CN105486675A - Laser Raman detection method for quantitative analysis of CO2 gas carbon isotope composition - Google Patents

Laser Raman detection method for quantitative analysis of CO2 gas carbon isotope composition Download PDF

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CN105486675A
CN105486675A CN201511018657.1A CN201511018657A CN105486675A CN 105486675 A CN105486675 A CN 105486675A CN 201511018657 A CN201511018657 A CN 201511018657A CN 105486675 A CN105486675 A CN 105486675A
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李荣西
李佳佳
董会
王志海
赵帮胜
王宁
程敬华
覃小丽
李得路
吴小力
王永炜
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Changan University
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Abstract

The invention provides a laser Raman detection method for quantitative analysis of a CO2 gas carbon isotope composition, comprising the following steps: 1, calculating Raman quantification factor F12CO2 of 12CO2; 2, calculating Raman quantification factor F13CO2 of 13CO2; 3, calculating the mole ratio C[12CO2]/C[13CO2] of 12CO2 and 13CO2 in CO2 gas according to the formulation of C[12CO2]/C[13CO2]=(Al2CO2/Al3CO2)*(F13CO2/F12CO2). The detection method disclosed by the invention is used for microscopic laser Raman test analysis on 12CO2/N2 mixed gas and 13CO2/N2 mixed gas in different proportions, the adopted microscopic laser Raman spectroscopy has the characteristics of high precision, in-situ detection, no loss, rapidness and the like, and the CO2 gas carbon isotope composition can be quantitatively analyzed by utilizing the microscopic laser Raman spectroscopy. The laser Raman detection method disclosed by the invention has a wide application prospect.

Description

Quantitative test CO 2the laser raman detection method of gaseous carbon isotopics
Technical field
The invention belongs to field of spectral analysis technology, be specifically related to a kind of quantitative test CO 2the laser raman detection method of gaseous carbon isotopics.
Background technology
Raman spectrum is an important modern molecular spectral technique, has been widely used in the fields such as physics, chemistry, material, oil, biology, environment, geology, celestial body.Laser micro-raman spectrometry (LRM) focuses on sample by incident laser by microscope, not by under ambient substance disturbed condition, accurately obtain the information such as the relevant chemical composition of product microcell, crystal structure, interaction of molecules and molecular orientation in the same old way.Laser Raman spectroscopy becomes important analysis means in geoscience fundamental research gradually.
Fluid inclusion is that mineral are captured and are kept at the original geologic fluids in mineral crystal defect in crystalline growth process, by studying composition and the character of mineral fluid inclusions, Diagenesis And Mineralization physicochemical condition, fluid composition, Material Source and geologic function etc. can be understood.CO 2a kind of important volatile constituent in fluid inclusion, CO 2stable isotope have 12cO 2with 13cO 2.CO in fluid inclusion 2gaseous carbon Isotope Compositions has important geological Significance in Research on Crustal and upper mantle Minerals origin and fluid Evolution etc., and for research mineral deposit mineralization, Gas Accumulation and Cheng Zang, geologic fluids develop and tectonodynamics etc. provides important information.
At present when carrying out analytical test to inclusion isotope, classic method opens inclusion by thermal explosion method, polishing, crush method etc., then by CO that spectrometer analysis inclusion discharges 2carbon isotope.But the CO being mineral under not same period time, different origins source obtained in this way 2carbon isotope mixing resultant, can not obtain the Individual fluid inclusion CO representing certain specific Diagenesis And Mineralization stage in mineral 2the composition of carbon isotope.But micro-Raman spectroscopy has high precision, original position, the feature such as harmless and quick.Therefore, micro-Raman spectroscopy quantitative test Individual fluid inclusion CO is utilized 2the composition of carbon isotope has good application prospect.
