JP4413734B2 - Firing furnace and firing method - Google Patents

Description

  The present invention relates to a firing furnace and a firing method, and more specifically, carbon dioxide contained in combustion exhaust gas when a combustion gas containing carbon dioxide obtained by burning a fuel containing methane is discharged as combustion exhaust gas. The present invention relates to a firing furnace and a firing method capable of significantly reducing the amount, effectively using and recovering heat of combustion gas, and further reducing fuel costs.

  Conventionally, an industrial furnace is used as an apparatus for heating an object to be heated in various industrial fields. Among these industrial furnaces, what heats an object to be heated by burning a fuel containing carbon generates high-temperature combustion gas containing carbon dioxide simultaneously with heat generated by the combustion of the fuel. Then, the generated combustion gas is discharged to the outside (hereinafter, the combustion gas discharged to the outside may be referred to as “combustion exhaust gas” or simply “exhaust gas”). In recent years, adverse effects on the environment due to the discharge of such high-temperature exhaust gas have become a problem, and it has also become a problem to effectively recover and reuse the heat of combustion exhaust gas. In addition, the problem of the generation of exhaust gas containing carbon dioxide has been highlighted in recent years especially due to the problem of global warming, etc. Has been strongly demanded.

On the other hand, for firing furnaces that fire ceramics, which are relatively small-scale industrial furnaces, there have been few measures to recover the heat of combustion exhaust gas and to reduce carbon dioxide emissions so far. The combustion gas containing carbon dioxide used for heating the object to be heated (the material to be fired) was not discharged as it was, but was directly released into the atmosphere as exhaust gas. On the other hand, for example, a method for recovering the thermal energy of the exhaust gas by returning the exhaust gas emitted from the calcining furnace main body to the calcining furnace main body again has been proposed (see, for example, Patent Document 1). Since a part of the thermal energy of the exhaust gas is recovered, the total amount of fuel used is reduced, but the energy recovery amount and the fuel reduction amount are not so large. In addition, the amount of carbon dioxide generated is reduced, but the reduction amount is not so large.
JP 2002-340482 A

  The present invention has been made in view of such problems of the prior art, and a combustion gas containing carbon dioxide obtained by burning a fuel containing carbon, particularly a fuel containing methane, is externally provided. An object of the present invention is to provide a firing furnace and a firing method capable of effectively recovering the heat of combustion gas when discharged and further reducing the fuel cost. Moreover, according to the aspect which fixes the amount of carbon dioxide contained in combustion gas, the amount of carbon dioxide discharged | emitted outside can be reduced significantly.

  The firing furnace and firing method of the present invention for solving the above-described problems are as follows.

[1] Combustion means for generating a combustion gas by combusting a fuel containing methane that has flowed in, and firing the fired body carried into the interior by the combustion gas, and the combustion gas after firing And a reforming raw material comprising a reforming methane auxiliary fuel mainly composed of methane that has flowed into the methane reforming catalyst and steam. and containing the methane said reacting the vapor with hydrogen and carbon dioxide in the reforming feedstock by contacting the methane reforming catalyst with heating radiation heat from the shrink deposition jig and furnace wall A space in which the methane reformer is disposed in the firing furnace body, and the firing furnace body is disposed on the inner furnace wall by the methane reformer. And to-be-fired body A firing furnace partitioned into a space for firing with combustion gas .

[2] A fuel cell that generates electricity by reacting hydrogen with oxygen or air is further provided, and a part or all of hydrogen contained in the reformed gas is used as fuel cell hydrogen. The firing furnace according to [1], which is used for reaction with air .

[3] The hydrogen gas in the reformed gas is selectively separated by flowing the reformed gas generated in the methane reformer into the interior, and contains hydrogen fuel containing hydrogen as a main component and carbon dioxide The firing furnace according to [1] or [2] , further comprising a hydrogen separator that separates the residual gas from the residual gas .

[4] The firing furnace according to [3], wherein a part or all of the hydrogen fuel is used as a fuel cell hydrogen for a reaction with oxygen or air in the fuel cell .

[5] A firing furnace according to [3], wherein a part or all of the hydrogen fuel is mixed with a mixing methane main fuel containing methane as a main component to form a mixed fuel, and the mixed fuel is burned by the combustion means. .

[6] A part of the hydrogen fuel is used as a fuel cell hydrogen for the reaction with oxygen or air in the fuel cell, and the remainder is mixed with a methane main fuel for mixing mainly composed of methane. The firing furnace as set forth in [3], wherein a mixed fuel is used and the mixed fuel is burned by the combustion means .

[7] The volume ratio of the reforming methane auxiliary fuel to the mixing methane main fuel (reforming methane auxiliary fuel: mixing methane main fuel) is 5:95 to 100: 0 [5] or [ 6] .

[8] The firing furnace according to any one of [3] to [7], wherein the residual gas discharged from the hydrogen separator is burned by the combustion means .

[9] Any of [3] to [8] , further comprising a carbon dioxide fixing device for fixing carbon dioxide in the residual gas separated by the hydrogen separator so that the carbon dioxide is not released to the outside in a gas state. A firing furnace according to any one of the above.

[10] The carbon dioxide fixing device has sodium hydroxide as a fixing agent for fixing carbon dioxide, and can react with the sodium hydroxide and carbon dioxide to generate sodium carbonate [9]. The firing furnace described in 1.

[11] The firing furnace body is a continuous firing furnace body in which the body to be fired is continuously carried into the interior, the body to be fired is heated inside, and then continuously carried out to the outside. ] The baking furnace in any one of [10] .

[12] The firing furnace according to any one of [1] to [11] , wherein at least one of the reforming methane auxiliary fuel and the mixing methane main fuel is liquefied natural gas (LNG) .

[13] The firing furnace according to any one of [1] to [12] , wherein the material to be fired is ceramic .

[14] The firing furnace according to [13] , wherein the ceramic is fired with a heat amount of 1 million to 100 million (kJ / Hr) .

[15] The firing furnace according to any one of [1] to [14] , wherein the fired body is a honeycomb structure .

[16] A combustion gas is generated by injecting and burning a fuel containing methane into the combustion means, and the combustion gas generated by the combustion means is introduced into the firing furnace main body, and the combustion gas causes the combustion gas to enter the combustion means. A firing method for heating and firing the carried object to be fired and discharging the combustion gas after firing to the outside of the firing furnace main body, in a methane reformer filled with a methane reforming catalyst. Then, a reforming raw material consisting of methane auxiliary fuel for reforming mainly composed of methane and steam is introduced, and the reforming raw material is heated to the methane reforming catalyst while being heated by radiant heat from the firing jig and the furnace wall. The methane and the water vapor in the reforming raw material are reacted with each other to generate a reformed gas containing hydrogen and carbon dioxide, and the methane reformer is disposed in the main body of the firing furnace. Is A firing method wherein the sintering furnace main body, the inner furnace wall, a space for disposing the methane reformer, in which partitioned into a space fired combustion gases to be fired.

[17] The firing method according to [16], in which part or all of the hydrogen contained in the reformed gas is used as fuel cell hydrogen to generate power by reacting with oxygen or air in the fuel cell .

[18] Hydrogen containing hydrogen as a main component by allowing the reformed gas generated in the methane reformer to flow into a hydrogen separator and selectively separating the hydrogen in the reformed gas. The firing method according to [16] or [17], wherein the fuel and the residual gas containing carbon dioxide are separated .

[19] The firing method according to [18] , wherein a part or all of the hydrogen fuel is used for reaction with oxygen or air in the fuel cell as hydrogen for a fuel cell .

[20] The firing method according to [18], wherein a part or all of the hydrogen fuel is mixed with a mixing methane main fuel containing methane as a main component to form a mixed fuel, and the mixed fuel is burned by the combustion means. .

[21] A part of the hydrogen fuel is used for a reaction with oxygen or air in the fuel cell, and the remaining part is mixed with a methane main fuel for mixing mainly composed of methane to obtain a mixed fuel, The firing method according to [18] , wherein the mixed fuel is combusted by the combustion means .

[22] The reforming methane auxiliary fuel and the mixing methane main fuel are used so that the volume ratio (reforming methane auxiliary fuel: mixing methane main fuel) is 5:95 to 100: 0. [20] or the firing method according to [21] .

[23] The firing method according to any one of [18] to [22], wherein the residual gas discharged from the hydrogen separator is burned by the combustion means .

[24] The residual gas separated by the hydrogen separator is allowed to flow into a carbon dioxide fixing device, and the carbon dioxide in the residual gas is fixed so as not to be released to the outside in a gas state. [23] The firing method according to any one of [23] .

[25] The carbon dioxide fixing device has sodium hydroxide as a fixing agent for fixing carbon dioxide, and can react with the sodium hydroxide and carbon dioxide to generate sodium carbonate [24]. The firing method described in 1.

[26] As the firing furnace body, a continuous firing furnace body that continuously carries the body to be fired therein, heats the body to be fired inside, and then continuously unloads the body to the outside [16] ] The firing method according to any one of [25] .

[27] The firing method according to any one of [16] to [26], wherein liquefied natural gas (LNG) is used as at least one of the reforming methane auxiliary fuel and the mixing methane main fuel .

[28] The firing method according to any one of [16] to [27], in which ceramic is used as a material of the body to be fired .

[29] The firing furnace according to [28] , wherein the ceramic is fired with a heat amount of 1 million to 100 million (kJ / Hr) .

[30] The firing method according to any one of [16] to [29] , wherein a honeycomb structure is used as the fired body .

  According to the firing furnace of the present invention, the amount of heat of the combustion gas that has been released to the outside is used because the amount of heat of the combustion gas is used as the amount of heat necessary for the endothermic reaction when the reforming raw material is reacted with the methane reforming catalyst. A part can be effectively recovered as the combustion heat of the fuel, and the total amount of fuel used can be reduced. In addition, as a method of recovering the heat of the combustion gas, a method of recovering from the combustion gas discharged to the outside of the firing furnace body (hereinafter sometimes referred to as “combustion exhaust gas”), and a combustion gas in the firing furnace body. And / or a method using radiant heat from a firing object and a furnace wall heated by a combustion gas, and both of them may be performed simultaneously. Use of the heat of the combustion gas and / or the object to be fired heated by the combustion gas, the firing jig, and the radiant heat from the furnace wall in the main body of the firing furnace can eliminate heat dissipation when the combustion exhaust gas moves. The amount of heat can be recovered more efficiently. Hereinafter, “heat of combustion gas” may include “radiant heat from an object to be fired, a firing jig and a furnace wall heated by the combustion gas”.

  According to a preferred embodiment of the firing furnace of the present invention, as fuel containing methane to be combusted by the combustion means, methane main fuel for mixing mainly composed of methane, methane auxiliary fuel for reforming mainly composed of methane, and steam As a result of using a mixed fuel of hydrogen fuel obtained by reacting a reforming raw material comprising a methane reforming catalyst, the amount of fuel containing methane can be reduced, and in the combustion exhaust gas from fuel containing methane The carbon dioxide content of can be greatly reduced. In addition, since the carbon dioxide produced when the reforming raw material is reacted with the methane reforming catalyst is fixed by the carbon dioxide fixing device, the carbon dioxide produced from the reforming raw material is released to the outside in a gas state. Never happen. The carbon dioxide fixed here corresponds to the reduced carbon dioxide in the carbon dioxide in the combustion exhaust gas. Further, as the amount of heat necessary for the endothermic reaction when the reforming raw material is reacted with the methane reforming catalyst, the calorific value of the combustion gas in the main body of the firing furnace and / or the object to be fired, the firing jig In addition, the amount of heat of the radiant heat from the furnace wall or the amount of heat of the combustion exhaust gas discharged from the calcining furnace body is used as hydrogen fuel, so a part of the heat of the combustion gas (part of the exhaust heat of the combustion exhaust gas) is used as fuel. Can be effectively recovered as the combustion heat of the fuel, and the total amount of fuel used can be reduced.

  According to another preferred embodiment of the firing furnace of the present invention, the calorific value of the combustion gas in the calcining furnace body and / or the calcined object heated by the combustion gas, the calcining jig and the calorific value of the radiant heat from the furnace wall, or the calcining The heat of the combustion exhaust gas discharged from the furnace body is used to generate hydrogen and carbon dioxide (reformed gas) from methane and steam in the methane reformer, and the hydrogen separator separates hydrogen from the reformed gas. Thus, the hydrogen fuel is taken out and the hydrogen fuel is used as fuel cell hydrogen to generate power in the fuel cell. Therefore, the heat of the combustion gas (combustion exhaust gas) can be effectively recovered and used for power generation by the fuel cell. A part of the hydrogen fuel can be used as the mixed fuel, and the remaining part can be used as hydrogen for the fuel cell. Further, all of the hydrogen fuel may be used as the mixed fuel.

  In addition, according to the firing method of the present invention, as in the case of firing using the firing furnace of the present invention described above, the calorific value necessary for the endothermic reaction when the reforming raw material is reacted with the methane reforming catalyst is calcined. To use the amount of combustion gas in the furnace body and / or the amount of radiant heat from the object to be fired, the firing jig and the furnace wall heated by the combustion gas, or the amount of combustion exhaust gas discharged from the body of the firing furnace Thus, a part of the heat of the combustion gas (combustion exhaust gas) is recovered as the combustion heat of the fuel, and the total amount of fuel used can be reduced. In addition, by using the heat of the combustion gas instead of using the heat of the combustion exhaust gas, it is possible to eliminate heat dissipation when the combustion exhaust gas moves, and to recover heat more efficiently.

  According to a preferred embodiment of the firing method of the present invention, hydrogen and carbon dioxide (reformed gas) are generated from methane and steam in a methane reformer using the heat of combustion exhaust gas discharged from the firing furnace body, The separator separates the hydrogen from the reformed gas to take out the hydrogen fuel, and the hydrogen fuel is used as fuel cell hydrogen to generate electricity in the fuel cell, so that the heat of the combustion exhaust gas is effectively recovered and used for power generation by the fuel cell. Can be used.

  According to another preferred embodiment of the firing method of the present invention, as fuel containing methane to be burned by the combustion means, methane main fuel for mixing mainly composed of methane, and methane auxiliary fuel for reforming mainly composed of methane, Since a mixed fuel of hydrogen obtained by reacting a reforming raw material consisting of water vapor with a methane reforming catalyst is used, the carbon dioxide content in the combustion exhaust gas can be greatly reduced. In addition, when carbon dioxide produced when the reforming raw material is reacted with the methane reforming catalyst is fixed by a carbon dioxide fixing device, the carbon dioxide produced from the reforming raw material is externally in a gas state. This is preferable because it can be prevented from being released. The carbon dioxide fixed here corresponds to the reduced carbon dioxide in the carbon dioxide in the combustion exhaust gas.

  Next, embodiments of the present invention will be described in detail with reference to the drawings. However, the present invention is not limited to the following embodiments, and is within the scope of the present invention. Based on this knowledge, it should be understood that design changes, improvements, etc. can be made as appropriate.

