Co2 quantification apparatus for combustion ash and co2 quantification method for combustion ash

Abstract

To appropriately quantify CO2 fixed in combustion ash.SOLUTION: A CO2 quantification apparatus for combustion ash supplies a combustion aid to combustion ash 2 housed in a sample holder 3, maintains the combustion ash 2 at a first predetermined temperature for a first predetermined time and starts replacement of the atmosphere inside the sample holder 3 to N2 gas, heats the combustion ash 2 to a second predetermined temperature after the predetermined replacement time for stabilization to temperature rise has passed, gasifies CO2 gas fixed in the combustion ash 2 inside the sample holder 3 which has been replaced with N2 gas during the process of heating to the second predetermined temperature, and measures CO2 concentration by transporting the gasified CO2 by N2 gas to quantification means 8.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a CO2 quantification device for combustion ash that quantifies CO2 immobilized in combustion ash and a method for quantifying CO2 in combustion ash.

Background Art

[0002] Towards the decarbonization of thermal power plants and incineration facilities, the establishment of carbon recycling technology is underway. For example, it is conceivable to immobilize CO2 in combustion ash and mineralize it as a carbonate. By quantifying the CO2 immobilized in the combustion ash, the carbon recycling technology can be objectively evaluated.

[0003] As a technology for quantifying CO2, for example, a technology is known in which an acid is added to desulfurization slurry to generate carbon dioxide gas and the concentration of CO2 in the gas is measured (for example, Patent Document 1). In addition, a technology has been conventionally proposed in which soil or organic matter is heated, and then the carbon component is quantified by measuring the CO2 gas generated by the thermal oxidation of the carbon component.

[0004] As fuels for thermal power plants, coal, biomass, etc. are used, and various incineration wastes are burned in incineration facilities. Therefore, the combustion ash of thermal power plants and incineration facilities contains various components. Therefore, there are components and temperature conditions that inhibit quantification, and at present, even using conventional technologies, it has not been possible to appropriately quantify the CO2 immobilized in the combustion ash.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] The present invention has been made in view of the above circumstances, and an object thereof is to provide a CO2 quantification device for combustion ash that can appropriately quantify CO2 immobilized in combustion ash, and a method for quantifying CO2 in combustion ash.

Means for Solving the Problems

[0007] The CO2 quantification device for combustion ash according to claim 1 of the present invention for achieving the above object includes a sample holder for accommodating combustion ash in which CO2 is fixed, a combustion aid supply means for supplying a combustion aid to the sample holder, and a temperature adjustment means (heating means) for gasifying the CO2 fixed in the combustion ash by thermal decomposition by adjusting the inside of the sample holder to a desired temperature, a gas supply means for supplying O2 gas and an inert gas to the inside of the sample holder in a desired state, a quantification means for measuring the concentration of CO2 by a measuring function (spectroscopic means) in which the CO2 heated by the temperature adjustment means and gasified by thermal decomposition is transported (by the inert gas), and a control means for operating the combustion aid supply means, the temperature adjustment means (each heating means), the gas supply means, and the quantification means (such as spectroscopic means) in a desired state. The control means has an auxiliary agent supply function for controlling the supply of the combustion aid by the combustion aid supply means, and while operating the gas supply means to supply the O2 gas and the inert gas, maintains the inside of the sample holder at a first predetermined temperature corresponding to the combustion ash for a first predetermined time, and then maintains the inside of the sample holder at a second predetermined temperature higher than the first predetermined temperature for a second predetermined time. It has a temperature control function for operating the temperature adjustment means (each heating means), a replacement function for starting the replacement of the inside of the sample holder with the inert gas (stopping the supply of O2 from the state where O2 gas and inert gas are supplied) while the inside of the sample holder is maintained at the first predetermined temperature for the first predetermined time, and in the process of raising the temperature from the first predetermined temperature to the second predetermined temperature in a state where the inside of the sample holder is replaced with the inert gas, the CO2 fixed in the combustion ash inside the sample holder is gasified by thermal decomposition, and the gasified CO2 is transported to the measuring device by the inert gas, and it is characterized by having a measuring function for operating the quantification means to measure the CO2 concentration.