Summary of the invention
Technical matters to be solved by this invention is for above-mentioned the deficiencies in the prior art, provides a kind of quantitative test CO 2the laser raman detection method of gaseous carbon isotopics.The micro-Raman spectroscopy that the method adopts has high precision, original position, the feature such as harmless and quick, and therefore, the method can utilize micro-Raman spectroscopy quantitative test Individual fluid inclusion CO 2the composition of carbon isotope, has good application prospect.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of quantitative test CO 2the laser raman detection method of gaseous carbon isotopics, it is characterized in that, the method comprises the following steps:
Step one, calculating 12cO 2raman quantizing factor F 12CO2, concrete grammar is:
Step 101, employing gas proportion mixing device are incited somebody to action 12cO 2and N 2to mix by different volumes ratio, obtain a series of different ratio 12cO 2/ N 2mixed gas;
Step 102, to adopt Laser-Raman microspectroscopy to proportioning various in step 101 12cO 2/ N 2mixed gas carries out micro laser Raman spectroscopy detection respectively, obtains N 2characteristic peak ν [N2]and 12cO 2the double characteristic peak ν of Fermi resonance - [12CO2]and ν + [12CO2], then calculate ν under various conditions of mixture ratios respectively - [12CO2]the peak area A at place - [12CO2], ν + [12CO2]the peak area A at place + [12CO2]and ν [N2]the peak area A at place 1 [N2]; Described ν - [12CO2], ν + [12CO2]and ν [N2]unit be cm -1;
Step 103, according to A described in step 102 - [12CO2]and A + [12CO2]under calculating various conditions of mixture ratios 12cO 2the peak area A of characteristic peak [12CO2], described A [12CO2]=A - [12CO2]+ A + [12CO2], then according to described A [12CO2]under calculating various conditions of mixture ratios 12cO 2with N 2characteristic peak peak area ratio K 1, described K 1=[A [12CO2]/ Σ 12CO2)/A 1 [N2]; Described Σ 12CO2for 12cO 2relative raman scattering cross section normalization factor;
Step 104, with K described in step 103 1as ordinate, with 12cO 2and N 2mol ratio C [12CO2]/ C [N2]to go forward side by side line linearity matching as horizontal ordinate throwing figure, calculate the slope of fitting a straight line, obtain F 12CO2;
Step 2, calculating 13cO 2raman quantizing factor F 13CO2, concrete grammar is:
Step 201, employing gas proportion mixing device are incited somebody to action 13cO 2and N 2to mix by different volumes ratio, obtain a series of different ratio 13cO 2/ N 2mixed gas;
Step 202, to adopt Laser-Raman microspectroscopy to proportioning various in step 201 13cO 2/ N 2mixed gas carries out micro laser Raman spectroscopy detection respectively, obtains N 2characteristic peak ν [N2]and 13cO 2the double characteristic peak ν of Fermi resonance - [13CO2]and ν + [13CO2], then calculate ν under various conditions of mixture ratios respectively - [13CO2]the peak area A at place - [13CO2], ν + [13CO2]the peak area A at place + [13CO2]and ν [N2]the peak area A at place 2 [N2]; Described ν - [12CO2]and ν + [12CO2]unit is cm -1;
Step 203, according to A described in step 202 - [13CO2]and A + [13CO2]under calculating various conditions of mixture ratios 13cO 2the peak area A of characteristic peak [13CO2], described A [13CO2]=A - [13CO2]+ A + [13CO2], then according to described A [13CO2]under calculating various conditions of mixture ratios 13cO 2with N 2characteristic peak peak area ratio K 2, described K 2=[A [13CO2]/ Σ 13CO2)/A 2 [N2]; Described Σ 13CO2for 13cO 2relative raman scattering cross section normalization factor;
Step 204, with K described in step 203 2as ordinate, with 13cO 2and N 2mol ratio C [13CO2]/ C [N2]to go forward side by side line linearity matching as horizontal ordinate throwing figure, calculate the slope of fitting a straight line, obtain F 13CO2;
Step 3, adopt Laser-Raman microspectroscopy to by 12cO 2with 13cO 2the CO mixed 2gas carries out micro laser Raman spectroscopy detection, obtains CO 2in gas 12cO 2the peak area A of characteristic peak 12CO2and 13cO 2the peak area A of characteristic peak 13CO2, then according to formula C [12CO2]/ C [13CO2]=(A 12CO2/ A 13CO2) × (F 13CO2/ F 12CO2) calculate CO 2in gas 12cO 2with 13cO 2mol ratio C [12CO2]/ C [13CO2].
Above-mentioned quantitative test CO 2the laser raman detection method of gaseous carbon isotopics, is characterized in that, ν described in step 102 - [12CO2]=1287cm -1, described ν + [12CO2]=1390cm -1, described ν [N2]=2332cm -1.
Above-mentioned quantitative test CO 2the laser raman detection method of gaseous carbon isotopics, is characterized in that, Σ described in step 103 12CO2=1.49.