  FIG. 1 is a block flow diagram schematically showing one embodiment of a firing furnace of the present invention. And the arrow in FIG. 1 has shown the state to which each fuel, combustion exhaust gas, water vapor | steam, another substance, etc. move.

  As shown in FIG. 1, the firing furnace 100 of the present embodiment includes a combustion means 2 that burns fuel 11 containing methane that has flowed in to generate combustion gas, and a firing object that is carried into the interior by the combustion gas. A calcining furnace main body 1 for heating and calcining the body and discharging the burned combustion gas to the outside. The reforming raw material 23 composed of the quality methane auxiliary fuel 21 and the water vapor 22 is reformed by being brought into contact with the methane reforming catalyst 6 while being heated by the combustion gas (combustion exhaust gas 12) discharged from the calcining furnace body 1 to the outside. It further comprises a methane reformer 3 that reacts methane in the raw material 23 with water vapor 22 to generate a reformed gas 24 containing hydrogen and carbon dioxide (to cause a methane reforming reaction).

  According to the firing furnace 100 of the present embodiment, the heat of the combustion exhaust gas 12 can be effectively reused by performing the methane reforming reaction in the methane reformer 3 while using the heat of the combustion exhaust gas 12. it can.

  Further, as shown in FIG. 1, the firing furnace 100 of the present embodiment selectively separates hydrogen in the reformed gas 24 by flowing the reformed gas 24 generated in the methane reformer 3 into the interior. The hydrogen separator 4 for separating the hydrogen fuel 25 mainly containing hydrogen and the residual gas 26 containing carbon dioxide, and the carbon dioxide in the residual gas 26 separated by the hydrogen separator 4 in a gas state. And a carbon dioxide fixing device 5 that is fixed so as not to be released to the outside.

In the firing furnace 100 of the present embodiment, the combustion means 2 flows into the mixing methane main fuel 31 containing methane as a main component and the hydrogen fuel 25 separated by the hydrogen separator 4 (mixing hydrogen fuel 28). It is possible to reduce the carbon dioxide content in the combustion exhaust gas 12 by burning the mixed fuel 32 with the fuel), that is, by using the mixed fuel 32 as the fuel 11 containing methane and generating combustion gas. It is said. As a result, after the combustion exhaust gas 12 is used in the methane reformer 3, the amount of carbon dioxide discharged to the outside as the reformer exhaust gas 43 is reduced. And by performing the methane reforming reaction in the methane reformer 3 while using the heat of the combustion exhaust gas, the heat of the combustion exhaust gas can be effectively reused. Further, the carbon dioxide fixing device 5 allows sodium hydroxide to flow in as a fixing agent 41 for fixing carbon dioxide inside, and makes the fixing agent 41 and the residual gas 26 contact with each other. Carbon dioxide contained in the residual gas 26 is absorbed to generate sodium carbonate, and the waste liquid 42 containing sodium carbonate is discharged to the outside. Here, in the mixing methane main fuel 31 containing methane as a main component, “having methane as a main component” means that the content of methane is 80 (volume%) or more. The immobilizing agent 41 is not particularly limited as long as it can react with carbon dioxide or absorb carbon dioxide, and examples thereof include NaOH and Mg (OH) ₂ . In addition, each device is connected by a predetermined pipe, and each fuel, water vapor, and the like flow and move in the pipe.

  Thus, according to the firing furnace 100 of the present embodiment, the mixed fuel of the mixing methane main fuel 31 and the hydrogen fuel 25 (mixing hydrogen fuel 28) as the fuel 11 containing methane to be combusted by the combustion means 2. Since 32 is used, the generation of carbon dioxide can be reduced by the amount that the mixed fuel 32 (fuel 11) contains hydrogen (hydrogen fuel 25) that does not generate carbon dioxide even when burned. At this time, the hydrogen content (hydrogen / mixed fuel) contained in the mixed fuel 32 is preferably 5 to 95 (volume%), 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%), not only the combustion exhaust gas but also other heat sources are used when performing the methane reforming reaction. You may need it. Further, since the carbon dioxide produced when the reforming raw material 23 is reacted with the methane reforming catalyst 6 is fixed by the carbon dioxide fixing device 5, the carbon dioxide produced from the reforming raw material 23 is in a gas state. It is not released to the outside. Further, since the calorific value of the flue gas 12 discharged from the calcining furnace body 1 is used as the amount of heat necessary for the endothermic reaction when the reforming raw material 23 is reacted with the methane reforming catalyst 6, the exhaust heat of the flue gas 12 is used. By using a part of the fuel as hydrogen fuel, it is possible to effectively recover the heat of combustion of the fuel, thereby reducing the total amount of fuel used. Here, as the heat source for the methane reforming reaction, the heat discarded from the furnace wall as well as the heat dissipated from the furnace wall and the cooling of the kiln tool used during ceramic firing can be used.

  As shown in FIG. 1, the firing furnace 100 of the present embodiment further includes a fuel cell 7. The fuel cell 7 generates power by reacting hydrogen (hydrogen for fuel cells) with oxygen or air. As shown in FIG. 1, it is preferable that a part of the hydrogen fuel 25 obtained by separation by the hydrogen separator 4 is branched as hydrogen 28 for a fuel cell and used for the fuel cell 7 to generate electric power. The reformed gas 24 discharged from the mass device 3 may be used directly in the fuel cell 7 without passing through the hydrogen separator 4. Since the hydrogen fuel 25 obtained by separation with the hydrogen separator 4 has a high purity of hydrogen contained therein, the fuel cell 7 can efficiently generate power. For example, when the fuel cell is generated using normal hydrogen, the power efficiency is about 40%, but in the fuel cell 7 used in the present embodiment, the power efficiency is drastically 60 to 70%. To be high. Further, a part of the hydrogen fuel 25 obtained by separation by the hydrogen separator 4 is finally burned by the combustion means 2 as the mixing hydrogen fuel 28, and the rest is generated as the fuel cell hydrogen 27 by the fuel cell 7. By using it, the amount of carbon dioxide contained in the combustion exhaust gas 12 can be reduced, and at the same time, the heat of the combustion exhaust gas 12 can be effectively recovered and used for power generation.

  Further, when the reformed gas 24 discharged from the reformer 3 is directly used in the fuel cell 7 without passing through the hydrogen separator 4, hydrogen in the reformed gas 24 is used for power generation. Residual gas is discharged from the fuel cell 7. This residual gas is preferably mixed with fuel and burned by a combustion means. In addition, when part or all of the hydrogen fuel 25 obtained by separation in the hydrogen separator 4 is used in the fuel cell 7, the remaining gas is discharged from the fuel cell 7, so that the remaining gas is also mixed with the fuel. Then, it is preferable to burn with combustion means.

  In addition, when carbon dioxide is contained in the residual gas discharged from the fuel cell and a carbon dioxide fixing device is used, the residual gas discharged from the fuel cell is passed through the carbon dioxide fixing device to remove carbon dioxide. Then, it is preferable to mix with fuel and burn it with a combustion means.

  The entire amount of the hydrogen fuel 25 may be used as the mixing hydrogen fuel 28 or may be divided into the mixing hydrogen fuel 28 and the fuel cell hydrogen 27. The ratio when dividing into the mixing hydrogen fuel 28 and the fuel cell hydrogen 27 is not particularly limited, and the carbon dioxide emission amount and the power generation amount may be appropriately balanced so as to be an optimum value. .

  In the firing furnace 100 of the present embodiment shown in FIG. 1, the firing furnace body 1 is not particularly limited, and ceramic or the like is carried into the body as a body to be fired, and fuel 11 containing methane by the combustion means 2. A fired body such as ceramic is fired by a combustion gas generated by burning the fired steel. As the body to be fired, a ceramic honeycomb structure can be suitably fired. Here, the ceramic honeycomb structure is a honeycomb structure having a plurality of cells made of ceramic and serving as a flow path of fluid partitioned by partition walls. The firing furnace body 1 may be a batch type in which a predetermined amount of a body to be fired is used as a unit for one firing, and is fired intermittently once, but a body to be fired such as a ceramic honeycomb structure may be used. The continuous firing furnace body 1 is preferably a continuous firing furnace body 1 that is continuously carried into the interior, heated and fired inside the fired body, and then continuously carried out to the outside. By continuously firing, the combustion exhaust gas 12 can be discharged from the firing furnace main body 1 stably and stably, so that in the methane reformer 3, the methane reforming reaction is stabilized by the heat of the combustion exhaust gas 12. Accordingly, the hydrogen fuel 25 can be stably supplied, and the mixed fuel 32 obtained by mixing the hydrogen fuel 25 and the methane main fuel 31 for mixing can be stably combusted. Can be supplied to.

  In the firing furnace 100 of the present embodiment shown in FIG. 1, the combustion means 2 is not particularly limited as long as it can efficiently burn the fuel 11 containing methane and hydrogen. The combustion means 2 may be disposed outside the firing furnace body 1 so that the combustion gas flows into the firing furnace body 1 through a pipe. Good. Further, only one combustion means 2 or a plurality of combustion means 2 may be provided in the firing furnace main body 1 depending on its capacity, the size of the combustion furnace main body 1 and the like. The combustion means 2 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.

  In the firing furnace 100 of the present embodiment shown in FIG. 1, the methane reformer 3 is filled with a methane reforming catalyst 6 inside a container made of stainless steel or ceramics, and has methane flowing therein as a main component. The reforming raw material 23 composed of the reforming methane auxiliary fuel 21 and the steam 22 is brought into contact with the methane reforming catalyst 6 while being heated by the combustion exhaust gas 12, thereby reacting the methane and the steam 22 in the reforming raw material 23. Thus, a reformed gas 24 containing hydrogen and carbon dioxide is generated (a methane reforming reaction is performed). As the methane reformer 3 used in the present embodiment, hydrogen can be obtained by reacting methane, and carbon in the methane can be finally fixed without being released to the outside If it is. The immobilization of carbon in methane may be performed in a subsequent process of the methane reformer 3. In the present embodiment, the carbon dioxide fixing unit 5 fixes carbon dioxide. The reaction rate of methane and water in the methane reformer 3 (the ratio of the amount of hydrogen actually generated to the theoretical value of the amount of hydrogen to be generated relative to the input raw materials (methane and water)) is 50 (mol%). ) Or more. If it is lower than 50 (mol%), the amount of fuel used may increase. Moreover, the higher the reaction rate of methane and water, the better.

  The hydrogen content in the reformed gas 24 produced by the methane reformer 3 is preferably 10 to 80 mol%, and the carbon dioxide content is preferably 1 to 20 mol%.

  The shape of the container filled with the methane reforming catalyst 6 is not particularly limited, and may be any shape such as a cylindrical shape or a box shape.

As a specific example of the methane reformer 3, for example, called “ICI method”, methane (1 mol) and water (2 mol) are heated at a temperature of 700 to 950 (° C.) under a nickel-containing catalyst and a pressure of 1. Preferably used is a method utilizing an endothermic reaction under conditions of 01 × 10 ^{5 to} 40.52 × 10 ⁵ (N / m ² ) to generate hydrogen (4 mol) and carbon dioxide (1 mol). can do. As the nickel-containing catalyst, for example, a Synexix catalyst manufactured by Johnson Matthey can be suitably used. Further, effective catalysts include Ni-based, Cu-based, transition metal-based, platinum-based and the like.

  In the methane reformer 3, since the reaction for generating hydrogen from methane is an endothermic reaction, it is necessary to carry out the reaction while heating. In the present embodiment, this heating is performed by the combustion exhaust gas 12 discharged from the firing furnace body 1. Therefore, it is possible to effectively recover the heat of the combustion exhaust gas 12 without newly generating heat. Thereby, the total amount of fuel used can be reduced, and energy resources can be utilized efficiently. Here, the temperature of the combustion exhaust gas 12 is preferably 200 to 950 (° C.). If it is lower than 200 (° C.), it may be difficult to react methane and water vapor, and if it is higher than 950 (° C.), the durability of the members constituting the reactor may be lowered. Moreover, since the calorie | heat amount which the combustion exhaust gas 12 has changes with kinds, magnitude | sizes, etc. of the baking furnace main body 1, it is not specifically limited.

  In the firing furnace 100 of the present embodiment shown in FIG. 1, the hydrogen separator 4 causes the reformed gas 24 containing hydrogen and carbon dioxide generated in the methane reformer 3 to flow into the reformed gas 24. The hydrogen in the gas is selectively separated and separated into a hydrogen fuel 25 containing hydrogen as a main component and a residual gas 26 containing carbon dioxide. The hydrogen separator 4 is not particularly limited as long as it can selectively separate hydrogen from a mixed gas containing hydrogen. For example, palladium or an alloy containing palladium 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 and the space on the outer peripheral side are not connected. Then, a hydrogen-containing mixed gas is introduced into the cylindrical container and introduced into the inside of the cylinder of the hydrogen separation membrane, and only hydrogen is selectively permeated from the inside of the hydrogen separation membrane to the outer peripheral side. Then, the hydrogen flowing out to the outer peripheral side of the cylinder of the hydrogen separation membrane is caused to flow out as hydrogen fuel 25 to the outside of the cylindrical container, and the other gas passes through the inside of the cylinder of the hydrogen separation membrane as it is as the residual gas 26. So that it flows out of the container. Can be suitably used were ones. The mixed gas containing hydrogen may be introduced to the outside of the cylinder of the hydrogen separation membrane so that the hydrogen flows out to the inside of the cylinder of the hydrogen separation membrane. Here, the separated hydrogen is used as the hydrogen fuel 25 containing hydrogen as a main component, and the remaining gas 26 containing other carbon dioxide is sent to the carbon dioxide fixing device 5. The term “having hydrogen as a main component” in the hydrogen fuel 25 having hydrogen as a main component means that the hydrogen content is 50 (volume%) or more. Moreover, the said cylindrical container does not need to be cylindrical, for example, a box shape etc. may be sufficient if it is a shape which has space inside. In order to improve the mechanical strength, the hydrogen separation membrane may be formed so as to be disposed on the surface or inside of a porous body made of ceramic or the like. Further, the hydrogen separation membrane does not need to be cylindrical, and may be planar or any other shape.

  The hydrogen separator 4 is formed integrally with the methane reformer 3, and hydrogen generated in the methane reformer 3 is selectively separated by the hydrogen separator 4 disposed in the methane reformer 3. Alternatively, the hydrogen may be discharged from the methane reformer 3 and used as the hydrogen fuel 25. As a method of disposing the hydrogen separator 4 in the methane reformer 3, for example, a hydrogen separation membrane formed in a cylindrical shape is disposed in the methane reformer 3, and the methane reforming catalyst 6 is disposed inside the cylinder. Can be disposed. In this case, the hydrogen separation membrane functions as the hydrogen separator 4, and the hydrogen separator 4 is disposed in the methane reformer 3. Thereby, the reforming raw material 23 is introduced into the cylinder of the hydrogen separation membrane, hydrogen is generated by the methane reforming catalyst 6 disposed inside the cylinder of the hydrogen separation membrane, and the generated hydrogen is removed from the hydrogen separation membrane. Can flow out to the outer peripheral side of the tube. The outflowed hydrogen is used as the hydrogen fuel 25.

