WO2008004369A1 - Procédé pour traiter du gaz contenant de l'oxyde d'azote - Google Patents
Procédé pour traiter du gaz contenant de l'oxyde d'azote Download PDFInfo
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- WO2008004369A1 WO2008004369A1 PCT/JP2007/058143 JP2007058143W WO2008004369A1 WO 2008004369 A1 WO2008004369 A1 WO 2008004369A1 JP 2007058143 W JP2007058143 W JP 2007058143W WO 2008004369 A1 WO2008004369 A1 WO 2008004369A1
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- concentration
- gas
- carbon monoxide
- concentration ratio
- ratio
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8696—Controlling the catalytic process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23C—METHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN A CARRIER GAS OR AIR
- F23C13/00—Apparatus in which combustion takes place in the presence of catalytic material
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23C—METHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN A CARRIER GAS OR AIR
- F23C13/00—Apparatus in which combustion takes place in the presence of catalytic material
- F23C13/06—Apparatus in which combustion takes place in the presence of catalytic material in which non-catalytic combustion takes place in addition to catalytic combustion, e.g. downstream of a catalytic element
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23C—METHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN A CARRIER GAS OR AIR
- F23C13/00—Apparatus in which combustion takes place in the presence of catalytic material
- F23C13/08—Apparatus in which combustion takes place in the presence of catalytic material characterised by the catalytic material
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23N—REGULATING OR CONTROLLING COMBUSTION
- F23N1/00—Regulating fuel supply
- F23N1/02—Regulating fuel supply conjointly with air supply
- F23N1/022—Regulating fuel supply conjointly with air supply using electronic means
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23N—REGULATING OR CONTROLLING COMBUSTION
- F23N5/00—Systems for controlling combustion
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23N—REGULATING OR CONTROLLING COMBUSTION
- F23N5/00—Systems for controlling combustion
- F23N5/003—Systems for controlling combustion using detectors sensitive to combustion gas properties
- F23N5/006—Systems for controlling combustion using detectors sensitive to combustion gas properties the detector being sensitive to oxygen
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J2219/00—Treatment devices
- F23J2219/10—Catalytic reduction devices
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23N—REGULATING OR CONTROLLING COMBUSTION
- F23N2235/00—Valves, nozzles or pumps
- F23N2235/02—Air or combustion gas valves or dampers
- F23N2235/06—Air or combustion gas valves or dampers at the air intake
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23N—REGULATING OR CONTROLLING COMBUSTION
- F23N2235/00—Valves, nozzles or pumps
- F23N2235/02—Air or combustion gas valves or dampers
- F23N2235/10—Air or combustion gas valves or dampers power assisted, e.g. using electric motors
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23N—REGULATING OR CONTROLLING COMBUSTION
- F23N2235/00—Valves, nozzles or pumps
- F23N2235/12—Fuel valves
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23N—REGULATING OR CONTROLLING COMBUSTION
- F23N2237/00—Controlling
- F23N2237/12—Controlling catalytic burners
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23N—REGULATING OR CONTROLLING COMBUSTION
- F23N2241/00—Applications
- F23N2241/04—Heating water
Definitions
- the present invention relates to a method for treating a gas containing nitrogen oxides applied to a water tube boiler, a regenerator of an absorption chiller, and the like.
- the low NOx technology described in Patent Documents 3 and 4 belongs to a so-called high air ratio combustion region Z1 having an air ratio of 1.38 or more as shown in FIG.
- the combustion zone Z2 with an air ratio of 1.1 or less hereinafter referred to as “low air ratio”
- the amount of nitrogen oxides generated increases, making it difficult to achieve both low NOx and low CO.
- the low air ratio combustion region Z2 since stable combustion control is difficult, such as causing backfire when the air ratio is 1 or less, the low air ratio combustion region Z2 has been a force that has not been a subject of research and development until now.
- lines F and E schematically show the NOx characteristics and CO characteristics of the primary side by the combustion apparatus of the present invention, respectively, and lines U and J respectively represent NOx of the catalyst secondary side by the combustion apparatus of the present invention.
- the characteristics and CO characteristics are shown schematically.
- the low NOx technology in Patent Documents 3 and 4 basically suppresses NOx generation by burning the burner in the high air ratio region Z1, thereby making it an oxidation catalyst (Patent Documents 3 and 4). This technology removes the generated CO.
- the inventors of this application have been researching and developing a combustion method capable of reducing nitrogen oxides to almost zero using an oxidation catalyst.
- Patent Document 5 is known as a method for treating a nitrogen oxides-containing gas generated by combustion of a panner.
- the burner is burned at an air ratio of less than 1.0, so that the combustion exhaust gas does not contain oxygen, and unburned components of CO and HC (hydrocarbon) are removed.
- CO and HC hydrocarbon
- NOx reduction catalyst nitrogen oxides are reduced with unburned components to purify the nitrogen oxides, and air is added to the exhaust gas after purification, and the unburned components are added with the acid catalyst. It is something that purifies.
- Patent Document 6 discloses a method for purifying nitrogen oxide-containing gas from a gas engine. This Patent Document 6 purifies nitrogen oxides and carbon monoxide using a three-way catalyst, but the existence of hydrocarbons in the gas is essential and the theoretical air ratio in which no excess oxygen is present. The power cannot be applied to any gas. Therefore, the treatment method of Patent Document 6 is not suitable for the combustion gas treatment of a combustion apparatus such as a boiler that occurs due to burner combustion and contains excess oxygen.
- Patent Document 7 discloses a technique for reducing nitrogen oxides in the exhaust gas of an incinerator using an acid catalyst using monoxide carbon.
- the exhaust gas is in an oxygen-free state by burning the fuel richly (less than air ratio 1) in the primary combustion. It is what.
- it since it is restricted by fuel rich combustion, it is difficult to apply to a combustion apparatus that contains oxygen in exhaust gas such as a boiler using a panner.
- Patent Document 1 Japanese Patent No. 3221582
- Patent Document 2 US Patent No. 5353748
- Patent Document 3 Japanese Patent Application Laid-Open No. 2004-125378
- Patent Document 4 U.S. Patent No. 6792895
- Patent Document 5 Japanese Unexamined Patent Publication No. 2001-241619
- Patent Document 6 Japanese Patent Laid-Open No. 5-38421
- Patent Document 7 Japanese Patent Laid-Open No. 2003-275543
- the problem to be solved by the present invention is to solve the problem by a simple method using an acid catalyst. Nitrogen oxides and carbon monoxide emissions contained in the contained gas can be reduced to a value close to zero or reduced to an acceptable range. Is to provide.
- the concentration ratio is close to the reference predetermined concentration ratio.
- the concentration ratio simply means the concentration ratio of oxygen, nitrogen oxide and carbon monoxide on the primary side of the oxidation catalyst.
- the oxidation catalyst may be a new oxidation catalyst which may be a known oxidation catalyst.
- the tasks include the following sub-tasks.
- the first sub-task is a harmful substance of the oxidation catalyst
- Hydrocarbons that inhibit the reduction of (NOx and CO) are included in the gas produced by PANA It is not allowed. This can be solved without using hydrocarbon removal means by using combustion without rapid cooling as in an internal combustion engine.
- a second sub-task is how to set the gas concentration ratio to the reference predetermined concentration ratio.
- the reference predetermined concentration cannot be obtained simply by burning the panner.
- adjustment using the concentration ratio characteristics of the burner, adjustment using the concentration ratio characteristics of the burner and the endothermic means for absorbing heat of the burner gas, in addition to these adjustments, This can be solved by adjusting the density ratio by any one of the auxiliary adjustment means.
- the present invention can easily solve the above-described problems by the technical means of adjusting the concentration ratio using a conventional PANA and an oxidation catalyst, which does not require power if it is remarkable in the harmful substance reduction effect. It is an epoch-making invention.
- the present invention can be applied to a method for treating a gas containing nitrogen oxides produced by a panner without being limited to a boiler.
- the invention according to claim 1 is a nitrogen oxide-containing gas that reduces a nitrogen oxide contained in the gas by bringing a gas generated by burning fuel in a burner into contact with an oxidation catalyst.
- the concentration ratio of oxygen, nitrogen oxide and carbon monoxide is such that the nitrogen oxide concentration on the secondary side of the oxidation catalyst is substantially zero or a predetermined value or less, and the carbon monoxide concentration is substantially zero or a predetermined value or less.
- a predetermined concentration ratio It is characterized by including a specific adjustment scan Tetsupu, Ru.
- the nitrogen oxide concentration is substantially zero, preferably 5 ppm, more preferably 3 ppm, and still more preferably zero.
- the substantially zero carbon monoxide concentration is 30 ppm, more preferably lOppm.
- the oxygen concentration is substantially zero, which is 10 Oppm or less, but is preferably less than the measurement limit value.
- the nitrogen oxide concentration and carbon monoxide concentration below the specified values mean below the emission standard concentration defined in each country and region. It tastes, but it is almost as close to zero as possible, and it is preferable to set it to a value.
