CN110514621A - Ocean original position pCO2Sensor - Google Patents
Ocean original position pCO2Sensor Download PDFInfo
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- CN110514621A CN110514621A CN201910778590.3A CN201910778590A CN110514621A CN 110514621 A CN110514621 A CN 110514621A CN 201910778590 A CN201910778590 A CN 201910778590A CN 110514621 A CN110514621 A CN 110514621A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/39—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using tunable lasers
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/39—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using tunable lasers
- G01N2021/396—Type of laser source
- G01N2021/399—Diode laser
Abstract
The invention discloses ocean original position pCO2Sensor, gas-liquid separation part include immersible pump, filter, flowmeter, degasser, gas-drying apparatus；Water sample to be measured is drawn into pipeline by immersible pump, and degasser is entered after filtering, and the gas of abjection enters in gas sample chamber after gas-drying apparatus is dry to be detected, and sample rate is measured by flowmeter and recorded by data collecting card；Detection of gas part includes Laser emission and modulation module, optical alignment and detecting module, multiple reflections cavity mold block and data acquisition and processing module.
Description
Technical field
The invention belongs to seawater field of measuring technique, are related to a kind of ocean original position pCO2(carbon dioxide partial pressure) sensor.
Background technique
CO2It is dissolved gas particularly important in ocean, dissolves CO in seawater2Research of the measurement for global carbon
It is of great significance.Currently, molten in water deposit CO2Measurement method include Raman spectrum, electrochemical process, mass spectrography and infrared absorption
Spectrum etc., in these methods, Raman spectrum is uniquely can be to the CO dissolved in ocean2Carry out the technology of direct detection, In
Deep-sea hydrothermal, cold spring are all applied successfully, but are influenced by sensitivity, and some high concentration regions are only used for.Other are several
Although method detection principle is different, gas-liquid separation mostly uses the mode of permeable membrane, and most of is when gas reaches balance
It measures again, therefore the response time is longer.For example, PMEL MAPCO2Being currently the only one may be implemented long-term observation
CO2Sensor, carrying platform are buoy, can be to extra large surface and Atmospheric CO2It measures, response time 20min；Underwater CO2It is former
Position detection sensor is with widely used Contros Hydro CTM CO2With Pro-Oceanus CO2-ProTMFor, in water pump
Auxiliary under, the response time of the two is respectively 1min and 2.5min.The response time of these instruments as unit of minute, with
General underwater 1 section movement velocity of carrying platform calculates, and the response time move distance of 1min is about 30 meters, for seabed resources
For investigation, 30 meters of distance may will miss some great discoveries.Therefore, current commercialization CO2Underwater in-situ detection
The response time of sensor still needs to further shorten.The present invention is directed to ocean CO2The demand of concentration rapid survey, using TDLAS
(Tunable Diode Laser Absorption Spectroscopy, tunable semiconductor diode absorption spectral technique)
Method, and combine efficient gas-liquid separation device, have developed a kind of ocean original position pCO2Sensor deposits CO for ocean is molten2Company
Continuous, real-time, in-situ observation provides experiment support and data basis.
Summary of the invention
The purpose of the present invention is to provide ocean original position pCO2Sensor, the beneficial effects of the invention are as follows deposit CO for ocean is molten2
Continuous, real-time, in-situ observation experiment be provided support and data basis.
The technical scheme adopted by the invention is that including gas-liquid separation and detection of gas two parts, gas-liquid separation part includes
Immersible pump, filter, flowmeter, degasser, gas-drying apparatus；Water sample to be measured is drawn into pipeline by immersible pump, filtering
Enter degasser afterwards, the gas of abjection enters in gas sample chamber after gas-drying apparatus is dry to be detected, sample rate
It is measured by flowmeter and is recorded by data collecting card；
Detection of gas part includes Laser emission and modulation module, optical alignment and detecting module, multiple reflections cavity mold block
With data acquisition and processing module, Laser emission and modulation module include signal generating module and laser controller, and signal occurs
Module output low frequency sawtooth signal is adjusted by output wavelength of the laser controller to tunable diode laser,
Make the absorption peak of wavelength tuning range covering under test gas, laser enters repeatedly anti-after optical alignment and detecting module collimation
The multiple reflections chamber of cavity mold block is penetrated, is gas sample chamber outside multiple reflections chamber, there are two valves to distinguish on gas sample chamber
For controlling air inlet and outlet, and pressure and temperature sensor is housed, laser be emitted after multiple reflections and by data acquisition and
The photodetector of processing module receives, and the spectroscopic data detected and the pressure in gaseous sample room and temperature can pass through number
It is recorded according to acquisition and the data collecting card of processing module, and stores progress data processing in a computer and obtain gas concentration.