  As the hydrogen separation efficiency when hydrogen is separated from the reformed gas 24 by the hydrogen separator 4, (amount of hydrogen contained in the reformed gas 24: amount of separated hydrogen) is 50:50 to 1: 99 (volume ratio) is preferable. If it is lower than 50:50 (volume ratio), the fuel may not be used efficiently. The higher the separation efficiency, the better. However, if it is 1:99 (volume ratio), the recovery efficiency of combustion hydrogen is sufficient, and in order to realize a higher separation efficiency, the cost may be higher. is there.

  In the firing furnace 100 of the present embodiment shown in FIG. 1, the carbon dioxide fixing device 5 is fixed so that carbon dioxide in the residual gas 26 separated by the hydrogen separator 4 is not released to the outside in a gas state. It is something to be made. The carbon dioxide fixing device 5 is not particularly limited as long as it can fix the carbon dioxide contained in the residual gas 26 and prevent the carbon dioxide from being released to the outside in a gas state. For example, an aqueous solution of sodium hydroxide is placed as a fixing agent 41 for fixing carbon dioxide in a predetermined container, a residual gas 26 is introduced into the aqueous solution, and the aqueous solution of sodium hydroxide is bubbled with the residual gas 26. Thus, a method of immobilizing carbon dioxide by reacting carbon dioxide contained in the residual gas 26 with sodium hydroxide to produce sodium carbonate can be suitably used. Here, immobilizing carbon dioxide refers to preventing carbon dioxide from being released in the form of gas by reacting with another substance or absorbing the substance.

  As described above, by using a sodium hydroxide-containing material (solution) such as an aqueous solution of sodium hydroxide as the fixing agent 41, sodium carbonate can be generated by the carbon dioxide fixing device 5. The waste liquid 42 discharged from the vessel 5 can be a sodium carbonate-containing solution, and the carbon dioxide fixing device 5 can be used as a sodium carbonate generator. Hereinafter, the carbon dioxide fixing device 5 will be described in more detail by taking as an example the case of use as a sodium carbonate generator.

  The structure of the predetermined container constituting the carbon dioxide fixing device 5 is not particularly limited as long as sodium hydroxide can be put in the container and reacted with carbon dioxide to generate sodium carbonate. For example, at least one introduction pipe for introducing residual gas and sodium hydroxide, and a cylindrical container having a discharge part for discharging waste liquid (hereinafter sometimes referred to as “sodium carbonate-containing solution”) are used. can do. The shape of the container is not particularly limited, and includes a cylindrical shape, a polygonal cylinder (including a box shape) such as a square bottom shape, a cylinder (including a box shape) whose bottom shape is indefinite, etc. can do. The carbon dioxide fixing device 5 may be provided with a stirrer, a jacket for heating and cooling, and a coil as necessary. Further, as the carbon dioxide fixing device 5, one container is provided, and when almost all of the sodium hydroxide has reacted, the inflow of residual gas is stopped and the sodium carbonate-containing solution is discharged. It may be a batch type in which the inflow of residual gas is started again, but two or more of the above containers are provided, and when almost all of the sodium hydroxide has reacted in one container, the residual gas A semi-batch system in which the inflow is switched from one container to another, and the production of sodium carbonate is started in the other container, while the sodium carbonate-containing solution in the container in which almost all sodium hydroxide has reacted is discharged. It is good.

  Further, as a method of immobilizing carbon dioxide to produce sodium carbonate, a sodium hydroxide aqueous solution is used as the fixing agent 41, the sodium hydroxide aqueous solution is circulated, and the residual gas 26 is circulated in the circulating sodium hydroxide aqueous solution. May be introduced and mixed to react sodium hydroxide and carbon dioxide. As a method of circulating the sodium hydroxide aqueous solution (sodium carbonate is also contained after the sodium carbonate is generated), for example, the sodium hydroxide aqueous solution is put in a container, and the sodium hydroxide aqueous solution discharged from the container through a pipe is again pumped. It can be returned to the container. At this time, 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 is carbonated. The carbon dioxide fixing device 5 may be continuously operated by extracting it as a sodium-containing solution (waste liquid) 42.

  When the carbon dioxide fixing device 5 is used as a sodium carbonate generator, the carbon dioxide content in the residual gas 26 after hydrogen is separated from the reformed gas 24 by the hydrogen separator 4 is 15 to 99.9 masses. %, And more preferably 60% by mass or more. If it is lower than 15% by mass, the amount of impurities in the residual gas 26 increases, so it may be difficult to increase the purity of the sodium carbonate that is obtained by purifying the sodium carbonate-containing solution 42 discharged from the carbon dioxide fixing device 5. Further, when the carbon dioxide content in the residual gas 26 is low or when it is desired to increase the carbon dioxide content in the residual gas 26, a transformer (carbon monoxide transformer) may be installed. In this case, the residual gas 26 discharged from the hydrogen separator 4 is caused to flow into the transformer, and the residual gas 26 that has been transformed and has a high carbon dioxide content is caused to flow into the carbon dioxide fixing device 5.

  When the residual gas 26 contains a large amount of carbon monoxide generated as a by-product in the methane reformer 3, a carbon monoxide converter is installed to convert the residual gas 26 into the carbon monoxide. May flow into the vessel. As the carbon monoxide converter, the one that converts carbon monoxide by bringing the residual gas 26 adjusted to 350 ° C. to 360 ° C. into contact with the Fe—Cr catalyst can be preferably used. . In this case, the carbon monoxide transformer generates carbon dioxide and hydrogen using carbon monoxide and water as raw materials. Thereby, the carbon monoxide contained in the residual gas 26 is transformed into carbon dioxide, and the carbon monoxide content in the residual gas 26 can be reduced. The residual gas 26 having a reduced carbon monoxide content can be caused to flow into the carbon dioxide fixing device 5. Since the carbon monoxide converter generates hydrogen in addition to carbon dioxide, the residual gas 26 flowing out from the carbon monoxide converter is passed through the hydrogen separator, thereby separating the hydrogen and mixing the hydrogen into the mixed fuel 32. You may use it. At this time, a hydrogen separator may be newly installed to allow the entire amount of the residual gas 26 to flow, or a part of the residual gas 26 may be extracted and flowed into the hydrogen separator 4 together with the reformed gas 24. A part of the residual gas 26 may be circulated. The residual gas 26 that has been transformed and has a high carbon dioxide content (the residual gas 26 that has flowed out of the hydrogen separator when it is passed through the hydrogen separator after the transformation) is caused to flow into the carbon dioxide fixing device 5.

  Further, after the residual gas 26 is transformed by the carbon monoxide converter, carbon monoxide still remains in the residual gas 26, or the residual gas 26 in which carbon monoxide remains is not transformed by the carbon monoxide transformer. In this case, the residual gas 26 flows into the carbon dioxide fixing device 5, and the carbon monoxide remaining in the residual gas 26 is added to the exhaust gas 44 (carbon dioxide fixing exhaust gas) 44 after the carbon dioxide is reacted. Will be contained. As a method of treating carbon monoxide contained in the carbon dioxide fixing exhaust gas 44, it is preferable to mix the carbon dioxide fixing exhaust gas 44 into the mixed fuel 32 and burn it by the combustion means 2. At this time, when the carbon dioxide fixing exhaust gas 44 contains hydrogen, it is preferable because hydrogen is also burned by the combustion means 2 as fuel.

  When the carbon dioxide fixing exhaust gas 44 is mixed with the mixed fuel 32, the sodium hydroxide in the carbon dioxide fixing device 5 may be scattered and the droplets may be contained in the carbon dioxide fixing exhaust gas 44. In some cases, sodium hydroxide contained invades into the firing furnace body 1 and corrodes the firing furnace body 1. Therefore, when the carbon dioxide fixing exhaust gas 44 is mixed with the mixed fuel 32 and burned, it is preferable to remove sodium hydroxide before combustion. The sodium hydroxide may be removed before or after the carbon dioxide fixing exhaust gas 44 is mixed with the mixed fuel 32. For example, before the carbon dioxide fixing exhaust gas 44 is mixed into the mixed fuel 32, the sodium hydroxide can be removed by passing it through a sodium hydroxide remover (not shown). As the sodium hydroxide remover, a trap filled with water or the like can be used, and is preferably installed in the middle of the piping.

  If carbon dioxide in the residual gas 26 does not react completely in the carbon dioxide fixing device 5 and unreacted carbon dioxide remains in the carbon dioxide fixing device exhaust gas 44, a part of the carbon dioxide fixing device exhaust gas 44 It is preferable to extract the gas and flow it into the carbon dioxide fixing device 5 again. Thereby, the residual carbon dioxide can be reduced. Further, another carbon dioxide fixing device may be provided, and the carbon dioxide fixing exhaust gas 44 may be caused to flow into the second carbon dioxide fixing device to generate sodium carbonate. Thereby, the remaining carbon dioxide can be further reduced.

  The method for treating the residual gas 26 with the carbon monoxide converter, the method for mixing the carbon dioxide fixer exhaust gas 44 into the mixed fuel 32, and the method for causing the carbon dioxide fixer exhaust gas 44 to flow into the carbon dioxide fixator are as follows. Depending on the amount of carbon monoxide contained in the residual gas 26 and the amount of carbon monoxide and the amount of carbon dioxide contained in the carbon dioxide fixer exhaust gas 44, either operation may be used alone, or each of them may be optimized. You may use it combining, so that it may become conditions.

  The sodium carbonate produced in the carbon dioxide fixing device 5 is discharged from the carbon dioxide fixing device 5 as a sodium carbonate-containing solution 42, then purified in a sodium carbonate purification step (not shown), and taken out as high-purity sodium carbonate. It is preferable. Therefore, the content rate of the sodium carbonate contained in the sodium carbonate-containing solution 42 generated in the carbon dioxide fixing device 5 with respect to the remaining substance excluding water from the sodium carbonate-containing solution 42 is set to 80 to 99.9% by mass. It is preferable that the content be 95% by 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.

  Thus, in order to make sodium carbonate obtained by purification high purity, it is preferable to use high purity sodium hydroxide to be reacted with carbon dioxide in the carbon dioxide fixing device 5. That is, the remaining substance obtained by removing water from the fixing agent 41 of sodium hydroxide in the fixing agent 41 put into the carbon dioxide fixing device 5 (when the fixing agent 41 does not contain water, the fixing agent 41) is preferably 80 to 99.9% by mass, and 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. As the fixing agent 41, an aqueous solution of sodium hydroxide may be used as described above, or molten sodium hydroxide may be used. Moreover, when the sodium hydroxide aqueous solution is used as the fixing agent 41, the content of sodium hydroxide in the entire aqueous solution is preferably 30 to 95% by mass. If it is lower than 30% by mass, the concentration of sodium hydroxide is low, so that it is difficult to react efficiently with carbon dioxide, and the content of carbon dioxide remaining in the carbon dioxide fixer exhaust gas 44 may increase. On the other hand, when the content is higher than 95% by mass, the viscosity of the aqueous sodium hydroxide solution is increased and the fluidity is deteriorated, 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 42 discharged from the carbon dioxide fixing device 5 in a purification step (not shown) is preferably 98 to 99.9% by mass. More preferably, it is 0 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 with respect to the entire sodium carbonate-containing solution 42 is preferably 60 to 95% by mass. If it is lower than 60% by mass, the concentration of sodium carbonate is low, and it may be difficult to efficiently produce sodium carbonate crystals. On the other hand, if it is higher than 95% by mass, when sodium carbonate is crystallized with a crystallizer, the slurry concentration due to the sodium carbonate crystal becomes high, and the fluidity may deteriorate.

  As a purification method for purifying the sodium carbonate-containing solution 42 discharged from the carbon dioxide fixing device 5, sodium carbonate crystals are precipitated from the sodium carbonate-containing solution 42, and the precipitated sodium carbonate is separated from the mother liquor. The method of taking out is preferable. This purification method includes a crystallizer (not shown) for precipitating sodium carbonate crystals from the sodium carbonate-containing solution 42, and a filter (not shown) for separating the sodium carbonate crystals precipitated by the crystallizer from the mother liquor. It is preferable to be carried out in a purification step (not shown) comprising

  As the crystallizer, a crystallizer that is usually used in industry can be used, for example, a stirrer, a jacket, a coil, etc., and a cylindrical shape that can precipitate crystals by cooling the solution. The crystallizer can be used. When the temperature of the sodium carbonate-containing solution 42 is low and a part of the contained sodium carbonate has already precipitated, it is filtered directly with a filter without crystallization with a crystallizer, or Alternatively, it may be filtered through a filter after passing through a crystallizer.

  As the filter, a basket-type centrifugal filter, a gravity-type filter, a vacuum filter, or the like, which is usually used industrially, can be used. Since sodium carbonate is dissolved in the mother liquor discharged from the filter, sodium carbonate is precipitated by lowering the temperature of the mother liquor by using another crystallizer. The crystals may be filtered off with a filter. In addition, since the mother liquor discharged from the filter contains unreacted sodium hydroxide, the sodium hydroxide concentration can be reduced by further adding sodium hydroxide in order to effectively use this sodium hydroxide. It may be adjusted and returned to the carbon dioxide fixing device 5.

  In general, as a method for producing sodium carbonate, a method of synthesizing by a Solvay method, a method of purification using a natural raw material typified by trona ash produced from the Green River deposit in Wiming, and the like are known. However, in these methods, it is difficult to increase the purity of sodium carbonate, and there is a problem that the purification cost increases if it is desired to increase the purity. For example, in the Solvay method, since sodium chloride is used as a raw material, it is necessary to remove chlorine after sodium carbonate is produced. If this removal of chlorine is insufficient, the purity of sodium carbonate will be low, and if the chlorine is sufficiently removed to increase the purity of sodium carbonate, the purification cost will increase. In addition, when natural raw materials are used, since the natural raw materials themselves contain many impurities, the purification cost for removing these impurities increases. On the other hand, if sodium carbonate is generated by the carbon dioxide fixing device constituting the firing furnace of the present embodiment, since carbon dioxide obtained by methane reforming and high-purity sodium hydroxide are used as raw materials, High purity sodium carbonate can be obtained while simplifying the purification process and reducing the purification cost.

  In the firing furnace 100 of the present embodiment shown in FIG. 1, a commercially available system can be used for the fuel cell 7. Any of a polymer type, a phosphoric acid type, a molten carbonate type, a solid electrolyte type, and the like may be used, but a phosphoric acid type, a molten carbonate type, or a solid electrolyte type is preferable because exhaust heat is high. Further, the power capacity that can be generated is about 100 KW to 200 KW per system based on the performance of the current commercial system. However, if a method such as parallel installation is adopted, the power capacity can be freely designed. A part of the hydrogen fuel 25 is sent as a fuel cell hydrogen 27 through a pipe. In the fuel cell 7, the fuel cell hydrogen 27 reacts with air (oxygen in the air) to generate power.