- “predetermined values” and below can be referred to as “allowable values” and “emission standard values”.
- the concentration ratio of the gas is set to the predetermined concentration ratio, whereby the hazardous substance reduction step.
- the carbon monoxide concentration is adjusted by effectively utilizing the acid action of oxygen monoxide and carbon by oxygen, and the nitrogen oxide concentration on the secondary side of the oxidation catalyst is substantially zero or a predetermined value.
- the carbon monoxide concentration can be reduced to substantially zero or a predetermined value or less.
- combustion control is easier compared to the method of burning to discharge hydrocarbons as in Patent Document 7. Yes.
- the invention according to claim 2 is a nitrogen oxide-containing gas that reduces a nitrogen oxide contained in the gas by bringing a gas generated by burning fuel in a burner into contact with an oxidation catalyst.
- a concentration ratio adjusting step for adjusting the concentration ratio K of oxygen, nitrogen oxide and carbon monoxide, and the concentration ratio adjusting step is any one of the following adjustment 0, adjustment 1, and adjustment 2.
- Adjustment 1 The concentration ratio K is adjusted to a first predetermined concentration ratio K1 that makes the concentration of nitrogen oxides on the secondary side of the oxidation catalyst substantially zero and the concentration of carbon monoxide below a predetermined value.
- Adjustment 2 The concentration ratio K is set so that the carbon monoxide concentration on the secondary side of the oxidation catalyst is substantially zero.
- the nitrogen oxide concentration is adjusted to a second predetermined concentration ratio K2 that makes the concentration lower than a predetermined value.
- the invention according to claim 3 is the invention according to claim 2, wherein the expression for determining the reference predetermined concentration ratio ⁇ ⁇ is the following expression (1), and the reference predetermined concentration ratio ⁇ ⁇ ⁇ satisfies the following expression (2):
- the first predetermined concentration ratio K1 is smaller than the reference predetermined concentration ratio ⁇ ⁇
- the second predetermined concentration ratio ⁇ 2 is larger than the reference predetermined concentration ratio ⁇ .
- [CO], [NOx] and [O] are the carbon monoxide concentration and nitrogen acid, respectively.
- the adjustment 0, that is, the concentration ratio K of the gas is set to the reference predetermined concentration ratio K0.
- the exhaust nitrogen oxide concentration and the exhaust carbon monoxide concentration can be made substantially zero.
- the concentration ratio K of the gas is made substantially zero using the oxidation catalyst, and the exhaust monoxide and carbon The concentration can be set to a predetermined value or less.
- the concentration ratio of the gas that is, the gas concentration ratio to the second predetermined concentration ratio
- the exhausted carbon monoxide concentration is made substantially zero using the oxidation catalyst, and the exhausted nitrogen oxide concentration is less than a set value It can be.
- the other effects described in claim 1 can be similarly achieved in claim 2 or claim 3.
- the invention according to claim 4 is a nitrogen oxide-containing gas that reduces a nitrogen oxide contained in the gas by contacting a gas generated by burning fuel with a burner and an oxidation catalyst.
- a combustion step in which a hydrocarbon-containing fuel is combusted in the above-mentioned panner to produce a gas that does not contain hydrocarbons but contains oxygen, nitrogen oxides, and monoxide-carbon.
- the concentration ratio of the gas is set to the predetermined concentration ratio.
- the carbon monoxide concentration is adjusted by effectively utilizing the carbon monoxide produced by the carbon monoxide, and the exhausted nitrogen oxide concentration is made substantially zero by using the oxidation catalyst. Therefore, it can be zero or less than a predetermined value.
- the other effects described in claim 1 can be similarly achieved in claim 4.
- the invention as set forth in claim 5 is characterized in that, in any one of claims 1 to 4, the air ratio of the burner is 1.1 or less.
- the invention of claim 6 is characterized in that, in any one of claims 1 to 4, the concentration ratio K is adjusted using the concentration ratio characteristics of the PANANA.
- the concentration ratio adjustment uses the concentration ratio characteristic of the panner. Therefore, it is possible to achieve the effect that no separate means for adjusting the concentration ratio is required.
- the invention according to claim 7 is the invention according to any one of claims 1 to 4, wherein the adjustment of the concentration ratio K is performed between the spanner, the spanner, and the oxidation catalyst. It is characterized by the fact that it is performed using the concentration ratio characteristic with the endothermic means that absorbs heat from the gas power.
- the concentration ratio adjustment is performed by adjusting the concentration of the burner and the endothermic device. Since the ratio characteristic is used, no separate means for adjusting the concentration ratio is required. In addition, the temperature of the gas can be suppressed by the endothermic means, and the durability of the oxidation catalyst The effect that it can improve can be show
- the invention according to claim 8 is the force 1 according to any one of claims 1 to 4, wherein the adjustment of the concentration ratio K utilizes the concentration ratio characteristics of the panner, and the It is characterized in that it is carried out by using an auxiliary adjusting means which is arranged between the oxidation catalysts and auxiliaryly adjusts the concentration ratio K.
- the concentration ratio adjustment is added to the concentration ratio characteristic of the panner. Since the auxiliary adjustment means is used, the range of the panner and the heat absorption means to which the present invention is applicable can be expanded.
- the invention according to claim 9 is the force 1 according to any one of claims 1 to 4, wherein the adjustment of the concentration ratio K is arranged between the spanner, the spanner, and the oxidation catalyst.
- Gas concentration is performed using an auxiliary adjustment means that uses the concentration ratio characteristic with the endothermic means that absorbs heat and is arranged between the PANA and the oxidation catalyst to supplementarily adjust the concentration ratio K.
- the concentration ratio adjustment is performed by adjusting the concentration of the burner and the endothermic means. Since the auxiliary adjustment means is used in addition to the specific characteristics, there is an effect that the range of the above-described panner and the endothermic means to which the present invention can be applied can be expanded.
- the invention according to claim 10 is caused by combustion of the panner, and by contacting a gas containing nitrogen oxides and carbon monoxide with an acid catalyst, exhausted nitrogen oxides and exhausted monoacids.
- a method for treating a nitrogen oxide-containing gas that reduces the concentration of carbon, wherein the gas contains oxygen, and the nitrogen oxide on the primary side of the acid catalyst in the gas By adjusting the concentration ratio of carbon oxide and oxygen to a predetermined concentration ratio, the emission concentration of nitrogen oxides and carbon monoxide is substantially zero or a predetermined value or less.
- the concentration ratio of nitrogen oxide, carbon monoxide and oxygen is adjusted by the presence of oxygen, the predetermined concentration ratio can be easily adjusted, and the acid concentration can be adjusted.
- the nitrogen oxide and carbon monoxide emission concentrations can be made substantially zero or a predetermined value or less.
- the invention of claim 11 is characterized in that, in claim 10, the set air ratio by the air ratio adjusting means is 1.1 or less.
- the discharge amount of nitrogen oxides and carbon monoxide can be reduced to a value close to zero as much as possible, or can be easily reduced to a predetermined value within the allowable range.
- FIG. 1 is an explanatory view of a longitudinal section of a steam boiler according to a first embodiment.
- FIG. 2 is a sectional view taken along line II—II in FIG.
- FIG. 3 is a diagram showing a configuration of a main part when the acid catalyst of FIG. 2 is viewed from the flow direction of exhaust gas.
- FIG. 4 is a diagram showing the air ratio- ⁇ ⁇ CO characteristics of Example 1.
- FIG. 5 is an explanatory view of a partial cross section of the damper position adjusting device according to the first embodiment when used.
- FIG. 6 is a cross-sectional explanatory view of a main part of the damper position adjusting device.
- Fig. 7 is a schematic diagram for explaining the characteristics of the burner and endothermic means and the acid catalyst of Example 1.
- FIG. 8 is a diagram for explaining output characteristics of the sensor of the first embodiment.
- FIG. 9 is a diagram for explaining motor control characteristics of the first embodiment.
- FIG. 10 is a diagram for explaining NOx and CO reduction characteristics of Example 1.
- FIG. 11 is an explanatory view of a longitudinal section of a steam boiler according to a second embodiment.
- FIG. 12 is a diagram illustrating motor control characteristics of the second embodiment.
- FIG. 13 is a diagram illustrating air ratio control using the air ratio NOx′CO characteristic of the third embodiment.
- FIG. 14 is an explanatory view of a longitudinal section of a steam boiler according to a fourth embodiment.
- FIG. 15 is a diagram for explaining NOx′CO secondary characteristics and secondary characteristics according to the present invention. Explanation of symbols
- Gas refers to the gas that passes through the catalyst until it has passed through the oxidation catalyst (which can be referred to as “oxidation / reduction catalyst”, hereinafter simply referred to as “catalyst”), and the gas that has passed through the catalyst. It is called “exhaust gas”. Therefore, the gas includes a gas in the combustion reaction (combustion process) and a gas in which the combustion reaction is completed, and can be referred to as a combustion gas.
