CN111812057B - Biomass co-combustion ratio on-line monitoring system based on stable carbon isotope and analysis method - Google Patents
Biomass co-combustion ratio on-line monitoring system based on stable carbon isotope and analysis method Download PDFInfo
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Abstract
An online biomass co-combustion ratio monitoring system and an analysis method based on stable carbon isotopes are characterized in that flue gas is taken from a flue of a coal and biomass co-combustion boiler to be cooled and dedusted, and stable carbon isotope ratio delta of the mixed flue gas is measured by adopting infrared laser detection equipment in stable carbon isotopes 13 C, the testing error of the equipment is only +/-0.025 thousandths, the equipment is not influenced by water content, and the equipment cost is far lower than that of the equipment 14 And C, an online analysis device, which has economic competitiveness. Establishing linear regression equation fitting goodness of fit R obtained by correcting carbon content or calorific value by using online analysis method 2 >And 0.99, judging that the error of the biomass co-combustion ratio is controlled within 2.0 percent, and monitoring the change of the biomass co-combustion ratio in real time. The invention can accurately monitor the biomass blending combustion ratio in real time, provides technical support for the formulation and implementation of a policy of subsidy of biomass usage amount, and can also be used for carbon emission monitoring and carbon trading markets.
Description
Technical Field
The invention relates to a method for monitoring delta in coal and biomass mixed combustion flue gas on line in real time by adopting stable carbon isotope mid-infrared laser equipment 13 A real-time online detection method is established for the C value to determine the biomass blending combustion ratio, and belongs to the technical detection field of isotope detection and boiler combustion.
Background
Biomass energy is a clean renewable energy source, biomass power generation is gradually started in recent years, and CO can be effectively reduced by using biomass to replace fossil fuel for power generation 2 And SO 2 And (5) discharging. The biomass and coal mixed combustion power generation is brought into the national industrial planning, the electricity price is subsidized aiming at the biomass power generation part, and the problem of biomass electric quantity metering is involved, but the scientific and fair online detection of biomass is still the biggest problem in the prior art of coal-fired biomass coupled power generation. The detection of the biomass fuel proportion can be divided into two technologies of front-end detection and rear-end detection according to the difference of the acquisition and detection positions, the mixed combustion power generation is greatly developed in the European Union, but the existing method mostly adopts the front-end detection, and has the defects of more tests, more calculation, more reports, labor consumption and the like. The current advanced back-end detection method mainly comprises SO 2 Concentration detection method and 14 c content detection method. As the biomass contains some alkali metals, the biomass can react with S to influence SO 2 A concentration monitoring result; 14 the natural abundance of C is too low, and the requirement on the precision of equipment is extremely high, so that 14 The accuracy and reliability of the C content detection method are still in the exploratory stage, and simultaneously 14 The C technology mostly adopts flue gas side sampling to carry out laboratory analysis, and used analysis equipment is mostly expensive precision instruments such as nuclear magnetism, mass spectrum and the like, so that the popularization and the application of a biomass application quantity rear-end detection technology are limited. The published master thesis (research on mixed fuel ratio detection and fine particle removal technology in biomass mixed fuel power generation, mei Cao Yuan, qing Hua university, 2015) reports that laboratory Accelerated Mass Spectrometry (AMS) is subjected to offline test 14 C concentration content judges that the mixing combustion ratio error of the biomass is 10 to 16 percent. Therefore, research and developmentThe biomass application quantity rapid and accurate detection device is suitable for popularization in the industry, and can provide technical support for implementation of government subsidy policies.
At present, the problems of real-time detection, expensive equipment and the like are urgently to be solved in the rear-end detection of the application amount of biomass. The mid-infrared laser isotope detection technology can realize the rapid real-time detection of the stable carbon isotope ratio delta 13 C ( 13 CO 2 / 12 CO 2 ). Delta of biomass and coal 13 The C values are clearly different according to respective delta 13 And detecting the blending ratio of the coal and the biomass according to the difference of the C values. Meanwhile, the intermediate infrared laser isotope detection equipment has low manufacturing cost and is successfully applied to oil and gas field exploration. The existing carbon isotope mid-infrared laser detection equipment is designed and developed a set of multi-channel optical detection core device based on a continuously mature developed quantum cascade laser, the detection error of the equipment is only +/-0.025 per thousand, the accurate evaluation requirement of the application amount of biomass can be met, the installation and maintenance difficulty of a mid-infrared laser detection instrument is greatly reduced, a laser detector can be rapidly replaced, the requirements of instruments with different wavelengths are met, the substitution of expensive equipment such as mass spectrums is realized, and the corresponding evaluation method is blank at home and abroad. Therefore, the establishment of the real-time online detection and analysis method for monitoring the biomass mixing combustion ratio based on the stable carbon isotope mid-infrared laser detection equipment is very important, the technical support can be provided for the implementation of government subsidy policies, and meanwhile, the method can be used for carbon investigation and carbon trading markets, and the healthy and ordered development of clean energy is promoted.
Disclosure of Invention
The invention provides a system and an analysis method for monitoring biomass blending combustion ratio on line based on a stable carbon isotope, which are used for realizing real-time online detection of the biomass blending combustion ratio and controlling the error within 2.0%.
