Laser absorption spectroscopy isotopic gas analyzer

• US 10,330,592 B2
• Filed: 12/27/2017
• Issued: 06/25/2019
• Est. Priority Date: 07/21/2017
• Status: Active Grant

• Current Assignee: Serguei Koulikov
• Original Assignee: Serguei Koulikov
• Inventors: Koulikov, Serguei
• Primary Examiner(s): Amara, Mohamed K
• Application Number:
  US15/854,801
• Publication Number:
  US 20190025199A1
• Time in Patent Office: 545 Days
• Field of Search: 356432-440
• CPC Class Codes: G01J 3/42 Absorption spectrometry; Double beam spectrometry; Flicker spectrometry; Reflection spectrometry beam switching arrangements G01J3/08
• CPC Class Codes: G01N 2021/1704 in gases
• CPC Class Codes: G01N 2021/1748 Comparative step being essential in the method
• CPC Class Codes: G01N 2021/399 Diode laser
• CPC Class Codes: G01N 21/27 using photo-electric detection G01N21/31 takes precedence; circuits for computing concentration logarithmic circuits G06G7/24; photometric circuits in general G01J
• CPC Class Codes: G01N 21/31 Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry G01N21/72 takes precedence
• CPC Class Codes: G01N 21/3504 for analysing gases, e.g. multi-gas analysis
• CPC Class Codes: G01N 21/39 using tunable lasers
• CPC Class Codes: G01N 21/716 by measuring the radiation emitted by a test object treated by combustion gases for investigating the composition of gas mixtures
• CPC Class Codes: G01N 2201/0612 Laser diodes
• CPC Class Codes: G01N 33/15 Medicinal preparations ; Physical properties thereof, e.g. dissolubility

Abstract

The present invention provides systems and methods for measuring the isotope ratios of one or more trace gases based on optical absorption spectroscopy methods. The system includes an optical cavity containing a gas. The system also includes a laser optically coupled with the optical cavity, and a detector system for measuring absorption of laser light by the gas in the cavity.

Claims

1. A gas analyzer system for measuring an isotopic ratio of a gaseous chemical species by an optical absorption spectroscopy method, the system comprises:

an optical cavity containing a gas with the chemical species to be measured;

a laser optically coupled to an optical cavity;

a detector system for measuring absorption of laser light by the gas; and

an intelligence module comprising a processor adapted to determine a concentration ratio of two different isotopologues, wherein rotational-vibrational spectra of the chemical species are measured at least within two non-overlapping spectral intervals separated by a minimum of 50 nm between any two spectral points from each of the spectral intervals and selected in such a way that a first rotational-vibrational line of a first rotational-vibrational band of a less abundant isotopologue is located in a first spectral interval, and a second rotational-vibrational line of a second rotational-vibrational band of a more abundant isotopologue is located in a second spectral interval, and a line intensity of the strongest line of the first rotational-vibrational band of the less abundant isotopologue is two or more times stronger than a line intensity of the strongest line of the second rotational-vibrational band of the more abundant isotopologue, and a ratio of an absorption spectrum of the less abundant isotopologue to the sum of absorption spectra of all other isotopologues of the chemical species weighted by mole-fraction abundance figures exceeds two somewhere in the first spectral interval, and a ratio of an absorption spectrum of the more abundant isotopologue to the sum of absorption spectra of all other isotopologues of the chemical species weighted by mole-fraction abundance figures exceeds two somewhere in the second spectral interval.

2. The system of claim 1, wherein the pressure broadening coefficients of the first line and the second line are different by no more than 50%.

3. The system of claim 1, wherein the temperature dependence coefficients of the first line and the second line are different by no more than 50%.

4. The system of claim 1, wherein the optical absorption spectroscopy method comprising of at least one of the following methods:

the cavity ring down spectroscopy method, the cavity enhanced absorption spectroscopy method, the cavity phase shift spectroscopy method, the integrated cavity output spectroscopy method, or the cavity enhanced photo-acoustic spectroscopy method.

5. The system of claim 1, wherein the optical cavity is a resonant optical cavity.

6. The system of claim 1, wherein the detector system includes one of a photo-detector configured to measure an intensity of the intra-cavity light or both a photo-acoustic sensor configured to measure photo-acoustic waves generated in the cavity and a photo-detector configured to measure an intensity of the intra-cavity light.