- gas refers to the gas that has passed through the final stage catalyst
- exhaust gas refers to the final stage catalyst. The gas after passing through.
- the "primary side of the catalyst” is the side where the catalyst is provided with a partner! /, And unless otherwise specified, means the gas immediately before passing through the catalyst. “Next side” refers to the opposite side of the primary side of the catalyst.
- not containing hydrocarbons does not mean that no hydrocarbons are produced in the course of the combustion reaction, but some hydrocarbons are produced in the course of the combustion reaction. This means that the combustion reaction is completed, that is, the gas flowing into the catalyst contains substantially no hydrocarbons that reduce nitrogen oxides (below the measurement limit). .
- This invention is a small once-through boiler Applicable to any water tube boiler, hot water heater, refrigerating machine of absorption chiller, etc. (also referred to as heat equipment or combustion equipment).
- a combustion apparatus such as a boiler to which an embodiment of the method for treating a nitrogen oxides-containing gas of the present invention is applied typically has a burner and an endotherm that absorbs heat from the gas generated by the burner.
- a can body including a heat transfer tube (water tube) group as a means, and a gas containing oxygen, nitrogen oxide, and carbon monoxide after passing through the heat transfer tube group in a predetermined concentration ratio are in contact with each other to pass through the carbon monoxide.
- An oxidation catalyst that oxidizes and reduces nitrogen oxides fuel supply means for supplying gaseous fuel to the burner, combustion air supply means for supplying combustion air to the burner and premixing combustion air and fuel, and A sensor for detecting the oxygen concentration downstream of the oxidation catalyst and a controller for controlling the fuel supply means and the combustion air supply means by inputting signals from the sensor and the like are provided as main parts. .
- Embodiment 1 of the present invention that is preferably implemented in such a combustion apparatus is such that a gas generated by burning fuel in a burner and an acid catalyst are brought into contact with each other in the gas.
- a method of treating a nitrogen oxide-containing gas that reduces the nitrogen oxide contained in the fuel, wherein a hydrocarbon-containing fuel is combusted in the above-mentioned panner, and contains no hydrocarbon, oxygen, nitrogen oxide, and one A combustion step for generating a gas containing carbon oxide; and contacting the gas with an oxidation catalyst to oxidize the carbon monoxide contained in the gas with oxygen and to convert the nitrogen oxide to the carbon monoxide carbon.
- a concentration ratio of oxygen, nitrogen oxide, and carbon monoxide in the gas on the primary side of the oxidation catalyst, and the nitrogen oxide concentration on the secondary side of the oxidation catalyst is substantially zero or predetermined.
- the carbon monoxide concentration is virtually zero
- Other is characterized in that it comprises a concentration ratio adjusting step of adjusting the predetermined concentration ratio equal to or less than a predetermined value.
- Embodiment 2 of the present invention provides a nitrogen oxide-containing gas that reduces the nitrogen oxides contained in the gas by bringing the gas generated by burning the fuel in the burner into contact with the acid catalyst.
- a combustion method wherein a hydrocarbon-containing fuel is burned in the above-mentioned panner to produce a gas containing oxygen, nitrogen oxides and carbon monoxide without containing hydrocarbons;
- a harmful substance reducing step of contacting the gas with an oxidation catalyst to oxidize carbon monoxide contained in the gas with oxygen and reducing the nitrogen oxide with carbon monoxide; and oxygen and nitrogen in the gas on the primary side of the oxidation catalyst A concentration ratio adjusting step for adjusting the concentration ratio K of oxide and carbon monoxide, wherein the concentration ratio adjusting step is any one of the following adjustments 0 to 2.
- Adjustment 0 Adjustment is made to a reference predetermined concentration ratio K0 that makes the nitrogen oxide concentration and carbon monoxide concentration on the secondary side of the oxidation catalyst substantially zero.
- Adjustment 1 The concentration ratio ⁇ is adjusted to a first predetermined concentration ratio K1 that makes the nitrogen oxide concentration on the secondary side of the oxidation catalyst substantially zero and the carbon monoxide concentration below a predetermined value.
- Adjustment 2 The concentration ratio K is adjusted to a second predetermined concentration ratio K2 that makes the carbon monoxide concentration on the secondary side of the oxidation catalyst substantially zero and the nitrogen oxide concentration not more than a predetermined value.
- the catalyst makes the nitrogen oxide concentration and the carbon monoxide concentration on the catalyst secondary side substantially zero, and when the adjustment 1 is performed, the catalyst secondary side
- the nitrogen oxide concentration of the catalyst is substantially zero, the carbon monoxide concentration is set to a predetermined value or less, and when the adjustment 2 is performed, the carbon monoxide concentration on the secondary side of the oxidation catalyst is substantially zero.
- the nitrogen oxide concentration is set to a predetermined value or less.
- the concentration ratio means a mutual relationship among the carbon monoxide concentration, the nitrogen oxide concentration, and the oxygen concentration.
- the reference predetermined concentration ratio KO in the adjustment 0 is preferably determined by a determination formula of the following equation (1), and preferably satisfies the following equation (2), and the first predetermined concentration ratio K1 is set as the reference predetermined concentration ratio K1.
- the second predetermined concentration ratio K2 smaller than the ratio KO is set to be larger than the reference predetermined concentration ratio KO.
- [CO], [NOx] and [O] are the carbon monoxide concentration and nitrogen acid, respectively.
- the reference predetermined concentration ratio K0 is defined as the oxygen and nitrogen oxides on the primary side of the oxidation catalyst in which the oxygen concentration, nitrogen oxide concentration and carbon monoxide concentration on the secondary side of the oxidation catalyst are substantially zero, respectively. And the concentration ratio of carbon monoxide.
- the formula (1) is the reference predetermined concentration.
- Equation (2) shows a condition for making the oxygen concentration, nitrogen oxide concentration, and carbon monoxide concentration on the secondary side of the oxidation catalyst substantially zero, respectively, for determining the ratio KO. .
- the upper limit 2.0 of the ⁇ depends on the characteristics of the catalyst. Taking a value greater than 0 is not considered.
- the concentration ratio ⁇ ⁇ on the primary side of the oxidation catalyst is set so that the reference predetermined concentration ratio ⁇ is lower than the value, that is, the ⁇ ⁇ in formula (1) is the first predetermined concentration ratio K1 smaller than ⁇ .
- the oxygen concentration and nitrogen oxide concentration on the secondary side of the oxidation catalyst become substantially zero, and the carbon monoxide concentration becomes a predetermined value or less.
- the predetermined value of the carbon monoxide concentration is preferably set below the emission standard value (this value varies depending on the country and can be changed for each country).
- the first predetermined concentration ratio K1 can be determined experimentally.
- the concentration ratio ⁇ is adjusted so that the concentration ratio ⁇ is smaller than ⁇ and becomes the first predetermined concentration ratio K1, specifically, the ratio of the oxygen concentration to the carbon monoxide concentration on the primary side of the oxidation catalyst. Is less than the ratio of the oxygen concentration to the carbon monoxide concentration that satisfies the reference predetermined concentration ratio ⁇ 0.
- the concentration ratio ⁇ on the primary side of the oxidation catalyst is adjusted so that the concentration ratio ⁇ is larger than ⁇ ⁇ the second predetermined concentration ratio ⁇ 2 (the adjustment 2), and the oxidation catalyst
- the concentration of carbon monoxide on the secondary side becomes substantially zero, and the concentration of nitrogen oxides is below a predetermined value.
- the oxygen concentration on the secondary side of the oxidation catalyst is a predetermined concentration.
- the predetermined value of the nitrogen oxide concentration is a value different from the predetermined value of the carbon monoxide concentration, and is preferably less than or equal to the emission standard value determined in each country.
- the second concentration ratio 2 can be determined experimentally.
- the adjustment of the concentration ratio ⁇ to obtain the second predetermined concentration ratio ⁇ 2 specifically, the ratio of the oxygen concentration to the carbon monoxide concentration on the primary side of the oxidation catalyst satisfies the reference predetermined concentration ratio ⁇ . This can be achieved by increasing the oxygen concentration relative to the carbon monoxide concentration.
- Embodiment 1 of this treatment method first, in the combustion step, the PANA contains nitrogen oxides and carbon monoxide, and does not contain hydrocarbons! / Gas generated It is.
- concentration ratio K of oxygen, nitrogen oxides, and carbon monoxide in the gas on the primary side of the catalyst is adjusted according to any one of the adjustment 0, the adjustment 1, and the adjustment 2 described above by the concentration ratio adjustment step.
- the concentration ratio adjustment step Are adjusted to the reference predetermined concentration ratio K0, the first predetermined concentration ratio K1, and the second predetermined concentration ratio K2, respectively.
- the gas comes into contact with the catalyst, so that monoxide and carbon are oxidized by oxygen in the gas, and nitrogen oxides are reduced by the acid and carbon.
