Biomass blending combustion coal-fired unit carbon emission monitoring device and method based on < 13 > C and < 15 > N multi-isotope complementary method

Abstract

The invention discloses a biomass blending combustion coal-fired unit carbon emission monitoring device and method based on a < 13 > C and < 15 > N multi-isotope complementary method. The invention discloses a biomass blending combustion coal-fired unit carbon emission monitoring device based on a 13C and 15N multi-isotope complementary method. The biomass blending combustion coal-fired unit carbon emission monitoring device comprises a flue gas sampling unit, a flue gas pretreatment unit, a flue gas analysis unit and a data acquisition and calculation unit, the flue gas sampling unit comprises a grid type multi-point flue gas sampling branch pipe, a primary flue gas filtering device, a back flushing electromagnetic valve, a sampling electromagnetic valve, a mixing main pipe, a first flow regulating valve, a diluting unit, a probe controller and the like. The biomass blending combustion coal-fired unit carbon emission monitoring device and the biomass blending combustion coal-fired unit carbon emission monitoring method based on the 13C and 15N multi-isotope complementary method have the beneficial effects that the 13C isotope method is adopted to monitor the blending combustion flue gas, so that biomass source carbon emission monitoring is realized at relatively low cost; for an existing unit, an old SCR sampling system can be used as a flue gas sampling system.

Description

Technical Field

[0001] The present invention belongs to the field of biomass fuel combustion, and specifically relates to a carbon emission monitoring device for a biomass co-firing coal-fired unit based on 13 C, 15 N multi-isotope complementary method, and a carbon emission monitoring method for a biomass co-firing coal-fired unit based on 13 C, 15 N multi-isotope complementary method. Background Art

[0002] Biomass fuel combustion belongs to zero carbon emission. Therefore, accurately monitoring, distinguishing and eliminating the carbon emission part from biomass in the flue gas of a biomass co-firing coal-fired unit is an important means to establish and improve the carbon trading market. The following describes several existing carbon emission monitoring methods for biomass sources.

[0003] First, the mass and energy balance measurement method.

[0004] Referring to the Figure 1 , according to the fuel information of the mixed fuel, the flue gas information and the ash information generated by combustion, the mass and energy balance measurement method uses five balance equations of mass balance, ash balance, carbon balance, energy balance and oxygen balance to calculate the proportion of biomass components in the mixed fuel, and the calculation process is as Figure 1 shown.

[0005] The mass and energy balance measurement method has the advantages of real-time online calculation, low cost, and high accuracy under certain conditions; the disadvantages are that it has high requirements for instrument accuracy, poor fuel universality, and low calculation accuracy for coal-biomass co-fired power plants with a blending ratio generally below 20% (only high accuracy under the condition of 50% blending ratio).

[0006] Second, the SO2 method.

[0007] The SO2 method infers the blending ratio of biomass in the mixed fuel by detecting the content of SO2 in the flue gas generated after the combustion of the mixed fuel according to the difference in sulfur content between biomass and coal (the sulfur content of biomass is generally lower than that of coal).

[0008] The advantage of the SO2 method is that the detection cost is low; the disadvantage is that different mixed fuels have a great influence on the generation and conversion of gaseous SO2, resulting in large errors in the calculation results under a single model and unable to form a unified discrimination measurement standard. This method currently remains in the theoretical stage and is difficult to apply in practice.

[0009] Third, 14 C method.

[0010] Referring to the Figure 2 , 14 The 14 C method is based on the difference in14 When C is close to 0, the blending ratio of biomass fuel is calculated by detecting the C content in CO2 in the mixed combustion flue gas and related fuel information. The detection process is as follows: 14 shown. Figure 2 as follows

[0011] 14 The advantage of the C method is its high measurement accuracy, while the disadvantages are the high cost of equipment and the need to sample and convert the flue gas during the measurement process. Therefore, its industrial promotion is still limited.

[0012] In summary, the above existing carbon emission monitoring methods for biomass sources fail to further solve problems such as insufficient discrimination of single isotopes and the consistency problem of seawater desulfurization and common carbonate desulfurizers such as limestone in terms of statistical methods, and need to be further improved. Summary of the Invention

[0013] In view of the existing technology, the present invention overcomes the above defects and provides a carbon emission monitoring device for a biomass co-fired coal-fired unit based on the multi-isotope complementary method of 13 C and 15 N, and a carbon emission monitoring method for a biomass co-fired coal-fired unit based on the multi-isotope complementary method of 13 C and 15 N.