[0008] In the present invention according to claim 1, the CO2 immobilized in the combustion ash can be appropriately quantified.

[0009] In the presence of a combustion aid, during the temperature increase from the state maintained at the first predetermined temperature to the second predetermined temperature, the gas is replaced with an inert gas, and the CO2 concentration is measured during the temperature increase from the first predetermined temperature to the second predetermined temperature in the state replaced with the inert gas. Therefore, the separation of the peak of the CO2 detection value can be appropriately performed, and the CO2 concentration can be accurately measured based on the peak area of the CO2 detection value without being affected by other elements.

[0010] In the state replaced with the inert gas, for example, almost no CO2 gas is generated from the unburned carbon contained in the coal ash. Therefore, the CO2 detected in this state is derived from the carbonate carbon mineralized by the fixation of CO2 to the combustion ash. Thereby, regardless of the state of the coal ash (regardless of how much CO2 was contained in the raw ash), the concentration of CO2 fixed in the combustion ash can be measured.

[0011] By mixing a combustion aid with the combustion ash sample, the generation of interfering CO2 based on oxygen generated when heated in the state replaced with the inert gas can be suppressed. For example, coal ash contains oxide substances that generate oxygen during temperature increase, and based on this, unburned carbon may be oxidized to generate CO2. Since the combustion aid adsorbs the oxygen generated from the oxide substances, the generation of interfering CO2 can be suppressed.

[0012] When a low-volatility sulfur component is included, the reaction of the following formula (1) or (2) occurs in the sample holder, and the temperature at which carbonate is conventionally generated decreases. Therefore, in the incineration residue containing a low-volatility sulfur substance, it is necessary to set a temperature range for reliably measuring the CO2 generated at a lower temperature. CaCO3 + SO2 + 1 / 2O2 → CaSO4 + CO2 ···(1) CaCO3 + SO2 → CaSO3 + CO2 ···(2)

[0013] And, the CO₂ quantification device for combustion ash of the present invention according to claim 2 is the CO₂ quantification device for combustion ash according to claim 1, wherein the combustion ash is coal ash containing unburned carbon or incineration residue containing unburned carbon and a low-volatility sulfur component, and the first predetermined temperature adjusted by the temperature control function of the control means is from 100°C to 200°C (150°C: moisture evaporation and device stabilization temperature range), the second predetermined temperature is from 800°C to 1000°C (900°C), and the heating rate when shifting from the first predetermined temperature to the second predetermined temperature is (50°C to 100°C: 70°C) / min.

[0014] In the present invention according to claim 2, the combustion ash can appropriately quantify the CO₂ immobilized in the coal ash or the incineration residue. The normal temperature time until the gas is switched at the second predetermined temperature is between 250 seconds and 350 seconds: 300 seconds. The immobilized CO₂ is detected between 400°C and 900°C including the influence of the low-volatility sulfur component. The temperature is controlled at ±2.5°C.

[0015] Also, the CO₂ quantification device for combustion ash of the present invention according to claim 3 is the CO₂ quantification device for combustion ash according to claim 1, wherein the combustion ash is biomass ash containing unburned carbon, and the first predetermined temperature adjusted by the temperature control function of the control means is from 350°C to 450°C (400°C: temperature range for combustion of unburned carbon contained in biomass ash), the second predetermined temperature is from 800°C to 1000°C (900°C), and the heating rate when shifting from the first predetermined temperature to the second predetermined temperature is (50°C to 100°C: 70°C) / min.

[0016] In the present invention according to claim 3, for example, the CO₂ immobilized in biomass ash derived from plants can be appropriately quantified. The combustion ash includes, for example, biomass ash (wood biomass ash) and unburned carbon (such as cellulose and lignin).

[0017] Further, the CO2 quantification device for combustion ash of the present invention according to claim 4 is the CO2 quantification device for combustion ash according to any one of claims 1 to 3, wherein the sample holder sequentially accommodates combustion ash with an increased amount of CO2 for CO2 fixation, and the measurement function of the control means has a storage function for storing the detection result of the CO2 concentration for the sequentially accommodated combustion ash, and compares the detection result of the CO2 concentration stored in the storage function, and determines the CO2 fixation ability of the combustion ash based on the increase situation (change situation of the increase) of the CO2 concentration.