- the role of oxygen in the hazardous substance reduction step is to adjust the concentration of monoxide and carbon, that is, reduce the concentration of nitrogen oxides to substantially zero. It consumes and reduces the amount of carbon monoxide present in excess of the amount necessary to achieve this.
- This hazardous substance reduction step reduces the amount of nitrogen oxides in the gas to substantially zero, and the amount of carbon monoxide to substantially zero or below a predetermined value. .
- the reference predetermined concentration ratio KO of the adjustment 0 and the first predetermined concentration ratio K1 of the adjustment 1 are expressed by being included by the following equation (3). That is, when the expression (3) is satisfied, the nitrogen oxide concentration on the secondary side of the catalyst is substantially zero, and the carbon monoxide concentration is substantially zero or reduced. In order to reduce the carbon monoxide concentration below the predetermined value, the concentration ratio K on the primary side of the oxidation catalyst is set so that the value on the left side of Equation (3) is smaller than K0! Adjust to the first predetermined concentration ratio K1.
- the reduction action in the harmful substance reduction step will be further described.
- This reduction is considered to be performed as follows.
- a first reaction that oxidizes carbon monoxide and a second reaction that reduces nitrogen oxides with monoxide carbon occur.
- the first reaction in the presence of oxygen, the first reaction is superior to the second reaction.
- carbon monoxide is consumed by oxygen.
- the nitrogen oxide is reduced by the second reaction.
- the first reaction is a competitive reaction with the second reaction, but the reaction between carbon monoxide and oxygen is performed in the presence of oxygen. In this case, it appears to be faster than the second reaction. Therefore, in the first stage, the acid of carbon monoxide and carbon (first reaction) is performed, and in the second stage, nitrogen oxides are reduced (second reaction). It is thought that
- the value of ([NOx] + 2 [0]) / [CO] (value of the concentration ratio) is 2.0 or less as described above.
- [NOx] in the above formula (1) is the total concentration of nitrogen monoxide concentration: [NO] and nitrogen dioxide concentration: [NO].
- NO is used without using NOx.
- the reason why NO is used is that the composition of the produced nitrite in the high temperature field is NO because the main component is NO and NO is only a few percent.
- the first reaction and the second reaction force are theoretically derived.
- the NO reduction reaction by CO in the second reaction (i) proceeds in an atmosphere in which no oxygen exists.
- the CO concentration, NO concentration, and O concentration are set to [CO] ppm, [NO] ppm, [O
- concentration ratio K value exceeding 1.0 is considered to be due to the reason of the force, which is an experimentally obtained value.
- the reaction occurring in the catalyst has not been completely elucidated, and it is considered that a side reaction has occurred in addition to the main reaction of the first reaction and the second reaction.
- One of the side reactions may be a reaction in which hydrogen is generated by the reaction between steam and carbon monoxide, and nitrogen oxides and oxygen are reduced by this hydrogen.
- the combustion step is performed by burning a hydrocarbon-containing fuel in the panner, and a gas containing nitrogen oxides, carbon monoxide, and oxygen is generated without containing hydrocarbons.
- This combustion is combustion performed in a normal combustion apparatus such as a boiler, and does not involve rapid cooling as in an internal combustion engine, so the exhaust gas does not contain hydrocarbons.
- the air ratio is 1.1 or less. This saves energy by low air ratio combustion.
- the panner is a combustion device that continuously supplies fuel and combustion air and continuously burns it, and does not include an internal combustion engine.
- An internal combustion engine such as an automobile engine, discontinuously supplies and burns fuel and combustion air, so that a large amount of hydrocarbons and carbon monoxide and carbon are generated as unburned components in the exhaust gas. Therefore, it is suitable for the nitrogen oxide-containing gas treatment method of the present invention.
- the above-mentioned panner is preferably an all-primary-air premixed panner that premixes and burns gas fuel.
- the concentration ratio K as shown in the above formulas (2) and (3) regarding oxygen, nitrogen oxides, and carbon monoxide is reduced. Adjustment is important.
- the pre-mixing burner as the burner, the reference predetermined concentration ratio KO can be obtained relatively easily in a low air ratio region.
- oxygen, nitrogen oxides, and carbon monoxide in the gas on the primary side of the catalyst are uniformly mixed, and the respective concentrations are controlled to the predetermined concentration ratio, thereby performing partial premixing other than the premixing panner. It can be a PANA or a premixed PANA.
- the concentration ratio adjusting step is a step of adjusting the concentration ratio K on the primary side of the oxidation catalyst to the reference predetermined concentration ratio K0, the first predetermined concentration ratio K1, or the second predetermined concentration K2. However, it can be performed using the following first to fourth concentration ratio adjusting means.
- the first concentration ratio adjusting means adjusts the concentration ratio K using the concentration ratio characteristics of the panner.
- This first concentration ratio adjusting means is preferably performed by setting the air ratio of the above-mentioned panner.
- no concentration ratio adjusting means other than the panner is required, so that the configuration of the apparatus can be simplified.
- the concentration ratio characteristic of the panner is a characteristic in which the amount of carbon monoxide and nitrogen oxide produced is changed by burning the panner while changing the air ratio.
- the second concentration ratio adjusting means uses an endothermic means that adjusts the concentration ratio K using the concentration ratio characteristics of the burner and that is disposed between the burner and the oxidation catalyst and absorbs heat from the gas. This is performed using the concentration ratio characteristics, that is, using the concentration ratio characteristics of the PANANER and the endothermic means.
- This concentration ratio characteristic means that the amount of carbon monoxide and nitrogen oxides after passing through all or part of the endothermic means generated by burning the PANA by changing the air ratio changes.
- the concentration ratio characteristic is basically determined by the concentration ratio characteristic of the panner, and the endothermic means typically changes or maintains the concentration ratio characteristic of the spanner. Has the function to have.
- the endothermic means is the first aspect, the carbon monoxide concentration is increased and the nitrogen oxide concentration is suppressed.
- the endothermic means is the second aspect, typically, the concentration ratio characteristic by the panner is held with almost no change.
- the heat absorption means may be a group of water tubes constituting a can body such as a boiler.
- This heat absorption means is preferably a water tube group constituting a can such as a boiler.
- a form of the heat absorption means there are a first aspect (corresponding to Patent Documents 1 to 4) in which a combustion pipe is arranged in the combustion space with almost no combustion space in the immediate vicinity of the panner, and the panner. And a second form having a combustion space between the water tube group.
- the endothermic means is the first aspect, the carbon monoxide concentration is increased and the nitrogen oxide concentration is suppressed.
- the concentration ratio characteristic by the panner is kept almost unchanged.
- the water pipe group is a plurality of water pipes that exchange heat with the gas from the panner, but a plurality of water pipes can be configured by meandering one water pipe like a water pipe of a water heater.
- the endothermic means can have the function of adjusting the concentration ratio by suppressing the nitrogen oxide concentration by suppressing the combustion gas temperature of the panner.
- the endothermic means suppresses the temperature of the gas from rising to about 900 ° C. or more, suppresses the oxidation of carbon monoxide and carbon, and does not change the concentration ratio of the burner gas. In this sense, the concentration ratio K is adjusted.
- the heat absorbing means absorbs heat from the gas generated by the panner and uses the heat, and the temperature of the gas is controlled by the acid contact. It is possible to have a function of suppressing the temperature to be not lower than the activation temperature of the medium and not higher than the temperature at which thermal deterioration is prevented.
- concentration ratio K is adjusted using the second concentration ratio adjusting means, no concentration ratio adjusting means is required in addition to the above-mentioned panner and the endothermic means! Can be In addition, the temperature of the gas can be suppressed by the endothermic means, and the durability of the oxidation catalyst can be improved.
- the third concentration ratio adjusting means adjusts the concentration ratio K by using the concentration ratio characteristics of the panner, and is arranged between the panner and the oxidation catalyst to supplementarily adjust the concentration ratio. This is performed using auxiliary adjustment means.
- the auxiliary adjusting means is located between the burner and the oxidation catalyst (including the middle of the endothermic means), and by injecting carbon monoxide carbon or adsorbing and removing oxygen, It has the function of assisting the adjustment by increasing the ratio of the concentration of carbon monoxide and carbon to the oxygen concentration.
- this auxiliary adjustment means it is possible to use a CO generator or an auxiliary partner that can adjust the amount of oxygen or CO in the exhaust gas.
- the concentration ratio adjustment is performed using the auxiliary adjusting means in addition to the concentration ratio characteristics of the panner.
- the scope of application of the above-mentioned panner can be expanded without being limited to the one having a specific structure.
- the fourth concentration ratio adjusting means uses the concentration ratio characteristics of the Parner and an endothermic means that is disposed between the Parner and the oxidation catalyst and absorbs heat from the gas to adjust the concentration ratio K.
- the auxiliary adjustment means disposed between the PANA and the acid catalyst is used.