Above-mentioned quantitative test CO 2the laser raman detection method of gaseous carbon isotopics, is characterized in that, ν described in step 202 - [13CO2]=1267cm -1, described ν + [13CO2]=1372cm -1.
Above-mentioned quantitative test CO 2the laser raman detection method of gaseous carbon isotopics, is characterized in that, Σ described in step 203 13CO2=1.437.
The present invention compared with prior art has the following advantages:
The present invention is by preparing different proportion 12cO 2/ N 2with 13cO 2/ N 2blend sample also carries out micro laser Raman spectroscopy test analysis, and the raman characteristic peak peak area ratio of gas is with its mole fraction than direct proportionality, and the slope of fitting a straight line is considered to Raman quantizing factor.CO 2gaseous carbon isotope mole fraction is than obtaining according to the product of Raman peaks peak area ratio and Raman quantizing factor ratio.The present invention has high precision, original position, the feature such as harmless and quick due to the micro-Raman spectroscopy adopted, and therefore, utilizes micro-Raman spectroscopy can quantitative test Individual fluid inclusion CO 2the composition of carbon isotope, is with a wide range of applications.
Below in conjunction with drawings and Examples, the present invention is described in further detail.
Accompanying drawing explanation
Fig. 1 is the present invention 12cO 2with N 2characteristic peak peak area ratio K 1with mol ratio C [12CO2]/ C [N2]fitting a straight line figure.
Fig. 2 is the present invention 13cO 2with N 2characteristic peak peak area ratio K 2with mol ratio C [13CO2]/ C [N2]fitting a straight line figure.
Embodiment
The present invention by the method for laser micro-raman spectrometry analysis and linear fit to CO 2in gas, the composition of carbon isotope carries out quantitative test.Quantitative test CO of the present invention 2the laser raman detection method of gaseous carbon isotopics comprises the following steps:
Step one, calculating 12cO 2raman quantizing factor F 12CO2, concrete grammar is:
Step 101, employing gas proportion mixing device are incited somebody to action 12cO 2and N 2to mix by different volumes ratio, obtain a series of different ratio 12cO 2/ N 2mixed gas;
Step 102, adopt Laser-Raman microspectroscopy respectively to proportioning various in step 101 12cO 2/ N 2mixed gas carries out micro laser Raman spectroscopy detection, obtains N 2characteristic peak ν [N2]and 12cO 2the double characteristic peak ν of Fermi resonance - [12CO2]and ν + [12CO2], then calculate ν under various conditions of mixture ratios respectively - [12CO2]the peak area A at place - [12CO2], ν + [12CO2]the peak area A at place + [12CO2]and ν [N2]the peak area A at place 1 [N2]; Described ν - [12CO2], ν + [12CO2]and ν [N2]unit be cm -1;
Step 103, according to A described in step 102 - [12CO2]and A + [12CO2]under calculating various conditions of mixture ratios 12cO 2the peak area A of characteristic peak [12CO2], described A [12CO2]=A - [12CO2]+ A + [12CO2], then according to described A [12CO2]under calculating various conditions of mixture ratios 12cO 2with N 2characteristic peak peak area ratio K 1, described K 1=[A [12CO2]/ Σ 12CO2)/A 1 [N2]; Described Σ 12CO2for 12cO 2relative raman scattering cross section normalization factor;
Step 104, with K described in step 103 1as ordinate, with 12cO 2and N 2mol ratio C [12CO2]/ C [N2]to go forward side by side line linearity matching as horizontal ordinate throwing figure, calculate the slope of fitting a straight line, obtain F 12CO2;
Step 2, calculating 13cO 2raman quantizing factor F 13CO2, concrete grammar is:
Step 201, employing gas proportion mixing device are incited somebody to action 13cO 2and N 2to mix by different volumes ratio, obtain a series of different ratio 13cO 2/ N 2mixed gas;