[0018] In the present invention according to claim 4, combustion ash with an increased amount of CO2 for fixation is sequentially accommodated and the CO2 concentration is detected. When the detected CO2 concentration does not increase with respect to the increase in the amount of CO2 for fixation, the integrated amount of the increase amount until then can be determined as the CO2 fixation ability of the target combustion ash. Therefore, the CO2 fixation ability of the combustion ash can be grasped without pretreatment depending on the CO2 fixation situation in the combustion ash.

[0019] The CO2 quantification method for combustion ash of the present invention according to claim 5 for achieving the above object supplies a combustion aid containing iron to the combustion ash accommodated in the sample holder, maintains the combustion ash supplied with the combustion aid at a first predetermined temperature for a first predetermined time, and starts replacing the atmosphere inside the sample holder with an inert gas. After a predetermined replacement time for stability until the temperature rises has elapsed, the combustion ash is heated to a second predetermined temperature at a predetermined heating rate. In the process of heating to the second predetermined temperature, the CO2 fixed in the combustion ash inside the sample holder replaced with the inert gas is gasified, and the gasified CO2 is conveyed to the measurement function by the inert gas to measure the CO2 concentration.

[0020] In the present invention according to claim 5, the CO2 fixed in the combustion ash can be appropriately quantified.

[0021] And the method for quantifying CO2 in combustion ash according to claim 6 is the method for quantifying CO2 in combustion ash according to claim 5, wherein the combustion ash is coal ash containing unburned carbon or incineration residue containing a low-volatile sulfur component, the first predetermined time for maintaining the first predetermined temperature is between 350 seconds and 400 seconds (380 seconds), the predetermined replacement time for stability until the temperature rise is between 150 seconds and 200 seconds (180 seconds), and the time for maintaining the second predetermined temperature is between 400 seconds and 600 seconds (500 seconds).

[0022] Before starting the replacement with the inert gas, for example, the O2 gas and the inert gas are being supplied. At the second predetermined temperature, the time (normal temperature time) for switching from the state replaced with the inert gas to the state before being replaced (re-supply of O2 gas) is preferably between 250 seconds and 350 seconds (300 seconds).

[0023] In the present invention according to claim 6, the CO2 immobilized in coal ash containing unburned carbon or incineration residue containing a low-volatile sulfur component can be appropriately quantified.

[0024] Also, the method for quantifying CO2 in combustion ash according to claim 7 is the method for quantifying CO2 in combustion ash according to claim 5, wherein the combustion ash is biomass ash, the first predetermined time for maintaining the first predetermined temperature is between 450 seconds and 550 seconds (480 seconds), the predetermined replacement time for stability until the temperature rise is between 150 seconds and 200 seconds (180 seconds), and the time for maintaining the second predetermined temperature is between 400 seconds and 600 seconds (500 seconds).

[0025] Before starting the replacement with the inert gas, for example, the O2 gas and the inert gas are being supplied. At the second predetermined temperature, the time (normal temperature time) for switching from the state replaced with the inert gas to the state before being replaced (re-supply of O2 gas) is preferably between 200 seconds and 300 seconds (250 seconds).

[0026] In the present invention according to claim 7, CO2 immobilized in biomass ash can be appropriately quantified.

[0027] Further, the method for quantifying CO2 in combustion ash according to claim 8 of the present invention is the method for quantifying CO2 in combustion ash according to any one of claims 5 to 7, wherein the sample holder sequentially accommodates combustion ash with an increased amount of CO2 to be fixed, stores the detection results of the CO2 concentration for the sequentially accommodated combustion ash, compares the stored detection results of the CO2 concentration, and determines the CO2 fixation ability of the combustion ash based on the increase situation (change situation of the increase) of the CO2 concentration.

