CN111812057A - Biomass blending combustion ratio on-line monitoring system based on stable carbon isotope and analysis method - Google Patents
Biomass blending 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 of mixed flue gas is measured by adopting infrared laser detection equipment in stable carbon isotopes13C, 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 equipment14C, an online analysis device, and has economic competitiveness. Establishing linear regression equation fitting goodness R obtained by correcting carbon content or calorific value through an online analysis method2>And 0.99, judging that the error of the biomass blending combustion ratio is controlled within 2.0 percent, and monitoring the change of the biomass blending 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 real-time on-line monitoring method for coal and biomass mixed combustion flue gas by adopting stable carbon isotope mid-infrared laser equipment13A 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 generation2And SO2And (5) discharging. The biomass and coal mixed combustion power generation is brought into the national industrial planning, the electricity price subsidy is carried out on the biomass power generation part, the measurement problem of the biomass electric quantity is involved, but the scientific and fair online detection of the biomass is still the biggest problem in the prior art of coal-fired biomass coupled power generation. The biomass fuel proportion detection can be divided into a front-end detection technology and a rear-end detection technology 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 SO2Concentration detection method and14c content detection method. As the biomass contains some alkali metals, the biomass can react with S to influence SO2A concentration monitoring result;14the natural abundance of C is too low, and the requirement on the precision of equipment is extremely high, so that14The accuracy and reliability of the C content detection method are still in the exploratory stage, and simultaneously14The C technology mostly adopts flue gas side sampling for 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 the biomass application quantity rear-end detection technology are limited. Master thesis (biomass mixed combustion power generation mixed combustion ratio detection and fine particle removal technology)Art research, mecaca yuan, university of qinghua, 2015) reported that laboratory Accelerated Mass Spectrometry (AMS) was tested offline14And C concentration content judges that the mixed combustion ratio error of the biomass is 10-16%. Therefore, the rapid and accurate detection equipment suitable for the biomass application amount popularized in the industry is researched and developed, and the technical support can be provided for the 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 ratio13C (13CO2/12CO2). Of biomass with coal13The C values are obviously different according to each13And 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 into 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 thousandth, the accurate evaluation requirement of biomass application amount can be met, the installation and maintenance difficulty of a mid-infrared laser detection instrument is greatly reduced, a laser detector can be quickly replaced, the requirements of instruments with different wavelengths are met, the substitution of expensive equipment such as a mass spectrum 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, can provide technical support for implementation of government subsidy policies, and can be used for carbon investigation and carbon trading markets to promote healthy and ordered development of clean energy.
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 blending 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.
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 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 side13CO2Absorption peak and right side12CO2Absorption peak, from which the isotope ratio contained in carbon dioxide gas is obtained13C (13C/12C) 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 components12C/13C) 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 of the QCL is completely different from that of the conventional semiconductor laser, the QCL breaks through the electron-hole composite stimulated radiation mechanism of the conventional p-n junction type semiconductor laser, and single electron injection and multi-photon output are realized by utilizing the particle number reversal generated between separated electron states caused by the quantum confinement effect in a semiconductor heterojunction thin layer. QCL has small, easy operation, low price, the low advantage of environmental sensitivity.
The invention is also characterized in that: before the carbon isotope mid-infrared laser detection equipmentA back pressure valve is arranged, so that continuous sample introduction can be realized; the carbon isotope mid-infrared laser detector can detect simultaneously12CO2、13CO2Stable 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 for co-firing coal and biomass comprises12CO2、13CO2The mixed gas is introduced into carbon isotope mid-infrared laser detection equipment for stable carbon isotope analysis, and the stable carbon isotope mid-infrared laser detection equipment can directly test the carbon isotope ratio of the mixed flue gas13C(13C/12C)。
The carbon isotope ratio detected by the carbon isotope mid-infrared laser detection equipment13C(13C/12C) Defined according to the following formula:
13C = [(Rp/Rs-1)]×1000
wherein Rp is the abundance ratio of the heavy and light isotopes of carbon in the sample (13Cp/12Cp), Rs is the ratio of the abundance of heavy and light isotopes of the international universal standard (C/S13Cs/12Cs)。
The stable carbon isotope mid-infrared laser detection equipment can directly test the carbon isotope ratio of the mixed flue gas13C, of different coal samples and different biomasses13There is a significant difference between the C values according to13C, 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,yshown for carbon isotope laser detection equipment13The value of C is the sum of the values of,xis the biomass blending combustion ratio corrected by the carbon content, can eliminate the influence of interference factors such as moisture, ash content, volatile matter and the like after the carbon content correction,ais a mixed combustion place for mixing different coal types and different biomassesThe slope of the linear regression equation is obtained,bbeing coal samples13C value; in the formula (2), the first and second groups,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 is the biomass carbon content.