7. The system of claim 1, wherein one of the measured isotopologues is ¹⁶O¹³C¹⁶O and another measured isotopologue is ¹⁶O¹²C¹⁶O.

8. The system of claim 1, further comprising a temperature sensor for measuring a temperature of the gas in the optical cavity;

and a pressure sensor for measuring a pressure of the gas in the optical cavity.

9. The system of claim 8, further comprising a temperature control element configured to control a temperature of the gas in the optical cavity and a pressure control element configured to control a pressure of the gas in the optical cavity.

10. A gas analyzer system for measuring an isotopic ratio of a gaseous chemical species by an optical absorption spectroscopy method, the system comprises:

an optical cell containing a gas with the chemical species to be measured;

a laser configured to emit light into an optical cell;

a detector system for measuring absorption of laser light by the gas; and

an intelligence module comprising a processor adapted to determine a concentration ratio of two different isotopologues, wherein rotational-vibrational spectra of the chemical species are measured at least within two non-overlapping spectral intervals separated by a minimum of 50 nm between any two spectral points from each of the spectral intervals and selected in such a way that a first rotational-vibrational line of a first rotational-vibrational band of a less abundant isotopologue is located in a first spectral interval, and a second rotational-vibrational lines of a second rotational-vibrational band of a more abundant isotopologue is located in a second spectral interval, and a line intensity of the strongest line of the first rotational-vibrational band of the less abundant isotopologue is two or more times stronger than a line intensity of the strongest line of the second rotational-vibrational band of the more abundant isotopologue, and a ratio of an absorption spectrum of the less abundant isotopologue to the sum of absorption spectra of all other isotopologues of the chemical species weighted by mole-fraction abundance figures exceeds two somewhere in the first spectral interval, and a ratio of an absorption spectrum of the more abundant isotopologue to the sum of absorption spectra of all other isotopologues of the chemical species weighted by mole-fraction abundance figures exceeds two somewhere in the second spectral interval.

11. A method of measuring an isotopic ratio of a gaseous chemical species, the method comprising:

coupling laser light to an optical cavity containing a gas with the chemical species to be measured;

measuring an absorption of the laser light by the gas;

determining the concentration ratio of two different isotopologues, wherein rotational-vibrational spectra of the chemical species are measured at least within two non-overlapping spectral intervals separated by a minimum of 50 nm between any two spectral points from each of the spectral intervals and selected in such way that a first rotational-vibrational line of a first rotational-vibrational band of a less abundant isotopologue is located in a first spectral interval, and a second rotational-vibrational line of a second rotational-vibrational band of a more abundant isotopologue is located in a second spectral interval, and a line intensity of the strongest line of the first rotational-vibrational band of the less abundant isotopologue is two or more times stronger than a line intensity of the strongest line of the second rotational-vibrational band of the more abundant isotopologue, and a ratio of an absorption spectrum of the less abundant isotopologue to the sum of absorption spectra of all other isotopologues of the chemical species weighted by mole-fraction abundance figures exceeds two somewhere in the first spectral interval, and a ratio of an absorption spectrum of the more abundant isotopologue to the sum of absorption spectra of all other isotopoloques of the chemical species weighted by mole-fraction abundance figures exceeds two somewhere in the second spectral interval.

12. The method of claim 11, wherein the pressure broadening coefficients of the first line and the second line are different by no more than 50%.

13. The method of claim 11, wherein the temperature dependence coefficients of the first line and the second line are different by no more than 50%.

14. The method of claim 11, wherein the optical absorption spectroscopy method comprising at least one of the following methods:

the cavity ring down spectroscopy method, the cavity enhanced absorption spectroscopy method, the cavity phase shift spectroscopy method, the integrated cavity output spectroscopy method, or the cavity enhanced photo-acoustic spectroscopy method.

15. The method of claim 11, wherein the optical cavity is a resonant optical cavity.

16. The method of claim 11, wherein one of the measured isotopologues is ¹³C¹⁶O₂ and another measured isotopologue is ¹²C¹⁶O₂.

17. The method of claim 11, further comprising:

measuring a temperature of the gas in the optical cavity by a temperature sensor and measuring a pressure of the gas in the optical cavity by a pressure sensor.

18. The method of claim 17, further comprising:

controlling a temperature of the gas in the optical cavity by a temperature control element and controlling a pressure of the gas in the optical cavity by a pressure control element.