[0028] In the present invention according to claim 8, combustion ash with an increased amount of CO2 to be fixed is sequentially accommodated and the CO2 concentration is detected. When the detected CO2 concentration does not increase with respect to the increase in the amount of CO2 to be fixed, the integrated amount of the increase up to that point can be determined as the CO2 fixation ability of the target combustion ash. Therefore, the CO2 fixation ability of the combustion ash can be grasped without pretreatment based on the CO2 fixation situation in the combustion ash.

Advantages of the Invention

[0029] The apparatus for quantifying CO2 in combustion ash and the method for quantifying CO2 in combustion ash of the present invention can appropriately quantify CO2 immobilized in combustion ash.

Brief Description of the Drawings

[0030]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Embodiments for Carrying Out the Invention

[0031] Based on FIGS. 1 and 2, the CO2 quantification device for combustion ash of the present invention will be described.

[0032] FIG. 1 conceptually shows the overall configuration of the CO2 quantification device for combustion ash according to an embodiment of the present invention, and FIG. 2 shows a block configuration for explaining the operation of the control means.

[0033] As shown in FIG. 1, the CO2 quantification device 1 includes a sample holder 3 in which combustion ash 2 with CO2 fixed is accommodated. Inside the sample holder 3, a combustion aid (tungsten oxide powder + iron powder) is supplied from the combustion aid supply means 4.

[0034] And a temperature adjustment means 5 (heating means: electric furnace) for gasifying the CO2 fixed in the combustion ash 2 by thermal decomposition is provided, and a gas supply means 6 for supplying O2 gas and inert gas (N2 gas) in a desired state is provided inside the sample holder 3.

[0035] A quantification means 8 (such as a spectroscopic means) is connected to the exhaust path 7 of the sample holder 3, and the CO2 fixed in the combustion ash and gasified is conveyed to the quantification means 8 (measuring instrument) by N2 gas. The concentration of CO2 in the exhaust gas conveyed to the quantification means 8 (measuring instrument) is measured by the quantification means 8.

[0036] A control means 9 is provided for operating the combustion aid supply means 4, the temperature adjustment means 5 (each heating means), and the gas supply means 6 in a desired state, and for inputting the information on the concentration of CO2 measured by the quantification means 8.

[0037] As shown in Fig. 2, the control means 9 has an auxiliary agent supply function 11 for controlling the supply of the combustion auxiliary agent (tungsten oxide powder + iron powder) by the combustion auxiliary agent supply means 4 (see Fig. 1), and in a state where the gas supply means 6 (see Fig. 1) is operating to supply O2 gas and N2 gas, the inside of the sample holder 3 (see Fig. 1) is maintained at a first predetermined temperature for a first predetermined time according to the combustion ash (according to the combustion ash derived from coal, incineration residue, biomass), and then, the temperature control means 5 (see Fig. 1) is operated so that the inside of the sample holder 3 (see Fig. 1) is maintained at a second predetermined temperature higher than the first predetermined temperature for a second predetermined time. It has a temperature control function 12.

[0038] Also, when the inside of the sample holder 3 (see Fig. 1) is maintained at the first predetermined temperature for the first predetermined time, the control means 9 has a replacement function 13 for operating the gas supply means 6 (see Fig. 1) to start replacing the inside of the sample holder 3 (see Fig. 1) with an inert gas (stopping the supply of O2 from the state where O2 gas and N2 gas are supplied).

[0039] Furthermore, in a state where the inside of the sample holder 3 (see Fig. 1) is replaced with N2 gas, in the process of heating up from the first predetermined temperature to the second predetermined temperature, the CO2 fixed to the combustion ash inside the sample holder 3 (see Fig. 1) is gasified by thermal decomposition, and the gasified CO2 is conveyed from the exhaust path 7 (see Fig. 1) to the quantification means 8 (see Fig. 1) by N2 gas, and it has a measurement function 14 for operating the quantification means 8 (see Fig. 1) to measure the CO2 concentration.

[0040] Returning to Fig. 1, the sample holder 3 of the CO2 quantification device 1 houses the combustion ash 2 fixed with CO2. In this case, the combustion ash 2 is sequentially housed in a state where the amount of CO2 for fixing is increased.

