ANALYTES MONITORING BY DIFFERENTIAL SWEPT WAVELENGTH ABSORPTION SPECTROSCOPY METHODS

• US 20160084757A1
• Filed: 09/21/2015
• Published: 03/24/2016
• Est. Priority Date: 09/22/2014
• Status: Active Grant

• Current Assignee: NGP Incorporated
• Original Assignee: NGP Incorporated
• Inventors: Miron, Nicolae
• Granted Patent: US 9,784,674 B2
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: G01J 2003/423 Spectral arrangements using lasers, e.g. tunable
• CPC Class Codes: G01J 3/10 Arrangements of light sources specially adapted for spectrometry or colorimetry
• CPC Class Codes: G01J 3/42 Absorption spectrometry; Double beam spectrometry; Flicker spectrometry; Reflection spectrometry beam switching arrangements G01J3/08
• CPC Class Codes: G01N 2021/399 Diode laser
• CPC Class Codes: G01N 21/031 Multipass arrangements
• CPC Class Codes: G01N 21/05 Flow-through cuvettes G01N21/09 takes precedence; handling fluid samples G01N1/10
• CPC Class Codes: G01N 21/39 using tunable lasers

Abstract

The present invention relates to a method, apparatus and system for measuring the content of either one or more gas analytes that may be part of a gas. The present invention applies a spectroscopic method that utilizes an extremely narrow linewidth laser beam that is absorbed when its wavelength is swept across the interval containing the absorption line of the analyte. The method, apparatus and system of the present invention is applicable to any analyte in gas phase that is part of a gas mixture, or to any analyte in a plasma phase, as well as analytes in other environments.

Claims

1. An apparatus operable to measure the content of one or more gas analytes within a gas mixture, said apparatus comprising:

a. a measuring module, comprising;

i. a controller operable to activate a laser beam generator to generate a laser beam;

ii. a processor operable to determine the content of the one or more gas analytes within the gas mixture based upon information collected from one or more sensors;

b. a gas cell module connected to the measuring whereby information and commands are transferable between the measuring module and the gas cell module, said gas cell module comprising;

iii. closed gas cell containing the gas mixture and the one or more analytes, said closed gas cell having two transparent windows therein on opposite sides of the closed gas cell;

iv. two mirrors having reflective surfaces facing each other positioned on opposite sides of the closed gas cell and each being positioned proximate to one of the transparent windows;

v. the laser beam generator operable to generate or direct a laser beam, said laser beam generator being positioned in proximity to one of the two mirrors, when generated the laser beam being directed towards the mirror on the side of the closed gas cell opposite the laser beam generator, the laser beam being directed so is reflected one or more times between the two mirrors, and in each reflection it passes through all of following;

the window in the closed gas cell closest to the laser beam generator;

the gas mixture inside the closed gas cell; and

the other window in the closed gas cell, the laser beam generator further being operable to send laser beam input power information to the measuring module; and

vi. a laser beam output operable to receive the laser beam after it has been reflected and send laser beam output power information to the measuring module;

vii. the one more sensors being operable to sense and transfer information pertaining to the laser beam, the gas mixture, and the one or more analytes interaction with the laser beam;

wherein the measuring module utilizes the input laser power information and the output laser beam power information to determine the absorption of the one or more analytes.

2. The apparatus of claim 1, wherein the gas cell module further comprises:

a. the laser beam generator being an input collimator;

b. a low loss input optical port positioned as integrated in the mirror proximate to the input collimator;

c. the laser beam output being a low loss optical output port positioned as integrated in the mirror opposite the mirror wherein the low loss input optical port is integrated;

d. the laser beam being a collimated input optical beam that is directed through the low loss input optical port at an incidence angle that is in relation to a gas cell axis of the gas cell so that the one or more reflections of the input optical beam between the mirrors gradually direct the collimated input optical beam towards the low loss optical output port;

e. an output collimator operable to collect the optical beam passing through the low loss output optical port; and

f. the one or more sensors including the following;

a temperature transducer operable to emit a signal proportional to a temperature of at least one of one or more the analytes; and

a pressure transducer operable to emit a signal proportional to the pressure of at least one of one or more the analytes.

3. The apparatus of claim 1, wherein the gas cell module further comprises:

a. the laser beam generator being an input collimator;

b. a low loss input optical port and the laser beam output being a low loss optical output being positioned as integrated in the mirror proximate to the input collimator;

c. the laser beam being a collimated input optical beam that is directed through the low loss input optical port at an incidence angle that is in relation to a gas cell axis of the gas cell so that the one or more reflections of the input optical beam between the mirrors gradually direct the collimated input optical beam towards the low loss optical output port;

d. an output collimator operable to collect the optical beam passing through the low loss output optical port; and

e. the one or more sensors including the following;

a temperature transducer operable to emit a signal proportional to a temperature of at least one of one or more the analytes; and

a pressure transducer operable to emit a signal proportional to the pressure of at least one of one or more the analytes.