- the concentration ratio adjustment is added to the concentration ratio characteristics of the panner and the endothermic means, and the auxiliary adjusting means is used. Therefore, the scope of application of the above-described panner and the above-mentioned heat absorbing means can be expanded without being limited to the one having a specific structure.
- the catalyst is a catalyst having a function of efficiently reducing the nitrogen oxides in a state where hydrocarbons are not contained in the gas, and the downstream of the endothermic means or the endothermic hand.
- a structure in which a catalytically active substance is supported on a gas permeable base material provided in the middle of the stage is not limited to a specific structure.
- a metal such as stainless steel or ceramic is used, and a surface treatment is performed so as to increase the contact area with the exhaust gas.
- Platinum is generally used as the catalytically active substance.
- noble metals represented by platinum (Ag, Au, Rh, Ru, Pt, Pd) or metal oxides should be used. Can do.
- the catalyst When the catalyst is provided in the middle of the endothermic means, the catalyst can be provided in a gap between a plurality of endothermic means, or a heat-absorbing means such as a water pipe can be used as a base material and a catalytically active substance can be supported on the surface.
- a heat-absorbing means such as a water pipe can be used as a base material and a catalytically active substance can be supported on the surface.
- FIG. 1 is an explanatory view of a longitudinal section of the steam boiler of the first embodiment
- FIG. 2 is a sectional view taken along the line II-II in FIG. 1
- FIG. 4 is a diagram illustrating the air ratio NOx′CO characteristic of the first embodiment
- FIG. 5 is a damper position adjusting device of the first embodiment
- FIG. 6 is an explanatory view of a partial cross section of the damper position adjusting device in use
- FIG. 7 is a graph showing the characteristics of the panner and heat absorption means of the first embodiment.
- FIG. 8 is a schematic diagram for explaining the characteristics of the catalyst
- FIG. 8 is a diagram for explaining the output characteristics of the sensor of the first embodiment
- FIG. 9 is a diagram for explaining the motor control characteristics of the first embodiment.
- FIG. 10 is a diagram for explaining the NOx and CO reduction characteristics of the first embodiment.
- This steam boiler is composed of a can 3 including a heat exchanger tube (water tube) group 2 as a heat absorption means for absorbing heat generated by the gas generator 1 and the gas generated from the heat generator tube 1, and the oxygen after passing through the heat transfer tube group 2.
- a catalyst containing nitrogen oxides and carbon monoxide at a predetermined concentration ratio passes through them to oxidize carbon monoxide and reduce nitrogen oxides (hereinafter simply referred to as “catalyst”).
- fuel supply means 5 for supplying gaseous fuel to the burner 1
- combustion air supply means 6 for supplying combustion air to the burner 1 and premixing combustion air and fuel
- a sensor 7 for detecting the oxygen concentration in the downstream of the catalyst 4
- a boiler controller for controlling the fuel supply means 5 and the combustion air supply means 6 by inputting signals from the sensor 7 and the like
- the controller 8 is provided as a main part.
- the burner 1 is a complete premix burner having a flat combustion surface (premixed gas ejection surface).
- This panner 1 has the same configuration as the panner described in Patent Document 1.
- the can body 3 includes an upper header 9 and a lower header 10, and a plurality of inner water tubes 11, 11,... Constituting the water tube group 2 are disposed between both headers. Then, as shown in FIG. 2, a pair of water pipe walls 14, 14 formed by connecting outer water pipes 12, 12,... With connecting members 13, 13,. A first gas passage 15 is formed between the water pipe walls 14 and 14 and the upper header 9 and the lower header 10 so that the gas from the Parner 1 flows almost linearly. One end of the first gas passage 15 is provided with the above-described Parner 1, and a second gas passage (smoke) 17 through which exhaust gas flows is connected to the exhaust gas outlet 16 at the other end.
- the parner 1 and the can 3 are known ones.
- the second gas passage 17 includes a horizontal portion 18 and a vertical portion 19, and the catalyst 4 is attached to the horizontal portion 18.
- a feed water preheater 20 as an exhaust heat recovery device is attached to the vertical portion 19 so as to be located downstream of the catalyst 4, and the sensor 7 is disposed between the catalyst 4 and the feed water preheater 20. ing.
- the components from the Parner 1 including the Parner 1 and the front water pipe group 2 to the catalyst 4 are the gas in the primary gas of the catalyst 4 It functions to adjust the concentration ratio K to the predetermined concentration ratios K0 and K1. That is, the air ratio is adjusted to the set air ratio by the air ratio adjusting means 28 described later, so that the air ratio equal to N Ox 'CO characteristics shown in FIG. 4 can be obtained.
- This air ratio one NOx'CO characteristic is obtained by controlling the air ratio adjusting means 28 to change the air ratio and combusting the primary ratio of the catalyst 4 on the primary side. , Called primary characteristics).
- the catalyst 4 has a secondary side air ratio NOx′CO characteristic (hereinafter referred to as a secondary characteristic) of the catalyst 4 obtained by bringing the gas having the primary characteristic into contact with the catalyst 4.
- the primary characteristic is a concentration ratio characteristic due to components from the PANA 1 to the catalyst 4
- the secondary characteristic is a characteristic due to the catalyst 4.
- the primary characteristic is determined by adjusting the NOx concentration and monoacid on the secondary side of the catalyst 4 when the set air ratio is adjusted to 1.0.
- the carbonized carbon concentration is substantially zero.
- the reference predetermined concentration ratio K0 in the primary side gas of the catalyst 4 becomes the specific reference predetermined concentration ratio K0X (see FIG. 7).
- FIG. 4 is a schematic diagram in which the low air ratio region Z2 in FIG.
- the first line (characteristic line) E indicates the CO concentration on the primary side of the catalyst 4
- the second line F indicates the NOx concentration on the primary side.
- the third line J shows the CO concentration on the secondary side of the catalyst 4. The CO concentration becomes substantially zero when the air ratio is 1.0 or more, and the concentration rapidly increases as the air ratio becomes smaller than 1.0. It has an increasing characteristic.
- the fourth line U indicates the NOx concentration on the secondary side of the catalyst 4. The NOx concentration becomes substantially zero in a predetermined region where the air ratio is 1.0 or less, and the air ratio exceeds 1.0.
- a region where the secondary side NOx concentration of the catalyst 4 is equal to or lower than the air ratio where the secondary side concentration is equal to the primary side concentration is referred to as a NOx′CO reduction region.
- the lower limit of this ⁇ ⁇ CO reduction region can be the air ratio at which the CO concentration on the secondary side of the catalyst 4 is 300 ppm (Japan's CO emission standard). This air ratio in the low air ratio region is a new characteristic that has not been studied so far.
- the catalyst 4 functions to oxidize carbon monoxide (first reaction) and reduce nitrogen oxide (second reaction) contained in the gas not containing hydrocarbons after passing through the water tube group 2
- a catalyst in which the catalytically active substance is platinum is used.
- the gas and the catalyst satisfying the concentration ratio formula of the formula (3) are theoretically considered in consideration of the experimental results. It is considered that contact with the catalytically active substance of 4 causes a first reaction that mainly oxidizes carbon monoxide and a second reaction that reduces nitrogen oxides with carbon monoxide. Whether or not the reaction proceeds in the first reaction is determined depending on the oxygen concentration. In this catalyst 4, the first reaction is considered to be superior to the second reaction.
- This catalyst has a structure as shown in FIG. 3 and is formed, for example, as follows. A large number of fine irregularities are formed on the surfaces of the flat plate 21 and the corrugated plate 22 both made of stainless steel as the base material, and a catalytically active material (not shown) is carried on the surfaces. Next, the flat plate 21 and the corrugated plate 22 having a predetermined width are overlapped. After joining together, it is wound into a spiral to form a roll. This roll-shaped product is surrounded and fixed by the side plate 23. Platinum is used as the catalytically active material. In FIG. 3, only a part of the flat plate 21 and the corrugated plate 22 is shown.
- the catalyst 4 has an acid activity in a low temperature region, is the horizontal portion 18 in the middle of the second gas passage 17, and has an exhaust gas temperature of about 100 ° C to 350 ° C, preferably It is placed at a position of about 150 ° C to 350 ° C.
- the catalyst 4 is detachably attached to the second gas passage 17 so that it can be replaced when the performance deteriorates.
- the fuel supply means 5 includes a gas fuel supply pipe 24 and a flow rate adjusting valve 25 for adjusting the fuel flow rate provided in the gas fuel supply pipe 24.
- the flow rate adjusting valve 25 has a function of controlling the fuel supply amount to a high combustion flow rate and a low combustion flow rate.
- the combustion air supply means 6 adjusts the amount of combustion air flowing through the air supply passage 27, the air supply passage 27 that supplies the combustion air from the air blower 26 to the burner 1, and the air supply passage 27.
- the air ratio adjusting means 28 for adjusting the air ratio of the PANA 1 is included.