[0014] The present invention adopts the following technical solutions. The carbon emission monitoring device for a biomass co-fired coal-fired unit based on the multi-isotope complementary method of 13 C and 15 N includes a flue gas sampling unit, a flue gas pretreatment unit, a flue gas analysis unit, and a data acquisition and calculation unit, wherein:

[0015] The flue gas sampling unit includes a grid-type multi-point flue gas sampling branch pipe, a primary flue gas filtering device, an anti-blow solenoid valve, a sampling solenoid valve, a primary mixing main pipe, a first flow regulating valve, a dilution unit, a probe controller, and a secondary mixing main pipe. The grid-type multi-point flue gas sampling branch pipes are arranged in the area from the outlet of the economizer at the tail flue of the boiler to the inlet of the SCR denitration system according to the grid method. The input end of the grid-type multi-point flue gas sampling branch pipe is connected to the primary flue gas filtering device, the output end of the grid-type multi-point flue gas sampling branch pipe is connected to the input end of the anti-blow solenoid valve, the output end of the anti-blow solenoid valve is connected to the input end of the sampling solenoid valve, the output end of the sampling solenoid valve is connected to the input end of the first flow regulating valve, the output end of the first flow regulating valve is connected to the input end of the primary mixing main pipe, the output ends of multiple primary mixing main pipes are simultaneously connected to the input end of the secondary mixing main pipe, the output end of the secondary mixing main pipe is connected to the input end of the dilution unit, the dilution gas is simultaneously introduced into the input end of the dilution unit, the output end of the dilution unit is connected to the input end of the probe controller, the calibration gas and the anti-blow gas are simultaneously introduced into the input end of the probe controller, and the output end of the probe controller is sequentially connected to the flue gas pretreatment unit and the flue gas analysis unit.

[0016] As a preferred technical solution of the above technical solution, the flue gas pretreatment unit includes a secondary flue gas filtering device, an ozone generating device, and a flue gas condensation device. The output end of the probe controller is connected to the input end of the secondary flue gas filtering device, the output end of the secondary flue gas filtering device is connected to the input end of the ozone generating device, the output end of the ozone generating device is connected to the input end of the flue gas condensation device, and the output end of the flue gas condensation device is connected to the input end of the three-way valve.

[0017] As a preferred technical solution of the above technical solution, the flue gas analysis unit includes a three-way valve, a second flow regulating valve, a rotameter, a near-infrared sample cell, a mid-infrared sample cell, and a laser detector. The two output ends of the three-way valve are respectively connected to the input ends of the second flow regulating valve. The output end of the second flow regulating valve is connected to the input end of the rotameter. The output end of the rotameter is respectively connected to the input end of the near-infrared sample cell or the input end of the mid-infrared sample cell. The output ends of the near-infrared sample cell and the mid-infrared sample cell are respectively connected to the input end of the laser detector. The output end of the laser detector is connected to the data acquisition and calculation unit.

[0018] As a preferred technical solution of the above technical solution, the flue gas analysis unit further includes a temperature control device and a pressure control device. The temperature control device respectively regulates the near-infrared sample cell and the mid-infrared sample cell, and the pressure control device respectively regulates the near-infrared sample cell and the mid-infrared sample cell.

[0019] As a preferred technical solution of the above technical solution, the flue gas analysis unit further includes a near-infrared laser generator, a mid-infrared laser generator, and a laser collimator. The near-infrared laser generator and the mid-infrared laser generator are respectively connected to the input ends of the corresponding laser collimators. The laser collimator of one of them is connected to the input end of the near-infrared sample gas cell, and the laser collimator of the other is connected to the input end of the mid-infrared sample gas cell.

[0020] As a preferred technical solution of the above technical solution, the flue gas analysis unit further includes a vacuum pump and an exhaust gas cell. The output end of the near-infrared sample gas cell is sequentially connected to the vacuum pump and the exhaust gas cell of one of them, and the output end of the mid-infrared sample gas cell is sequentially connected to the vacuum pump and the exhaust gas cell of the other.

[0021] As a preferred technical solution of the above technical solution, the data acquisition and calculation unit includes a DCS online data acquisition module, an abnormal data identification and cleaning module, a local data upload and sharing and acquisition module, and a data model calculation and output module. The output end of the laser detector is sequentially connected to the DCS online data acquisition module, the abnormal data identification and cleaning module, the local data upload and sharing and acquisition module, and the data model calculation and output module.

[0022] As a preferred technical solution of the above technical solution, the flue gas pretreatment unit, the flue gas analysis unit, and the data acquisition and calculation unit are respectively installed and arranged in the denitration CEMS small room.

[0023] The present invention adopts the following technical solution, based on 13 C, 15 N multi-isotope complementary method for carbon emission monitoring of biomass co-fired coal-fired units, applied to the 13 C, 15 N multi-isotope complementary method for carbon emission monitoring device of biomass co-fired coal-fired units, based on 13 C, 15 N multi-isotope complementary method for carbon emission monitoring of biomass co-fired coal-fired units, including the following steps:

[0024] Step S1: The boiler flue gas enters the flue gas sampling unit from the outlet of the economizer in the flue, is extracted through the grid-type multi-point flue gas sampling branch pipe, and enters the primary mixing main pipe as mixed flue gas after removing particulate matter through the primary flue gas filtration device; the mixed flue gas enters the flue gas pretreatment unit, enters the ozone generation device through the secondary flue gas filtration device. In the ozone generation device, carbon monoxide generated due to incomplete combustion in the mixed flue gas is oxidized to carbon dioxide by ozone. After sufficient oxidation, the flue gas enters the flue gas condensation device to be cooled and remove moisture to become low-temperature flue gas; the low-temperature flue gas enters the flue gas analysis unit, and after debugging, it is shunted into the near-infrared sample gas cell and the mid-infrared sample gas cell at a preset temperature, pressure, and flow rate. In the near-infrared sample gas cell, near-infrared light is combined with formula 1 for 13 C,12 Detection of C isotope abundance, using mid-infrared light in a mid-infrared sample gas cell 15 N, 14 Detection of N isotope abundance and CO2 concentration. The detected data is recorded by the data acquisition and calculation unit, which uses the "3δ method" to identify and clean abnormal data;

[0025] Formula 1: δ 13 C represents 13 C isotope abundance; 13 C / 12 C represents the molar ratio of 13 C, 12 C in the sample; ([[]] 13 C / 12 C)[[]] std represents the molar ratio of 13 C, 12 C in the reference material; The reference material is the belemnite fossil in the Cretaceous Peedee Formation in South Carolina, USA, and its value is (11237.2 ± 90) × 10 -6 ;

[0026] Step S2: Establish the carbon-based ratio X of biomass-derived carbon dioxide emissions using Formulas 2-1 and 2-2 as mathematical models bio Same as in flue gas 13 C isotope abundance δ flue gas 13 C, 15 N isotope abundance δ flue gas 15 N to establish a relational database. The relational database is attached with online boiler evaporation parameters as a matching basis; The measured 13 C, 15 N isotope abundance data from the near-infrared and mid-infrared sample gas cells are combined with the online boiler evaporation parameters, local biomass blending type information and this relational database for real-time matching and calculation, and the obtained results are substituted into Formula 3; Combining relevant DCS online data to obtain the real-time fossil source carbon emission rate; Calculating the desulfurization source carbon emission rate from Formula 4;

[0027] Formula 2-1: X bio = k i ·δ flue gas 13 C + b i ; Formula 2-2: X bio = p i ·δ flue gas 15 N + q i ; X bioIndicates the carbon-based ratio of biomass origin in flue gas; δ flue gas 13 C represents the 13 C isotope abundance in flue gas; k i , p i Represents the slope constant of the fitting equation corresponding to the co-firing of the i-th biomass; b i , q i Represents the intercept constant of the fitting equation corresponding to the co-firing of the i-th biomass;

[0028] Formula 3: E fuel = CO 2 flue gas ·q flue gas ·(1 - X bio )×10 -6 ; E fuel Represents the carbon emission rate from fossil sources, in units of t / h; CO 2 flue gas Represents the concentration of carbon dioxide in the flue gas detected in the mid-infrared gas cell, in units of mg / Nm 3 ; q flue gas Represents the flue gas flow rate at the measuring point section, in units of Nm 3 / h;

[0029] Formula 4: E 脱硫 Represents the carbon emission rate from desulfurization sources, in units of t / h; Represents the molar mass of CO2, with a value of 44 g / mol; Represents the molar mass of SO2, with a value of 64 g / mol; SO 2in Represents the concentration of SO2 at the inlet of the absorption tower, in units of mg / Nm 3 ; SO 2out Represents the concentration of SO2 at the outlet of the absorption tower, in units of mg / Nm 3 ; q in Represents the original flue gas volume at the inlet of the absorption tower, in units of Nm 3 / h; q out Represents the net flue gas volume at the outlet of the absorption tower, in units of Nm 3 / h.

[0030] The carbon emission monitoring device and method for a coal-fired power unit co-firing biomass based on the 13 C, 15 N multi-isotope complementary method disclosed by the present invention has the following beneficial effects:

[0031] 1. Using the 13 C isotope method to monitor the co-fired flue gas, realizing the monitoring of biomass source carbon emissions at a relatively low cost; for existing units, the flue gas sampling system can utilize the old SCR sampling system; 13 The

[0032] 2. The double infrared gas cells are adopted to assist in monitoring the 15 N isotope in the flue gas, making up for the deficiency that it is difficult to distinguish between biomass and coal combustion due to the very close 13 C isotope abundances in special cases, and improving the monitoring accuracy; for biomass from some C3 plants, its 13 C content is quite the same as that of coal combustion and it is difficult to distinguish. The multi-isotope complementary method can effectively solve problems such as insufficient discrimination power of single isotope. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 is a schematic diagram of the mass and energy balance measurement method in the prior art.

[0034] Figure 2 is in the prior art 14 schematic diagram of the

[0035] Figure 3 is the overall system diagram of the present invention.

[0036] Figure 4 is a schematic diagram of the flue gas sampling unit of the present invention.

[0037] Figure 5 is a schematic diagram of the flue gas pretreatment unit of the present invention.

[0038] Figure 6 is a schematic diagram of the flue gas analysis unit of the present invention.