Step 202, adopt Laser-Raman microspectroscopy respectively to proportioning various in step 201 13cO 2/ N 2mixed gas carries out micro laser Raman spectroscopy detection, obtains N 2characteristic peak ν [N2]and 13cO 2the double characteristic peak ν of Fermi resonance - [13CO2]and ν + [13CO2], then calculate ν under various conditions of mixture ratios respectively - [13CO2]the peak area A at place - [13CO2], ν + [13CO2]the peak area A at place + [13CO2]and ν [N2]the peak area A at place 2 [N2]; Described ν - [12CO2]and ν + [12CO2]unit is cm -1;
Step 203, according to A described in step 202 - [13CO2]and A + [13CO2]under calculating various conditions of mixture ratios 13cO 2the peak area A of characteristic peak [13CO2], described A [13CO2]=A - [13CO2]+ A + [13CO2], then according to described A [13CO2]under calculating various conditions of mixture ratios 13cO 2with N 2characteristic peak peak area ratio K 2, described K 2=[A [13CO2]/ Σ 13CO2)/A 2 [N2]; Described Σ 13CO2for 13cO 2relative raman scattering cross section normalization factor;
Step 204, with K described in step 203 2as ordinate, with 13cO 2and N 2mol ratio C [13CO2]/ C [N2]to go forward side by side line linearity matching as horizontal ordinate throwing figure, calculate the slope of fitting a straight line, obtain F 13CO2;
Step 3, adopt Laser-Raman microspectroscopy to by 12cO 2with 13cO 2the CO mixed 2gas carries out micro laser Raman spectroscopy detection, obtains CO 2in gas 12cO 2the peak area A of characteristic peak 12CO2and 13cO 2the peak area A of characteristic peak 13CO2, then according to formula C [12CO2]/ C [13CO2]=(A 12CO2/ A 13CO2) × (F 13CO2/ F 12CO2) calculate CO 2in gas 12cO 2with 13cO 2mol ratio C [12CO2]/ C [13CO2].
In specific implementation process, carrying out 12cO 2/ N 2when mixed gas micro laser Raman spectroscopy detects: to different ratio 12cO 2/ N 2mixed gas carries out Laser Roman spectroscopic analysis of composition, can find: at CO on spectrogram 2raman spectrum in occur two strong characteristic spectral lines, this is CO 2fermi resonance doublet, frequency is respectively at 1287cm -1and 1390cm -1(i.e. ν - [12CO2]and ν + [12CO2]).Be 2332cm in frequency -1place has the intensity at a peak very strong, and this is N 2characteristic peak (i.e. ν [N2]).
In specific implementation process, right 12cO 2/ N 2when mixed gas carries out the analysis of laser micro-raman spectrometry characteristic peak: go out peak position, shape and the intensity of Raman bands of a spectrum only depend on this change in vibration processes Middle molecule polarizability of molecule.Therefore, each material with Raman active has its specific raman spectral characteristics, and the Raman spectrum according to material can recognize substance classes, the ultimate principle of Raman spectra qualitative analysis that Here it is.Σ jbe relative raman scattering cross section normalization factor, specify N in the world 2Σ jvalue is 1, obtains under this Laboratory Instruments condition through test of many times 12cO 2Σ jvalue is 1.49.The raman characteristic peak peak area of molecule is A/ Σ with the ratio of its corresponding relative raman scattering cross section normalization factor Σ, and this ratio is directly proportional to the relative molar concentration of molecule, that is: (A a/ Σ a)/(A b/ Σ b)=(C a/ C b) (F a/ F b), wherein A, C, F are respectively raman characteristic peak peak area, mole fraction, Raman quantizing factor.Table 1 lists 12cO 2/ N 2the Raman spectrum data of mixed gas under different conditions of mixture ratios.By 1287cm -1(ν - [12CO2]), 1390cm -1(ν + [12CO2]) and 2332cm -1(ν [N2]) the characteristic peak peak area at place is designated as A respectively - [12CO2], A + [12CO2]and A 1 [N2].
Table 1 12cO 2/ N 2the Raman spectrum data of mixed gas
In specific implementation process, obtain Raman quantizing factor F by fitting a straight line 12CO2time: 12cO 2raman spectrum to occur that Fermi vibrates bimodal, when with 12cO 2with N 2characteristic peak peak area ratio K 1as ordinate, with mol ratio C [13CO2]/ C [N2]when carrying out throwing figure (as shown in Figure 1) as horizontal ordinate, obtain the straight-line equation of zero crossing: y=1.16349x, and coefficient R 2be 0.99919.The slope of fitting a straight line and F 12CO2, its value is 1.16349.