The technical scheme of the invention is as follows: a biomass co-combustion ratio real-time on-line monitoring system and an analysis method based on stable carbon isotopes are characterized in that: the system comprises a flue gas online sampling channel, a condenser, a filter, a back pressure valve and carbon isotope mid-infrared laser detection equipment.
Carbon isotope mid-infrared laserThe detector mainly comprises a quantum cascade laser, a hollow waveguide tube and a mid-infrared laser detector, wherein the hollow waveguide tube comprises a multi-channel light path, a laser inlet and a gas inlet/outlet. The mixed flue gas enters a multi-channel light path system in the hollow waveguide tube through the air inlet, the quantum cascade laser emits mid-infrared laser in the spectrum, the mid-infrared laser interacts with carbon dioxide gas molecules in the hollow waveguide tube through the hollow waveguide tube, the infrared laser is absorbed by the carbon dioxide gas molecules according to the Lambert beer law, and the absorption spectrum receives signals through the detector, so that the absorption value of the carbon isotope is measured. The carbon isotope mid-infrared laser detector can measure a plurality of spectral absorption peaks by measuring absorption spectrum, wherein two main absorption peaks are on the left side 13 CO 2 Absorption peak and right side 12 CO 2 An absorption peak from which an isotope ratio delta contained in carbon dioxide gas is obtained 13 C ( 13 C/ 12 C) The isotope value can be given in real time. The carbon isotope mid-infrared laser detection equipment device is used for accurately measuring the content of carbon elements and the stable isotope value (C) in various carbon-containing components 12 C/ 13 C) The analyzer of (1). The carbon isotope analyzer creatively uses a plurality of advanced optical measurement technologies, namely a mid-infrared Quantum Cascade Laser (QCL) and a hollow waveguide tube (HWG), so that high-precision laser carbon isotope measurement is realized. The QCL is a unipolar semiconductor laser based on the electron transition between the semiconductor coupling quantum well sub-bands, the working principle is completely different from the conventional semiconductor laser, the electronic-hole composite stimulated radiation mechanism of the traditional p-n junction type semiconductor laser is broken through, and the single electron injection and the multi-photon output are realized by utilizing the particle number reversal generated between the separated electronic states caused by the quantum confinement effect in the semiconductor heterojunction thin layer. QCL has small, easy operation, low price, the low advantage of environmental sensitivity.
The invention is also characterized in that: a back pressure valve is arranged in front of the carbon isotope mid-infrared laser detection equipment, so that continuous sample introduction can be realized; the carbon isotope mid-infrared laser detector can detect simultaneously 12 CO 2 、 13 CO 2 Stable carbon isotope value.
The invention provides a biomass mixed combustion ratio on-line monitoring system based on stable carbon isotopes and an analysis method, which are characterized in that: the flue gas taken from the boiler on-line combusting coal and biomass comprises 12 CO 2 、 13 CO 2 The mixed gas is introduced into carbon isotope mid-infrared laser detection equipment for stable carbon isotope analysis, and the carbon isotope ratio delta of the mixed flue gas can be directly tested by the stable carbon isotope mid-infrared laser detection equipment 13 C( 13 C/ 12 C)。
The carbon isotope ratio delta detected by the carbon isotope mid-infrared laser detection equipment 13 C( 13 C/ 12 C) Defined according to the following formula:
δ 13 C = [(Rp/Rs-1)]×1000
wherein Rp is the abundance ratio of the heavy and light isotopes of carbon in the sample ( 13 Cp/ 12 Cp), rs is the ratio of the abundance of heavy and light isotopes of the international common standard ( 13 Cs/ 12 Cs)。
The stable carbon isotope mid-infrared laser detection equipment can directly test the carbon isotope ratio delta of the mixed flue gas 13 C, delta of different coal samples and different biomasses 13 There is a significant difference between the C values, in terms of the delta 13 C, obtaining a linear regression equation after the carbon content of the coal and the biomass is corrected by using the difference, and calculating the co-combustion proportion of the biomass in the co-combustion substance:
in the formula (1), the first and second groups of the compound,ydelta shown for carbon isotope laser detection apparatus 13 The value of C is the sum of the values of,xthe biomass blending combustion ratio after carbon content correction can eliminate the influence of interference factors such as moisture, ash content, volatile matter and the like after carbon content correction,athe slope of a linear regression equation is obtained by proportioning different coal types and different biomass mixed combustion,bis delta of coal sample 13 C value; in the formula (2), the first and second groups,ris biomass blending combustion ratio without carbon content correction，C C Is the carbon content of a coal sample,C B is the biomass carbon content.
The stable carbon isotope mid-infrared laser detection equipment can directly test the carbon isotope ratio delta of the mixed flue gas 13 C, delta of different coal samples and different biomass 13 The C value has obvious difference, and a linear regression equation can be obtained after the heat productivity of the coal and the biomass is corrected, and is used for judging the co-combustion ratio of the biomass:
in the formula (3), the first and second groups of the compound,ydelta shown for carbon isotope laser inspection apparatus 13 The value of C is the sum of the values of,x 1 is the biomass blending combustion ratio after the heat productivity is corrected,a 1 the slope of a linear regression equation is obtained by proportioning different coal types and different biomass mixed combustion,bis delta of coal sample 13 The value C can eliminate the influence of interference factors such as moisture, ash content, volatile matter and the like after the heat productivity is corrected; in the formula (4), the first and second groups of the chemical reaction are shown in the specification,r 1 is the biomass blending combustion ratio without heat quantity correction,Q C is the calorific value of the coal sample and is,Q B is the biomass heating value.