[0039] Reference numerals include: 31 - flue gas sampling unit; 32 - flue gas pretreatment unit; 33 - flue gas analysis unit; 34 - data acquisition and calculation unit; 41 - primary flue gas filtration device; 42 - grid-type multi-point flue gas sampling branch pipe; 43 - backflush solenoid valve; 44 - sampling solenoid valve; 45 - first flow regulating valve; 46 - primary mixing main pipe; 47 - dilution unit; 48 - probe controller; 49 - secondary mixing main pipe; 51 - secondary flue gas filtration device; 52 - ozone generation device; 53 - flue gas condensation device; 61 - three-way valve; 62 - second flow regulating valve; 63 - rotameter; 64 - temperature control device; 65 - pressure control device; 66 - near-infrared sample gas cell; 67 - mid-infrared sample gas cell; 68 - near-infrared laser generator; 69 - mid-infrared laser generator; 70 - laser collimator; 71 - vacuum pump; 72 - waste gas cell; 73 - laser detector. DETAILED DESCRIPTION OF THE INVENTION

[0040] The present invention discloses a carbon emission monitoring device for a biomass co-firing coal-fired unit based on the 13 C, 15 N multi-isotope complementary method and based on the 13 C, 15Carbon emission monitoring method for biomass co-fired coal-fired units by using multiple isotope complementary method. The following combines with the preferred embodiment (Embodiment 1) and refers to the attached drawings Figures 3 to 6 to further describe the specific implementation manners of the present invention.

[0041] Referring to the attached drawings Figures 3 to 6 , Figures 3 to 6 shows the system architecture, flue gas sampling unit, flue gas pretreatment unit and flue gas analysis unit.

[0042] Embodiment 1.

[0043] Preferably, a carbon emission monitoring device for biomass co-fired coal-fired units based on 13 C, 15 multiple isotope complementary method includes a flue gas sampling unit 31, a flue gas pretreatment unit 32, a flue gas analysis unit 33 and a data acquisition and calculation unit 34, wherein:

[0044] The flue gas sampling unit 31 includes a grid-type multi-point flue gas sampling branch pipe 42, a primary flue gas filtering device 41, a backflush solenoid valve 43, a sampling solenoid valve 44, a primary mixing main pipe 46, a first flow regulating valve 45, a dilution unit 47, a probe controller 48 and a secondary mixing main pipe 49. The grid-type multi-point flue gas sampling branch pipe 42 (which can refer to the GB / T 16157-1996 standard) is arranged in the area from the outlet of the economizer at the tail flue of the (existing) boiler to the inlet of the (existing) SCR denitration system (for existing coal-fired boilers) according to the grid method. The input end of the grid-type multi-point flue gas sampling branch pipe 42 is connected to the primary flue gas filtering device 41, the output end of the grid-type multi-point flue gas sampling branch pipe 42 is connected to the input end of the backflush solenoid valve 43, the output end of the backflush solenoid valve 43 is connected to the input end of the sampling solenoid valve 44, the output end of the sampling solenoid valve 44 is connected to the input end of the first flow regulating valve 45, the output end of the first flow regulating valve 45 is connected to the input end of the primary mixing main pipe 46, the output ends of multiple primary mixing main pipes 46 are simultaneously connected to the input end of the secondary mixing main pipe 49, the output end of the secondary mixing main pipe 49 is connected to the input end of the dilution unit 47, the dilution gas is simultaneously introduced into the input end of the dilution unit 47, the output end of the dilution unit 47 is connected to the input end of the probe controller 48, the standard gas and the backflush gas are simultaneously introduced into the input end of the probe controller 48, and the output end of the probe controller 48 is sequentially connected to the flue gas pretreatment unit 32 and the flue gas analysis unit 33.

[0045] Among them, the flue gas pretreatment unit 32 includes a secondary flue gas filtration device 51, an ozone generation device 52, and a flue gas condensation device 53. The output end of the probe controller 48 is connected to the input end of the secondary flue gas filtration device 51. The output end of the secondary flue gas filtration device 51 is connected to the input end of the ozone generation device 52. The output end of the ozone generation device 52 is connected to the input end of the flue gas condensation device 53. The output end of the flue gas condensation device 53 is connected to the input end of the three-way valve 61.

[0046] Among them, the flue gas analysis unit 33 includes a three-way valve 61, a second flow regulating valve 62, a rotameter 63, a near-infrared sample gas cell 66, a mid-infrared sample gas cell 67, and a laser detector 73. The two output ends of the three-way valve 61 are respectively connected to the input end of the second flow regulating valve 62. The output end of the second flow regulating valve 62 is connected to the input end of the rotameter 63. The output end of the rotameter 63 is respectively connected to the input end of the near-infrared sample gas cell 66 or the input end of the mid-infrared sample gas cell 67. The output ends of the near-infrared sample gas cell 66 and the mid-infrared sample gas cell 67 are respectively connected to the input end of the laser detector 73. The output end of the laser detector 73 is connected to the data acquisition and calculation unit 34.