[0041] Returning to Fig. 2, the measurement function 14 of the control means 9 has a storage function 15 for storing the detection results of the CO2 concentration for the sequentially housed combustion ash 2 (see Fig. 1), and compares the detection results of the CO2 concentration stored in the storage function 15, and has a determination function 16 for determining the CO2 fixation ability of the combustion ash 2 (see Fig. 1) based on the increase situation (change situation of the increase) of the CO2 concentration.

[0042] That is, in the determination function 16, when the combustion ash 2 with an increased amount of CO2 for fixation is sequentially accommodated to detect the CO2 concentration, when the detected CO2 concentration does not increase with respect to the increase in the amount of CO2 for fixation, the CO2 fixation ability of the combustion ash 2 is determined.

[0043] In the CO2 quantification device 1 having the above configuration, a combustion aid containing iron is supplied to the combustion ash 2 accommodated in the sample holder 3, and the combustion ash 2 supplied with the combustion aid is maintained at a first predetermined temperature for a first predetermined time. At the same time, the replacement of the atmosphere inside the sample holder 3 with N2 gas (stopping of O2 gas) is started. After the elapse of a predetermined replacement time for stabilization until the temperature rises, the combustion ash 2 is heated to a second predetermined temperature at a predetermined heating rate. In the process of heating to the second predetermined temperature, the CO2 fixed in the combustion ash 2 inside the sample holder 3 replaced with N2 gas is gasified, and the gasified CO2 is conveyed to the quantification means 8 by N2 gas and the CO2 concentration is measured.

[0044] In the presence of the combustion aid, during the temperature increase from the state maintained at the first predetermined temperature to the second predetermined temperature, it is replaced with N2 gas, and the CO2 concentration is measured during the temperature increase from the first predetermined temperature to the second predetermined temperature in the state replaced with N2 gas. For this reason, the separation of the peak of the CO2 detection value (elimination of the detection signal by other elements such as interfering components) can be appropriately carried out, and the CO2 concentration can be accurately measured by the peak area of the CO2 detection value without being affected by other elements.

[0045] In the state replaced with N2 gas, for example, almost no CO2 gas is generated from the unburned carbon contained in the coal ash. Therefore, the CO2 detected in this state is derived from the carbonate carbon mineralized by the fixation of CO2 to the combustion ash. Thereby, regardless of the state of the coal ash (regardless of how much CO2 is contained), the concentration of CO2 fixed in the combustion ash can be measured.

[0046] By mixing a combustion aid into the combustion ash sample, it is possible to suppress the generation of interfering CO2 based on oxygen generated when heating in a state replaced with N2 gas. For example, coal ash contains oxide substances that generate oxygen during temperature rise, and based on this, unburned carbon may be oxidized and CO2 may be generated. Since the combustion aid adsorbs the oxygen generated from the oxide substances, the generation of interfering CO2 can be suppressed.

[0047] In the case of incineration residues containing low-volatility sulfur components, the reactions of the following formula (3) or (4) occur in the sample holder 3, and the temperature at which carbonates are conventionally generated decreases. Therefore, in the incineration residue containing low-volatility sulfur substances, it is necessary to set a temperature range for reliably measuring CO2 generated at a lower temperature. CaCO3 + SO2 + 1 / 2O2 → CaSO4 + CO2 ···(3) CaCO3 + SO2 → CaSO3 + CO2 ···(4)

[0048] Since the combustion ash 2 with an increased amount of CO2 for fixation is sequentially accommodated and the CO2 concentration is detected, when the detected CO2 concentration does not increase with respect to the increase in the amount of CO2 for fixation, it is possible to determine the CO2 fixation ability of the target combustion ash 2. For this reason, based on the CO2 fixation status in the combustion ash, the CO2 fixation ability of the combustion ash can be grasped without pretreatment.

[0049] Based on FIGS. 3 and 4, the measurement status of CO2 in the combustion ash 2 derived from coal containing unburned carbon or incineration residue containing low-volatility sulfur components will be described.