The above method of the present invention is characterized in that: the error of the stable carbon isotope on-line detection equipment is only +/-0.025 per thousand, and a linear regression equationy= ax+bGoodness of fit R 2 >0.99, and the error range of the test biomass blending combustion ratio (such as 20%) is controlled within 2.0%.
The invention has the following advantages and prominent effects: (1) The testing error of the infrared laser detection equipment in the stable carbon isotope is only +/-0.025 per thousand, and the obtained carbon isotope ratio delta 13 C is not interfered by water content, ash content, volatile matter and the like, and the equipment cost is far lower than that of 14 C, online analysis equipment is simple, practical and portable, and has economic competitiveness; (2) Establishing an online analysis method, monitoring the biomass mixed combustion ratio in real time, and fitting to obtain a linear regression equation after carbon content correction or heat productivity correctiony= ax+bOry=a 1 x 1 +bGoodness of fit R 2 >0.99, the error range of the biomass blending combustion ratio (such as 20%) is controlled within 2.0%, and the accuracy is better; (3) The on-line analysis method is suitable for mixed combustion detection of various coals and biomasses, and is slightly limited by the types of raw materials; meanwhile, the analysis method obtained by carbon content correction can be used for carbon emission monitoring and carbon trading markets; (4) Linear regression equation obtained after correcting calorific valuey=a 1 x 1 +bImportant reference data can be provided for the generated energy obtained by co-burning biomass in a power plant; (5) If there is a significant difference between the actual co-combustion ratio of the biomass and the supply ratio obtained by the analysis method, it can be concluded that the biomass contains more water or is adulterated.
Drawings
FIG. 1 is a schematic diagram of a sample testing system according to an embodiment of the present invention. Fig. 2 is a multi-port coupled optical path system of a mid-infrared laser. Fig. 3 is a measurement schematic diagram of a carbon isotope measuring apparatus used in the present invention. FIG. 4 is a fitting linear relation obtained after carbon content correction in example 3 of the present invention. FIG. 5 is a fitting linear relation obtained after the calorific value correction of example 3 of the present invention. FIG. 6 is a fitted linear relationship obtained after carbon content correction in example 5 of the present invention. FIG. 7 is a fitted linear relation obtained after the calorific value was corrected in example 5 of the present invention. FIG. 8 is a fitted linear relationship obtained after carbon content correction in example 7 of the present invention. FIG. 9 is a fitted linear relation obtained after the calorific value correction of example 7 of the present invention.
FIG. 10 is a fitted linear relationship obtained after carbon content correction in example 8 of the present invention. FIG. 11 is a fitted linear relation obtained after the calorific value correction of example 8 of the present invention. FIG. 12 shows the linear relationship obtained in example 9 of the present invention. FIG. 13 is a fitted linear relationship obtained after carbon content correction in example 12 of the present invention. FIG. 14 shows a fitted linear relationship obtained by heating value correction in example 12 of the present invention. FIG. 15 is a fitted linear relationship obtained after carbon content correction in example 13 of the present invention. FIG. 16 is a fitted linear relation obtained after the calorific value was corrected in example 13 of the present invention.
In the figure, 1-a boiler, 2-a flue gas channel, 3-a sampling channel, 4-a condenser, 5-a filter, 6-a back pressure valve and 7-carbon isotope mid-infrared laser detection equipment.
Detailed Description
In order to make the monitoring system, the real-time on-line analysis method and the advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings in combination with the specific embodiments.
The invention discloses a biomass mixed combustion ratio real-time monitoring system based on stable carbon isotopes and an analysis method, wherein fig. 1 is a schematic structural diagram of a biomass mixed combustion ratio monitoring system device according to the invention, and the system comprises a boiler 1, a flue gas channel 2, a sampling channel 3, a condenser 4, a filter 5, a back pressure valve 6 and a carbon isotope mid-infrared laser detector 7. Wherein, the carbon isotope mid-infrared laser detector 7 obtains delta by that flue gas generated by mixing fire coal and biomass in a boiler sequentially passes through a condenser, a filter and a back pressure valve through a flue sampling channel and then enters carbon isotope laser detection equipment 13 C value (C 13 CO 2 / 12 CO 2 ) Substituting the calculation formulas (1) and (3) to obtain the biomass mixed combustion ratio.
The carbon isotope mid-infrared laser detector mainly comprises a quantum cascade laser (AdTech, USA), a hollow waveguide tube and a mid-infrared laser detector (THORLABS, DET 10A/M), wherein the hollow waveguide tube comprises a multi-channel optical path, a laser inlet and a gas inlet/outlet, as shown in figure 2.