[0047] Among them, the flue gas analysis unit 33 further includes a temperature control device 64 and a pressure control device 65. The temperature control device 64 respectively regulates the near-infrared sample gas cell 66 and the mid-infrared sample gas cell 67. The pressure control device 65 respectively regulates the near-infrared sample gas cell 66 and the mid-infrared sample gas cell 67.

[0048] Among them, the flue gas analysis unit 33 further includes a near-infrared laser generator 68, a mid-infrared laser generator 69, and a laser collimator 70. The near-infrared laser generator 68 and the mid-infrared laser generator 69 are respectively connected to the input end of the corresponding laser collimator 70. One of the laser collimators 70 is connected to the input end of the near-infrared sample gas cell 66, and the other laser collimator 70 is connected to the input end of the mid-infrared sample gas cell 67.

[0049] Among them, the flue gas analysis unit 33 further includes a vacuum pump 71 and an exhaust gas tank 72. The output end of the near-infrared sample gas cell 66 is sequentially connected to one of the vacuum pumps 71 and the exhaust gas tank 72. The output end of the mid-infrared sample gas cell 67 is sequentially connected to the other vacuum pump 71 and the exhaust gas tank 72.

[0050] Among them, the data acquisition and calculation unit 34 includes a DCS online data acquisition module, an abnormal data identification and cleaning module, a local data upload and sharing and acquisition module, and a data model calculation and output module. The output end of the laser detector 73 is sequentially connected to the DCS online data acquisition module, the abnormal data identification and cleaning module, the local data upload and sharing and acquisition module, and the data model calculation and output module.

[0051] Among them, the flue gas pretreatment unit 32, the flue gas analysis unit 33, and the data acquisition and calculation unit 34 are respectively installed in the denitration CEMS small chamber (not shown in the figure).

[0052] Among them, the flue gas sampling unit 31 can be transformed based on the existing SCR denitration inlet flue gas sampling unit. Specifically, for boilers with a low-dust layout SCR system, the flue gas sampling unit 31 should be arranged in the area from the outlet of the economizer in the flue to the inlet of the electrostatic precipitator.

[0053] Preferably, based on 13 C, 15 The carbon emission monitoring method for biomass co-fired coal-fired units based on the C and N multi-isotope complementary method is applied to the 13 C, 15 The carbon emission monitoring device for biomass co-fired coal-fired units based on the C and N multi-isotope complementary method, based on 13 C, 15 The carbon emission monitoring method for biomass co-fired coal-fired units based on the C and N multi-isotope complementary method includes the following steps:

[0054] Step S1: The boiler flue gas enters the flue gas sampling unit 31 from the outlet of the economizer in the flue, is extracted by the grid-type multi-point flue gas sampling branch pipe 42, and after removing particulate matter through the primary flue gas filtration device 41, enters the primary mixing main pipe 46 to be converted into mixed flue gas; the mixed flue gas enters the flue gas pretreatment unit 32, enters the ozone generation device 52 through the secondary flue gas filtration device 51. In the ozone generation device 52, the carbon monoxide generated due to incomplete combustion in the mixed flue gas is oxidized by ozone to carbon dioxide. After sufficient oxidation, the flue gas enters the flue gas condensation device 53 to be cooled and remove moisture to be converted into low-temperature flue gas; the low-temperature flue gas enters the flue gas analysis unit 33, and after debugging, is shunted into the near-infrared sample gas cell 66 and the mid-infrared sample gas cell 67 at a preset temperature, pressure, and flow rate. In the near-infrared sample gas cell 66, the 13 C, 12 C isotope abundance detection is carried out with near-infrared light, and in the mid-infrared sample gas cell 67, the 15 N, 14 N isotope abundance and CO2 concentration detection are carried out with mid-infrared light. The detection data is recorded by the data acquisition and calculation unit 34, and the data acquisition and calculation unit 34 uses the "3δ method" to identify and clean abnormal data;

[0055] Formula 1: δ 13 C represents 13 C isotope abundance; 13 C / 12 C represents the 13 C, 12 C molar ratio in the sample; ( 13 C / 12 C)std Indicates the 13 C, 12 molar ratio of C in the reference material; the reference material is the belemnite fossil in the Cretaceous Peedee Formation, South Carolina, USA, and its value is (11237.2 ± 90) × 10 -6 ;