In specific implementation process, carrying out 13cO 2/ N 2when mixed gas micro laser Raman spectroscopy detects, to different ratio 13cO 2/ N 2mixed gas carries out Laser Roman spectroscopic analysis of composition, can find: at CO on spectrogram 2raman spectrum in occur two strong characteristic spectral lines, this is CO 2fermi resonance doublet, frequency is respectively at 1267cm -1and 1372cm -1(i.e. ν - [13CO2]and ν + [13CO2]).Be 2332cm in frequency -1place has the intensity at a peak very strong, and this is N 2characteristic peak (i.e. ν [N2]).
In specific implementation process, right 13cO 2/ N 2when mixed gas carries out the analysis of laser micro-raman spectrometry characteristic peak: go out peak position, shape and the intensity of Raman bands of a spectrum only depend on this change in vibration processes Middle molecule polarizability of molecule.Therefore, each material with Raman active has its specific raman spectral characteristics, and the Raman spectrum according to material can recognize substance classes, the ultimate principle of Raman spectra qualitative analysis that Here it is.Σ jbe relative raman scattering cross section normalization factor, specify N in the world 2Σ jvalue is 1, obtains through computational analysis 13cO 2Σ jvalue is 1.437.The raman characteristic peak peak area of molecule is A/ Σ with the ratio of its corresponding relative raman scattering cross section normalization factor Σ, and this ratio is directly proportional to the relative molar concentration of molecule, that is: (A a/ Σ a)/(A b/ Σ b)=(C a/ C b) (F a/ F b), wherein A, C, F are respectively raman characteristic peak peak area, mole fraction, Raman quantizing factor.Table 2 lists 13cO 2/ N 2mixed gas mol ratio is respectively the Raman spectrum data of 0,0.166,0.8,1 and 1.5.By 1267cm -1(ν - [13CO2]), 1372cm -1(ν + [13CO2]) and 2332cm -1(ν [N2]) the characteristic peak peak area at place is designated as A respectively - [13CO2], A + [13CO2]and A 2 [N2].
Table 2 13cO 2/ N 2the Raman spectrum data of mixed gas
In specific implementation process, obtain Raman quantizing factor F by fitting a straight line 13CO2time, 13cO 2raman spectrum to occur that Fermi vibrates bimodal, when with 13cO 2fermi resonance doublet peak area sum and N 2peak area ratio K 2as ordinate, mol ratio C [13CO2]/ C [N2]when carrying out throwing figure (as shown in Figure 2) as horizontal ordinate, obtain the straight-line equation of zero crossing: y=1.61086x and coefficient R 2=0.99975.The straight-line equation slope of matching and F 13CO2, its value is 1.61086.
In specific implementation process, according to formula C [12CO2]/ C [13CO2]=(A 12CO2/ A 13CO2) × (F 13CO2/ F 12CO2) calculate in mixed gas 12cO 2with 13cO 2mol ratio C [12CO2]/ C [13CO2]time: specifically, known Raman quantizing factor F 13CO2and F 12CO2equal 1.61086 and 1.16349 respectively, their ratio F 13CO2/ F 12CO2being 1.3845, is a constant.Therefore, if can measure with micro-Raman spectroscopy 13cO 2with 12cO 2raman characteristic peak peak area value, then mol ratio C 12CO2/ C 13CO2can according to A 12CO2/ A 13CO2and F 13CO2/ F 12CO2product draw.
Utilize result of study of the present invention to CO below 2in gas, the composition of carbon isotope carries out quantitative test and is illustrated.
Embodiment 1
Prepare in laboratory 12cO 2/ 13cO 2mixed type CO 2artificial inclusion, known CO 2in artificial inclusion 12cO 2with 13cO 2mol ratio C [12CO2]/ C [13CO2]=1, then according to formula C [12CO2]/ C [13CO2]=(A 12CO2/ A 13CO2) × (F 13CO2/ F 12CO2), estimate in artificial inclusion 12cO 2with 13cO 2mol ratio, and compare relative error.Be 1 in mol ratio 12cO 2/ 13cO 2in the Raman spectrogram of artificial inclusion, significantly can see and peak position at 1267cm -1(ν - [13CO2]), 1372cm -1(ν + [13CO2]), 1287cm -1(ν - [12CO2]) and 1390cm -1(ν + [12CO2]) peak at place, they are 12cO 2with 13cO 2raman characteristic peak, the peak area of characteristic peak is A - [13CO2], A + [13CO2], A - [12CO2], A + [12CO2], peak area sum A - [12CO2]+ A + [12CO2]with A - [13CO2]+ A + [13CO2]be designated as A respectively 12CO2, A 13CO2.List in table 3 in artificial inclusion 12cO 2with 13cO 2fermi's doublet peak area value and the mol ratio that estimates with formula.Through calculating, the mol ratio of artificial inclusion is 1.03542, and their relative error is 3.54%.This just shows to work as F 13CO2and F 12CO2when being respectively 1.61086 and 1.16349, if adopt micro-Raman spectroscopy to measure 13cO 2with 12cO 2raman characteristic peak peak area value, just can according to A 12CO2/ A 13CO2and F 13CO2/ F 12CO2product estimate CO 2mol ratio C [12CO2]/ C [13CO2], therefore can set up quantitative test CO 2gaseous carbon isotope laser raman method of testing.