The carbon isotope ratio of the flue gas detected by the carbon isotope measuring instrument is detected as follows: the mixed flue gas enters a multi-channel light path system in the hollow waveguide tube through the air inlet, the quantum cascade laser emits mid-infrared laser in the spectrum, the mid-infrared laser interacts with carbon dioxide gas molecules in the hollow waveguide tube through the hollow waveguide tube, the infrared laser is absorbed by the carbon dioxide gas molecules according to the Lambert beer law, and the absorption spectrum receives signals through the detector, so that the absorption value of the carbon isotope is measured. The measurement chart of the carbon isotope measuring instrument is shown in fig. 3, and a plurality of spectral absorption peaks can be measured by measuring the absorption spectrum, wherein two major absorption peaks are shown on the left side in fig. 3 13 CO 2 Absorption ofPeak and right side 12 CO 2 Absorption peak, and the isotope ratio delta contained in carbon dioxide gas is obtained from the absorption peak area 13 C ( 13 C/ 12 C) The isotope value can be given in real time.
7 samples of Shanxi coal, inner Mongolia coal, guizhou coal, corn straw, cotton straw, wood chips and rice hull are subjected to industrial analysis, elemental analysis and heat value measurement, and the samples are shown in Table 1. The real-time on-line analysis method of the present invention is further illustrated by the mixed combustion of different coal samples (shanxi coal, inner Mongolia coal, guizhou coal) and different biomass species (corn stalk, cotton stalk, wood chips, rice hull), but the present invention is not limited by these examples.
Example 1: carbon isotope mid-infrared laser detector for on-line detection of coal sample delta 13 A method of C value comprising the steps of: adding pure Shanxi coal into boiler for full combustion, obtaining flue gas from sampling pipeline of flue in real time during combustion process, passing through condenser and filter in sequence, passing through backpressure valve, and detecting by carbon isotope mid-infrared laser detection equipment to obtain gas mixture containing 13 CO 2 、 12 CO 2 Spectral absorption peak area of (2), comparison 13 CO 2 、 12 CO 2 The difference of the isotope peak areas of the coal to obtain the carbon isotope delta of the coal in Shanxi province 13 C value, standard CO 2 Carbon isotope delta 13 After C value is corrected, delta of Shanxi coal is obtained 13 The C value was-20.61.
Example 2: online detection of biomass delta by carbon isotope intermediate infrared laser detector 13 A method of C value comprising the steps of: carbon isotope mid-infrared laser detector for on-line detection of delta of coal sample 13 Adding pure corn straw into a boiler for full combustion at the C value, obtaining flue gas from a sampling pipeline of a flue in real time during the combustion process, sequentially passing through a condenser, a filter and a back pressure valve, and finally measuring the content of the mixed gas by carbon isotope mid-infrared laser detection equipment 13 CO 2 、 12 CO 2 Spectral absorption peak area of (1), comparison 13 CO 2 、 12 CO 2 Obtaining the corn straw carbon by the isotope peak area difference valueIsotope delta 13 C value, standard CO 2 Carbon isotope delta 13 After C value is corrected, the delta of the corn straws is obtained 13 The C value was-11.91.
Example 3: the method for monitoring the biomass blending combustion ratio on line by using the carbon isotope mid-infrared laser detector comprises the following steps: adding Shanxi coal and corn straws with different mixing ratios into a boiler for full combustion, wherein the mixing ratio of the corn straws is 2.5%, 5%, 7.5%, 10%, 15%, 20%, 25% and 30%, flue gas can be obtained from a sampling pipeline of a flue in real time in the combustion process, the flue gas sequentially passes through a condenser, a filter and a back pressure valve, and finally the content of the mixed gas is detected by carbon isotope mid-infrared laser detection equipment 13 CO 2 、 12 CO 2 Spectral absorption peak area of (1), comparison 13 CO 2 、 12 CO 2 The carbon isotope delta of the Shanxi coal and the corn straw is obtained by the isotope peak area difference 13 C value, standard CO 2 Carbon isotope delta 13 After C value is corrected, delta of different corn straw mixing ratios is obtained 13 C values are respectively: -21.4, -21.224, -21.09, -20.91, -20.68, -20.32, -19.95, -19.56. The biomass blending ratio after carbon content correction is as follows: 1.41%, 2.86%, 4.33%, 5.84%, 8.97%, 12.25%, 15.69%, 19.31%, with this as the abscissa, to obtain the corresponding δ 13 The C value is plotted as a vertical coordinate, a linear equation is obtained after linear fitting, and as shown in figure 4, the fitting linear relation of the blending of the Shanxi coal and the corn stalks with different proportions is obtained, wherein y = 0.1x-21.55 (x is the blending combustion ratio of the biomass after carbon content correction, and y is the carbon isotope delta 13 C value), goodness of fit R 2 =0.997, indicating that the linear relationship of the relational expression is good. The combustion ratio of Shanxi coal and corn stalks is analyzed according to the relation, and when the mixed combustion ratio of the corn stalks is 20%, the error range is 2.0%.
In addition, the biomass blending ratio can also be determined by correcting the calorific value, and the biomass blending ratio after correcting the calorific value is: 1.44%, 2.91%, 4.41%, 5.95%, 9.13%, 12.46%, 15.95%, 19.61%, with this as the abscissa, to obtain the corresponding δ 13 C value is plotted on the ordinateLinear fitting is carried out to obtain a linear equation, and as shown in fig. 5, a fitting linear relation of blending of the shanxi coal and the corn straws with different proportions is obtained, wherein y = 0.1x-21.55 (x is the blending ratio of the biomass after corrected calorific value, and y is the carbon isotope delta) 13 C value), goodness of fit R 2 =0.9973, indicating that the linear relationship of the relational expression is good. The error degree analysis is carried out on the combustion ratio of the Shanxi coal and the corn stalks according to the relational expression, and when the mixed combustion ratio of the corn stalks is 20%, the error range is 1.9%.