4. The apparatus of claim 1, wherein the measuring module further comprises:

a. the processor receiving information from the gas cell module being operable to determine a single absorption line of the analyte that is unique among all the absorption lines of the gases contained in the gas cell;

b. one or more tunable lasers operable in a spectral interval broader than the absorption linewidth of the analyte to deliver one or more tunable laser beams through a tunable laser single mode optical fiber;

c. one or more reference lasers operable to generate a single line delivery of one or more reference beams through a reference laser single mode optical fiber;

d. a beam combiner operable to merge into a single laser source optical fiber the one or more tunable laser beams and the one or more reference laser beams as a combined beam;

e. a beam splitter operable to receive the combined beam having a tap output through which a fraction of optical power of the combined beam is directed as a fraction beam and a main output through which the balance of the optical power of the combined beam is directed as an output beam, said output beam being directed to the laser beam generator;

f. a reference photodiode operable to receive the fraction beam;

g. a signal photodiode operable to receive the laser beam from the gas cell;

h. a reference logarithmic amplifier operable to convert to reference voltage a high dynamic range photocurrent generated by the reference photodiode;

i. a signal logarithmic amplifier operable to convert to signal voltage a high dynamic range photocurrent generated by the signal photodiode;

j. a DLOG differential amplifier connected at its non-inverting input to the reference logarithmic amplifier, and connected at is inverting input to the signal logarithmic amplifier, said DLOG differential amplifier being operable to generate a referenced absorption signal proportional to the difference between reference voltage at output from reference logarithmic amplifier and signal voltage at output of the signal logarithmic amplifier, and

k. the controller being operable to;

receive analog signals from the DLOG differential amplifier, and at least one of the one or more sensor, convert analog input voltages to digital output;

generate control signals for the one or more tunable lasers and for the one or more reference lasers;

communicate with a host processor; and

perform determinations;

l. a real time clock;

m. a non-volatile memory operable to store data that Is determinations and information generated by the apparatus.

5. The apparatus of claim 1, wherein the closed gas cell is formed of corrosion resistant material shaped in a tubular form and the windows are positioned at each end of the tubular form on an optical axis of the tubular form, said optical axis being collinear with a geometric axis of the tubular form, said tubular form incorporating a gas input port whereby the gas mixture enters the gas cell, and a gas output port operable as a gas exhaust for the gas mixture, and said closed gas cell being operable to prevent contact of the one or more analytes with optical elements of the apparatus, and said closed gas cell being positioned between the mirrors so as to be perpendicular to each mirror.

6. The apparatus of claim 1, wherein the mirrors are positioned to be parallel and each comprise a circular mirror substrate having a reflective flat surface coated with a low loss coating, and having an anti-reflective surface another surface coated with a low loss antireflective coating, the reflective surface of one mirror incorporating one or more transparent optical ports operable to direct input and output laser beams

7. The apparatus of claim 1, wherein a display is connected to the measuring module, whereby output information generated by the measuring module is communicated to a user.

8. The apparatus of claim 1, wherein the measuring module is formed of bulk optical components.

9. An apparatus for measuring the content of one or more gas analytes within a gas mixture, said apparatus comprising:

a. a measuring module, comprising;

i. a controller operable to activate a laser beam generator to generate a laser beam;

ii. a processor operable to determine the content of the one or more gas analytes within the gas mixture based upon Information collected from one or more sensors;

b. an open gas cell module comprising;

iii. an open gas cell wherein the gas mixture and the one or more analytes are present;

iv. a reflecting target positioned on one side of the open gas cell;

v. the laser beam generator operable to generate or direct a laser beam, said laser beam generator being positioned opposite to the reflecting target having the one or more analytes between the laser beam generator and the reflecting target, the laser beam being directed from the laser beam generator towards the reflecting target and being reflected from the reflecting target, said laser beam generator being operable to send laser beam input power information to the measuring module; and

vi. a telescope integrated with a transceiver, said telescope being operable to collect the laser beam reflected by the reflective target and to send laser beam output power information to the measuring module;

wherein the measuring module utilizes the input laser power information and the output laser beam power information to determine the absorption of the one or more analytes.

10. The apparatus of claim 9, wherein the open gas cell having at one end the transceiver that is an optical transceiver composed of an input collimator and an output collimator, the input and output collimators facing the reflective target that is a retro-reflector.