Table 3 embodiment 1 inclusion sample detection data
Embodiment 2
Prepare in laboratory 12cO 2/ 13cO 2mixed type CO 2artificial inclusion is known 12cO 2with 13cO 2mol ratio C [12CO2]/ C [13CO2]=2, then according to formula C [12CO2]/ C [13CO2]=(A 12CO2/ A 13CO2) × (F 13CO2/ F 12CO2), estimate in artificial inclusion 12cO 2with 13cO 2mol ratio, and compare relative error.Be 2 in mol ratio 12cO 2/ 13cO 2significantly can see in the Raman spectrogram of artificial inclusion and peak position at 1267cm -1(ν - [13CO2]), 1372cm -1(ν + [13CO2]), 1287cm -1(ν - [12CO2]) and 1390cm -1(ν + [12CO2]) peak at place, they are 12cO 2with 13cO 2raman characteristic peak, note characteristic peak peak area be A - [13CO2], A + [13CO2], A - [12CO2], A + [12CO2], peak area sum A - [12CO2]+ A + [12CO2]with A - [13CO2]+ A + [13CO2]be designated as A respectively 12CO2, A 13CO2.List in table 4 in artificial inclusion 12c and 13fermi's doublet peak area value of C and the mol ratio estimated with formula.Through calculating, the mol ratio of artificial inclusion is respectively 1.93855, and their relative error is-1.53%.This just shows to work as F 13CO2and F 12CO2when being respectively 1.61086 and 1.16349, if adopt micro-Raman spectroscopy to measure 13cO 2with 12cO 2raman characteristic peak peak area value, just can according to A 12CO2/ A 13CO2and F 13CO2/ F 12CO2product estimate CO 2mol ratio C [12CO2]/ C [13CO2], therefore can set up quantitative test CO 2gaseous carbon isotope laser raman method of testing.
Table 4 embodiment 2 inclusion sample detection data
In sum, the present invention is the different proportion to preparation 12cO 2/ N 2with 13cO 2/ N 2mixed gas sample carries out micro laser Raman spectroscopy and detects analysis, and the raman characteristic peak peak area ratio of gas and its mol ratio direct proportionality, the slope of fit equation is considered to Raman quantizing factor.CO 2gaseous carbon isotope mol ratio can be obtained according to the product of Raman peaks peak area ratio and Raman quantizing factor ratio.The present invention has high precision, original position, the feature such as harmless and quick due to the micro-Raman spectroscopy adopted, and therefore, utilizes micro-Raman spectroscopy can quantitative test Individual fluid inclusion CO 2the composition of carbon isotope, has good application prospect.
The above is only preferred embodiment of the present invention, not imposes any restrictions the present invention.Every above embodiment is done according to invention technical spirit any simple modification, change and equivalence change, all still belong in the protection domain of technical solution of the present invention.