The linear equation obtained after carbon content and heat productivity correction is compared, the two correction modes can obtain the real function relation of the biomass mixing ratio and the carbon isotope ratio, and the error analysis is similar.
Example 4: the method for monitoring the biomass blending combustion ratio on line by using the carbon isotope mid-infrared laser detector comprises the following steps: adding pure cotton straw into a boiler for full combustion, obtaining flue gas from a sampling pipeline of a flue in real time during the combustion process, sequentially passing through a condenser, a filter and a back pressure valve, and finally measuring the content of the mixed gas by carbon isotope mid-infrared laser detection equipment 13 CO 2 、 12 CO 2 Spectral absorption peak area of (2), comparison 13 CO 2 、 12 CO 2 The difference of the isotope peak areas to obtain the carbon isotope delta of the cotton straw 13 C value, standard CO 2 Carbon isotope delta 13 After C value is corrected, delta of cotton straw is obtained 13 The C value was-26.09.
Example 5: the method for monitoring the biomass blending combustion ratio on line by using the carbon isotope mid-infrared laser detector comprises the following steps: the Shanxi coal and the cotton straws with different blending ratios are added into a boiler to be fully combusted, wherein the blending ratios of the cotton straws are 5%, 10%, 20% and 30%, and the same parts as the embodiment 3 are not repeated, and the differences are as follows: obtaining delta of different blending ratios of cotton straws 13 C values of-21.88, -22.14, -22.60 and-23.25, the blending ratio is 3.09%, 6.31%, 13.16% and 20.62% after carbon content correction, and the blending ratio is used as an abscissa to obtain corresponding delta 13 The C value is plotted as a vertical coordinate, and a linear equation is obtained after linear fitting, such as a graph6, obtaining a fitting linear relation formula of the blending of the Shanxi coal and the cotton straws in different proportions, wherein the fitting linear relation formula is y = -0.0781x-21.62, and the fitting goodness R 2 =0.996, indicating that the linear relationship of the relational expression is good. The error degree analysis is carried out on the combustion ratio of the Shanxi coal and the cotton straws according to the relational expression, and when the mixed combustion ratio of the cotton straws is 20%, the error range is 1.0%. Meanwhile, when the blending ratios after the calorific values were corrected were 3.12%, 6.36%, 13.26%, 20.76%, the linear fitting equation obtained by plotting was y = -0.0777x-21.61, see fig. 7, and the goodness of fit R was 2 =0.996, the linear relationship of the relational expression is better. The error degree analysis is carried out on the combustion ratio of the Shanxi coal and the cotton straws according to the relational expression, and when the mixed combustion ratio of the cotton straws is 20%, the error range is 0.8%. The linear equations obtained after carbon content and heat productivity correction are similar, the biomass mixing ratio and the carbon isotope ratio are in a real function relation, and error analysis is similar.
Example 6: online detection of biomass delta by carbon isotope intermediate infrared laser detector 13 A method of C value comprising the steps of: adding pure wood dust into a boiler for full combustion, obtaining flue gas from a sampling pipeline of a flue in real time in the combustion process, sequentially passing through a condenser, a filter and a back pressure valve, and finally measuring the content of the mixed gas by carbon isotope mid-infrared laser detection equipment 13 CO 2 、 12 CO 2 Spectral absorption peak area of (1), comparison 13 CO 2 、 12 CO 2 The difference of the isotope peak areas of the carbon isotopes is obtained to obtain the carbon isotope delta of the sawdust 13 C value, standard CO 2 Carbon isotope delta 13 After C value correction, the delta of the wood chip is obtained 13 The C value was-26.99.
Example 7: the method for monitoring the biomass blending combustion ratio on line by using the carbon isotope mid-infrared laser detector comprises the following steps: adding Shanxi coal and wood chips with different blending ratios into a boiler for full combustion, wherein the blending ratios of the wood chips are 5%, 10%, 20% and 30%, and the same parts as the embodiment 3 are not repeated, except that: obtaining delta of different wood chip mixing ratios 13 C values of-21.84, -22.16, -22.60 and-23.20, and the mixing ratios are 3.14%, 6.40%, 13.34% and 20.88% after carbon content correction, respectivelyThis is the abscissa to obtain the corresponding delta 13 The C value is plotted as a vertical coordinate, a linear equation is obtained after linear fitting, as shown in figure 8, the fitting linear relation formula of blending of the Shanxi coal and the wood chips with different proportions is obtained as y = -0.077x-21.62, and the fitting goodness R is 2 If =0.995, the linear relationship of the relational expression is preferable. The error degree analysis is carried out on the combustion ratio of the Shanxi coal and the wood chips according to the relational expression, and when the wood chip mixed combustion ratio is 20%, the error range is 1.0%. Meanwhile, the linear fitting equation obtained by plotting the blending ratios after the calorific value correction of 3.20%, 6.52%, 13.57% and 21.21% is y = -0.0762x-21.62, as shown in fig. 9, and the goodness of fit R is 2 If =0.995, the linear relationship of the relational expression is preferable. The error degree analysis is carried out on the combustion ratio of the Shanxi coal and the wood chips according to the relational expression, and when the wood chip blending combustion ratio is 20%, the error range is 1.0%. The comparison shows that the linear equations obtained after the carbon content and the calorific value are corrected are similar, the real function relation of the biomass blending ratio and the carbon isotope ratio is similar, and the error analysis is similar.