  In the firing furnace 100 of the present embodiment shown in FIG. 1, as fuel to be burned by the combustion means 2, a mixing methane main fuel 31 mainly composed of methane and a hydrogen fuel 25 separated by the hydrogen separator 4 are used. A mixed fuel 32 is used. At the start of the operation of the firing furnace 100, the combustion exhaust gas 12 is not constantly discharged (the combustion exhaust gas 12 has not yet been generated or gradually increased), so the methane reformer 3 is difficult to perform while using the combustion exhaust gas 12, the use of the mixed fuel 32 stabilizes the inside of the calcining furnace body 1, and the combustion exhaust gas 12 is steadily discharged. (When a methane reformer, which will be described later, is disposed in the main body of the firing furnace, the temperature of the combustion gas may be stabilized). In this case, at the start of operation of the firing furnace 100, firing is performed only with the mixing methane main fuel 31 mainly composed of methane. Further, when the inside of the calcining furnace body 1 is not stabilized like the start time and the combustion exhaust gas 12 is not constantly discharged, the methane reformer 3 is supplied with another heating device (such as steam or electricity). (Not shown) may be provided, and the methane reformer 3 may be operated while using the heating device.

  The firing furnace 100 of the present embodiment shown in FIG. 1 can be suitably used as a firing furnace for firing ceramics having a calorific value required for firing of 1 million to 100 million (kJ / Hr).

  The volume ratio of the reforming methane auxiliary fuel 21 and the mixing methane main fuel 31 (reforming methane auxiliary fuel 21: mixing methane main fuel 31) is 5:95 to 100: 0 (volume ratio). preferable. If the ratio of the reforming methane auxiliary fuel 21 is smaller than 5 (volume ratio), carbon dioxide may not be sufficiently reduced. Further, at least one of the mixing methane main fuel 31 and the reforming methane auxiliary fuel 21 may be liquefied natural gas (LNG). By using LNG, it can be burned efficiently due to the good flammability of LNG, and LNG is a clean and inexpensive fuel, which is preferable because it does not generate harmful substances such as sulfur oxides and dust by combustion. .

  Next, in the firing furnace 100 of the present embodiment shown in FIG. 1, when the mixed fuel 32 of the methane main fuel 31 for mixing and the hydrogen fuel 25 is used for combustion in the combustion means 2 (the present embodiment). And the difference between the amount of used fuel and the amount of generated heat when only methane gas (a gas having a methane content of 100 (%)) is used as the fuel 11 and burned by the combustion means 2 (comparative example) The difference in the amount of carbon dioxide generated will be described.

For example, methane gas is used as the reforming methane secondary fuel 21 and the mixing methane main fuel 31, and the reaction rate by the methane reformer 3 is 100 (%) (1 mole of methane and 2 moles of water are converted into a methane reformer. 4), 4 moles of hydrogen are generated), and the hydrogen separation efficiency in the hydrogen separator 4 is 100% (all the hydrogen contained in the reformed gas 24 is separated by the hydrogen separator 4, It is assumed that the entire amount of the hydrogen fuel 25 is mixed with the mixing methane main fuel 31 as the mixing hydrogen fuel 28. In this case, for example, if only 1 (Nm ³ / Hr) of methane gas is used and burned by the combustion means 2, a heat amount of 39800 (kJ / Hr) is generated (comparative example). In contrast, as an example of the present embodiment, as the mixing of methane main fuel, methane gas 0.5 (Nm ³ / Hr) using, methane gas 0.4 (Nm ³ / Hr as methane secondary reforming fuel ) If used, 1.6 (Nm ³ / Hr) of hydrogen is generated from the methane reformer 3, which is separated by the hydrogen separator 4, and the separated hydrogen is used as the hydrogen fuel 25 for the above reforming. A mixed fuel 32 (mixed gas of methane gas of 0.5 (Nm ³ / Hr) and hydrogen of 1.6 (Nm ³ / Hr)) is mixed with the methane auxiliary fuel (methane gas). When this mixed fuel 32 is combusted by the combustion means 2, a calorific value of 19900 (kJ / Hr) is generated from methane gas 0.5 (Nm ³ / Hr), and 20480 from hydrogen 1.6 (Nm ³ / Hr). An amount of heat (kJ / Hr) is generated. Therefore, the amount of heat obtained by burning the mixed fuel 32 is 40380 (kJ / Hr).

From the above, when only methane gas is burned, when the amount of methane gas used is 1 (Nm ³ / Hr), a heat amount of 39800 (kJ / Hr) is obtained, whereas in the case of the present embodiment, A calorific value of 40380 (kJ / Hr) can be obtained when the total amount of methane gas used (the sum of the methane main fuel 31 for mixing and the methane secondary fuel 21 for reforming) is 0.9 (Nm ³ / Hr). become. In addition, since the amount of carbon dioxide generated when 1 mol of methane gas is burned is 1 mol (theoretical amount), in the case of the above comparative example, the amount of carbon dioxide generated is 1 (Nm ³ / Hr). On the other hand, in the example of the present embodiment, the amount of carbon dioxide generated is 0.5 (Nm ³ / Hr). Therefore, when this embodiment is compared with the comparative example, the amount of methane gas used to make the amount of heat generated by the combustion in the combustion means 2 substantially equal (this embodiment is slightly larger). The present embodiment is reduced by 10% compared to the comparative example, and the amount of carbon dioxide generated is reduced by 50% compared to the comparative example. become.

  Next, another embodiment of the firing furnace of the present invention will be described with reference to the drawings. FIG. 2 is a block flow diagram schematically showing the firing furnace of the present embodiment. And the arrow in FIG. 2 has shown the state to which each fuel, combustion exhaust gas, water vapor | steam, another substance, etc. move.

  As shown in FIG. 2, the firing furnace 200 of the present embodiment includes a combustion means 52 that burns fuel 61 containing inflowed methane to generate combustion gas, and a firing object that is carried into the interior by the combustion gas. A firing furnace main body 51 that heats the body and calcines it, and discharges the burned combustion gas to the outside as combustion exhaust gas (combustion gas discharged to the outside) 62 containing carbon dioxide. A reforming raw material 73 composed of reforming methane auxiliary fuel 71 and water vapor 72 mainly composed of methane flowing therein is brought into contact with the methane reforming catalyst 56 while being heated by the combustion exhaust gas 62. Thus, methane in the reforming raw material 73 reacts with the steam 72 to generate a reformed gas 74 containing hydrogen and carbon dioxide (to cause a methane reforming reaction). 3 and hydrogen gas 75 containing hydrogen as a main component and carbon dioxide containing hydrogen gas in the reformed gas 74 by selectively flowing the reformed gas 74 generated in the methane reformer 53 into the interior. A hydrogen separator 54 to be separated into a residual gas 76, and a carbon dioxide fixing device 55 to fix carbon dioxide in the residual gas 76 separated by the hydrogen separator 54 so as not to be released to the outside in a gas state; The fuel cell further includes a fuel cell hydrogen 77 containing the hydrogen fuel 75 separated by the hydrogen separator 54 and a fuel cell 57 that generates electricity by reacting oxygen or air.

The firing furnace 200 of the present embodiment performs the methane reforming reaction in the methane reformer 53 while using the heat of the combustion exhaust gas 62, thereby effectively reusing the heat of the combustion exhaust gas 62. Can do. In addition, the carbon dioxide fixing device 55 allows sodium hydroxide to flow in as a fixing agent 91 for fixing carbon dioxide inside, and brings the fixing agent 91 and the residual gas 76 into contact with each other. Carbon dioxide contained in the residual gas 76 is absorbed to generate sodium carbonate, and the waste liquid 92 containing sodium carbonate is discharged to the outside. The unreacted gas is discharged to the outside as the carbon dioxide fixing exhaust gas 94. The immobilizing agent 91 is not particularly limited as long as it can react with carbon dioxide or absorb carbon dioxide, and examples thereof include NaOH and Mg (OH) ₂ . In addition, each device is connected by a predetermined pipe, and each fuel, water vapor, and the like flow and move in the pipe.

  As described above, the firing furnace 200 of the present embodiment includes the fuel cell 57 and generates power using the fuel cell hydrogen 77 containing the hydrogen fuel 75, and thus the thermal energy of the combustion exhaust gas 62 is converted into electricity. It can be converted efficiently into energy. That is, the reformed gas 74 containing hydrogen is generated in the methane reformer 53 using the heat of the combustion exhaust gas 62, and the hydrogen fuel 75 is separated from the reformed gas 74 by the hydrogen separator 54. By using the entire amount of the hydrogen fuel 75 as fuel cell hydrogen 77 for power generation in the fuel cell 57, the thermal energy of the combustion exhaust gas 62 is efficiently converted into electric energy having higher utility value. The fuel cell 57 generates power by reacting hydrogen (hydrogen for fuel cell) with oxygen or air, but the hydrogen fuel 75 used as the fuel cell hydrogen 77 has a high purity of hydrogen contained therein. Power generation can be performed efficiently. For example, when the fuel cell is generated using normal hydrogen, the power efficiency is about 40%. However, in the fuel cell 57 used in the present embodiment, the power efficiency is drastically 60 to 70%. To be high. In the firing furnace of the present embodiment, the reformed gas 74 may be used directly in the fuel cell 57 without passing through the hydrogen separator 54. Regarding carbon dioxide emissions, fuel cells are about twice as efficient in converting thermal energy into electrical energy compared to thermal power generation. Therefore, if the electric power derived from the fuel cell is used instead of the electric power derived from the thermal power generation for the reduction of the carbon dioxide emission, the carbon dioxide gas reduction amount for the same electric energy is halved. Therefore, it is possible to reduce the generated carbon dioxide without intentionally fixing the carbon dioxide. If carbon dioxide is immobilized, a higher carbon dioxide reduction effect is produced.

  Further, according to the firing furnace 200 of the present embodiment, the carbon dioxide produced when the reforming raw material 73 is reacted with the methane reforming catalyst 56 is fixed by the carbon dioxide fixing device 55, so that the reforming raw material is Carbon dioxide produced from 73 is not released to the outside in the form of gas. Here, the heat source for the methane reforming reaction can use not only the combustion exhaust gas but also the heat dissipated from the furnace wall and the heat discarded when the kiln tool used for firing the ceramic is cooled. Can be planned.

  In the firing furnace 200 of the present embodiment, the residual gas 76 may contain a combustible substance such as carbon monoxide. Therefore, when such a combustible substance is contained, the residual gas A part or all of 76 may be burned by the burning means 52. This is preferable because fuel is recovered.

  The firing furnace body 51, the combustion means 52, the methane reformer 53, the hydrogen separator 54, the carbon dioxide fixing device 55, and the fuel cell 57 in the firing furnace 200 of the present embodiment shown in FIG. In the embodiment of the firing furnace of the present invention shown in FIG. 1, each of the firing furnace body 1, combustion means 2, methane reformer 3, hydrogen separator 4, carbon dioxide fixing device 5 and fuel cell 7 is shown. It is preferable to configure in the same manner as in the case, whereby the same effect can be obtained. However, the fuel 61 containing methane is preferably composed mainly of methane, and the combustion means 52 is preferably capable of efficiently combusting the fuel 61 composed mainly of methane. Here, “having methane as a main component” means that the content of methane is 80 (% by volume) or more. In addition, since the firing furnace 200 of the present embodiment uses the entire amount of the hydrogen fuel 75 for power generation in the fuel cell 57, a branching pipe or the like for mixing a part of the hydrogen fuel 75 with the fuel 61 is necessary. do not do.

  The firing furnace 200 according to the present embodiment shown in FIG. 2 can be suitably used as a firing furnace for firing ceramics having a calorific value required for firing of 1 million to 100 million (kJ / Hr). Moreover, as a to-be-fired body, the ceramic honeycomb structure can be suitably fired as in the case of the embodiment of the firing furnace of the present invention.

  Next, still another embodiment of the firing furnace of the present invention will be described with reference to the drawings. FIG. 3 is a block flow diagram schematically showing the firing furnace of the present embodiment. And the arrow in FIG. 3 has shown the state to which each fuel, combustion exhaust gas, water vapor | steam, another substance, etc. move.

  As shown in FIG. 3, the firing furnace 300 of the present embodiment includes a combustion means 102 for burning a fuel 111 containing inflowing methane to generate combustion gas, and a firing object carried into the interior by the combustion gas. A firing furnace main body 101 that heats and burns the body, and discharges the fired combustion gas to the outside as combustion exhaust gas (combustion gas discharged to the outside) 112 containing carbon dioxide. The reformed raw material 123 composed of the reformed methane auxiliary fuel 121 and the water vapor 122 mainly composed of methane that has flowed into the methane reforming catalyst 106 is disposed by combustion of the fuel 111. While being heated by the generated combustion gas, the reforming raw material 1 is brought into contact with the methane reforming catalyst 106 while being heated by radiant heat transfer generated in the firing furnace main body 101. The methane reformer 103 that generates hydrogen and carbon dioxide-containing reformed gas 124 (reacts the methane reforming reaction), and the methane reformer 103 A hydrogen separator that causes reformed gas 124 to flow into the interior and selectively separates hydrogen in reformed gas 124 to separate hydrogen fuel 125 mainly containing hydrogen and residual gas 126 containing carbon dioxide. 104 and a carbon dioxide fixing device 105 for fixing the carbon dioxide in the residual gas 126 separated by the hydrogen separator 104 so that the carbon dioxide is not released to the outside in the state of gas.

  Thus, according to the firing furnace of the present embodiment, the methane reformer 103 is disposed in the firing furnace main body 101, the reforming raw material 123 is heated by the combustion gas instead of the combustion exhaust gas 112, and further In order to generate the reformed gas 124 by being brought into contact with the methane reforming catalyst 106 while being heated by the radiant heat transfer generated in the firing furnace body 101, the heat of the combustion gas is directly used in the firing furnace body 1. Therefore, the heat of the combustion gas can be used effectively with little loss. This is because, for example, compared to the case where the combustion gas is once discharged from the firing furnace body 1 to the outside and then heat recovery is performed by equipment installed outside the firing furnace body 1, heat radiation of the combustion gas, etc. The loss due to is significantly reduced. As a result, the total amount of fuel used can be further reduced, and energy resources can be utilized more efficiently. In addition, the radiant heat transfer generated in the firing furnace body 101 is a fired object in the firing furnace body 101, a firing jig, a furnace wall, or the like heated by the combustion gas and heated to a high temperature. It is radiant heat transfer emitted from a jig and a furnace wall. The reforming raw material 123 and the methane reforming catalyst 106 are heated by combustion gas and / or radiant heat transfer. The ratio of the amount of heat of heating by radiant heat transfer (radiant heat) and heating by combustion gas at a temperature at which normal reforming reaction occurs (800 ° C. or higher) is radiant heat: combustion gas = 2: 1 to 4: 1. It is preferable that it is the range of these. At about 800 ° C., the ratio of radiant heat to the total heating amount is preferably 60%, and at 1000 ° C. or higher, the ratio of radiant heat is preferably 80%. In addition, the radiant heat becomes dominant as the temperature rises.