[0056] Step S2: (Based on the results of a large number of tests with different biomass blends) Establish the carbon-based ratio X of carbon dioxide emissions from biomass sources using Formulas 2-1 and 2-2 as mathematical models bio the same as that in the flue gas 13 C isotope abundance δ flue gas 13 C, 15 N isotope abundance δ flue gas 15 relationship database between C and N; the relationship database is attached with online boiler evaporation parameters as the matching basis; the C and N isotope abundance data measured by the near-infrared gas cell 66 and the mid-infrared gas cell 67 are combined with the online boiler evaporation parameters, the local biomass blend type information and this relationship database for real-time matching and calculation, and the obtained results are substituted into Formula 3; combined with the relevant online data of DCS to obtain the real-time carbon emission rate from fossil sources; the carbon emission rate from desulfurization sources is calculated by Formula 4, solving the consistency problem of seawater desulfurization and common carbonate desulfurizing agents such as limestone in terms of statistical methods 13 C, 15 N isotope abundance data, combined with online boiler evaporation parameters, local biomass blend type information and this relationship database for real-time matching and calculation, and the obtained results are substituted into Formula 3; combined with the relevant online data of DCS to obtain the real-time carbon emission rate from fossil sources; the carbon emission rate from desulfurization sources is calculated by Formula 4, solving the consistency problem of seawater desulfurization and common carbonate desulfurizing agents such as limestone in terms of statistical methods

[0057] Formula 2-1: X bio = k i ·δ flue gas 13 C + b i ; Formula 2-2: X bio = p i ·δ flue gas 15 N + q i ; X bio represents the carbon-based ratio of biomass sources in the flue gas; δ flue gas 13 C represents 13 C isotope abundance in the flue gas; k i , p i represent the slope constant of the fitting equation corresponding to the co-combustion of the i-th biomass; b i , q i represent the intercept constant of the fitting equation corresponding to the co-combustion of the i-th biomass

[0058] Formula 3: E fuel = CO 2 flue gas ·q flue gas ·(1 - Xbio )×10 -6 ; E fuel represents the carbon emission rate from the fossil fuel source (coal - fired, oil - fired), unit: t / h; CO 2 flue gas represents the carbon dioxide concentration in the flue gas detected in the mid - infrared gas cell, unit: mg / Nm 3 ; q flue gas represents the flue gas flow rate at the measuring point section (from DCS online data), unit: Nm 3 / h;

[0059] Formula 4: E 脱硫 represents the carbon emission rate from the desulfurization source (carbonate desulfurizer), unit: t / h; represents the molar mass of CO2, with a value of 44 g / mol; represents the molar mass of SO2, with a value of 64 g / mol; represents the SO2 concentration at the inlet of the absorption tower, unit: mg / Nm 3 ; SO 2out represents the SO2 concentration at the outlet of the absorption tower, unit: mg / Nm 3 ; q in represents the original flue gas volume at the inlet of the absorption tower, unit: Nm 3 / h; q out represents the net flue gas volume at the outlet of the absorption tower, unit: Nm 3 / h.

[0060] Among them, the "preset temperature, pressure, and flow rate" in step S1 can be specifically implemented as: temperature: 3 - 10 °C; pressure: - 90 - - 100 KPa; flow rate: 1 - 1.5 L / min.

[0061] Among them, step S2 further includes the following steps:

[0062] Calculate the carbon emissions from the net purchased and used electricity sources within the preset period T according to formula 5;

[0063] Formula 5: E 电,T = AD 电，T × EF 电 ; E 电,T represents the carbon dioxide emissions generated from the net purchased and used electricity within the period T, unit: t; AD 电，T represents the net purchased electricity of the enterprise within the period T, unit: MWh; EF 电 represents the annual average power supply emission factor of the regional power grid, unit: t CO2 / MWh.

[0064] Among them, step S2 further includes the following steps:

[0065] Calculate the monthly total plant carbon emissions according to formula 6;

[0066] Formula 6: E m represents the monthly carbon emissions of the whole plant, in t;

[0067] represents the monthly average hourly carbon emission rate from fossil sources of a single unit, in t / h; represents the monthly average hourly carbon emission rate from desulfurization sources of a single unit, in t / h; T m represents the number of hours in the current month, in h; E 电,m represents the carbon dioxide emissions generated from the net purchased electricity used in the current month, in t.

[0068] Among them, the "preset period T" in step S2 can be specifically implemented as: T = monthly (m) / quarterly (q) / yearly (y).

[0069] The following elaborates on the overall concept of the carbon emission monitoring device and method for a biomass co-firing coal-fired unit based on 13 C, 15 the C, N multi-isotope complementary method.

[0070] Specifically, with a relatively low cost, it realizes the online accurate monitoring of the carbon emissions from fossil fuels (coal, oil) in the flue gas of biomass-coal co-combustion. At the same time. For 13 the case of co-combining C3 biomass with similar C content to coal, the 15 N method is used for differentiation. In addition, combined with information collection, the carbon emissions of power generation enterprises within a certain period (month, year) are calculated.

[0071] It is worth mentioning that the specific calculation methods and other technical features of the "3δ method" involved in this invention patent application should be regarded as prior art. For the specific structures, working principles, and possible control methods and spatial layout methods involved in these technical features, conventional selections in the art can be adopted and should not be regarded as the invention points of this invention patent. This invention patent will not be further specifically elaborated.

[0072] For those skilled in the art, it is still possible to modify the technical solutions described in the foregoing embodiments, or make equivalent replacements for some of the technical features. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included in the protection scope of the present invention.