The stable carbon isotope mid-infrared laser detection equipment can directly test the carbon isotope ratio of the mixed flue gas13C, of different coal samples and different biomasses13The 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,yshown for carbon isotope laser detection equipment13The 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,bbeing coal samples13The 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,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.
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 R2>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 ratio of the obtained carbon isotope is13C is not interfered by water content, ash content, volatile matter and the like, and the equipment cost is far lower than that of14C, online analysis equipment is simple, practical and portable, and has economic competitiveness; (2) establishing an on-line analysis methodThe method can monitor the biomass mixed combustion ratio in real time, and the linear regression equation is obtained by fitting after carbon content correction or heat productivity correctiony= ax+bOry=a 1 x 1 +bGoodness of fit R2>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 correcting the carbon content 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 the power plant mixed combustion of biomass; (5) if the actual blending combustion ratio and the providing ratio of the biomass obtained by the analysis method are obviously different, the fact that the biomass contains more water or has a blending phenomenon can be inferred.
Drawings
FIG. 1 is a schematic diagram of a sample testing system connection according to an embodiment of the present invention. Fig. 2 is a multi-pass to coupling optical path system for 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 correction 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 after the calorific value was corrected 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-boiler, 2-flue gas channel, 3-sampling channel, 4-condenser, 5-filter, 6-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 is obtained by the way 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 equipment13C value (C13CO2/12CO2) And 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 in the United states), a hollow waveguide tube and a mid-infrared laser detector (THORLABS, DET10A/M), wherein the hollow waveguide tube comprises a multi-channel light 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. FIG. 3 shows a measurement chart of a carbon isotope measuring instrument by measuring an absorption spectrumMultiple spectral absorption peaks were measured, two of the major absorption peaks being to the left as shown in FIG. 313CO2Absorption peak and right side12CO2Absorption peak, from which the isotope ratio contained in carbon dioxide gas is obtained13C (13C/12C) The isotope value can be given in real time.
The industrial analysis, element analysis and heat value determination of 7 samples of Shanxi coal, inner Mongolia coal, Guizhou coal, corn straw, cotton straw, wood chip and rice hull 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 on-line detection coal sample13A method of C value comprising the steps of: adding pure Shanxi coal 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 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 equipment13CO2、12CO2Spectral absorption peak area of (1), comparison13CO2、12CO2The difference of the isotope peak areas is obtained to obtain the coal carbon isotopes in Shanxi province13C value, standard CO2Carbon isotope13Obtaining coal of Shanxi province after C value correction13The C value was-20.61.
Example 2: online detection of biomass by carbon isotope intermediate infrared laser detector13A method of C value comprising the steps of: carbon isotope mid-infrared laser detector for on-line detection of coal sample13Adding 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 equipment13CO2、12CO2Spectral absorption peak area of (1), comparison13CO2、12CO2The difference of the isotope peak areas to obtain the carbon isotope of the corn straw13C value, standard CO2Carbon isotope13Obtaining maize stalks after C value correction13The 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 equipment13CO2、12CO2Spectral absorption peak area of (1), comparison13CO2、12CO2The carbon isotopes of the Shanxi coal and the corn stalks are obtained according to the difference of the isotope peak areas13C value, standard CO2Carbon isotope13After C value is corrected, different mixing ratios of corn straws are obtained13C 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 corresponding13The 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 blending of the Shanxi coal and the corn straws with different proportions is obtained as y = 0.1x-21.55 (wherein x is the blending ratio of the biomass after carbon content correction, and y is the carbon isotope13C value), goodness of fit R2=0.997, the linear relationship of the relational expression is better. The combustion ratio of the Shanxi coal and the corn stalks is analyzed by the error degree according to the relational expression, 