[0050] FIG. 3 shows a graph representing the change over time in the temperature and gas supply status of coal ash containing unburned carbon or combustion ash derived from incineration residue containing low-volatile components, and FIG. 4 shows a graph representing the change over time in the detection signal intensity of CO2.

[0051] The temperature inside the sample holder 3 adjusted by the temperature control function 12 of the control means 9 is maintained at a first predetermined temperature between time t1 and t3 as shown by the solid line in FIG. 3. The first predetermined temperature is from 100°C to 200°C (for example, 150°C: the temperature range for moisture evaporation and apparatus stabilization), and the first predetermined time for maintaining the first predetermined temperature is between 350 seconds and 400 seconds (for example, 380 seconds).

[0052] And the replacement predetermined time for stabilization until the temperature rise to the second predetermined temperature, that is, the time from when O2 gas shown by the two-dot chain line in FIG. 3 and N2 gas shown by the one-dot chain line in FIG. 3 are being supplied until the supply of O2 gas is stopped and replaced with N2 gas and the temperature rise to the second predetermined temperature is started (time t2 to time t3) is between 150 seconds and 200 seconds (for example, 180 seconds).

[0053] Also, the heating rate when shifting from the first predetermined temperature to the second predetermined temperature is (50°C to 100°C: 70°C) / min, and the time for maintaining the second predetermined temperature (time t4 to time t6) is between 400 seconds and 600 seconds (for example, 500 seconds). And at time t5 when the second predetermined temperature is being maintained, the supply of O2 gas is restarted.

[0054] That is, the inside of the sample holder 3 is replaced with N2 gas, and in the process of shifting from the first predetermined temperature to the second predetermined temperature (time t3 to time t4), as shown in FIG. 4, carbonate carbon (the solid line is coal ash, the one-dot chain line is incineration residue) is detected, and the carbonate carbon is quantified from the area (integral value) of the time axis of the detected signal intensity, and the CO2 concentration is measured.

[0055] When the replacement with N2 gas is started while being maintained at the first predetermined temperature and the inside of the sample holder 3 is in a state of being replaced with N2 gas and carbonate carbon is being detected, the separation of the peaks of the detected values can be appropriately carried out, and the CO2 concentration can be accurately measured by the peak area without being affected by other elements.

[0056] At the second predetermined temperature, the time (normal temperature time) for switching from the state replaced with the inert gas to the state before replacement (re - supply of O2 gas) is 300 seconds (between 250 seconds and 350 seconds). That is, at time t5 when 300 seconds have elapsed from time t4 while maintaining the second predetermined temperature, the supply of O2 gas is resumed. Since O2 gas is re - supplied at time t5, complete combustion is promoted, and it is possible to prevent soot from adhering to pipes and the like.

[0057] Based on FIGS. 5 and 6, the measurement situation of CO2 in the combustion ash 2 derived from biomass will be described.

[0058] FIG. 5 shows a graph representing the change over time in the temperature and gas supply situation of the combustion ash derived from biomass (for example, woody biomass), and FIG. 6 shows a graph representing the change over time in the detection signal intensity of CO2.

[0059] The temperature inside the sample holder 3 adjusted by the temperature control function 12 of the control means 9 is maintained at the first predetermined temperature between time t1 and t3 as shown by the solid line in FIG. 5. The first predetermined temperature is from 350°C to 450°C (for example, 400°C: the temperature range for burning unburned carbon contained in biomass ash), and the first predetermined time for maintaining the first predetermined temperature is between 450 seconds and 550 seconds (for example, 480 seconds).

[0060] And the predetermined replacement time for stability until the temperature rises to the second predetermined temperature, that is, the time (from time t2 to time t3) for stopping the supply of O2 gas and replacing it with N2 gas from the state where O2 gas shown by the two - dotted chain line in FIG. 5 and N2 gas shown by the one - dotted chain line in FIG. 5 are being supplied and then starting to raise the temperature to the second predetermined temperature is between 150 seconds and 200 seconds (for example, 180 seconds).