Claims

1. A carbon emission monitoring device for a biomass co-firing coal-fired unit based on 13 C, 15 the multi-isotope complementary method of N, characterized in that It includes a flue gas sampling unit, a flue gas pretreatment unit, a flue gas analysis unit and a data acquisition and calculation unit, where: The flue gas sampling unit includes a grid-type multi-point flue gas sampling branch pipe, a primary flue gas filtering device, an anti-blow solenoid valve, a sampling solenoid valve, a primary mixing main pipe, a first flow regulating valve, a dilution unit, a probe controller and a secondary mixing main pipe. The grid-type multi-point flue gas sampling branch pipes are arranged in the area from the outlet of the economizer at the tail flue of the boiler to the inlet of the SCR denitration system according to the grid method. The input end of the grid-type multi-point flue gas sampling branch pipe is connected to the primary flue gas filtering device, the output end of the grid-type multi-point flue gas sampling branch pipe is connected to the input end of the anti-blow solenoid valve, the output end of the anti-blow solenoid valve is connected to the input end of the sampling solenoid valve, the output end of the sampling solenoid valve is connected to the input end of the first flow regulating valve, the output end of the first flow regulating valve is connected to the input end of the primary mixing main pipe, the output ends of multiple primary mixing main pipes are simultaneously connected to the input end of the secondary mixing main pipe, the output end of the secondary mixing main pipe is connected to the input end of the dilution unit, the dilution gas is simultaneously introduced into the input end of the dilution unit, the output end of the dilution unit is connected to the input end of the probe controller, the standard gas and the anti-blow gas are simultaneously introduced into the input end of the probe controller, and the output end of the probe controller is sequentially connected to the flue gas pretreatment unit and the flue gas analysis unit.

2. According to claim 1, based on 13 C, 15 The carbon emission monitoring device for biomass co-firing coal-fired units based on the C and N multi-isotope complementary method is characterized in that The flue gas pretreatment unit includes a secondary flue gas filtering device, an ozone generation device and a flue gas condensation device. The output end of the probe controller is connected to the input end of the secondary flue gas filtering device, the output end of the secondary flue gas filtering device is connected to the input end of the ozone generation device, the output end of the ozone generation device is connected to the input end of the flue gas condensation device, and the output end of the flue gas condensation device is connected to the input end of the three-way valve.

3. According to claim 2, based on 13 C, 15 The carbon emission monitoring device for a biomass co-firing coal-fired unit based on the C, N multi-isotope complementary method is characterized in that The flue gas analysis unit includes a three-way valve, a second flow regulating valve, a rotameter, a near-infrared sample cell, a mid-infrared sample cell and a laser detector. The two output ends of the three-way valve are respectively connected to the input ends of the second flow regulating valve, the output end of the second flow regulating valve is connected to the input end of the rotameter, the output end of the rotameter is respectively connected to the input end of the near-infrared sample cell or the input end of the mid-infrared sample cell, the output ends of the near-infrared sample cell and the mid-infrared sample cell are respectively connected to the input end of the laser detector, and the output end of the laser detector is connected to the data acquisition and calculation unit.

4. According to claim 3, based on 13 C, 15 The carbon emission monitoring device for a biomass co-firing coal-fired unit using the C and N multi-isotope complementary method is characterized in that The flue gas analysis unit also includes a temperature control device and a pressure control device. The temperature control device respectively regulates the near-infrared sample cell and the mid-infrared sample cell, and the pressure control device respectively regulates the near-infrared sample cell and the mid-infrared sample cell.

5. According to claim 3, the carbon emission monitoring device for a biomass co-fired coal-fired unit based on 13 C, 15 the N multiple isotope complementary method, characterized in that The flue gas analysis unit also includes a near-infrared laser generator, a mid-infrared laser generator and a laser collimator. The near-infrared laser generator and the mid-infrared laser generator are respectively connected to the input ends of the corresponding laser collimators. The laser collimator of one of them is connected to the input end of the near-infrared sample cell, and the laser collimator of the other is connected to the input end of the mid-infrared sample cell.

6. According to claim 3, the biomass co-firing coal-fired unit carbon emission monitoring device based on 13 C, 15 the N isotope complementary method, characterized in that The flue gas analysis unit also includes a vacuum pump and an exhaust gas tank. The output end of the near-infrared sample cell is sequentially connected to one of the vacuum pumps and the exhaust gas tank, and the output end of the mid-infrared sample cell is sequentially connected to the other vacuum pump and the exhaust gas tank.

7. According to claim 1, the biomass co-firing coal-fired power unit carbon emission monitoring device based on 13 C, 15 the N multi-isotope complementary method, characterized in that The data acquisition and calculation unit includes a DCS online data acquisition module, an abnormal data identification and cleaning module, a local data upload, sharing and acquisition module, and a data model calculation and output module. The output end of the laser detector is successively connected to the DCS online data acquisition module, the abnormal data identification and cleaning module, the local data upload, sharing and acquisition module, and the data model calculation and output module.