In the firing furnace 300 of the present embodiment, the combustion means 102 has the mixing fuel methane main fuel 131 mainly containing the inflowing methane and the hydrogen fuel 125 separated by the hydrogen separator 104 (mixing hydrogen fuel 128). In other words, by using the mixed fuel 132 as the fuel 111 containing methane and generating combustion gas, the carbon dioxide content in the combustion exhaust gas 112 is reduced, The amount of discharge to the outside can be reduced. In addition, the carbon dioxide fixing device 105 allows sodium hydroxide to flow in as a fixing agent 141 for fixing carbon dioxide inside, and makes the fixing agent 141 and the residual gas 126 come into contact with each other. Carbon dioxide contained in the residual gas 126 is absorbed to form sodium carbonate, and the waste liquid 142 containing sodium carbonate is discharged to the outside. The unreacted gas is discharged to the outside as the carbon dioxide fixing exhaust gas 144. Here, in the mixing methane main fuel 131 containing methane as a main component, “mainly containing methane” means that the content of methane is 80 (volume%) or more. The immobilizing agent 141 is not particularly limited as long as it can react with carbon dioxide or absorb carbon dioxide, and examples thereof include NaOH and Mg (OH) ₂ . In addition, each device is connected by a predetermined pipe, and each fuel, water vapor, and the like flow and move in the pipe.

  Thus, according to the firing furnace 300 of the present embodiment, the mixed fuel of the mixing methane main fuel 131 and the hydrogen fuel 125 (mixing hydrogen fuel 128) as the fuel 111 containing methane to be burned by the combustion means 102. Since 132 is used, generation of carbon dioxide can be reduced by the amount of hydrogen (hydrogen fuel 125) in which the mixed fuel 132 (fuel 111) does not generate carbon dioxide even when burned. Further, since the carbon dioxide produced when the reforming raw material 123 is reacted with the methane reforming catalyst 106 is fixed by the carbon dioxide fixing device 105, the carbon dioxide produced from the reforming raw material 123 is in a gas state. It is not released to the outside. Further, as the amount of heat necessary for the endothermic reaction when the reforming raw material 123 is reacted with the methane reforming catalyst 106, the amount of combustion gas in the firing furnace body 101 (combustion heat of the fuel 111) is used to Therefore, a part of the amount of heat of the combustion gas can be effectively recovered as the combustion heat of the fuel 111 and reused, thereby reducing the total amount of fuel used. Here, the heat of the combustion gas as the heat source for the methane reforming reaction is the combustion heat of the fuel 111, and the radiant heat at the time of combustion of the fuel 111, the firing of the object to be fired, the furnace wall, etc. It also includes radiant heat transfer from jigs for use. Moreover, the heat | fever etc. which are discarded when cooling the kiln tool used at the time of ceramic baking can also be used.

  As shown in FIG. 3, the firing furnace 300 of the present embodiment further includes a fuel cell 107. A part of the hydrogen fuel 125 obtained by separation in the hydrogen separator 104 is branched as fuel cell hydrogen 127 and used for the fuel cell 107 to generate power. Since the hydrogen fuel 125 has a high purity of hydrogen contained therein, the fuel cell 107 can efficiently generate power.

  The total amount of the hydrogen fuel 125 may be used as the mixing hydrogen fuel 128 or may be divided into the mixing hydrogen fuel 128 and the fuel cell hydrogen 127. The ratio when dividing into the mixing hydrogen fuel 128 and the fuel cell hydrogen 127 is not particularly limited, and the carbon dioxide emission amount and the power generation amount may be appropriately balanced so as to be an optimum value. .

  In the firing furnace of the present embodiment, the reformed gas 124 may be used directly in the fuel cell 107 without passing through the hydrogen separator 104.

  FIG. 5 is a cross-sectional view schematically showing the firing furnace body 101 constituting the firing furnace 300 of the present embodiment, cut along a plane perpendicular to the longitudinal direction thereof. The firing furnace body 101 shown in FIG. 5 is a continuous firing furnace body 101, and the longitudinal direction thereof is a direction in which the body to be fired m is carried into the firing furnace body 101 and travels. The to-be-fired body m is formed by the belt conveyor B so as to travel in the firing furnace main body 101 along the longitudinal direction. As shown in FIG. 5, the firing furnace main body 101 has a form in which the methane reformer 3 is disposed along the inner surface of the outer peripheral wall 101a. You may arrange | position in the space which burns the to-be-fired body m with a combustion gas inside the furnace wall 101b. Moreover, you may arrange | position in both of these. Further, in the cross section of the firing furnace main body 101 shown in FIG. 5, the methane reformer 3 may be disposed at a position where the temperature is optimal for performing the methane reforming reaction in the temperature distribution of the entire cross section. preferable. In addition, the position where the methane reformer 103 is disposed in the longitudinal direction of the firing furnace body 101 is preferably a position where the temperature distribution in the firing furnace body 101 becomes a temperature suitable for the methane reforming reaction. Further, in order to optimize the temperature state at the position where the methane reformer 103 is disposed, as shown in FIG. 5, the space in which the methane reformer 103 is disposed and the object m to be fired are fired with combustion gas. It is preferable to partition the space to be separated by the inner furnace wall 101b. By partitioning the inside of the firing furnace main body 101 with the inner furnace wall 101b, the combustion gas can be prevented from coming into direct contact with the methane reformer 103, or it can be made difficult to make contact with it. Therefore, the temperature of the methane reformer 103 can be adjusted more appropriately. This is effective when the methane reformer 103 is disposed in the high temperature region of the firing furnace main body 101.

  The methane reformer 103 is formed by filling a methane reforming catalyst 106 in a cylindrical reforming reaction tube 103a. In the methane reformer 103, both ends of the reforming reaction tube 103a communicate with the outside of the calcining furnace main body 101, and the reforming raw material flows in from one end, and in the calcining furnace main body 101, the heat of combustion gas and A methane reforming reaction is performed while heating by radiant heat transfer and a methane reforming catalyst, and the resulting reformed gas is formed to flow out of the firing furnace main body 101 from the other end of the reforming reaction tube 103a. Has been.

  In the present embodiment, the tubular reforming reaction tube shown in FIG. 5 is used as the container for filling the methane reforming catalyst 106, but the shape of the container is limited to a tubular shape (tubular shape). However, it may be any shape as long as the methane reforming catalyst 106 can be filled inside the calcining furnace main body 101 and the methane reforming reaction can be performed by the combustion gas.

  The firing furnace body 101, the combustion means 102, the methane reformer 103, the hydrogen separator 104, the carbon dioxide fixing device 105, and the fuel cell 107 in the firing furnace 300 of the present embodiment shown in FIG. 1 except that the methane reformer 103 is disposed in 101, the firing furnace body 1, the combustion means 2, and the methane reformer in the embodiment of the firing furnace of the present invention shown in FIG. 1 described above. 3, the hydrogen separator 4, the carbon dioxide fixing device 5, and the fuel cell 7 are preferably configured in the same manner as described above, whereby the same effect can be obtained.

  In the firing furnace of the present embodiment, the methane reformer is disposed in the firing furnace main body. In addition to that, in the embodiment of the firing furnace of the present invention shown in FIG. A methane reformer disposed outside the firing furnace main body, such as a methane reformer, may be further provided. In other words, a methane reformer is provided inside and outside the main body of the firing furnace, and methane reforming is performed using the heat and radiant heat of the combustion gas inside, and the heat of the combustion exhaust gas is used outside. Methane reforming may be performed.

  Next, still another embodiment of the firing furnace of the present invention will be described with reference to the drawings. FIG. 4 is a block flow diagram schematically showing still another embodiment of the firing furnace of the present invention. And the arrow in FIG. 4 has shown the state to which each fuel, combustion exhaust gas, water vapor | steam, another substance, etc. move.

  As shown in FIG. 4, the firing furnace 400 of the present embodiment includes a combustion means 152 that burns a fuel 161 containing inflowing methane to generate combustion gas, and a firing object that is carried into the interior by the combustion gas. A firing furnace body 151 that heats and burns the body and discharges the combustion gas after firing to the outside as a combustion exhaust gas 162 containing carbon dioxide, and is further disposed in the firing furnace body 151 and has methane inside. A reforming raw material 173 consisting of a reforming methane auxiliary fuel 171 mainly composed of methane flowing into the reforming catalyst 156 and steam 172 is heated by the combustion gas and generated in the calcining furnace main body 151. The methane in the reforming raw material 173 reacts with the water vapor 172 by contacting with the methane reforming catalyst 156 while being heated by the radiant heat transfer. A reformed gas 174 containing element (a methane reforming reaction) is generated, and a reformed gas 174 generated by the methane reformer 153 is flown into the reformed gas 174 A hydrogen separator 154 that selectively separates hydrogen into hydrogen fuel 175 mainly containing hydrogen and residual gas 176 containing carbon dioxide, and residual gas 176 separated by hydrogen separator 154 The carbon dioxide fixing device 155 for fixing the carbon dioxide in a gas state so as not to be released to the outside, the hydrogen 177 for the fuel cell containing the hydrogen fuel 175 separated by the hydrogen separator 154, and oxygen or air are reacted. And a fuel cell 157 that generates electric power by generating the electric power. Each device is connected by a predetermined pipe, and each fuel, water vapor, etc. flow and move in the pipe. The gas that has not been fixed by the carbon dioxide fixing device 155 is discharged to the outside as the carbon dioxide fixing device exhaust gas 194. Further, the radiant heat transfer generated in the firing furnace main body 151 is caused by the fired object, the firing jig, the furnace wall, etc. in the firing furnace main body 151 being heated by the combustion gas to become a high temperature. This is radiant heat transfer emitted from jigs, furnace walls, and the like. Radiant heat transfer becomes particularly large when the temperature in the firing furnace main body 151 is 1000 ° C. or higher. Further, the reforming raw material 173 and the methane reforming catalyst 156 are heated by the combustion gas and further heated by radiant heat transfer.

  As described above, in the firing furnace 400 of the present embodiment, the methane reformer 153 is disposed in the firing furnace main body 151, so that the heat and / or combustion of the combustion gas in the firing furnace main body 151 causes the methane reforming reaction. By using part of the radiant heat from the object to be fired, the firing jig and the furnace wall heated by the gas, the heat of the combustion gas can be used effectively. The firing furnace 400 of the present embodiment includes the fuel cell 157 and generates electricity using the fuel cell hydrogen 177 containing the hydrogen fuel 175, so that a part of the thermal energy of the combustion gas is electrically generated. It can be converted efficiently into energy. That is, the reformed gas 174 containing hydrogen is generated in the methane reformer 153 using the heat of the combustion gas, the hydrogen fuel 175 is separated from the reformed gas 174 by the hydrogen separator 154, and the separated hydrogen By using the entire amount of the fuel 175 as fuel cell hydrogen 177 for power generation in the fuel cell 157, a part of the thermal energy of the combustion gas is efficiently converted into electric energy having higher utility value. The fuel cell 157 generates power by reacting hydrogen (hydrogen for fuel cell) with oxygen or air. However, since the hydrogen fuel 175 used as the fuel cell hydrogen 177 has a high purity of hydrogen contained, Power generation can be performed efficiently. For example, when the fuel cell is generated using normal hydrogen, the power efficiency is about 40%. However, in the fuel cell 157 used in the present embodiment, the power efficiency is drastically 60 to 70%. To be high. In the firing furnace of the present embodiment, the reformed gas 174 may be used directly in the fuel cell 157 without passing through the hydrogen separator 154. Regarding carbon dioxide emissions, fuel cells are about twice as efficient in converting thermal energy into electrical energy compared to thermal power generation. Therefore, if the electric power derived from the fuel cell is used instead of the electric power derived from the thermal power generation for the reduction of the carbon dioxide emission, the carbon dioxide gas reduction amount for the same electric energy is halved. Therefore, it is possible to reduce the generated carbon dioxide without intentionally fixing the carbon dioxide. If carbon dioxide is immobilized, a higher carbon dioxide reduction effect is produced.

  The firing furnace main body 151, the combustion means 152, the methane reformer 153, the hydrogen separator 154, the carbon dioxide fixing device 155, and the fuel cell 157 in the firing furnace 400 of the present embodiment shown in FIG. Except that the methane reformer 153 is disposed in the furnace body 151, the firing furnace body 1, combustion means 2, methane reformer in the embodiment of the firing furnace of the present invention shown in FIG. It is preferable to configure in the same manner as each of the mass device 3, the hydrogen separator 4, the carbon dioxide fixing device 5, and the fuel cell 7, whereby the same effect can be obtained. The structure in which the methane reformer 153 is disposed inside the firing furnace main body 151 is preferably configured in the same manner as the firing furnace main body 101 shown in FIG. 5 or FIG. An effect can be obtained. However, the fuel 161 containing methane is preferably composed mainly of methane, and the combustion means 152 is preferably capable of efficiently combusting the fuel 161 composed mainly of methane.

  Next, an embodiment of the firing method of the present invention will be described with reference to FIG. 1 showing an embodiment of the firing furnace of the present invention described above.

  As the firing furnace 100 used in the firing method of the present embodiment, the embodiment of the firing furnace of the present invention described above with reference to FIG. 1 can be suitably used. In the firing method of the present embodiment, a combustion gas is generated by injecting and burning a fuel 11 containing methane into the combustion means 2, and the combustion gas generated by the combustion means 2 is introduced into the firing furnace body 1. This is a firing method in which the fired body carried into the inside is heated and fired by the combustion gas, and the burned combustion gas is discharged to the outside. Then, a reforming material 23 composed of reforming methane auxiliary fuel 21 and steam 22 containing methane as main components is caused to flow into the methane reformer 3 in which the methane reforming catalyst 6 is further filled. The methane in the reforming raw material 23 and the water vapor 22 are reacted with each other by contacting the methane reforming catalyst 6 while the gas 23 is heated by the combustion exhaust gas 12 to generate a reformed gas 24 containing hydrogen and carbon dioxide. It is.

  Thus, according to the firing method of the present embodiment, the methane reforming reaction in the methane reformer 3 is performed using the heat of the combustion gas (combustion exhaust gas 12) discharged to the outside of the firing furnace body 1. Thus, the heat of the combustion exhaust gas 12 can be effectively reused.

  Further, in the firing method of the present embodiment, the reformed gas 24 generated in the methane reformer 3 is caused to flow into the hydrogen separator 4 to selectively separate hydrogen in the reformed gas 24. Hydrogen gas 25 containing hydrogen as a main component and a residual gas 26 containing carbon dioxide are separated, and the residual gas 26 separated by the hydrogen separator 4 is caused to flow into the carbon dioxide fixing device 5. The carbon dioxide is fixed by a fixing agent 41 so that it is not released to the outside in the form of gas, and the combustion means 2 causes the methane main fuel 31 for mixing mainly containing methane and the hydrogen separated by the hydrogen separator 4 This is a firing method capable of reducing the carbon dioxide content in the combustion exhaust gas 12 by flowing in and burning the mixed fuel 32 with the fuel 25 (hydrogen fuel 28 for mixing) to generate combustion gas. The combustion exhaust gas 12 used in the methane reformer 3 is then discharged outside as the reformer exhaust gas 43. In addition, after carbon dioxide is immobilized by the immobilizing agent 41, it is discharged to the outside as the waste liquid 42.