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%, toThis is the abscissa, to obtain the corresponding13The C value is plotted as a vertical coordinate, a linear equation is obtained after linear fitting, and as shown in FIG. 5, a fitting linear relation formula of blending of Shanxi coal and corn straws with different proportions is obtained as y = 0.1x-21.55 (wherein x is the blending ratio of biomass after heat productivity correction, and y is a carbon isotope13C value), goodness of fit R2=0.9973, 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 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 equipment13CO2、12CO2Spectral absorption peak area of (1), comparison13CO2、12CO2The difference of the isotope peak areas to obtain the carbon isotope of the cotton straw13C value, standard CO2Carbon isotope13Obtaining cotton stalks after C value correction13The 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: adding Shanxi coal and cotton straws with different blending ratios into a boiler for full combustion, 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 difference is that: obtaining different blending ratios of cotton stalks13C 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 C values are used as abscissa to obtain corresponding values13C valuePlotting is carried out for the ordinate, a linear equation is obtained after linear fitting, as shown in figure 6, the fitting linear relation formula of the blending of the Shanxi coal and the cotton straws with different proportions is obtained as y = -0.0781x-21.62, and the fitting goodness R is2=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 1.0%. Meanwhile, the linear fitting equation obtained by plotting the blending ratios after the calorific value correction of 3.12%, 6.36%, 13.26% and 20.76% is y = -0.0777x-21.61, see fig. 7, and the goodness of fit R is2=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 by carbon isotope intermediate infrared laser detector13A 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 equipment13CO2、12CO2Spectral absorption peak area of (1), comparison13CO2、12CO2The difference of the isotope peak areas of the carbon isotopes is obtained to obtain the carbon isotopes of the sawdust13C value, standard CO2Carbon isotope13Obtaining wood chips after C value correction13The 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: to obtain different wood chip blending ratios13C values of-21.84, -22.16, -22.60 and-23.20, and mixing ratioCorrected by carbon content, the carbon content is 3.14%, 6.40%, 13.34% and 20.88%, and the corrected carbon content is used as an abscissa to obtain corresponding carbon content13The 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 is2If =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%. 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 is2If =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 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 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: to obtain different wood chip blending ratios13C 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 C value is used as an abscissa to obtain corresponding13The C value is plotted on the ordinate, and as shown in FIG. 10, the fitting linear relation of the Shanxi coal and the biomass (cotton straw and wood chip) with different blending ratios is obtained, wherein the fitting linear relation is y = -0.0744x-21.61, and the fitting goodness R is2=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%. The blending ratios after the correction of the calorific values were 3.16%, 6.44%, 13.41%, and 20.99%, as shown in the graphThe linear fitting equation is obtained as y = -0.07365x-21.6, see FIG. 11, and the goodness of fit R2=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 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 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: adding the Shanxi coal and the cotton straws and the sawdust with the mixing ratio of 20% into a boiler at the same time for full combustion, wherein the mixing ratio of the cotton straws and the sawdust is 0% sawdust +20% cotton straws, 5% sawdust +15% cotton straws, 10% sawdust +10% cotton straws, 15% sawdust +5% cotton straws, 20% sawdust +0% cotton straws, and the same parts as the embodiment 3 are not repeated, and the difference lies in that: to obtain different wood chip blending ratios13C values-22.5, -22.6, with the blending ratio being plotted on the abscissa, to obtain the corresponding values13The C value is plotted as the ordinate, 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 almost a straight line, which indicates that the coal can be mixed with various biomasses for combustion, and the carbon isotope of the obtained mixed gas13The 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 on-line detection coal sample13A 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 equipment13CO2、12CO2Spectral absorption peak area of (1), comparison13CO2、12CO2The difference of the isotope peak areas is obtained to obtain the Guizhou coal carbon isotope13C value, standard CO2Carbon isotope13Obtaining Guizhou coal after C value correction13The C value was-21.01.