11. The apparatus of claim 9, wherein the open gas cell is defined as the space between the reflecting target and the transceiver and can contain any of the following:

the one or more analytes;

vapors of the one or more analytes;

or plasma or liquid containing the one or more analytes.

12. The apparatus of claim 9, wherein converting elements are incorporated in the open gas cell module operable to convert the plasma or the liquid to a gas mixture.

13. A method for measuring the content of one or more gas analytes within a gas mixture and monitoring the mass of the one or more analytes, said method comprising the steps of:

a. generating a laser beam from a laser beam generator and gathering the input power of the laser beam;

b. directing the laser beam through a gas cell having a gas mixture containing the one or more analytes therein, the laser beam further being directed to a reflective surface, said reflective surface being operable to reflect the laser beam through the gas cell at least one more time;

c. gathering the output power of the laser beam at the point when the laser beam passes from the gas cell for the last time;

d. transferring the output power and input power to a measuring module;

e. one more sensors generating sensor information related to the laser beam, the gas mixture, and the one or more analytes interaction with the laser beam, and the one or more sensors transferring such sensor information to the measuring module; and

f. the measuring module utilizing the input power, the output beam and any of the sensor information to determine the absorption of the one or more analytes.

14. The of claim 13, further comprising the steps of:

a. sweeping a tunable laser beam wavelength from a minimum wavelength to a maximum wavelength in a spectral region containing the absorption line of the analyte, and sensing the output power of the tunable laser beam upon completion of the sweeping;

b. obtaining a maximum analog voltage at the output of a DLOG differential amplifier dependent on the transmittance of at least one of the one or more analytes at a resonance wavelength;

c. converting of a peak voltage at the output of the DLOG differential amplifier to a digital value with high resolution representing a non-compensated resonant peak absorption by at least one of the one or more analytes;

d. storing the non-compensated resonant peak absorption into a temporary peak register, said non-compensated resonant peak absorption containing a background noise;

e. disabling the tunable laser and activating a reference laser, said reference laser lasing in a spectral range wherein at least one of the one or more analytes are located, and further lasing in a spectral range wherein other gases of the gas mixture contained in the gas cell have negligible absorption, said reference laser beam utilizing the same photodiodes, logarithmic amplifiers, the DLOG differential amplifier and other components as the tunable laser beam; and

f. converting output of the DLOG differential amplifier to high resolution numerical value representing the background noise, and storing said high resolution numerical value in a temporary background noise register;

15. The method of claim 13, wherein the gas cell is a closed gas cell or an open gas cell.

16. The method of claim 13, further comprising the steps of the measuring module:

a. determining a compensated absorption utilizing at least one of the one or more analytes by subtracting background noise stored in the temporary background noise register from a peak absorption stored in the temporary peak register; and

b. determining the mass of at least one of the one or more analytes contained in the gas cell utilizing a compensated absorption of the at least one of the one or more analytes, temperature and pressure of the at least one of the one or more analytes, volume of the gas cell, and constants of the one or more sensors as collected by the during a calibration process;

17. The method of claim 13, further comprising the steps of:

a. determining a peak absorption of at least one of the one or more analytes to a wavelength accuracy limited by a linewidth of the a laser beam that is generated by a tunable laser;

b. determining a wavelength and a peak absorption value of at least one of the one or more analytes independent of other gases in the gas cell and of total pressure of the gas mixture in the gas cell; and

c. determining statistical Information utilizing one or more true absorption values for increasing the sensitivity of the instrument;

18. The method of claim 13, further comprising the step of utilizing one absorption line of at least one of the one or more analytes that overlap partially with another absorption line of other gas components contained in the gas cell;

19. The method of claim 18, wherein any one or more of the following:

a. a laser source is utilized that matches a selected absorption line of at least one of the one or more analytes as the laser generator;

b. a laser generator is utilized that is one or more tunable lasers generators for generating multiple tunable laser in different narrow spectral ranges;

c. the laser beam is multiple laser beams including laser beams that are tunable in a narrow tuning range and laser beams that are tunable in a broad tuning range;

d. the multiple laser beams covering a broad tuning range; and

e. multiple reference laser are utilized for measuring background noise.

20. The method of claim 13, utilizing a measuring module comprising bulk optical elements, further comprising the steps of:

a. combining the laser beams that are tunable laser beams and a reference laser beam into a combined laser source beam, said tunable laser beams being generated by a tunable laser generator and said reference laser beam being generated by a reference laser generator;

b. transmitting a sample of the laser source beam to a reference photodiode and transmitting the laser source beam content other than the sample to an input collimator of the gas cell;

c. collimating the laser beam directed to the gas cell; and

d. collecting the laser beam emerging from the gas cell and sending it to a signal photodiode.