  Here, in the mixing methane main fuel 31 containing methane as a main component, “mainly containing methane” means that the content of methane is 80 (% by volume) or more. Further, “having hydrogen as a main component” of the hydrogen fuel 25 having hydrogen as a main component means that the hydrogen content is 50 (volume%) or more.

  Thus, according to the firing method of the present embodiment, the mixed fuel 32 of the mixing methane main fuel 31 and the hydrogen fuel 25 (mixing hydrogen fuel 28) as the fuel 11 containing methane to be burned by the combustion means 2. Therefore, the generation of carbon dioxide can be reduced by the amount that contains hydrogen (hydrogen fuel for mixing 28) that does not generate carbon dioxide even when the mixed fuel 32 (fuel 11) is combusted. At this time, the hydrogen content (hydrogen / mixed fuel) contained in the mixed fuel 32 is preferably 5 to 95 (volume%), 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%), not only the combustion exhaust gas but also other heat sources are used when performing the methane reforming reaction. You may need it. Further, since the carbon dioxide produced when the reforming raw material 23 is reacted with the methane reforming catalyst 6 is fixed by the carbon dioxide fixing device 5, the carbon dioxide produced from the reforming raw material 23 is in a gas state. It is not released to the outside. Further, since the calorific value of the flue gas 12 discharged from the calcining furnace body 1 is used as the amount of heat necessary for the endothermic reaction when the reforming raw material 23 is reacted with the methane reforming catalyst 6, the exhaust heat of the flue gas 12 is used. By using a part of the fuel as hydrogen fuel, it is recovered as the combustion heat of the fuel, and the total amount of fuel used can be reduced.

  As shown in FIG. 1, the firing furnace 100 used in the firing method of the present embodiment further includes a fuel cell 7, and a part of the hydrogen fuel 25 can be used as the fuel cell hydrogen 27 to generate electricity. It is configured. The fuel cell 7 generates power by reacting hydrogen (hydrogen for fuel cell) with oxygen or air. In the firing method of the present embodiment, the hydrogen fuel 25 obtained by separation by the hydrogen separator 4 is used. Can be separated as hydrogen 27 for a fuel cell and used for the fuel cell 7 to generate electricity. Since the hydrogen fuel 25 has a high purity of hydrogen contained therein, the fuel cell 7 can efficiently generate power by using a part of the hydrogen fuel 25 as the fuel cell hydrogen 27. For example, when the fuel cell is generated using normal hydrogen, the power efficiency is about 40%. However, when the fuel cell 7 generates power in the present embodiment, the power efficiency is drastically 60 to 70%. improves. Further, a part of the hydrogen fuel 25 obtained by separation by the hydrogen separator 4 is finally burned by the combustion means 2 as the mixing hydrogen fuel 28, and the remainder is used as the fuel cell hydrogen 27 for power generation in the fuel cell 7. By using this, the amount of carbon dioxide contained in the combustion exhaust gas 12 can be reduced, and at the same time, the heat of the combustion exhaust gas 12 can be effectively recovered and used for power generation, thereby obtaining highly useful electrical energy. be able to.

  Regarding carbon dioxide emissions, fuel cells are about twice as efficient in converting thermal energy into electrical energy compared to thermal power generation. Therefore, if the electric power derived from the fuel cell is used instead of the electric power derived from the thermal power generation for the reduction of the carbon dioxide emission, the carbon dioxide gas reduction amount for the same electric energy is halved. Therefore, it is possible to reduce the generated carbon dioxide without intentionally fixing the carbon dioxide. If carbon dioxide is immobilized, a higher carbon dioxide reduction effect is produced.

  The entire amount of the hydrogen fuel 25 may be used as the mixing hydrogen fuel 28 or may be divided into the mixing hydrogen fuel 28 and the fuel cell hydrogen 27. The ratio when dividing into the mixing hydrogen fuel 28 and the fuel cell hydrogen 27 is not particularly limited, and the carbon dioxide emission amount and the power generation amount may be appropriately balanced so as to be an optimum value. .

  In the firing furnace 100 used in the firing method of the present embodiment shown in FIG. 1, the firing furnace body 1 is preferably configured in the same manner as the firing furnace body in the firing furnace of the present invention, Similar effects can be obtained. The firing furnace main body 1 may be a batch type in which a predetermined amount of the objects to be fired are fired intermittently. The continuous firing furnace body 1 is preferably a continuous firing furnace body 1 in which the fired body is heated and fired inside and then continuously carried out to the outside. By continuously firing, the combustion exhaust gas 12 can be discharged from the firing furnace main body 1 stably and stably, so that in the methane reformer 3, the methane reforming reaction is stabilized by the heat of the combustion exhaust gas 12. Accordingly, the hydrogen fuel 25 can be stably supplied, and the mixed fuel 32 obtained by mixing the hydrogen fuel 25 and the methane main fuel 31 for mixing can be stably combusted. Can be supplied to.

  In addition, as an object to be fired by the firing method of the present embodiment, ceramics such as tableware, tiles, sanitary ware, insulators, and ceramic honeycomb structures can be suitably fired. Here, the ceramic honeycomb structure is a honeycomb structure having a plurality of cells made of ceramic and serving as a flow path of fluid partitioned by partition walls.

  In the firing furnace 100 used in the firing method of the present embodiment shown in FIG. 1, the combustion means 2, the methane reformer 3, the hydrogen separator 4, and the carbon dioxide fixing device 5 are the above-described firing furnace of the present invention. It is preferable to configure in the same manner as in the case of the combustion means 2, the methane reformer 3, the hydrogen separator 4, and the carbon dioxide fixing device 5 in one embodiment, whereby the same effect can be obtained. Even when the carbon dioxide fixing device is used as a sodium carbonate generator, in the embodiment of the firing furnace of the present invention described above, the carbon dioxide fixing device may be the same as when the carbon dioxide fixing device is used as a sodium carbonate generator. preferable.

  In the firing method of the present embodiment, as in the case of firing using the embodiment of the firing furnace of the present invention described above, a mixture containing methane as a main component as the fuel burned by the combustion means 2 The mixed fuel 32 of the methane main fuel 31 for use and the hydrogen fuel 25 (hydrogen fuel 28 for mixing) separated by the hydrogen separator 4 is used. At the start of the operation of the firing furnace 100, the combustion exhaust gas 12 is not being discharged constantly (the combustion exhaust gas 12 has not yet been generated or gradually increased), so the methane reformer It is difficult to carry out the reaction according to No. 3 while using the combustion exhaust gas 12, and the mixed fuel 32 may be used even after the combustion exhaust gas 12 is constantly discharged. In this case, at the start of operation of the firing furnace 100, firing is performed only with the mixing methane main fuel 31 mainly composed of methane. Further, when the combustion exhaust gas 12 at the start is not steadily discharged, the methane reformer 3 is provided with another heating device (not shown) using steam, electricity, etc. The methane reformer 3 may be operated while being used.

  The firing method of the present embodiment can be suitably used when firing a ceramic with a heat amount of 1 million to 100 million (kJ / Hr). In the case of equipment smaller than 1 million (kJ / Hr), the present invention can be used by combining several small equipment. Although the present invention can be applied to facilities of 1 million (kJ / Hr) or less, the methane steam reforming facility is expensive and is not economical.

  In the firing method of the present embodiment, as in the case of firing using the embodiment of the firing furnace of the present invention described above, the reforming methane auxiliary fuel 21 and the mixing methane main fuel 31 are mixed. The volume ratio (reforming methane secondary fuel 21: mixing methane main fuel 31) is preferably 5:95 to 100: 0 (volume ratio). If the ratio of the reforming methane auxiliary fuel 21 is smaller than 5 (volume ratio), carbon dioxide may not be sufficiently reduced. Further, at least one of the mixing methane main fuel 31 and the reforming methane auxiliary fuel 21 may be liquefied natural gas (LNG). By using LNG, it can be burned efficiently due to the good flammability of LNG, and LNG is a clean and inexpensive fuel, which is preferable because it does not generate harmful substances such as sulfur oxides and dust by combustion. .

When the combustion means 2 is used to burn the mixed fuel 32 of the mixing methane main fuel 31 and the hydrogen fuel 25 (mixing hydrogen fuel 28) as the firing method of the present embodiment (this embodiment), When only methane gas (a gas having a methane content of 100 (%)) is used as the fuel 11 and burned by the combustion means 2 (comparative example), the difference between the amount of used fuel and the amount of generated heat, and When the difference in the amount of generated carbon dioxide is shown, the same result as that obtained when the same comparison is made in the embodiment of the firing furnace of the present invention described above can be obtained. That is, when only methane gas is burned as the fuel 11, a calorific value of 39800 (kJ / Hr) is obtained for the use of methane gas 1 (Nm ³ / Hr), whereas in the present embodiment, methane gas The total amount of use (total of the methane main fuel 31 for mixing and the methane secondary fuel 21 for reforming) is 0.9 (Nm ³ / Hr), whereas the amount of heat obtained is 40380 (kJ / Hr) It becomes. In addition, since the amount of carbon dioxide generated when 1 mol of methane gas is burned is 1 mol (theoretical amount), in the case of the comparative example, 1 (Nm ³ / Hr) of carbon dioxide is generated. On the other hand, in the case of the present embodiment, 0.5 (Nm ³ / Hr) of carbon dioxide is generated. Therefore, when this embodiment is compared with the comparative example, the amount of methane gas used to make the amount of heat generated by the combustion in the combustion means 2 substantially equal (this embodiment is slightly larger). The present embodiment is reduced by 10% compared to the comparative example, and the amount of carbon dioxide generated is reduced by 50% compared to the comparative example. become.

  Next, another embodiment of the firing method of the present invention will be described with reference to FIG. 2 showing another embodiment of the above-described firing furnace of the present invention.

  The firing furnace 200 used in the firing method of the present embodiment is preferably a firing furnace similar to the other embodiments of the firing furnace of the present invention described above with reference to FIG. In the firing method of the present embodiment, the combustion gas is generated by injecting and burning the fuel 61 containing methane into the combustion means 52, the combustion gas generated by the combustion means 52 is introduced into the firing furnace main body 51, and This is a firing method in which the burned gas is heated and fired by the combustion gas, and the burned combustion gas is discharged to the outside of the firing furnace body 51. Further, a reforming raw material 73 composed of reforming methane auxiliary fuel 71 and steam 72 containing methane as the main components is introduced into a methane reformer 53 filled with a methane reforming catalyst 56 inside, and the reforming raw material is introduced. 73 is heated by the combustion gas (combustion exhaust gas 62) discharged from the calcining furnace main body 51 and is brought into contact with the methane reforming catalyst 56, whereby the methane and the steam 72 in the reforming raw material 73 are reacted to generate hydrogen and carbon dioxide. A reformed gas 74 containing carbon is generated.

  Thus, according to the firing method of the present embodiment, the methane reforming reaction in the methane reformer 53 is performed while using the heat of the combustion exhaust gas 62, thereby effectively reusing the heat of the combustion exhaust gas 62. can do.

  Further, in the firing method of the present embodiment, the reformed gas 74 generated in the methane reformer 53 is caused to flow into the hydrogen separator 54 to selectively separate hydrogen in the reformed gas 74. The hydrogen fuel 75 containing hydrogen as a main component and the residual gas 76 containing carbon dioxide are separated, and the residual gas 76 separated by the hydrogen separator 54 is caused to flow into the carbon dioxide fixing device 55. The carbon dioxide is fixed by the fixing agent 91 so as not to be released to the outside in the state of gas, and the hydrogen fuel 75 separated by the hydrogen separator 54 is caused to flow into the fuel cell 57 as hydrogen 77 for the fuel cell, Electricity is generated by reacting the fuel cell hydrogen 77 with oxygen or air, thereby generating the reformed gas 74 containing hydrogen in the methane reformer 53 using the heat of the combustion exhaust gas 62, Separation 54, the hydrogen fuel 75 is separated from the reformed gas 74, and the hydrogen fuel 75 is used for power generation in the fuel cell 57 as hydrogen 77 for a fuel cell, so that the thermal energy of the combustion exhaust gas 62 can be converted into electric energy. It is a firing method. The combustion exhaust gas 62 used in the methane reformer 53 is then discharged outside as the reformer exhaust gas 93. Further, after carbon dioxide is immobilized by the immobilizing agent 91, it is discharged to the outside as a waste liquid 92.

  As described above, according to the firing method of the present embodiment, since the entire amount of the hydrogen fuel 75 is used as the fuel cell hydrogen 77 and the fuel cell 57 generates power, the heat of the combustion exhaust gas 62 is effectively recovered to generate power. It is possible to obtain electric energy with higher utility value. Since the hydrogen fuel 75 has a high purity of hydrogen contained therein, the fuel cell 57 can efficiently generate power by using it as the fuel cell hydrogen 77. For example, when the fuel cell is generated using normal hydrogen, the power efficiency is about 40%. However, when the fuel cell 57 generates power in the present embodiment, the power efficiency is drastically 60 to 70%. improves.

  Further, according to the firing method of the present embodiment, the carbon dioxide produced when the reforming raw material 73 is reacted with the methane reforming catalyst 56 is fixed by the carbon dioxide fixing device 55, and thus the reforming raw material 73. Carbon dioxide produced from the gas is not released to the outside in the form of gas.

  In the firing furnace 200 used in the firing method of the present embodiment shown in FIG. 2, the firing furnace body 51 is the case of the firing furnace body 1 in the embodiment of the firing furnace of the present invention shown in FIG. It is preferable to configure in the same manner as described above, whereby the same effect can be obtained. The firing furnace body 51 may be a batch type in which a predetermined amount of the objects to be fired are fired intermittently. However, the objects to be fired such as a ceramic structure are continuously carried into the furnace body. It is preferable to be a continuous firing furnace main body 51 in which the fired body is heated and fired inside and then continuously carried out to the outside. By performing continuous firing, the combustion exhaust gas 62 can be discharged from the firing furnace main body 51 stably and stably. Therefore, in the methane reformer 53, the methane reforming reaction is stabilized by the heat of the combustion exhaust gas 62. As a result, the hydrogen fuel 75 can be stably supplied, and the fuel cell 57 can stably generate power.

  In addition, as an object to be fired by the firing method of the present embodiment, ceramics such as tableware, tiles, sanitary ware, insulators, and ceramic honeycomb structures can be suitably fired. Here, the ceramic honeycomb structure is a honeycomb structure having a plurality of cells made of ceramic and serving as a flow path of fluid partitioned by partition walls.

  In the firing furnace 200 used in the firing method of the present embodiment shown in FIG. 2, the combustion means 52, the methane reformer 53, the hydrogen separator 54, and the carbon dioxide fixing device 55 are shown in FIG. It is preferable to configure in the same manner as in the case of the combustion means 2, the methane reformer 3, the hydrogen separator 4 and the carbon dioxide fixing device 5 in one embodiment of the firing furnace, thereby obtaining the same effect. be able to. However, the fuel 61 containing methane is preferably composed mainly of methane, and the combustion means 52 is preferably capable of efficiently combusting the fuel 61 composed mainly of methane. Here, “having methane as the main component” means that the content of methane is 80 (% by volume) or more.