Further, the process of retrieving concentration algorithm: first to the TDLAS spectrum of under test gas (include two absorption peaks) into
Then the pretreatment of row spectrum noise reduction carries out peak-seeking processing to eliminate the influence of detector dark current, that is, extract two absorption peaks pair
The sampled point S answered1And S2, and the corresponding wave number v of two absorption peaks is inquired in Hitran database1、v2, establish sampling
It puts the corresponding relationship between wave number and abscissa is converted into wave number by sampled point, while part is not absorbed according to peak position extraction
It carries out fitting of a polynomial and obtains I0, calculating-In (It/I0) to eliminate the influence of Laser Energy Change, light intensity is obtained with wave number
It selects one of absorption peak to carry out Lorentz fit after variation and obtains integral area A=∫-In (It/I0) dv, then by pressure P,
The strong S of line (T), light path L, area A substitute into the concentration that formula C=A/ (SPL) calculates under test gas in discharge chamber, finally by
Ocean temperature, salinity, the parameters such as sample rate are corrected result, molten in calculating seawater to deposit CO2Concentration.
Further, molten in the water based on TDLAS to deposit CO2The foundation of in-situ measurement system:
In order to realize the molten rapid survey for depositing gas in water, use big flow immersible pump and large area degassing film to increase
Add the amount of gas evolved in the unit time, cooperation aspiration pump improves the gas exchange rate in gaseous sample room, and plenum interior devises
The multiple reflections chamber of one long light path small size is to obtain higher detectivity.Wherein, immersible pump can be with 25mL/s's
Big flow continuous work；The internal membrane wire material of degasser is polypropylene hollow fiber, membrane area 0.54m2；Aspiration pump
Flow >=1.1L/min；The multiple reflections chamber of plenum interior be by two spherical reflectors D=25.4mm, f=50mm, R >
The Herriott chamber of 97.5%@2004nm composition, its spacing 10cm, order of reflection are 76 times, and total optical path is about 15m, gas chamber
Volume only 110mL.
Detailed description of the invention
Fig. 1 is inventive sensor structural schematic diagram；
Fig. 2 is retrieving concentration algorithm flow chart of the present invention.
Specific embodiment
The present invention is described in detail With reference to embodiment.
Ocean original position pCO of the present invention2Sensor is divided into gas-liquid separation and detection of gas two parts, as shown in Figure 1.Gas-liquid point
It include immersible pump 1, filter 2, flowmeter 3, degasser 4, gas-drying apparatus 5 from part.Water sample to be measured passes through 1 quilt of immersible pump
It is pumped into pipeline, degasser 4 is entered after being filtered by filter 2, the gas of abjection enters after gas-drying apparatus 5 is dry
It is detected in gas sample chamber 6, sample rate is measured and recorded by flowmeter 3.
Detection of gas part includes Laser emission and modulation module 7, optical alignment and detecting module 8, multiple reflections cavity mold
Block 9 and data acquisition and processing module 10.Laser emission and modulation module include signal generating module and laser controller, signal
Module output low frequency sawtooth signal occurs, is adjusted by output wavelength of the laser controller to tunable diode laser
Section makes the absorption peak of wavelength tuning range covering under test gas.Laser enters more after optical alignment and detecting module 8 collimate
The multiple reflections chamber of secondary reflection cavity mold block 9, is gas sample chamber 6 outside multiple reflections chamber, and there are two valves on gas sample chamber 6
Door is respectively intended to control air inlet and outlet, and pressure and temperature sensor is housed.Laser is emitted after multiple reflections and by data
Acquisition and the photodetector of processing module 10 receive, the spectroscopic data detected and pressure and temperature in gas sample chamber 6
Degree can be recorded by the data collecting card of data acquisition and procession module, and stored progress data processing in a computer and obtained gas
Bulk concentration.