Example 11: carbon isotope mid-infrared laser detector on-line detection coal sample13A 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 intermediate infrared laser detection equipment13CO2、12CO2Spectral absorption peak area of (1), comparison13CO2、12CO2The difference of the isotope peak areas to obtain the carbon isotope of the inner Mongolia coal13C value, standard CO2Carbon isotope13Obtaining internal Mongolia coal after C value correction13The 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 different blending ratios of corn stalks13C 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 C values are used as abscissa to obtain corresponding values13The 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 obtained2=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%. At the same time, the blending ratio after the calorific value correction is 3.19%, 6.50%, 13.52%, 21.14%The plotted linear fit equation was y = 0.095x-21.05, see fig. 14, goodness of fit R2=0.998, the linear relationship of the relational expression is better. And analyzing the error degree of the combustion ratio of the Guizhou coal and the corn straw according to the relational expression, wherein when the mixed combustion ratio of the corn straw 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 different blending ratios of corn stalks13C 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 C values are used as abscissa to obtain corresponding values13The C value is plotted as the ordinate, as shown in FIG. 15, the fitting linear relation of the blending of the inner Mongolia coal and the corn stalks with different proportions is obtained as y = 0.9048x-21.905, and the fitting goodness R is obtained2=0.999, 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 0.5%. 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 is2=0.999, 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.
Examples 3, 5 and 7 of the invention relate to the separate co-combustion of Shanxi coal with a single biomass, the biomass being formedThe substance relates to corn straw, cotton straw and wood dust, and the carbon isotope is obtained by carbon isotope laser detection equipment13C value, taking biomass mixed combustion ratio (0-30%) as abscissa, and mixing carbon isotopes of flue gas13C 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 equation2>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 and two biomasses of cotton straw and wood dust, and the carbon isotope of mixed flue gas is obtained by a carbon isotope laser detection device by adjusting the mixed combustion ratio of the two biomasses (0-30%, the two biomasses are uniformly distributed in proportion and are in horizontal coordinates)13C value (ordinate) to obtain goodness of fit R of linear regression equation2>0.99; the total mixed combustion ratio of the cotton straw and the sawdust is controlled to be 20%, the fitting linear relation obtained by modulating different proportions of the cotton straw and the sawdust is almost a straight line, the error analysis is within 2.0%, and the carbon isotope of the mixed flue gas is shown13The 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.
The embodiments 12 and 13 of the invention relate to the blending combustion of corn straws with different proportions and different coal samples (Guizhou coal and inner Mongolia coal) respectively, and the fitting degree goodness R of the obtained linear relation2>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 (5)
1. A biomass blending combustion ratio on-line monitoring system based on stable carbon isotopes is characterized in that: the system comprises a flue gas online sampling channel, a condenser, a filter, a back pressure valve and a carbon isotope mid-infrared laser detector.
2. The biomass co-combustion ratio on-line monitoring system 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 gas 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, 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 as to measure the absorption value of the carbon isotope; 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 side13CO2Absorption peak and right side12CO2Absorption peak, from which the isotope ratio contained in carbon dioxide gas is obtained13C (13C/12C) 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 components12C/13C) Of simultaneous detection12CO2、13CO2The carbon isotope value is stabilized, and the detection error of the equipment is only +/-0.025 per thousand.
3. An on-line monitoring method for biomass blending combustion ratio based on stable carbon isotope by adopting the system as claimed in claim 1 or 2, which is characterized in that: (1) the flue gas taken from the boiler on-line for co-firing coal and biomass comprises12CO2、13CO2The mixed gas is introduced into a carbon isotope mid-infrared laser detector for stable carbon isotope analysis, and the stable carbon isotope mid-infrared laser detector can directly test the carbon isotope ratio of the mixed flue gas13C(13C/12C) Of different coal samples and different biomasses13There was a significant difference between the C values; (2) according to the above13C, 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,yshown for carbon isotope laser detection equipment13The value of C is the sum of the values of,xis the biomass blending combustion ratio corrected by the carbon content, can eliminate the influence of interference factors such as moisture, ash content, volatile matter and the like after the carbon content correction,athe slope of a linear regression equation is obtained by proportioning different coal types and different biomass mixed combustion,bbeing coal samples13C value; in the formula (2), the first and second groups,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 is the biomass carbon content.
4. The method for on-line monitoring of stable carbon isotope-based biomass co-combustion ratio as claimed in claim 3, wherein the stable carbon isotope mid-infrared laser detection equipment can directly test the carbon isotope ratio of the mixed flue gas13C, of different coal samples and different biomasses13The 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,yshown for carbon isotope laser detection equipment13The value of C is the sum of the values of,x 1 is a warpThe 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,bbeing coal samples13The 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,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.
5. The biomass co-combustion ratio on-line monitoring method based on the stable carbon isotope as claimed in claim 4, 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 equation2>0.99, and the error range of the tested biomass fuel mixture ratio is controlled within 2.0 percent.
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