  In the firing furnace 200 of the present embodiment, the residual gas 76 may contain a combustible substance such as carbon monoxide. Therefore, when such a combustible substance is contained, the residual gas A part or all of 76 may be burned by the combustion means 152. This is preferable because fuel is recovered.

  The firing method of the present embodiment can be suitably used when firing a ceramic with a heat amount of 1 million to 100 million (kJ / Hr). In the case of equipment smaller than 1 million (kJ / Hr), the present invention can be used by combining several small equipment. Although the present invention can be applied to facilities of 1 million (kJ / Hr) or less, the methane steam reforming facility is expensive and is not economical.

  Next, still another embodiment of the firing method of the present invention will be described with reference to FIG. 3 showing still another embodiment of the above-described firing furnace of the present invention.

  The firing furnace 300 used in the firing method of the present embodiment is preferably a firing furnace similar to that of still another embodiment of the firing furnace of the present invention described above with reference to FIG. In the firing method of the present embodiment, a combustion gas is generated by injecting and burning a fuel 111 containing methane into the combustion means 102, and the combustion gas generated by the combustion means 102 is introduced into the firing furnace body 101, This is a firing method in which a body to be fired carried inside is heated and fired by combustion gas. Further, the methane reforming catalyst 106 is further filled therein, and the methane reformer 103 disposed in the calcining furnace main body 101 is reformed with a reforming methane auxiliary fuel 121 mainly composed of methane and steam 122. The reformed material 123 is heated by the combustion gas and brought into contact with the methane reforming catalyst 106 while being heated by the radiant heat generated in the calcining furnace main body 101. The methane and water vapor 122 are reacted to produce a reformed gas 124 containing hydrogen and carbon dioxide. In addition, the radiant heat transfer generated in the firing furnace body 101 is a fired object in the firing furnace body 101, a firing jig, a furnace wall, or the like heated by the combustion gas and heated to a high temperature. This is radiant heat transfer emitted from jigs, furnace walls, and the like. Radiant heat transfer becomes particularly large when the temperature in the firing furnace main body 101 is 1000 ° C. or higher. Further, the reforming raw material 123 and the methane reforming catalyst 106 are heated by the combustion gas and further heated by radiant heat transfer.

  As described above, according to the firing method of the present embodiment, the calorific value of the combustion gas in the calcining furnace body 101 and the heat amount necessary for the endothermic reaction when the reforming raw material 123 is reacted with the methane reforming catalyst 106 are as follows. In order to use the quantity of radiant heat from the object to be fired, the firing jig and the furnace wall heated by the combustion gas, a part of the heat of the combustion gas is used for hydrogen fuel generation, so that the combustion heat of the fuel As a result, the total amount of fuel used can be reduced.

  In the firing method of the present embodiment, the reformed gas 124 generated by the methane reformer 103 is further introduced into the hydrogen separator 104 to selectively separate hydrogen in the reformed gas 124. The hydrogen fuel 125 containing hydrogen as a main component and the residual gas 126 containing carbon dioxide are separated, and the residual gas 126 separated by the hydrogen separator 104 is caused to flow into the carbon dioxide fixing device 105. Of carbon dioxide is fixed by a fixing agent 141 so as not to be released to the outside in the form of gas, and the hydrogen separated by the hydrogen separator 104 and the methane main fuel 131 for mixing mainly composed of methane in the combustion means 102. The mixed fuel 132 with the fuel 125 (hydrogen fuel 128 for mixing) flows in and burns to generate combustion gas, thereby reducing the carbon dioxide content in the combustion gas and exhausting it to the outside. A firing method capable of reducing the carbon dioxide content in the combustion exhaust gas 112 to be. The combustion exhaust gas 112 is discharged to the outside. Further, after carbon dioxide is immobilized by the immobilizing agent 141, the carbon dioxide is discharged to the outside as the waste liquid 142.

  Here, in the mixing methane main fuel 131 containing methane as a main component, “mainly containing methane” means that the content of methane is 80 (volume%) or more. Further, “having hydrogen as a main component” of the hydrogen fuel 125 mainly containing hydrogen means that the hydrogen content is 50 (volume%) or more.

  Thus, according to the firing method of the present embodiment, the mixed fuel 132 of the mixing methane main fuel 131 and the hydrogen fuel 125 (mixing hydrogen fuel 128) as the fuel 111 containing methane to be burned by the combustion means 102. Therefore, the generation of carbon dioxide can be reduced by the amount that contains hydrogen (hydrogen fuel for mixing 128) that does not generate carbon dioxide even when the mixed fuel 132 (fuel 111) is combusted. At this time, the hydrogen content (hydrogen / mixed fuel) contained in the mixed fuel 132 is preferably 5 to 95 (volume%), 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%), not only the combustion gas but also other heat sources are used when performing the methane reforming reaction. You may need it. Further, since the carbon dioxide produced when the reforming raw material 123 is reacted with the methane reforming catalyst 106 is fixed by the carbon dioxide fixing device 105, the carbon dioxide produced from the reforming raw material 123 is in a gas state. It is not released to the outside.

  As shown in FIG. 3, the firing furnace 300 used in the firing method of the present embodiment further includes a fuel cell 107, and a part of the hydrogen fuel 125 can be used as the fuel cell hydrogen 127 to generate power. It is configured. The fuel cell 107 generates power by reacting hydrogen (hydrogen for fuel cell) with oxygen or air. In the firing method of the present embodiment (third invention), the fuel cell 107 is separated by the hydrogen separator 104. A part of the hydrogen fuel 125 obtained in this way can be separated as fuel cell hydrogen 127 and used for the fuel cell 107 to generate electric power. Since the hydrogen fuel 125 has a high purity of hydrogen, the fuel cell 107 can efficiently generate power by using a part of the hydrogen fuel 125 as the fuel cell hydrogen 127. For example, when the fuel cell is generated using normal hydrogen, the power efficiency is about 40%. However, when the fuel cell 107 generates power in the present embodiment, the power efficiency is drastically 60 to 70%. improves. Further, a part of the hydrogen fuel 125 obtained by separation in the hydrogen separator 104 is finally burned by the combustion means 102 as the mixing hydrogen fuel 128, and the remainder is used as the fuel cell hydrogen 127 for power generation in the fuel cell 107. By using this, the amount of carbon dioxide contained in the combustion exhaust gas 112 can be reduced, and at the same time, the heat possessed by the combustion gas can be effectively recovered and used for power generation, and electric energy with high utility value can be obtained. Can do.

  Regarding carbon dioxide emissions, fuel cells are about twice as efficient in converting thermal energy into electrical energy compared to thermal power generation. Therefore, if the electric power derived from the fuel cell is used instead of the electric power derived from the thermal power generation for the reduction of the carbon dioxide emission, the carbon dioxide gas reduction amount for the same electric energy is halved. Therefore, it is possible to reduce the generated carbon dioxide without intentionally fixing the carbon dioxide. If carbon dioxide is immobilized, a higher carbon dioxide reduction effect is produced.

  The total amount of the hydrogen fuel 125 may be used as the mixing hydrogen fuel 128 or may be divided into the mixing hydrogen fuel 128 and the fuel cell hydrogen 127. The ratio when dividing into the mixing hydrogen fuel 128 and the fuel cell hydrogen 127 is not particularly limited, and the carbon dioxide emission amount and the power generation amount may be appropriately balanced so as to be an optimum value. .

  In the firing furnace 300 used in the firing method of the present embodiment shown in FIG. 3, the firing furnace main body 101 is a firing furnace 100 that is an embodiment of the firing furnace of the present invention described with reference to FIG. 1. It is preferable to configure in the same manner as in the case of the firing furnace main body 1, and the structure in which the methane reformer 103 is disposed in the firing furnace main body 101 is the same as the firing furnace main body 101 shown in FIG. It is preferable to configure. Thereby, the same effect can be acquired. The firing furnace main body 101 may be a batch type in which a predetermined amount of the objects to be fired are fired intermittently, but the objects to be fired such as a ceramic structure are continuously carried into the interior of the body. The continuous firing furnace main body 101 is preferably a continuous firing furnace body 101 that heats and fires the fired body and then continuously carries it out of the fired body. By continuously firing, the temperature of the combustion gas can be steadily stabilized. Therefore, in the methane reformer 103 in the firing furnace main body 101, methane reforming is achieved by heating with the heat of the combustion gas and radiant heat transfer. The hydrogen fuel 125 can be stably supplied, and the mixed fuel 132 obtained by mixing the hydrogen fuel 125 and the mixing methane main fuel 131 can be stabilized. Can be supplied to the combustion means 102.

  In addition, as an object to be fired by the firing method of the present embodiment, ceramics such as tableware, tiles, sanitary ware, insulators, and ceramic honeycomb structures can be suitably fired. Here, the ceramic honeycomb structure is a honeycomb structure having a plurality of cells made of ceramic and serving as a flow path of fluid partitioned by partition walls.

  In the firing furnace 300 used in the firing method of the present embodiment shown in FIG. 3, the combustion means 102, methane reformer 103, hydrogen separator 104, carbon dioxide fixing device 105, and fuel cell 107 are shown in FIG. In the firing furnace 100 (first invention) of the present invention, it is preferable that the combustion means 2, the methane reformer 3, the hydrogen separator 4, the carbon dioxide fixing device 5 and the fuel cell 7 are configured in the same manner. Thereby, the same effect can be acquired.

  In the firing method of the present embodiment, as in the case of the embodiment of the firing method of the present invention described above, the mixing methane main fuel 131 containing methane as a main component as the fuel to be burned by the combustion means 102. And a hydrogen fuel 125 (hydrogen fuel 128 for mixing) separated by the hydrogen separator 104 is used. At the start of the operation of the firing furnace 300, the temperature of the combustion gas is not stable (the state where the combustion gas has not yet been generated or gradually increased), so the reaction by the methane reformer 103 However, the mixed fuel 132 may be used after the combustion gas has been discharged constantly. In this case, at the start of the operation of the firing furnace 300, firing is performed only with the mixing methane main fuel 131 containing methane as a main component. Further, when the combustion gas at the start is not constantly discharged and the temperature is not stable, the methane reformer 103 is provided with another heating device (not shown) such as steam or electricity. The methane reformer 103 may be operated while using the heating device.

  The firing method of the present embodiment can be suitably used when firing a ceramic with a heat amount of 1 million to 100 million (kJ / Hr). In the case of equipment smaller than 1 million (kJ / Hr), the present invention can be used by combining several small equipment. Although the present invention can be applied to facilities of 1 million (kJ / Hr) or less, the methane steam reforming facility is expensive and is not economical.

  In the firing method of the present embodiment, as in the case of the embodiment of the firing method of the present invention described above, the volume ratio (reformation) of the reforming methane secondary fuel 121 and the mixing methane main fuel 131 is improved. The methane secondary fuel 121: the mixing methane main fuel 131) is preferably 5:95 to 100: 0 (volume ratio). If the ratio of the reforming methane auxiliary fuel 121 is smaller than 5 (volume ratio), carbon dioxide may not be sufficiently reduced. Further, at least one of the mixing methane main fuel 131 and the reforming methane auxiliary fuel 121 may be liquefied natural gas (LNG). By using LNG, it can be burned efficiently due to the good flammability of LNG, and LNG is a clean and inexpensive fuel, which is preferable because it does not generate harmful substances such as sulfur oxides and dust by combustion. .

When the combustion means 102 is used to burn the mixed fuel 132 of the mixing methane main fuel 131 and the hydrogen fuel 125 (mixing hydrogen fuel 128) as the firing method of the present embodiment (this embodiment), When only methane gas (a gas having a methane content of 100 (%)) is used as the fuel 111 and burned by the combustion means 102 (comparative example), the difference between the amount of used fuel and the amount of generated heat, and When the difference in the amount of generated carbon dioxide is shown, the same result as that obtained when the same comparison is made in the firing furnace 100 of the present invention shown in FIG. 1 is obtained. That is, when only methane gas is burned as the fuel 111, a calorific value of 39800 (kJ / Hr) is obtained for the use of methane gas 1 (Nm ³ / Hr), whereas in the present embodiment, methane gas The total amount of use (total of the mixing methane main fuel 131 and the reforming methane auxiliary fuel 121) is 0.9 (Nm ³ / Hr), whereas the amount of heat obtained is 40380 (kJ / Hr) It becomes. In addition, since the amount of carbon dioxide generated when 1 mol of methane gas is burned is 1 mol (theoretical amount), in the case of the comparative example, 1 (Nm ³ / Hr) of carbon dioxide is generated. On the other hand, in the case of the present embodiment, 0.5 (Nm ³ / Hr) of carbon dioxide is generated. Therefore, when the present embodiment is compared with the comparative example, the amount of methane gas used to make the amount of heat generated by the combustion in the combustion means 102 substantially equal (this embodiment is slightly larger). The present embodiment is reduced by 10% compared to the comparative example, and the amount of carbon dioxide generated is reduced by 50% compared to the comparative example. become.

  Further, in the firing method of the present embodiment, the methane reformer is disposed in the firing furnace main body. In addition to this, one embodiment of the firing method of the present invention described with reference to FIG. A methane reformer disposed outside the main body of the firing furnace, such as a methane reformer used in the above-described form, may be further provided. In other words, a methane reformer is provided inside and outside the main body of the firing furnace, and methane reforming is performed using the heat and radiant heat of the combustion gas inside, and the heat of the combustion exhaust gas is used outside. Methane reforming may be performed.

  Next, still another embodiment of the firing method of the present invention will be described with reference to FIG. 4 showing still another embodiment of the above-described firing furnace of the present invention.

  The firing furnace 400 used in the firing method of the present embodiment is preferably a firing furnace similar to that of still another embodiment of the firing furnace of the present invention described above with reference to FIG. In the firing method of the present embodiment, a combustion gas is generated by flowing a fuel 161 containing methane into the combustion means 152 and burning it, and the combustion gas generated by the combustion means 152 is introduced into the firing furnace main body 151, This is a firing method in which a body to be fired carried inside is heated and fired by combustion gas. Further, a methane reforming catalyst 156 is filled inside, and a methane reformer 153 disposed in the calcining furnace body 151 is reformed into a reforming methane auxiliary fuel 171 mainly composed of methane and steam 172. The raw material 173 is introduced, the reforming material 173 is heated by the combustion gas, and is brought into contact with the methane reforming catalyst 156 while being heated by radiant heat transfer generated in the calcining furnace body 151. Methane and water vapor 172 are reacted to produce reformed gas 174 containing hydrogen and carbon dioxide. Further, the radiant heat transfer generated in the firing furnace main body 151 is caused by the fired object, the firing jig, the furnace wall, etc. in the firing furnace main body 151 being heated by the combustion gas to become a high temperature. This is radiant heat transfer emitted from jigs, furnace walls, and the like. Radiant heat transfer becomes particularly large when the temperature in the firing furnace main body 151 is 1000 ° C. or higher. Further, the reforming raw material 173 and the methane reforming catalyst 156 are heated by the combustion gas and further heated by radiant heat transfer.