Example 8: the method for monitoring the biomass blending combustion ratio on line by using the carbon isotope mid-infrared laser detector comprises the following steps: adding shanxi coal, cotton stalk and saw-dust into the boiler simultaneously and fully burning, wherein the common mixing ratio of cotton stalk and saw-dust is 5%, 10%, 20% and 30% (both divide equally according to mixing ratio), and the part the same with embodiment 3 is no longer repeated, the difference lies in: obtaining delta of different wood chip mixing ratio 13 C values of-21.85, -22.08, -22.6 and-23.15, the blending ratio is 3.11%, 6.36%, 13.25% and 20.75% after carbon content correction, and the blending ratio is used as an abscissa to obtain corresponding delta 13 The C value is plotted on the ordinate, as shown in FIG. 10, the fitting linear relation of the Shanxi coal and the biomass (cotton straw and wood dust) with different blending ratios is obtained, the fitting linear relation is y = -0.0744x-21.61, and the fitting goodness R is obtained 2 =0.998, the linear relationship of the relational expression is better. The error degree analysis is carried out on the combustion ratio of the Shanxi coal and the wood chips according to the relational expression, and when the biomass co-combustion ratio is 20%, the error range is 2.0%. Meanwhile, when the blending ratio after the calorific value correction is 3.16%, 6.44%, 13.41%, 20.99%, the linear fitting equation obtained by plotting is y = -0.07365x-21.6, see fig. 11,goodness of fit R 2 =0.999, the linear relationship of the relational expression is good. The error degree analysis is carried out on the combustion ratio of the Shanxi coal and the wood chips according to the relational expression, and when the biomass co-combustion ratio is 20%, the error range is 1.9%. The comparison shows that the linear equations obtained after the carbon content and the calorific value are corrected are similar, the real function relation of the biomass blending ratio and the carbon isotope ratio is similar, and the error analysis is similar.
Example 9: the method for monitoring the biomass blending combustion ratio on line by using the carbon isotope mid-infrared laser detector comprises the following steps: the Shanxi coal and the cotton straw and the wood chips with the mixing ratio of 20% are simultaneously added into a boiler to be fully combusted, wherein the mixing ratio of the cotton straw and the wood chips is 0% of wood chips +20% of cotton straw, 5% of wood chips +15% of cotton straw, 10% of wood chips +10% of cotton straw, 15% of wood chips +5% of cotton straw, and 20% of wood chips +0% of cotton straw, and the same parts as the embodiment 3 are not repeated, and the differences are as follows: obtaining delta of different wood chip mixing ratio 13 C values-22.5, -22.6, with the blend ratio on the abscissa, to obtain the corresponding delta 13 The C value is plotted as a vertical coordinate, as shown in FIG. 12, the fitting linear relation of the Shanxi coal and the cotton straws and the wood chips with different blending ratios is obtained and is almost a straight line, which indicates that the coal can be mixed and combusted with various biomasses, and the carbon isotope delta of the obtained mixed gas 13 The C value is independent of various biomass ratio changes. And (5) carrying out error degree analysis, wherein when the biomass mixed combustion ratio is 20%, the error range is 1.8%. Further analysis shows that the carbon isotope monitoring biomass mixed combustion ratio system and the analysis method are suitable for mixed combustion of coal samples and biomasses with different proportions, and the total mixing ratio of the obtained biomasses is hardly influenced by the change of the mixing ratio of the two biomasses.
Example 10: carbon isotope mid-infrared laser detector for on-line detection of coal sample delta 13 A method of C value comprising the steps of: adding pure Guizhou coal into a boiler for full combustion, obtaining flue gas from a sampling pipeline of a flue in real time in the combustion process, sequentially passing through a condenser and a filter, passing through a back pressure valve, and finally detecting the content of the mixed gas by carbon isotope mid-infrared laser detection equipment 13 CO 2 、 12 CO 2 Spectral absorption ofPeak area, comparison 13 CO 2 、 12 CO 2 The difference of the isotope peak areas is obtained to obtain the carbon isotope delta of the Guizhou coal 13 C value, standard CO 2 Carbon isotope delta 13 After C value is corrected, delta of Guizhou coal is obtained 13 The C value was-21.01.
Example 11: carbon isotope mid-infrared laser detector for on-line detection of coal sample delta 13 A method of C value comprising the steps of: adding pure inner Mongolia coal into a boiler for full combustion, obtaining flue gas from a sampling pipeline of a flue in real time in the combustion process, sequentially passing through a condenser and a filter, passing through a back pressure valve, and finally detecting the content of the mixed gas by carbon isotope mid-infrared laser detection equipment 13 CO 2 、 12 CO 2 Spectral absorption peak area of (1), comparison 13 CO 2 、 12 CO 2 The difference of the isotope peak areas is obtained to obtain the carbon isotope delta of the inner Mongolia coal 13 C value, standard CO 2 Carbon isotope delta 13 After C value is corrected, delta of inner Mongolia coal is obtained 13 The C value was-21.91.