Retrieving concentration algorithm flow as shown in Fig. 2, first to the TDLAS spectrum of under test gas (include two absorption peaks) into
Then the pretreatment of row spectrum noise reduction carries out peak-seeking processing to eliminate the influence of detector dark current, that is, extract two absorption peaks pair
The sampled point S answered1And S2, and the corresponding wave number v of two absorption peaks is inquired in Hitran database1、v2, establish sampling
It puts the corresponding relationship between wave number and abscissa is converted into wave number by sampled point, while part is not absorbed according to peak position extraction
It carries out fitting of a polynomial and obtains I0, calculating-In (It/I0) to eliminate the influence of Laser Energy Change, light intensity is obtained with wave number
It selects one of absorption peak to carry out Lorentz fit after variation and obtains integral area A=∫-In (It/I0) dv, then by pressure P,
The strong S of line (T), light path L, area A substitute into the concentration that formula C=A/ (SPL) calculates under test gas in discharge chamber, finally by
Ocean temperature, salinity, the parameters such as sample rate are corrected result, molten in calculating seawater to deposit CO2Concentration.
PCO of the invention2The response time of sensor can reach more than ten seconds, molten in water deposit the fast of gas in order to realize
Speed measurement uses big flow immersible pump and large area degassing film to increase the amount of gas evolved in the unit time, and cooperation aspiration pump improves
Gas exchange rate in gaseous sample room, plenum interior devise the multiple reflections chamber of a long light path small size to obtain more
High detectivity.Wherein, immersible pump can be with the big flow continuous work of 25mL/s；The internal membrane wire material of degasser
For polypropylene hollow fiber, membrane area 0.54m2；Flow >=1.1L/min of aspiration pump；The multiple reflections chamber of plenum interior is
The Herriott chamber being made of the two spherical reflector@of D=25.4mm, f=50mm, R > 97.5% 2004nm, its spacing are
10cm, order of reflection are 76 times, and total optical path is about 15m, chamber volume only 110mL.
The above is only not to make limit in any form to the present invention to better embodiment of the invention
System, any simple modification that embodiment of above is made according to the technical essence of the invention, equivalent variations and modification,
Belong in the range of technical solution of the present invention.
Claims (3)
1. ocean original position pCO2Sensor, it is characterised in that: including gas-liquid separation and detection of gas two parts, gas-liquid separation part
Including immersible pump, filter, flowmeter, degasser, gas-drying apparatus；Water sample to be measured is drawn into pipeline by immersible pump,
Enter degasser after filtering, the gas of abjection enters in gas sample chamber after gas-drying apparatus is dry to be detected, sample introduction
Rate is measured by flowmeter and is recorded by data collecting card；
Detection of gas part includes Laser emission and modulation module, optical alignment and detecting module, multiple reflections cavity mold block sum number
According to acquisition and processing module, Laser emission and modulation module include signal generating module and laser controller, signal generating module
Output low frequency sawtooth signal is adjusted by output wavelength of the laser controller to tunable diode laser, makes wave
The absorption peak of long tuning range covering under test gas, laser enter multiple reflections chamber after optical alignment and detecting module collimation
The multiple reflections chamber of module is gas sample chamber outside multiple reflections chamber, is respectively intended on gas sample chamber there are two valve
Air inlet and outlet are controlled, and pressure and temperature sensor is housed, laser is emitted after multiple reflections and by data acquisition and procession
The photodetector of module receives, and the spectroscopic data detected and the pressure in gaseous sample room and temperature can be adopted by data
Collection and the data collecting card of processing module record, and store progress data processing in a computer and obtain gas concentration.