[0061] Also, the heating rate when shifting from the first predetermined temperature to the second predetermined temperature is (50°C to 100°C: 70°C) / min, and the time for maintaining the second predetermined temperature (from time t4 to time t6) is between 400 seconds and 600 seconds (for example, 500 seconds). And at time t5 when the second predetermined temperature is being maintained, the supply of O2 gas is restarted.

[0062] That is, the inside of the sample holder 3 is replaced with N2 gas, and in the process of shifting from the first predetermined temperature to the second predetermined temperature (from time t3 to time t4), as shown in FIG. 6, carbonate carbon (shown by the solid line) is detected, and the carbonate carbon is quantified from the area (integrated value) of the time axis of the detected signal intensity, and the CO2 concentration is measured.

[0063] When the replacement with N2 gas is started while maintaining the first predetermined temperature, and carbonate carbon is detected with the inside of the sample holder 3 replaced with N2 gas, the separation of the peaks of the detected values can be appropriately carried out, and the CO2 concentration can be accurately measured by the peak area without being affected by other elements.

[0064] At the second predetermined temperature, the switching time (normal temperature time) from the state replaced with the inert gas to the state before replacement (re - supply of O2 gas) is 250 seconds (between 200 seconds and 300 seconds). That is, at time t5 when the second predetermined temperature is being maintained (at time t5 when 250 seconds have elapsed from time t4), the supply of O2 gas is restarted. Since O2 gas is re - supplied at time t5, complete combustion is promoted, and it is possible to prevent soot from adhering to pipes and the like.

[0065] By using the above - described CO2 quantification device 1 for combustion ash, it becomes possible to appropriately quantify the CO2 fixed in coal ash, or combustion ash of incineration residues, and the CO2 fixed in combustion ash of biomass.

[0066] In particular, by sequentially storing the combustion ash 2 with an increased amount of CO2 for fixation and detecting the CO2 concentration, when the detected CO2 concentration does not increase with respect to the increase in the amount of CO2 for fixation, it is possible to determine the CO2 fixation ability of the target combustion ash 2. Therefore, based on the CO2 fixation status of the combustion ash 2, the CO2 fixation ability of the combustion ash 2 can be grasped without pretreatment.

Industrial Applicability

[0067] The present invention can be used in the industrial field of a CO2 quantification device for combustion ash and a CO2 quantification method for combustion ash.

Explanation of Reference Numerals

[0068] 1 CO2 quantification device 2 Combustion ash 3 Sample holder 4 Combustion aid supply means 5 Temperature adjustment means 6 Gas supply means 7 Exhaust path 8 Quantification means 9 Control means 11 Aid supply function 12 Temperature control function 13 Replacement function 14 Measurement function 15 Memory function 16 Judgment function

Claims

1. CO 2 a sample holder for containing combustion ash with CO fixed, and Combustion aid supply means for supplying a combustion aid to the sample holder, Temperature adjusting means for gasifying CO fixed to the combustion ash by heating and decomposing it by adjusting the interior of the sample holder to a desired temperature 2 and a temperature adjusting means for gasifying by thermal decomposition Inside the sample holder, O 2 a gas supply means for supplying O gas and an inert gas in a desired state, CO that has been heated by the temperature adjustment means and gasified by thermal decomposition 2 is conveyed, and a quantification means that measures the concentration of CO 2 by a measurement function, Comprising combustion aid supply means, temperature adjustment means, gas supply means, and control means for operating the quantitative means in a desired state, The control means is, An aid supply function for controlling the supply of the combustion aid by the combustion aid supply means, Operating the gas supply means to supply the O 2 While supplying the O gas and the inert gas, maintaining the inside of the sample holder at a first predetermined temperature corresponding to the combustion ash for a first predetermined time, and then operating the temperature control means so as to maintain the inside of the sample holder at a second predetermined temperature higher than the first predetermined temperature for a second predetermined time. A temperature control function; A replacement function for starting the replacement of the inert gas inside the sample holder by operating the gas supply means when the inside of the sample holder is maintained at the first predetermined temperature for the first predetermined time, In the process of heating up from the first predetermined temperature to the second predetermined temperature with the inside of the sample holder replaced with the inert gas, CO fixed to the combustion ash inside the sample holder 2 is gasified by thermal decomposition, and the gasified CO 2 is transported to the measuring instrument by the inert gas, and the quantification means is operated to measure the CO 2 concentration, having a measuring function A CO quantification device for combustion ash, characterized by 2 this.