  As described above, according to the firing method of the present embodiment, the calorific value of the combustion gas in the calcining furnace main body 151 as the amount of heat necessary for the endothermic reaction when the reforming raw material 173 is reacted with the methane reforming catalyst 156, and In order to use the amount of radiant heat from the object to be fired, the firing jig and the furnace wall heated by the combustion gas, a part of the heat of the combustion gas is recovered and reused as the combustion heat of the fuel. Thus, the total amount of fuel used can be reduced.

  In the firing method of the present embodiment, the reformed gas 174 generated by the methane reformer 153 is further introduced into the hydrogen separator 154 to selectively separate hydrogen in the reformed gas 174. The hydrogen fuel 175 containing hydrogen as a main component and the residual gas 176 containing carbon dioxide are separated, and the residual gas 176 separated by the hydrogen separator 154 flows into the carbon dioxide fixing device 155, The carbon dioxide is fixed by a fixing agent 191 so that it is not released to the outside in the state of gas, and hydrogen fuel 175 separated by the hydrogen separator 154 is made to flow into the fuel cell 157 as hydrogen 177 for the fuel cell, Fuel cell hydrogen 177 is reacted with oxygen or air to generate power, and thus reforming containing hydrogen in methane reformer 153 using the heat of combustion gas 174 is generated, hydrogen fuel 175 is separated from reformed gas 174 by hydrogen separator 154, hydrogen fuel 175 is used as fuel cell hydrogen 177 for power generation in fuel cell 157, and one of the thermal energy possessed by the combustion gas It is a baking method which can convert a part into electrical energy. The combustion exhaust gas 162 is discharged to the outside. Further, after carbon dioxide is immobilized by the immobilizing agent 191, it is discharged to the outside as a waste liquid 192.

  As described above, according to the firing method of the present embodiment, the entire amount of the hydrogen fuel 175 is used as the fuel cell hydrogen 177 and is generated by the fuel cell 157. Therefore, the heat of the combustion gas is effectively recovered for power generation. It can be used and electric energy with higher utility value can be obtained. Since the hydrogen fuel 175 has a high purity of contained hydrogen, the fuel cell 157 can efficiently generate power by using it as the fuel cell hydrogen 177. For example, when the fuel cell is generated using normal hydrogen, the power efficiency is about 40%. However, when the fuel cell 157 generates power in the present embodiment, the power efficiency is drastically 60 to 70%. improves.

  Further, according to the firing method of the present embodiment, the carbon dioxide produced when the reforming raw material 173 is reacted with the methane reforming catalyst 156 is fixed by the carbon dioxide fixing device 155, so that the reforming raw material 173 Carbon dioxide produced from the gas is not released to the outside in the form of gas.

  In the firing furnace 400 used in the firing method of the present embodiment shown in FIG. 4, the firing furnace body 151 is the case of the firing furnace body 1 in the embodiment of the firing furnace of the present invention shown in FIG. The structure in which the methane reformer 153 is disposed in the firing furnace main body 151 is preferably the same as the firing furnace main body 101 shown in FIG. 5 or FIG. Thereby, the same effect can be acquired. Further, the firing furnace main body 151 may be a batch type in which a predetermined amount of the objects to be fired are fired intermittently, but the objects to be fired such as a ceramic structure are continuously carried into the interior thereof. A continuous firing furnace main body 151 that heats and fires the fired body and then continuously carries it out of the fired body is preferable. By continuously firing, the temperature of the combustion gas can be steadily stabilized in the firing furnace main body 151. Therefore, in the methane reformer 153, the methane reforming reaction is performed by the heat of the combustion gas and the radiant heat transfer. Thus, the hydrogen fuel 175 can be supplied stably, and the fuel cell 157 can stably generate power.

  In addition, as an object to be fired by the firing method of the present embodiment, ceramics such as tableware, tiles, sanitary ware, insulators, and ceramic honeycomb structures can be suitably fired. Here, the ceramic honeycomb structure is a honeycomb structure having a plurality of cells made of ceramic and serving as a flow path of fluid partitioned by partition walls.

  In the firing furnace 400 used in the firing method of the present embodiment shown in FIG. 4, the combustion means 152, the methane reformer 153, the hydrogen separator 154, the carbon dioxide fixing device 155, and the fuel cell 157 are shown in FIG. As in the case of the combustion means 2, the methane reformer 3, the hydrogen separator 4, the carbon dioxide fixing device 5, and the fuel cell 7 in the firing furnace 100 that is an embodiment of the firing furnace of the present invention shown above. It is preferable to configure, whereby the same effect can be obtained. However, the fuel 161 containing methane is preferably composed mainly of methane, and the combustion means 152 is preferably capable of efficiently combusting the fuel 161 composed mainly of methane. Here, “having methane as the main component” means that the content of methane is 80 (% by volume) or more.

  In the firing furnace 400 of the present embodiment, the residual gas 176 may contain a combustible substance such as carbon monoxide. Therefore, when such a combustible substance is contained, the residual gas A part or all of 176 may be burned by the burning means 152. This is preferable because fuel is recovered.

  The firing method of the present embodiment can be suitably used when firing a ceramic with a heat amount of 1 million to 100 million (kJ / Hr). In the case of equipment smaller than 1 million (kJ / Hr), the present invention can be used by combining several small equipment. Although the present invention can be applied to facilities of 1 million (kJ / Hr) or less, the methane steam reforming facility is expensive and is not economical.

  In the ceramic industry, etc., it can be used as a firing furnace for firing ceramics, etc., and thereby it is possible to recover the heat of the combustion gas generated in the firing furnace or the combustion exhaust gas discharged from the firing furnace. Become. Furthermore, carbon dioxide contained in the combustion exhaust gas can be reduced, the amount of carbon dioxide released into the atmosphere can be reduced, and fuel cost can be further reduced. Further, by recovering and using the thermal energy of the combustion exhaust gas, it is possible to generate power with the fuel cell.

It is a block flow figure showing typically one embodiment of a baking furnace of the present invention. It is a block flow figure showing other embodiments of a baking furnace of the present invention typically. It is a block flow figure showing still another embodiment of a baking furnace of the present invention typically. It is a block flow figure showing still another embodiment of a baking furnace of the present invention typically. It is sectional drawing which showed typically the baking furnace main body used for other embodiment of the baking furnace of this invention, and cut | disconnected by the plane perpendicular | vertical to the longitudinal direction. It is sectional drawing which showed typically the baking furnace main body used for other embodiment of the baking furnace of this invention, and cut | disconnected by the plane perpendicular | vertical to the longitudinal direction.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1,51,101,151 ... Firing furnace main body, 101a ... Outer peripheral wall, 101b ... Inner furnace wall, 2, 52, 102, 152 ... Combustion means, 3, 53, 103, 153 ... Methane reformer, 103a ... Kai Quality reaction tube, 4, 54, 104, 154 ... hydrogen separator, 5, 55, 105, 155 ... carbon dioxide fixator, 6, 56, 106, 156 ... methane reforming catalyst, 7, 57, 107, 157 ... Fuel cell, 11, 61, 111, 161 ... fuel, 12, 62, 112, 162 ... combustion exhaust gas, 21, 71, 121, 171 ... reforming methane auxiliary fuel, 22, 72, 122, 172 ... steam, 23 73, 123, 173 ... reforming raw material, 24, 74, 124, 174 ... reforming gas, 25, 75, 125, 175 ... hydrogen fuel, 26, 76, 126, 176 ... residual gas, 27, 77, 127 , 1 7 ... Hydrogen for fuel cell, 28, 128 ... Hydrogen fuel for mixing, 31, 131 ... Main fuel for mixing, 32, 132 ... Mixed fuel, 41, 91, 141, 191 ... Fixing agent, 42, 92, 142 , 192 ... waste liquid, 43, 93 ... reformer exhaust gas, 44, 94, 144, 194 ... carbon dioxide fixing exhaust gas, 100, 200, 300, 400 ... firing furnace, m ... body to be fired, B ... belt conveyor.

Claims (30)

Combustion means for generating a combustion gas by combusting the fuel containing the methane that has flowed in, and the fired body carried in the interior are heated and fired by the combustion gas, and the burned combustion gas is externally exposed. A firing furnace comprising a firing furnace body to be discharged,
A methane reforming catalyst is filled inside, and a reforming raw material composed of methane secondary fuel for reforming mainly composed of methane and steam, which is flowed into the reforming raw material, is heated by the combustion gas and / or the combustion gas. The methane and the steam in the reforming raw material are reacted with each other by contacting with the methane reforming catalyst while being heated by radiant heat from an object, a firing jig and a furnace wall, and contain hydrogen and carbon dioxide A methane reformer for generating reformed gas , wherein the methane reformer is disposed in a calcining furnace body, and the calcining furnace body has a space for disposing the methane reformer by an inner furnace wall; A firing furnace partitioned into a space for firing the object to be fired with combustion gas . A fuel cell that generates power by reacting hydrogen with oxygen or air is further provided, and a part or all of hydrogen contained in the reformed gas is used as fuel cell hydrogen, and oxygen or air in the fuel cell The firing furnace according to claim 1 used for reaction. The reformed gas generated by the methane reformer is introduced into the interior, and the hydrogen in the reformed gas is selectively separated so that a hydrogen gas containing hydrogen as a main component and a residual gas containing carbon dioxide. The firing furnace according to claim 1, further comprising a hydrogen separator that is separated into two . The firing furnace according to claim 3 , wherein a part or all of the hydrogen fuel is used as a fuel cell hydrogen for reaction with oxygen or air in the fuel cell. The firing furnace according to claim 3 , wherein a part or all of the hydrogen fuel is mixed with a mixing methane main fuel containing methane as a main component to form a mixed fuel, and the mixed fuel is burned by the combustion means. Part of the hydrogen fuel is used as a fuel cell hydrogen for the reaction with oxygen or air in the fuel cell, and the remainder is mixed with a methane main fuel for mixing mainly composed of methane to obtain a mixed fuel. The firing furnace according to claim 3 , wherein the mixed fuel is combusted by the combustion means. The volume ratio of the modified and matter for methane secondary fuel the mixed methane-main fuel (reforming methane secondary fuel: mixing methane main fuel) is 5: 95 to 100: according to claim 5 or 6 0 Firing furnace. The firing furnace according to any one of claims 3 to 7 , wherein the residual gas discharged from the hydrogen separator is burned by the combustion means. The calcination according to any one of claims 3 to 8 , further comprising a carbon dioxide fixing device for fixing carbon dioxide in the residual gas separated by the hydrogen separator so as not to be released to the outside in a gas state. Furnace. The carbon dioxide immobilizer is, carbon dioxide has a sodium hydroxide as the fixing agent to be immobilized according to claim 9, wherein by reacting sodium hydroxide and carbon dioxide can be generated sodium carbonate Firing furnace. The said firing furnace main body is a continuous firing furnace main body which carries the said to-be-fired body into the inside continuously, heats the said to-be-fired body inside, and continuously carries out to the exterior. The firing furnace according to any one of 0 . The firing furnace according to any one of claims 1 to 11, wherein at least one of the reforming methane auxiliary fuel and the mixing methane main fuel is liquefied natural gas (LNG). The firing furnace according to any one of claims 1 to 12 , wherein the material to be fired is ceramic. The firing furnace according to claim 13, wherein the ceramic is fired at a calorific value of 1 million to 100 million (kJ / Hr). The sintering furnace according to any of claims 1 to 1 4 wherein the sintered body is a honeycomb structure. A combustion gas is generated by injecting and burning a fuel containing methane into the combustion means, the combustion gas generated by the combustion means is introduced into the firing furnace main body, and the combustion gas is carried into the interior by the combustion gas. A firing method for heating and firing the object to be fired, and discharging the combustion gas after firing to the outside of the firing furnace body,
A reforming raw material consisting of methane auxiliary fuel for reforming mainly composed of methane and steam is caused to flow into a methane reformer filled with a methane reforming catalyst, and the reforming raw material is converted into the combustion gas and / or The methane and the water vapor in the reforming raw material react with each other by contacting the methane reforming catalyst while being heated by radiant heat from the object to be fired, a firing jig and a furnace wall heated by the combustion gas. To produce a reformed gas containing hydrogen and carbon dioxide ,
The methane reformer is disposed in the firing furnace body, the firing furnace body has a space in which the methane reformer is disposed by an inner furnace wall, and a space in which the body to be fired is fired with combustion gas. der Ru firing method that is partitioned into. The firing method according to claim 16 , wherein part or all of the hydrogen contained in the reformed gas is converted into hydrogen for a fuel cell to generate electricity by reacting with oxygen or air in the fuel cell. The reformed gas generated in the methane reformer is caused to flow into a hydrogen separator, and the hydrogen in the reformed gas is selectively separated to form hydrogen fuel and hydrogen dioxide mainly containing hydrogen. The firing method according to claim 16 or 17 , wherein the firing gas is separated into a residual gas containing carbon.   The firing method according to claim 18, wherein a part or all of the hydrogen fuel is used as a fuel cell hydrogen for the reaction with oxygen or air in the fuel cell.   The firing method according to claim 18, wherein a part or all of the hydrogen fuel is mixed with a mixing methane main fuel containing methane as a main component to form a mixed fuel, and the mixed fuel is burned by the combustion means.   A part of the hydrogen fuel is used for the reaction with oxygen or air in the fuel cell, and the remaining part is mixed with a methane main fuel for mixing mainly composed of methane to obtain a mixed fuel. The firing method according to claim 18, wherein combustion is performed by the combustion means.   21. The reforming methane auxiliary fuel and the mixing methane main fuel are used so that a volume ratio thereof (reforming methane auxiliary fuel: mixing methane main fuel) is 5:95 to 100: 0. Or the baking method of 21. The residual gas discharged from the hydrogen separator, a firing method according to any one of claims 18 to 2 2 to combust in the combustion unit. The residual gas separated in the hydrogen separator to flow into the carbon dioxide immobilizer, according to claim 18 to 2 3 of the carbon dioxide in the residual gas is immobilized so as not to be released to the outside in a state of gas The firing method according to any one of the above.   25. The carbon dioxide fixing device according to claim 24, wherein the carbon dioxide fixing device has sodium hydroxide as a fixing agent for fixing carbon dioxide, and the sodium hydroxide and carbon dioxide can be reacted to generate sodium carbonate. Firing method. Examples firing furnace body, the carried therein continuously to be fired, the use of continuous firing furnace body for unloading continuously its external after heating the sintered body inside the claims 1 6 - The firing method according to any one of 25 . Wherein as at least one in the reforming methane secondary fuel and the mixing methane main fuel, the firing method according to claim 1 6-2 6 using liquefied natural gas (LNG). Wherein the material of the object to be fired, firing method according to any one of claims 1 to 6 to 27 using a ceramic. The firing furnace according to claim 28, wherein the ceramic is fired at a calorific value of 1 million to 100 million (kJ / Hr). Examples to be fired, firing method according to any one of claims 1 6-29 using a honeycomb structure.

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