2. according to ocean original position pCO described in claim 12Sensor, it is characterised in that: the process of retrieving concentration algorithm: right first
The TDLAS spectrum (including two absorption peaks) of under test gas carries out the pretreatment of spectrum noise reduction, to eliminate the shadow of detector dark current
It rings, then carries out peak-seeking processing, that is, extract the corresponding sampled point S of two absorption peaks1And S2, and inquired in Hitran database
The corresponding wave number v of two absorption peaks1、v2, establish the corresponding relationship between sampled point and wave number and by abscissa by sampled point
Wave number is converted to, while part progress fitting of a polynomial is not absorbed according to peak position extraction and obtains I0, calculating-ln (lt/l0) to eliminate
The influence of Laser Energy Change obtains light intensity and obtains with selecting one of absorption peak to carry out Lorentz fit after the variation of wave number
Integral area A=∫-ln (lt/l0) dv, then pressure P, the strong S of line (T), light path L, area A are substituted into formula C=A/ (SPL)
The concentration of under test gas in discharge chamber is calculated, finally by ocean temperature, salinity, the parameters such as sample rate carry out school to result
Just, molten in calculating seawater to deposit CO2Concentration.
3. according to ocean original position pCO described in claim 12Sensor, it is characterised in that: molten in the water based on TDLAS to deposit CO2It is former
The foundation of level measuring system；
In order to realize the molten rapid survey for depositing gas in water, use big flow immersible pump and large area degassing film to increase list
Amount of gas evolved in the time of position, cooperation aspiration pump improve the gas exchange rate in gaseous sample room, and plenum interior devises one
The multiple reflections chamber of long light path small size is to obtain higher detectivity, wherein immersible pump can be with the big stream of 25mL/s
Measure continuous work；The internal membrane wire material of degasser is polypropylene hollow fiber, membrane area 0.54m2；The flow of aspiration pump
≥1.1L/min；The multiple reflections chamber of plenum interior is by two spherical reflector D=25.4mm, f=50mm, R > 97.5%@
The Herriott chamber of 2004nm composition, its spacing 10cm, order of reflection are 76 times, and total optical path is about 15m, and chamber volume is only
110mL。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910778590.3A CN110514621A (en) | 2019-08-22 | 2019-08-22 | Ocean original position pCO2Sensor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910778590.3A CN110514621A (en) | 2019-08-22 | 2019-08-22 | Ocean original position pCO2Sensor |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110954503A (en) * | 2019-12-18 | 2020-04-03 | 中国科学院合肥物质科学研究院 | In-situ online detection device for laser spectrum of seawater dissolved gas |
| CN112763467A (en) * | 2020-12-28 | 2021-05-07 | 中国科学院合肥物质科学研究院 | Underwater dissolved gas in-situ detection device and detection method thereof |
| CN113866123A (en) * | 2021-08-10 | 2021-12-31 | 中国海洋大学 | Detection device and detection method for carbon dioxide dissolved in degassing-free water |
| CN114414517A (en) * | 2021-12-17 | 2022-04-29 | 山东微感光电子有限公司 | Low-power intrinsic safety type laser carbon monoxide sensing control method and system |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110954503A (en) * | 2019-12-18 | 2020-04-03 | 中国科学院合肥物质科学研究院 | In-situ online detection device for laser spectrum of seawater dissolved gas |
| CN112763467A (en) * | 2020-12-28 | 2021-05-07 | 中国科学院合肥物质科学研究院 | Underwater dissolved gas in-situ detection device and detection method thereof |
| CN113866123A (en) * | 2021-08-10 | 2021-12-31 | 中国海洋大学 | Detection device and detection method for carbon dioxide dissolved in degassing-free water |
| CN113866123B (en) * | 2021-08-10 | 2023-11-24 | 中国海洋大学 | Degassing-free underwater dissolved carbon dioxide detection device and detection method |
| CN114414517A (en) * | 2021-12-17 | 2022-04-29 | 山东微感光电子有限公司 | Low-power intrinsic safety type laser carbon monoxide sensing control method and system |
| CN114414517B (en) * | 2021-12-17 | 2024-02-20 | 山东微感光电子有限公司 | Low-power-consumption intrinsic safety type laser carbon monoxide sensing control method and system |
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