Example 12: the method for monitoring the biomass blending combustion ratio on line by using the carbon isotope mid-infrared laser detector comprises the following steps: adding Guizhou coal and corn straws with different blending ratios into a boiler for full combustion, wherein the blending ratios of the corn straws are 5%, 10%, 20% and 30%, and the parts which are the same as the parts in the embodiment 3 are not repeated, and the differences are as follows: obtaining delta of different blending ratios of corn straws 13 C values of-20.77, -20.38, -19.78 and-19.05, the blending ratio is 3.17%, 6.47%, 13.47% and 21.06% after carbon content correction, and the blending ratio is used as an abscissa to obtain corresponding delta 13 The C value is plotted as the ordinate, and as shown in FIG. 13, the fitting linear relation of the Guizhou coal and the corn straw blending with different proportions is obtained, wherein the fitting linear relation is y = 0.095x-21.0, and the fitting goodness R is obtained 2 =0.998, the linear relationship of the relational expression is better. The error degree analysis is carried out on the combustion ratio of the Guizhou coal and the corn stalks according to the relational expression, and when the mixed combustion ratio of the corn stalks is 20%, the error range is 0.5%. Meanwhile, the linear fitting equation obtained by plotting the blending ratio of the corrected calorific value of 3.19%, 6.50%, 13.52% and 21.14%Y = 0.095x-21.05, see fig. 14, goodness of fit R 2 =0.998, indicating that the linear relationship of the relational expression is good. And analyzing the error degree of the combustion ratio of the Guizhou coal and the corn stalks according to the relation, wherein when the mixed combustion ratio of the corn stalks is 20%, the error range is 0.7%. The comparison shows that the linear equations obtained after the carbon content and the heat productivity are corrected are similar, the real function relation of the biomass blending ratio and the carbon isotope ratio is similar, and the error analysis is similar.
Example 13: the method for monitoring the biomass blending combustion ratio on line by using the carbon isotope mid-infrared laser detector comprises the following steps: the inner Mongolia coal and the corn straws with different blending ratios are added into a boiler to be fully combusted, wherein the blending ratio of the corn straws is 5%, 10%, 20% and 30%, and the same parts as the embodiment 3 are not repeated, and the difference is that: obtaining delta of different blending ratios of corn straws 13 C values of-21.65, -21.36, -20.81 and-20.14, the blending ratio is 3.17%, 6.47%, 13.47% and 21.06% after carbon content correction, and the blending ratio is used as an abscissa to obtain corresponding delta 13 The C value is plotted as a ordinate, as shown in FIG. 15, the fitting linear relation of the blending of the inner Mongolia coal and the corn straws with different proportions is obtained, y = 0.9048x-21.905, and the goodness of fit R 2 =0.999, the linear relationship of the relational expression is good. And (4) carrying out error degree analysis on the combustion ratio of the inner Mongolia coal and the corn stalks according to the relational expression, wherein when the mixed combustion ratio of the corn stalks is 20%, the error range is 0.5%. Meanwhile, when the blending ratio after the calorific value correction is 2.84%, 5.81%, 12.19%, 19.23%, the linear fitting equation obtained by plotting is y = 0.912x-21.904, see fig. 16, and the goodness of fit R is 2 =0.999, indicating that the linear relationship of the relational expression is good. And (3) analyzing the error degree of the combustion ratio of the inner Mongolia coal and the corn stalks according to the relational expression, wherein when the mixed combustion ratio of the corn stalks is 20%, the error range is 0.2%. The comparison shows that the linear equations obtained after the carbon content and the heat productivity are corrected are similar, the biomass blending ratio and the carbon isotope ratio are in a real function relation, and the error of the biomass blending ratio obtained after the heat productivity is corrected is lower.
The embodiments 3, 5 and 7 of the invention relate to the respective mixed combustion of Shanxi coal and single biomass, wherein the biomass relates to corn straws,Cotton stalk and wood dust, and carbon isotope delta is obtained by carbon isotope laser detection equipment 13 C value, the carbon isotope delta of mixed flue gas with biomass flame mixing ratio (0 to 30%) as abscissa 13 C value is ordinate, linear regression equation is obtained by fitting after correction of carbon content or calorific value of Shanxi coal and different biomasses respectively, and goodness of fit R of the linear regression equation 2 >0.99, the linear relation between the biomass and the flame retardant is better, and when the biomass blending ratio is 20%, the error range of the biomass blending ratio is judged to be within 2.0%, so that the accuracy is greatly improved compared with the prior art. Therefore, the accuracy of determining the biomass blending combustion ratio by the stable carbon isotope real-time online detection analysis method is higher.
Embodiments 8 and 9 of the invention relate to the simultaneous mixed combustion of Shanxi coal, cotton straw and wood dust, and the carbon isotope delta of mixed flue gas is obtained by modulating the mixed combustion ratio of the two biomasses (0-30%, the proportion of the two biomasses is evenly divided, and the abscissa) through carbon isotope laser detection equipment 13 C value (ordinate) to obtain goodness of fit R of linear regression equation 2 >0.99; the total mixed combustion ratio of the cotton straws and the sawdust is controlled to be 20 percent, the fitting linear relation obtained by modulating different proportions of the cotton straws and the sawdust is almost a straight line, the error analysis is within 2.0 percent, and the carbon isotope delta of the mixed flue gas is shown 13 The C value is related to the total amount of blending of the various biomasses (two or more) and not to the proportional relationship of the blending of each biomass.
