP2005/019043 WO2006046426A1 (ja) | 2004-10-26 | 2005-10-17 | 水蒸気改質装置及びそれを用いた水蒸気改質方法並びに工業炉 |
Country Status (7)
Country | Link |
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US (1) | US20070186471A1 (ja) |
EP (1) | EP1816101B1 (ja) |
JP (1) | JP4970949B2 (ja) |
CN (1) | CN101048339B (ja) |
CA (1) | CA2585624C (ja) |
PL (1) | PL1816101T3 (ja) |
WO (1) | WO2006046426A1 (ja) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008059871A (ja) * | 2006-08-30 | 2008-03-13 | Kyocera Corp | 反応装置、燃料電池システムおよび電子機器 |
JP2008059872A (ja) * | 2006-08-30 | 2008-03-13 | Kyocera Corp | 反応装置、燃料電池システムおよび電子機器 |
US8382866B2 (en) | 2006-08-30 | 2013-02-26 | Kyocera Corporation | Reaction apparatus, fuel cell system and electronic device |
US8382865B2 (en) | 2006-08-30 | 2013-02-26 | Kyocera Corporation | Reaction apparatus, fuel cell system and electronic device |
WO2023211836A1 (en) * | 2022-04-27 | 2023-11-02 | Saudi Arabian Oil Company | Co-production of hydrogen, carbon, electricity, and steel with carbon dioxide capture |
US11967745B2 (en) | 2022-04-27 | 2024-04-23 | Saudi Arabian Oil Company | Co-production of hydrogen, carbon, and electricity with carbon dioxide capture |
Families Citing this family (6)
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WO2008026654A1 (fr) * | 2006-08-30 | 2008-03-06 | Kyocera Corporation | dispositif à réaction, système DE pile À combustible, ET appareil électronique |
FR2914396A1 (fr) * | 2007-03-30 | 2008-10-03 | Inst Francais Du Petrole | Nouveau four de vaporeformage utilisant des bruleurs poreux |
KR20120028927A (ko) * | 2009-06-16 | 2012-03-23 | 쉘 인터내셔날 리써취 마트샤피지 비.브이. | 연료 전지 시스템을 작동시키기 위한 시스템 및 방법 |
US20120251899A1 (en) * | 2011-03-31 | 2012-10-04 | General Electric Company | Solid-oxide fuel cell high-efficiency reform-and-recirculate system |
EP2671842A1 (en) * | 2012-06-06 | 2013-12-11 | Ammonia Casale S.A. | A process for gas-heated reforming of a hydrocarbon source and a related plant |
JP2016513615A (ja) * | 2013-03-08 | 2016-05-16 | コーニング インコーポレイテッド | セラミックの高速焼成方法 |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2008059871A (ja) * | 2006-08-30 | 2008-03-13 | Kyocera Corp | 反応装置、燃料電池システムおよび電子機器 |
JP2008059872A (ja) * | 2006-08-30 | 2008-03-13 | Kyocera Corp | 反応装置、燃料電池システムおよび電子機器 |
US8382866B2 (en) | 2006-08-30 | 2013-02-26 | Kyocera Corporation | Reaction apparatus, fuel cell system and electronic device |
US8382865B2 (en) | 2006-08-30 | 2013-02-26 | Kyocera Corporation | Reaction apparatus, fuel cell system and electronic device |
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US11967745B2 (en) | 2022-04-27 | 2024-04-23 | Saudi Arabian Oil Company | Co-production of hydrogen, carbon, and electricity with carbon dioxide capture |
Also Published As
Publication number | Publication date |
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JP4970949B2 (ja) | 2012-07-11 |
CA2585624C (en) | 2010-06-22 |
PL1816101T3 (pl) | 2013-01-31 |
EP1816101A4 (en) | 2009-11-04 |
US20070186471A1 (en) | 2007-08-16 |
CN101048339A (zh) | 2007-10-03 |
EP1816101B1 (en) | 2012-08-22 |
JPWO2006046426A1 (ja) | 2008-05-22 |
EP1816101A1 (en) | 2007-08-08 |
CN101048339B (zh) | 2011-06-15 |
CA2585624A1 (en) | 2006-05-04 |
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