2. CO of the combustion ash according to claim 1 2 in the metering device The combustion ash is coal ash containing unburned carbon or incineration residue containing unburned carbon and a low-volatility sulfur component, Adjusted by the temperature control function of the control means, The first predetermined temperature is from 100°C to 200°C, the second predetermined temperature is from 800°C to 1000°C, and the heating rate when shifting from the first predetermined temperature to the second predetermined temperature is (50°C to 100°C) / min A CO quantification device for combustion ash, characterized by 2 this.

3. CO of the combustion ash according to claim 1 2 in the metering device The combustion ash is biomass ash containing unburned carbon, Adjusted by the temperature control function of the control means, The first predetermined temperature is from 350°C to 450°C, the second predetermined temperature is from 800°C to 1000°C, and the heating rate when shifting from the first predetermined temperature to the second predetermined temperature is (50°C to 100°C) / min A CO quantification device for combustion ash, characterized by the following. 2 Quantification device.

4. The CO of the combustion ash according to any one of claims 1 to 3 2 in the metering device, The sample holder sequentially contains combustion ash with an increased amount of CO for fixation 2 and is sequentially filled with combustion ash in which the amount of The measurement function of the control means is, CO concentration detection results for sequentially contained combustion ash 2 A memory function for storing the detection results, Compare the detection results of the CO concentration stored in the memory function, and have a determination function for determining the CO fixation ability of the combustion ash based on the increase situation of the CO concentration. 2 2 2 ​ A method for quantifying CO in combustion ash, characterized by the following: 2 quantitative method.

5. CO contained in the sample holder 2 A combustion aid containing iron is supplied to the combustion ash in which CO is fixed, and the combustion ash to which the combustion aid has been supplied is maintained at a first predetermined temperature for a first predetermined time. At the same time, replacement of the atmosphere inside the sample holder with an inert gas is started. After a predetermined replacement time for stabilization until the temperature rises has elapsed, the combustion ash is heated to a second predetermined temperature at a predetermined heating rate. In the process of heating to the second predetermined temperature, CO fixed to the combustion ash inside the sample holder replaced with the inert gas 2 is gasified, and the gasified CO 2 is conveyed to a measuring function by an inert gas to measure the CO 2 concentration A method for quantifying CO in combustion ash, characterized by... 2 Quantification method.

6. The method for quantitatively determining CO in the combustion ash according to claim 5 2 in the method The combustion ash is coal ash containing unburned carbon or incineration residue containing unburned carbon and a low-volatility sulfur component, The first predetermined time for maintaining at the first predetermined temperature is between 350 seconds and 400 seconds, The predetermined replacement time for stability until the temperature rise is between 150 seconds and 200 seconds, The time for maintaining at the second predetermined temperature is between 400 seconds and 600 seconds A method for quantifying CO in combustion ash, characterized by the following: 2 method.

7. The method for quantifying CO in the combustion ash according to claim 5 2 in the quantification method The combustion ash is biomass ash containing unburned carbon, and the first predetermined time for maintaining at the first predetermined temperature is between 450 seconds and 550 seconds, The predetermined replacement time for stability until the temperature rise is between 150 seconds and 200 seconds, The time for maintaining at the second predetermined temperature is between 400 seconds and 600 seconds A method for quantifying CO in combustion ash, characterized by the following. 2 Quantification method.

8. The method for quantifying CO in the combustion ash according to any one of claims 5 to 7 2 in the method The sample holder sequentially contains combustion ash with an increased amount of CO for fixation, and stores the detection results of the CO 2 concentration for the sequentially contained combustion ash. 2 ​ Stored CO 2 Compare the detection results of the concentration and determine the CO 2 Based on the increase in the concentration of CO in the combustion ash 2 Determine the CO fixation ability A method for quantifying CO in combustion ash, characterized by the following. 2 Quantification method.

Images