- the gas fuel supply pipe 24 is connected to the air supply passage 27 so as to eject fuel gas.
- the air ratio adjusting means 28 is a damper 29 as a flow rate adjusting means for adjusting the opening degree (flow passage cross-sectional area) of the air supply passage 27, and for adjusting the opening position of the damper 29.
- the damper position adjusting device 30 and the controller 8 for controlling the operation of the damper position adjusting device 30 are configured.
- the damper position adjusting device 30 includes a drive shaft 32 that is detachably connected to the rotary shaft 31 of the damper 29.
- the drive shaft 32 is connected via a speed reducer 33. It can be rotated by motor 34.
- motor 34 a motor capable of arbitrarily adjusting the rotation stop position is used. In this embodiment, a stepping motor (pulse motor) is used.
- the drive shaft 32 is connected to the rotary shaft 31 of the damper 29 via a coupling 35 so that the drive shaft 32 can rotate integrally on substantially the same axis.
- the coupling 35 has a stepped cylindrical shape, and a small-diameter hole 36 and a large-diameter hole 37 are formed in the central portion so as to penetrate in the axial direction.
- the drive shaft 32 is inserted into the small diameter hole 36, and the drive shaft 32 is integrated with the coupling 35 with a mounting screw 38.
- a rotary shaft 31 of the damper 29 can be inserted into the large-diameter hole 37, and the rotary shaft 31 can rotate integrally with the coupling 35 by a key 39.
- key grooves 40 and 41 are formed in the large-diameter hole 37 of the rotary shaft 31 and the coupling 35, respectively.
- Such a coupling 35 is rotatably held by the outer case 43 of the damper position adjusting device 30 via the bearing 42 at the other end with the drive shaft 32 inserted at one end. It is.
- the outer case 43 holds the speed reducer 33 and the motor 34 at one end, and exposes the large-diameter hole 37 with the keyway 41 of the coupling 35 at the other end.
- the ring 35 and the rotation abnormality detection means 44 are sealed inside.
- the rotation abnormality detection means 44 includes a detection plate 45 and a detector 46.
- the detected plate 45 is fixed to the stepped portion at the axially central portion of the coupling 35 so as to extend radially outward.
- the detection plate 45 is provided concentrically with the coupling 35 and the drive shaft 32.
- a slit forming region 48 in which a large number of slits 47, 47... Are formed at equal intervals in the circumferential direction is provided in a part of the outer peripheral portion of the detection plate 45.
- the slit forming region 48 is provided for the arc of a quarter (90 degrees).
- the slits 47 formed in the slit formation region 48 have the same shape and size. In this embodiment, elongated rectangular grooves along the radial direction of the plate 45 to be detected are punched and formed at equal intervals along the circumferential direction.
- the detector 46 for detecting the slit 47 is fixed to the outer case 43.
- the detector 46 is a transmissive photointerrupter, and is attached in a state where the outer peripheral portion of the detection plate 45 is interposed between the light emitting element 49 and the light receiving element 50.
- a position corresponding to the detector 46 from the light emitting element 49 to the light receiving element 50.
- Whether the light receiving element 50 receives light from the light emitting element 49 or not is switched depending on whether the slit 47 of the detection plate 45 is disposed at a position corresponding to the optical path). Thereby, the opening position of the damper 29 can be detected.
- the damper position adjusting device 30 is the clockwise direction of the slit forming region 48 in FIG. With the end slit 51 of the damper 29 disposed at a position corresponding to the detector 46, the damper 29 is positioned so as to fully close the air supply passage 27, and the damper 29 Mounted on the rotary shaft 31.
- the slit forming region 48 is formed by 90 degrees of the detection plate 45, the clockwise end slit 51 of the slit forming region 48 corresponds to the detector 46.
- the damper 29 In the state of being disposed at the position, as described above, the damper 29 fully closes the air supply passage 27, while the counter slit 52 in the counterclockwise direction of the slit forming region 48 corresponds to the detector 46. In the state of being arranged at the position, the damper 29 opens the supply passage 27 fully.
- the motor 34 and the detector 46 are connected to the controller 8, and the rotation of the motor 34 is controlled while monitoring the rotation abnormality of the damper 29. It is configured to be able to. That is, in order to control the motor 34, the damper position adjusting device 30 has a generation circuit of a control signal including a drive pulse to the motor 34, and the generated control signal can be output to the motor 34. It is. Thereby, the rotation angle of the motor 34 is arbitrarily controlled in accordance with the forward rotation or reverse rotation and the drive amount, that is, the number of drive pulses. In addition, the rotation speed can be controlled by changing the interval (feed speed) of the drive noise.
- the controller 8 When actually controlling the opening / closing of the damper 29, the controller 8 first performs an origin detection operation in order to set the fully closed position of the damper 29 as the origin. First, in FIG. 5, the detected plate 45 is rotated counterclockwise. Now, assuming that the detector 46 is disposed in the slit forming region 48 of the plate 45 to be detected, the detector 46 is periodically inserted into the slit 47 as the plate 45 is rotated. Therefore, the detected pulse is input to the controller 8 as a detection signal. Then, when the detection plate 45 is rotated until the detector 46 is disposed outside the slit forming region 48, no nose is detected.
- the controller 8 recognizes that the detector 46 is outside the slit forming region 48 and switches the rotation direction to the reverse direction. That is, in the present embodiment, the detected plate 45 is rotated in the clockwise direction, and the position where the pulse (the end slit 51 in the clockwise direction) is first detected is set as the origin. The origin confirmation by this clockwise rotation is This is performed at a lower speed than the counterclockwise rotation before the rotation direction is switched.
- the controller 8 Since the origin detected in this way corresponds to the fully closed position of the damper 29, on the basis of this state, the controller 8 outputs a drive signal to the motor 34, and The damper 29 can be controlled to open and close.
- the controller 8 drives the motor 34 to open and close the damper 29, the detection signal of the slit 47 is acquired as a pulse from the detector 46 accordingly. Therefore, the controller 8 can monitor the rotation abnormality of the damper 29 by comparing the detection signal from the detector 46 with the control signal to the motor 34. Specifically, a control signal that also has a driving pulse force to the motor 34 and a detection signal that also has a detection pulse force of the slit 47 by the detector 46 are compared, and the presence or absence of a rotation abnormality is monitored.
- the controller 8 determines that the rotation is abnormal.
- the detection pulse from the detector 46 is usually different from the frequency of the drive pulse to the motor 34, it is controlled in consideration of this difference. For example, if no pulse of the detection signal is detected even after the time corresponding to a predetermined pulse of the drive signal has elapsed, control is performed so that a rotation abnormality is determined for the first time.
- the controller 8 performs measures such as notifying abnormality and stopping combustion. Conversely, when a pulse is detected from the detector 46 even though no driving pulse is sent to the motor 34, a rotation abnormality can be detected.
- the controller 8 uses a prestored air ratio control program so that the air ratio of the PANA 1 becomes the set air ratio based on the detection signal of the sensor 7 (first control condition).
- the motor 34 is configured to control the motor 34 so that the concentration ratio K of the gas on the primary side of the catalyst 4 satisfies the following formula (3) (second control condition):
- the first control condition that is directly controlled.
- the second control condition is automatically satisfied. It is made. This point will be described below with reference to FIGS.
- the air ratio ⁇ ⁇ CO characteristic in FIG. 4 is expressed based on the primary characteristic of the constituent elements including the Parner 1 and the water pipe group 2 and the secondary characteristic by the catalyst 4.
- FIG. 7 represents this based on the primary characteristics of the constituent elements and the characteristics of the catalyst 4 with respect to the oxygen concentration on the primary side of the catalyst 4.
- the fifth line L has a nitrogen oxide concentration and a carbon monoxide concentration on the secondary side of the catalyst 4 of substantially zero when the concentration ratio on the primary side of the catalyst 4 is located (mounted) on the line. That is, the line satisfies the reference predetermined density ratio K0.
- the fifth line L corresponds to the case where the predetermined concentration ratio of the formula (3) is 1. That is, the fifth line L is a line representing the following formula (3 A).
- the NOx concentration characteristic with respect to the oxygen concentration is omitted in FIG. It is assumed that [NOx] can be ignored.
- the primary oxygen concentration is XI
- the reference predetermined concentration that makes the nitrogen oxide concentration and carbon monoxide concentration on the secondary side of the catalyst 4 substantially zero within the range of the concentration ratio K exceeding 1.0 and up to 2.0. Since it has been confirmed that the ratio K0 can be obtained, the fifth line L is not limited to the illustrated line L, and can be a line that satisfies the equation (2).
- Standard predetermined concentration ratios of oxygen, nitrogen oxides, and carbon monoxide at the intersections of the sixth line M representing the primary characteristic curves of the Parner 1 and the water pipe group 2 and the fifth line L K0 is a specific reference specific concentration ratio (hereinafter referred to as a specific reference concentration ratio) K0X.