Embodiments 12 and 13 of the present invention relate to a method for obtaining a linear relationship fitting degree goodness R by using corn stalks of different proportions to be respectively mixed and combusted with different coal samples (Guizhou coal and inner Mongolia coal) 2 >And 0.99, the real-time online monitoring system and the analysis method are suitable for mixed combustion of single biomass and different coal samples. The above examples show that the invention is suitable for mixed combustion detection of various coals and various biomasses, and is less limited by the types of raw materials. Table 1 table of coal and biomass materialization parameters.
Claims (4)
1. A biomass blending combustion ratio on-line monitoring method based on stable carbon isotopes is characterized by comprising the following steps: (1) The flue gas taken from the boiler on-line for co-firing coal and biomass comprises 12 CO 2 、 13 CO 2 Introducing the mixed gas into a carbon isotope mid-infrared laser detector for stable carbon isotope analysis, wherein the stable carbon isotope mid-infrared laser detector can directly test the carbon isotope ratio delta of the mixed flue gas 13 C( 13 C/ 12 C) Delta of different coal samples and different Biomass 13 There was a significant difference between the C values; (2) According to said delta 13 And C, obtaining a linear regression equation after the carbon content of the coal and the biomass is corrected by using the difference, wherein the linear regression equation is used for calculating the co-combustion proportion of the biomass in the co-combustion substance:
in the formula (1), the first and second groups of the compound,ydelta shown for carbon isotope laser detection apparatus 13 The value of C is selected from the group consisting of,xis the biomass blending combustion ratio corrected by the carbon content, can eliminate the influence of interference factors of moisture, ash content and volatile matter after the carbon content correction,athe slope of a linear regression equation is obtained by proportioning different coal types and different biomass mixed combustion,bis delta of coal sample 13 C value; in the formula (2), the first and second groups of the compound,ris the biomass blending combustion ratio without carbon content correction,C C the carbon content of the coal sample is shown as the content,C B biomass carbon content; the biomass blending combustion ratio on-line monitoring system based on the stable carbon isotope comprises a flue gas on-line sampling channel, a condenser, a filter, a back pressure valve and a carbon isotope mid-infrared laser detector.
2. The method for on-line monitoring of stable carbon isotope-based biomass co-combustion ratio as claimed in claim 1, wherein the stable carbon isotope mid-infrared laser detection equipment can directly test the carbon isotope ratio δ of the mixed flue gas 13 C, and delta of different coal samples and different biomasses 13 The C value has obvious difference, and a linear regression equation can be obtained after the heat productivity of the coal and the biomass is corrected and is used for judging the blending combustion ratio of the biomass:
in the formula (3), the first and second groups,ydelta shown for carbon isotope laser detection apparatus 13 The value of C is selected from the group consisting of,x 1 is the biomass blending combustion ratio after the calorific value is corrected,a 1 the slope of a linear regression equation obtained by mixing and burning different coals and different biomasses is obtained,bis delta of coal sample 13 The C value can eliminate the influence of interference factors of moisture, ash and volatile after the heat productivity is corrected; in the formula (4), the first and second groups,r 1 is the biomass blending combustion ratio without heat quantity correction,Q C is the calorific value of the coal sample,Q B is the biomass heating value.
3. The biomass co-combustion ratio on-line monitoring method based on the stable carbon isotope as claimed in claim 1, which is characterized in that: the error of the stable carbon isotope on-line detection equipment is only +/-0.025 thousandths, and the goodness of fit R of a linear regression equation 2 >0.99, and the error range of the tested biomass fuel mixture ratio is controlled within 2.0 percent.
4. The biomass co-combustion ratio on-line monitoring method based on the stable carbon isotope as claimed in claim 1, which is characterized in that: the carbon isotope intermediate infrared laser detector mainly comprises a quantum cascade laser, a hollow waveguide tube and an intermediate infrared laser detector, wherein the hollow waveguide tube comprises a multi-channel light path, a laser inlet and a gas inlet/outlet;
the mixed flue gas enters a multi-channel light path in the hollow waveguide tube through the air inlet, the quantum cascade laser in the spectrum emits mid-infrared laser, the mid-infrared laser interacts with carbon dioxide gas molecules in the hollow waveguide tube through the hollow waveguide tube, and the infrared laser is irradiated by the carbon dioxide gas according to the Lambert beer lawThe absorption spectrum receives signals through a detector so as to measure the absorption value of the carbon isotope; the carbon isotope mid-infrared laser detector can measure a plurality of spectrum absorption peaks by measuring an absorption spectrum, wherein two main absorption peaks are the left side 13 CO 2 Absorption peak and right side 12 CO 2 An absorption peak from which an isotope ratio delta contained in carbon dioxide gas is obtained 13 C, the isotope value can be given in real time; the infrared laser detector for carbon isotope is used for accurately measuring the content of carbon element and stable isotope value in various carbon-containing components 12 C/ 13 C) Of simultaneous detection 12 CO 2 、 13 CO 2 The stable carbon isotope value and the detection error of the carbon isotope mid-infrared laser detector are only +/-0.025 per thousand.
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