8. According to claim 1, the carbon emission monitoring device for a biomass co-fired coal-fired unit based on 13 C, 15 the N multi-isotope complementary method is characterized in that The flue gas pretreatment unit, the flue gas analysis unit, and the data acquisition and calculation unit are respectively installed and arranged in the denitration CEMS small chamber.

9. A method for monitoring carbon emissions of a biomass co-fired coal-fired power unit based on 13 C, 15 the complementary method of multiple isotopes of N, characterized in that Applied to the carbon emission monitoring device for a biomass co-fired coal-fired unit based on the 13 C, 15 carbon emission monitoring device for a biomass co-fired coal-fired unit based on the 13 C, 15 carbon emission monitoring method for a biomass co-fired coal-fired unit based on the C, N multi-isotope complementary method, comprising the following steps: Step S1: The boiler flue gas enters the flue gas sampling unit from the outlet of the economizer in the flue, is extracted by the grid-type multi-point flue gas sampling branch pipe, enters the primary mixing main pipe as mixed flue gas after removing particulate matter through the primary flue gas filtering device; the mixed flue gas enters the flue gas pretreatment unit, enters the ozone generator through the secondary flue gas filtering device. In the ozone generator, carbon monoxide generated due to incomplete combustion in the mixed flue gas is oxidized by ozone to carbon dioxide. The flue gas after sufficient oxidation enters the flue gas condensation device to be cooled and have moisture removed to become low-temperature flue gas; the low-temperature flue gas enters the flue gas analysis unit, and after debugging, it is shunted into the near-infrared sample gas cell and the mid-infrared sample gas cell at a preset temperature, pressure, and flow rate. In the near-infrared sample gas cell, 13 C, 12 C isotope abundance detection is carried out with near-infrared light in accordance with Formula 1, and 15 N, 14 N isotope abundance and CO2 concentration detection are carried out with mid-infrared light. The detection data is recorded by the data acquisition and calculation unit, and the data acquisition and calculation unit uses the "3δ method" to identify and clean abnormal data; Formula 1: δ 13 where C represents 13 the C isotope abundance; 13 C / 12 C represents the molar ratio of 13 C, 12 C in the sample; ([[]] 13 C / 12 C)[[]] std represents the molar ratio of 13 C, 12 C in the reference material; the reference material is the belemnite fossil in the Cretaceous Peedee Formation in South Carolina, USA, and its value is (11237.2 ± 90) × 10 -6 ; Step S2: Establish the carbon-based ratio X of carbon dioxide emissions from biomass sources using Formulas 2-1 and 2-2 as mathematical models bio Same as in flue gas 13 C isotope abundance δ flue gas 13 C, 15 N isotope abundance δ flue gas 15 The relational database between C and N, and the online boiler evaporation parameter is attached to the relational database as a matching basis; the C and N isotope abundance data measured by the near-infrared gas cell and the mid-infrared gas cell are combined with the online boiler evaporation parameter, the local biomass blending type information and the relational database for real-time matching and calculation, and the obtained result is substituted into Formula 3; the real-time carbon emission rate from fossil sources is obtained by combining the relevant online data of DCS; the carbon emission rate from desulfurization is calculated by Formula 4; 13 C, 15 N isotope abundance data, combined with the online boiler evaporation parameter, the local biomass blending type information and the relational database for real-time matching and calculation, and the obtained result is substituted into Formula 3; the real-time carbon emission rate from fossil sources is obtained by combining the relevant online data of DCS; the carbon emission rate from desulfurization is calculated by Formula 4; Formula 2-1: X bio = k i ·δ flue gas 13 C + b i ; Formula 2-2: X bio = p i ·δ flue gas 15 N + q i ; X bio represents the carbon-based ratio of biomass origin in flue gas; δ flue gas 13 C represents the 13 C isotope abundance in flue gas; k i , p i represent the slope constant of the fitting equation corresponding to the co-firing of the i-th biomass; b i , q i represent the intercept constant of the fitting equation corresponding to the co-firing of the i-th biomass; Formula 3: E fuel = CO 2 flue gas ·q flue gas ·(1 - X bio ) × 10 -6 ; E fuel represents the carbon emission rate from fossil sources, unit t / h; CO 2 flue gas represents the carbon dioxide concentration in the flue gas detected in the mid-infrared gas cell, unit mg / Nm 3 ; q flue gas represents the flue gas flow rate at the measuring point section, unit Nm 3 / h; Formula 4: E 脱硫 represents the carbon emission rate from desulfurization source, unit: t / h; represents the molar mass of CO2, with a value of 44 g / mol; represents the molar mass of SO2, with a value of 64 g / mol; represents the SO2 concentration at the inlet of the absorber, unit: mg / Nm 3 ; represents the SO2 concentration at the outlet of the absorber, unit: mg / Nm 3 ; q in represents the raw flue gas volume at the inlet of the absorber, unit: Nm 3 / h; q out represents the clean flue gas volume at the outlet of the absorber, unit: Nm 3 / h.

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