- the catalyst 4 has a characteristic of making the nitrogen oxide concentration and carbon monoxide concentration on the secondary side of the catalyst 4 substantially zero when the concentration ratio ⁇ on the primary side is set to the reference concentration ratio ⁇ 0 ⁇ . Have.
- the adjustment to make the reference density ratio ⁇ 0 ⁇ corresponds to the adjustment 0 of the present invention.
- the catalyst 4 has a difference between the primary oxygen concentration and the reference oxygen concentration on the secondary side of the catalyst 4. Is detected, the carbon monoxide concentration on the secondary side of the catalyst 4 is substantially zero, and the nitrogen oxide concentration on the secondary side of the catalyst 4 is reduced to the primary side by the reduction reaction. It has a characteristic of reducing the concentration of nitrogen oxides.
- the region in which oxygen is detected on the secondary side of the catalyst 4 and has a characteristic of reducing the nitrogen oxide concentration on the primary side is referred to as a secondary NOx leakage region R1.
- This secondary side NOx leakage region R1 is a region that realizes the adjustment 2 of the present invention, and the air ratio of the Parner 1 exceeds 1.0.
- the primary oxygen concentration is made lower than the reference oxygen concentration SK
- carbon monoxide having a concentration corresponding to the difference between the primary oxygen concentration and the reference oxygen concentration SK is detected on the secondary side of the catalyst 4.
- it has a characteristic that the concentration of nitrogen oxides on the secondary side of the catalyst 4 is substantially zero within a predetermined range.
- the region where carbon monoxide is detected on the secondary side of the catalyst 4 and the nitrogen oxide concentration is substantially zero is referred to as a secondary side CO leakage region R2.
- the secondary side CO leakage region R2 is a region where the adjustment 1 of the present invention is realized, and the air ratio of the Parner 1 is less than 1.0.
- the air ratio of the PANA 1 is set to be less than 1.0, it is set within the range containing oxygen but not containing hydrocarbons on the primary side of the catalyst 4.
- a region obtained by combining the secondary NOx leakage region R1 and the secondary CO leakage region R2 is referred to as a ⁇ ⁇ CO reduction region R3.
- the second control condition is a condition necessary to make the exhaust nitrogen oxide concentration substantially zero.
- ([NOx] + 2 [0]) Z [CO The concentration ratio K
- the output characteristic of the sensor 7 is an output related to the oxygen concentration on the positive side and an output related to the carbon monoxide concentration on the negative side. That is, the air ratio m is calculated from the measured oxygen concentration (oxygen excess region), carbon monoxide concentration, etc. (fuel excess region), and current or voltage output corresponding to the air ratio m is obtained.
- Q1 indicates an oxygen concentration detection zone
- Q2 indicates a carbon monoxide concentration detection zone.
- the air ratio control program controls the air ratio m of the burner to be the set air ratio mO based on the output signal of the sensor 7.
- the feed speed V (drive amount per unit time) of the motor 34 is changed according to the difference between the output value E from the sensor 7 and the set value corresponding to the set air ratio mO.
- the first control zone C1 and the second control zones C2 A and C2B are provided outside the first control zone C1 and the feed speed V is set to the first set value VI and the second set value V2, respectively.
- a control procedure for controlling the drive amount of the motor 34 is included.
- P1 indicates a damper open region
- P2 indicates a damper closed region.
- the setting range of the first control zone C1 is set with an oxygen concentration N1 (for example, lOOppm) and a carbon monoxide concentration, etc., N2 (for example, 50ppm). It corresponds to the reference oxygen concentration SK).
- N1 for example, lOOppm
- N2 for example, 50ppm
- the feed speed V in the first control zone C1 is calculated by the following equation (4).
- the feed speed V is a driving amount per unit time.
- the rotation angle of the motor 34 in the first embodiment in one step is 0.075 degrees, which corresponds to a fluctuation of about 30 ppm when converted to O.
- the combustion air (outside air) supplied from the blower 26 is premixed in the supply passage 27 with the fuel gas supplied from the gas fuel supply pipe 24.
- This premixed gas is ejected from the burner 1 toward the first gas passage 15 in the can 3.
- the premixed gas is ignited by an ignition means (not shown) and burns. This combustion takes place at a low air ratio around 1.0.
- the gas generated by this combustion crosses the upstream water tube group 2 and is cooled, and then is heat-exchanged with the downstream water tube group 2 to absorb heat, resulting in a gas of about 100 ° C to 350 ° C. It becomes.
- This gas does not contain hydrocarbons but contains oxygen, nitrogen oxides, and carbon monoxide, and is processed by the catalyst 4 so that the concentration of nitrogen oxides and carbon monoxide is almost zero. After that, the exhaust gas is discharged from the second gas passage 17 into the atmosphere as exhaust gas.
- the air ratio control by the air ratio adjusting means 28 will be described.
- the boiler of this embodiment is operated by switching between high combustion and low combustion.
- the damper 29 is positioned by selecting either! / Or a deviation between the high combustion air volume position and the low combustion air volume position.
- the position adjustment of the damper 29 is performed by the damper position adjusting device 30 according to a command from the controller 8. That is, the controller 8 inputs a selection signal for high combustion / low combustion and an output value corresponding to the detected air ratio of the sensor 7, and outputs a drive signal for the motor 34, Adjust the opening position of damper 29.
- the controller 8 stores the set opening position of the damper 29, which is a set value corresponding to each set air ratio mO at the time of high combustion and low combustion, as an initial value by the number of pulses from the origin.
- the controller 8 controls the current opening position of the damper 29 relative to the set opening position (open side if not controlled in the closing direction) or closed side (opened direction). If not, it is determined whether the motor side is) and the number of driving noises of the motor 34 is calculated. In addition, in FIG. 9, it is determined whether the output value belongs to the first control band C1 or the second control band C2A, C2B. To do.
- the motor 34 When belonging to the second control zone C2A, the motor 34 is driven at the first set feed speed V2 and the calculated drive pulse, and the damper 29 is closed at a high speed.
- the motor 34 When belonging to the second control zone C2B, the motor 34 is driven at the second set feed speed VI and the calculated driving pulse, and the damper 29 is opened at a high speed. In this way, when the set value corresponding to the reference set air ratio mO is relatively far from the set value, control is performed to bring the output value corresponding to the detected air ratio close to the set value corresponding to the reference set air ratio mO at a rapid speed. Therefore, air ratio control with good responsiveness can be performed.
- the feed rate of the motor 34 is calculated based on the formula (4), and the calculated feed rate is calculated.
- the motor 34 is driven by a driving pulse.
- the feed speed is increased as the set value force corresponding to the reference set air ratio mO increases.
- the stepping motor that can reliably control the rotational position is used, and the feed speed is slowed down as the output value corresponding to the detected air ratio approaches the set value corresponding to the reference set air ratio mO.
- the air ratio of the Parner 1 is controlled to a low air ratio mO close to 1.0, and the concentration ratio change width of the gas on the primary side of the catalyst 4 is controlled to be small. ) Can be satisfied stably.
- the concentration of nitrogen oxides on the secondary side of the catalyst 4 can be made substantially zero, and the concentration of carbon monoxide and carbon can be reduced to almost zero.
- the set air ratio mO is less than 1.0, the concentration of nitrogen oxides on the secondary side is almost zero, and the concentration of carbon monoxide on the secondary side is reduced below a predetermined value within the practical range.
- Can body 3 with 800 kg evaporation per unit time (Applicant's manufacturing model: can body called SQ-800) is burned with premixing burner 1 with a combustion volume of 45.2 m 3 N / h
- the reference set air ratio mO is 1, the carbon monoxide concentration, nitrogen oxide concentration, and oxygen concentration on the primary side of the catalyst 4 (before passing through the catalyst 4) are 2295 ppm on average for 10 minutes.
- the respective concentrations on the secondary side of the catalyst 4 (after passing through the catalyst 4) were less than 13 ppm, 0.3 ppm, and 1 OOppm on average for 10 minutes.
- the oxygen concentration lOOppm on the secondary side of the catalyst 4 is a measurement limit of the oxygen concentration.
- the gas temperatures before and after the catalyst 4 were 302 ° C and 327 ° C, respectively.
- the catalyst 4 is arranged slightly upstream of the feed water preheater 20, and measuring devices are arranged before and after the catalyst 4 so that each concentration after passing through the catalyst 4 is measured.
- the gas temperature was measured using PG-250 manufactured by Horiba, Ltd., and each concentration before passing was measured using COPA-2000 manufactured by Horiba.
- COPA-2000 manufactured by Horiba was measured by Horiba.
- the primary ratio of the catalyst 4 is controlled by controlling the air ratio to 1.0 by the damper position adjusting means (air ratio adjusting means) 30 for adjusting the ratio of combustion air and fuel.