Claims (5)

1. a quantitative test CO 2the laser raman detection method of gaseous carbon isotopics, it is characterized in that, the method comprises the following steps:
Step one, calculating 12cO 2raman quantizing factor F 12CO2, concrete grammar is:
Step 101, employing gas proportion mixing device are incited somebody to action 12cO 2and N 2to mix by different volumes ratio, obtain a series of different ratio 12cO 2/ N 2mixed gas;
Step 102, to adopt Laser-Raman microspectroscopy to proportioning various in step 101 12cO 2/ N 2mixed gas carries out micro laser Raman spectroscopy detection respectively, obtains N 2characteristic peak ν [N2]and 12cO 2the double characteristic peak ν of Fermi resonance - [12CO2]and ν + [12CO2], then calculate ν under various conditions of mixture ratios respectively - [12CO2]the peak area A at place - [12CO2], ν + [12CO2]the peak area A at place + [12CO2]and ν [N2]the peak area A at place 1 [N2]; Described ν - [12CO2], ν + [12CO2]and ν [N2]unit be cm -1;
Step 103, according to A described in step 102 - [12CO2]and A + [12CO2]under calculating various conditions of mixture ratios 12cO 2the peak area A of characteristic peak [12CO2], described A [12CO2]=A - [12CO2]+ A + [12CO2], then according to described A [12CO2]under calculating various conditions of mixture ratios 12cO 2with N 2characteristic peak peak area ratio K 1, described K 1=[A [12CO2]/ Σ 12CO2)/A 1 [N2]; Described Σ 12CO2for 12cO 2relative raman scattering cross section normalization factor;
Step 104, with K described in step 103 1as ordinate, with 12cO 2and N 2mol ratio C [12CO2]/ C [N2]to go forward side by side line linearity matching as horizontal ordinate throwing figure, calculate the slope of fitting a straight line, obtain F 12CO2;
Step 2, calculating 13cO 2raman quantizing factor F 13CO2, concrete grammar is:
Step 201, employing gas proportion mixing device are incited somebody to action 13cO 2and N 2to mix by different volumes ratio, obtain a series of different ratio 13cO 2/ N 2mixed gas;
Step 202, to adopt Laser-Raman microspectroscopy to proportioning various in step 201 13cO 2/ N 2mixed gas carries out micro laser Raman spectroscopy detection respectively, obtains N 2characteristic peak ν [N2]and 13cO 2the double characteristic peak ν of Fermi resonance - [13CO2]and ν + [13CO2], then calculate ν under various conditions of mixture ratios respectively - [13CO2]the peak area A at place - [13CO2], ν + [13CO2]the peak area A at place + [13CO2]and ν [N2]the peak area A at place 2 [N2]; Described ν - [12CO2]and ν + [12CO2]unit is cm -1;
Step 203, according to A described in step 202 - [13CO2]and A + [13CO2]under calculating various conditions of mixture ratios 13cO 2the peak area A of characteristic peak [13CO2], described A [13CO2]=A - [13CO2]+ A + [13CO2], then according to described A [13CO2]under calculating various conditions of mixture ratios 13cO 2with N 2characteristic peak peak area ratio K 2, described K 2=[A [13CO2]/ Σ 13CO2)/A 2 [N2]; Described Σ 13CO2for 13cO 2relative raman scattering cross section normalization factor;
Step 204, with K described in step 203 2as ordinate, with 13cO 2and N 2mol ratio C [13CO2]/ C [N2]to go forward side by side line linearity matching as horizontal ordinate throwing figure, calculate the slope of fitting a straight line, obtain F 13CO2;
Step 3, adopt Laser-Raman microspectroscopy to by 12cO 2with 13cO 2the CO mixed 2gas carries out micro laser Raman spectroscopy detection, obtains CO 2in gas 12cO 2the peak area A of characteristic peak 12CO2and 13cO 2the peak area A of characteristic peak 13CO2, then according to formula C [12CO2]/ C [13CO2]=(A 12CO2/ A 13CO2) × (F 13CO2/ F 12CO2) calculate CO 2in gas 12cO 2with 13cO 2mol ratio C [12CO2]/ C [13CO2].
2. quantitative test CO according to claim 1 2the laser raman detection method of gaseous carbon isotopics, is characterized in that, ν described in step 102 - [12CO2]=1287cm -1, described ν + [12CO2]=1390cm -1, described ν [N2]=2332cm -1.
3. quantitative test CO according to claim 1 2the laser raman detection method of gaseous carbon isotopics, is characterized in that, Σ described in step 103 12CO2=1.49.
4. quantitative test CO according to claim 1 2the laser raman detection method of gaseous carbon isotopics, is characterized in that, ν described in step 202 - [13CO2]=1267cm -1, described ν + [13CO2]=1372cm -1.
5. quantitative test CO according to claim 1 2the laser raman detection method of gaseous carbon isotopics, is characterized in that, Σ described in step 203 13CO2=1.437.
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