- the concentration ratio of oxygen, nitrogen oxide and carbon monoxide on the side can be controlled to the specific reference concentration ratio K0X (adjustment 0), and the exhaust NOx concentration and exhaust CO concentration can be reduced to substantially zero. Therefore, low NOx and low CO can be realized with a simple configuration using an air ratio adjusting means and a catalyst, compared to low NOx technology using water Z steam addition and low NOx technology using denitration agent. .
- the control is more stable than that provided with a sensor on the primary side of the catalyst 4. You can do it.
- the air ratio is controlled with a resolution of oxygen concentration of lOOppm or less, air ratio control in a region where the amount of CO is large and the CO increase rate in the air ratio CO characteristic is high should be stably controlled based on responsiveness. Can do.
- Example 2 Another embodiment 2 of the present invention will be described with reference to FIGS. 11 and 12.
- a sensor 7 for detecting the oxygen concentration is provided on the primary side connecting the secondary side of the catalyst 4.
- This sensor 7 is a sensor that detects only the oxygen concentration.
- FIG. 12 shows control characteristics of the motor 34 based on the sensor 7.
- Example 2 the sensor 7 causes the oxygen on the primary side of the catalyst 4 to be adjusted so that the reference set air ratio mO is 1.0 (the oxygen concentration on the secondary side of the catalyst 4 is zero). It detects the concentration and indirectly controls the air ratio. Based on various experimental results, when the oxygen concentration O on the primary side of the catalyst 4 is controlled to a value of 0% ⁇ O ⁇ 1.00%, the above equation (2) is satisfied,
- the air ratio control program of the second embodiment based on the detected value E (oxygen concentration signal) from the sensor 7, the detected value and the set oxygen concentration value
- the first control band C1 that changes the feed speed V (driving amount per unit time) of the motor 34 according to the difference between the first and second feed speed V outside the first control band C1, respectively.
- a control procedure for controlling the drive amount of the motor 34 by providing second control zones C2A and C2B as set values is included.
- the setting range of the first control zone C1 is a range set by the oxygen concentration N1 and the oxygen concentration N2. It is controlled to fit in the enclosure.
- the feed speed V in the first control zone C1 is calculated by the above equation (4) as in the first embodiment.
- Example 3 the set air ratio is set to a value at which the NOx concentration in the secondary characteristic substantially exceeds zero and lower than the NOx concentration in the primary characteristic, as shown in FIG. This is a fixed example. This value is the air ratio of the secondary side NOx leakage region R1 of the secondary characteristics where the set air ratio substantially exceeds 1.0.
- the adjustment of the concentration ratio K in Example 3 is the adjustment 2.
- the center of the control range is the air ratio 1.005 (0 concentration: about lOOOppm), and the left end is substantially the air ratio 1.0.
- Lower area is the air ratio 1.005 (0 concentration: about lOOOppm), and the left end is substantially the air ratio 1.0.
- the right end is the air ratio 1.01 (O concentration: about 2000ppm). This can be explained with Fig. 7.
- Example 3 when the experiment was performed under the same conditions as in Experimental Example 1 (excluding the set air ratio), the CO concentration, NOx concentration, O on the primary side of Catalyst 4 (before passing through Catalyst 4) Concentration is it
- the first control zone can be freely set within the range of the secondary NOx leakage region R1.
- the concentration of CO to be processed is high (the gradient may be steep)
- a large amount of catalyst is required, which makes CO leaking and difficult to control immediately. Therefore, if the first control zone is set on the right side away from the air ratio 1, the control As a result, the amount of the catalyst 4 can be reduced.
- the left end of the first control zone C1 can be set to an air ratio of 1.0 that is less than the air ratio of 1.0 or less in Example 3 (Fig. 13). It is also possible to set the left end of the first control zone C1 to a value exceeding the air ratio 1.0.
- the fourth embodiment includes the air ratio control means 28, a blower motor 52 that drives the blower 26, and an inverter 53 that controls the rotational speed of the motor 52. It is composed of In the fourth embodiment, the air ratio control and the concentration ratio constant control are performed using the inverter 53 instead of using the damper 29.
- the control of the blower motor 52 by the controller 8 can be a control that suppresses overshooting, notching, and unching shown in FIG. 9 of the first embodiment.
- the damper 29 lowers the opening when ignited, and increases the opening when performing steady combustion after ignition, and performs air volume control for high combustion and low combustion. This air flow control is a force that can be performed by using the inverter 53.
- the damper 29 and the inverter 53 are not limited to this, and the air flow control at the time of ignition or the like can be performed while shifting. Can do.
- the other configuration is the same as that of the first embodiment, and the description thereof is omitted.
- the present invention is not limited to Examples 1 to 4.
- the air ratio NOx ⁇ CO characteristics shown in FIG. 4 and FIG. 13 have different curves and concentration values depending on the structure of the burner 1 and the can 3 of the combustion apparatus, so that different characteristics can be used.
- the set air ratio is set to 1.0 or more. However, it can be set to a value lower than 1.0 in the range where the combustibility is not impaired and hydrocarbons are not generated.
- the sensor 7 is an O concentration sensor.
- the damper position adjusting device 30 can be a sensor. Further, the structure of the damper position adjusting device 30 can be variously modified.
- the motor 34 may be a gear motor (not shown) other than the stepping motor.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Environmental & Geological Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP07741579A EP2037169A1 (en) | 2006-07-04 | 2007-04-13 | Method of treating gas containing nitrogen oxide |
KR1020097000918A KR101362829B1 (ko) | 2006-07-04 | 2007-04-13 | 질소 산화물 함유 가스의 처리 방법 |
US12/158,166 US7972581B1 (en) | 2006-07-04 | 2007-04-13 | Method of treating nitrogen oxide-containing gas |
CN2007800121610A CN101415994B (zh) | 2006-07-04 | 2007-04-13 | 含氮氧化物气体的处理方法 |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
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JP2006-184879 | 2006-07-04 | ||
JP2006184879 | 2006-07-04 | ||
PCT/JP2006/313329 WO2008004281A1 (fr) | 2006-07-04 | 2006-07-04 | Appareil de combustion |
JPPCT/JP2006/313329 | 2006-07-04 | ||
JP2006-208520 | 2006-07-31 | ||
JP2006208520 | 2006-07-31 |
Publications (1)
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WO2008004369A1 true WO2008004369A1 (fr) | 2008-01-10 |
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PCT/JP2007/058143 WO2008004369A1 (fr) | 2006-07-04 | 2007-04-13 | Procédé pour traiter du gaz contenant de l'oxyde d'azote |
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US (1) | US7972581B1 (ja) |
EP (1) | EP2037169A1 (ja) |
KR (1) | KR101362829B1 (ja) |
WO (1) | WO2008004369A1 (ja) |
Families Citing this family (4)
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WO2008004370A1 (fr) * | 2006-07-04 | 2008-01-10 | Miura Co., Ltd. | Procédé de combustion et appareil de combustion |
US10767854B2 (en) * | 2018-03-07 | 2020-09-08 | Zhejiang Liju Boiler Co., Ltd. | Flameless steam boiler |
US10962220B2 (en) * | 2018-03-07 | 2021-03-30 | Zhejiang Liju Boiler Co., Ltd. | Flameless steam boiler |
CN113375175B (zh) * | 2021-07-15 | 2022-08-09 | 北京中源博智节能科技有限公司 | 煤矿瓦斯回热氧化方法 |
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JP2003275543A (ja) | 2002-03-22 | 2003-09-30 | Japan Steel Works Ltd:The | 廃棄物焼却炉の排気ガス処理方法 |
JP2004069139A (ja) * | 2002-08-05 | 2004-03-04 | Miura Co Ltd | 低NOx燃焼装置 |
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SE518816C2 (sv) | 1997-10-20 | 2002-11-26 | Kanthal Ab | Förfarande för avgasrening jämte gasbrännare |
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2007
- 2007-04-13 EP EP07741579A patent/EP2037169A1/en not_active Withdrawn
- 2007-04-13 KR KR1020097000918A patent/KR101362829B1/ko active IP Right Grant
- 2007-04-13 US US12/158,166 patent/US7972581B1/en active Active
- 2007-04-13 WO PCT/JP2007/058143 patent/WO2008004369A1/ja active Application Filing
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JPS61291026A (ja) * | 1985-06-17 | 1986-12-20 | Hitachi Ltd | 窒素酸化物と一酸化炭素とを同時に除去する方法 |
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JP2003275543A (ja) | 2002-03-22 | 2003-09-30 | Japan Steel Works Ltd:The | 廃棄物焼却炉の排気ガス処理方法 |
JP2004125378A (ja) | 2002-07-15 | 2004-04-22 | Miura Co Ltd | 低NOx燃焼方法とその装置 |
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KR101362829B1 (ko) | 2014-02-14 |
KR20090038875A (ko) | 2009-04-21 |
US7972581B1 (en) | 2011-07-05 |
EP2037169A1 (en) | 2009-03-18 |
US20110165048A1 (en) | 2011-07-07 |
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