CO
2carbon isotope infrared spectrum detection method and device
Technical field
the present invention relates to environmental monitoring technology and analysis and optical technical field, be specially a kind of CO
2carbon isotope infrared spectrum pick-up unit.
Background technology
CO
2one of most important greenhouse gases in atmosphere, because different isotopes exist different physics, chemistry, biological change procedure, therefore, Analysis for CO
2carbon isotope ratio is conducive to determine carbon source and remittance, for Global Carbon discharge budget provides Data support.In recent years, CO
2gaseous carbon isotopic ratio detection technique all is widely applied in a plurality of research fields.For example: in environmental science and ecosystem scientific domain, the conversion process of energy of occurring in nature can be supervened CO mostly
2, but different carbon isotopes reflects different courses of reaction, has disclosed the Different Effects of the natural cause such as soil, plant and all kinds of human activities; In volcanic explosion forecasting research, the earth's crust discharge gas can with earth's surface on by rock or other liquid reactions in path, therefore, δ
13cO
2the variation of value can be used as the judgement volcanicity and strengthens, the efficiency index of prediction of volcanic eruption; In area of medical diagnostics, gas isotope detects can also be as noninvasive medical diagnosis, CO
2isotopic ratio be considered to the mark (Nobel Prize in Physiology of Medicine in 2005) that helicobacter pylori exists, peptic ulcer is relevant to this bacterium with cancer of the stomach, therefore, can pass through characteristics of contaminated respiratory droplets CO
2gas δ
13cO
2the detection that value changes carrys out the diseases such as early diagnosis peptic ulcer and cancer of the stomach.
At present, CO
2the classic method that carbon isotope ratio detects is isotope mass spectrometry (IRMS) method.It is that the crooked route that causes according to the molecular mass difference is different and distinguish isotopic molecule that isotopic mass spectrometry is measured isotopic ultimate principle.The method but can't be differentiated the isomeride that molecular mass is identical, such as: molecular weight is all 45
13c
16o
2with
12c
16o
17o can't utilize isotopic mass spectrometry to be differentiated, and in addition, isotopic mass spectrometry detects needs the sampling pre-service, and instrument system is huge, complicated operation, can only carry out lab analysis, has certain limitation, especially is not suitable for real-time continuous coverage.
Infra-red sepectrometry is the spectral analysis technique that utilizes gas molecule infrared absorption spectrum characteristic to carry out the measurement of gas qualitative, quantitative, has measuring accuracy high, can realize in real time, the advantage such as online, unmanned, can realize CO
2carbon isotope ratio is tested on-the-spot on-line analysis and is measured, and utilizes the infra-red sepectrometry Analysis for CO
2carbon isotope ratio can effectively make up the defect of traditional detection technology.
Summary of the invention
The purpose of this invention is to provide a kind of CO
2carbon isotope infrared spectrum pick-up unit, to solve traditional detection CO
2carbon isotope ratio technology can't realize in real time, the online defect detected.
In order to achieve the above object, the technical solution adopted in the present invention is:
CO
2carbon isotope infrared spectrum pick-up unit, it is characterized in that: comprise reflection tank, reflection tank light inlet place is provided with infrared light supply, off-axis parabolic mirror, interferometer, reflection tank light-emitting window place is provided with the infrared eye be connected with computing machine, and the reflection tank air intake opening has access to input by T-valve and contains CO
2gas input gas circuit to be measured and the known δ of input of gas gas to be measured
13cO
2the standard C O of value
2the Standard Gases input gas circuit of gas, the infrared light supply radiation has the infrared light of continuous infrared waves, infrared light enters reflection tank by the light inlet of reflection tank successively after off-axis parabolic mirror collimation, interferometer modulation, and in reflection tank through repeatedly toward after interflection by the outgoing of reflection tank light-emitting window to infrared eye.
Described CO
2carbon isotope infrared spectrum pick-up unit, it is characterized in that: described gas input gas circuit to be measured comprises successively by the gas thief hatch to be measured of pipeline connection, dust filter unit, the Dewar tank of liquid nitrogen is housed, the Nafion pipe, the drying tube of HE-3 type drying agent is housed, gas meter, gas to be measured enters gas input gas circuit to be measured from gas thief hatch to be measured, filter dust through filtrator successively again, the Dewar tank carries out the one-level drying, the Nafion pipe carries out secondary drying, the drying tube that HE-3 type drying agent is housed carries out three-stage drying, after the gas meter metering, by T-valve, send in reflection tank.
Described Standard Gases input gas circuit comprises passes through Standard Gases air intake opening, the gas meter of pipeline connection successively, and Standard Gases is inputted gas circuit from Standard Gases air intake opening Engage of standard gas, then by T-valve, sends in reflection tank after the gas meter metering.
Described CO
2carbon isotope infrared spectrum pick-up unit, it is characterized in that: described T-valve has the valve port of a, b, tri-directions of c, T-valve a direction valve port is connected with the reflection tank air intake opening, T-valve b direction valve port access Standard Gases input gas circuit, T-valve c direction valve port accesses gas input gas circuit to be measured,, T-valve a direction valve port normal open; When the reflection tank air inlet is Standard Gases, the ventilation of T-valve a-b direction valve implication road, a-c direction valve implication road closure; When the reflection tank air inlet is gas to be measured, T-valve a-b direction valve implication mouth closure, the ventilation of a-c direction valve implication road.
Described CO
2carbon isotope infrared spectrum pick-up unit is characterized in that: described reflection tank gas outlet is communicated with the Nafion pipe by flowrate control valve, and the dry gas that reflection tank is discharged is sent into the Nafion pipe by flowrate control valve, as the purge gas of Nafion pipe.
Described CO
2carbon isotope infrared spectrum pick-up unit, it is characterized in that: described infrared light supply, infrared eye, interferometer form Fourier transform infrared spectrometer, its mid-infrared light source adopts Globar heating element, and infrared eye adopts indium antimonide detector, and interferometer is Michelson interferometer; Fourier infrared spectrograph and reflection tank are placed in seal box jointly, and described seal box has access to blow valve port, and seal box purges in real time high pure nitrogen with the 0.5l/min flow velocity in gathering spectroscopy procedure.
Described CO
2carbon isotope infrared spectrum pick-up unit is characterized in that: also comprise pressure monitor system, temperature monitoring system, temperature control system, wherein:
Pressure monitor system comprises that high-precision pressure sensing probe and the pressure be arranged in computing machine show logging software, the pressure sensing probe is placed in reflection tank, the data line of pressure sensing probe is received on computing machine with real time record reflection tank internal pressure data, and monitoring reflection tank internal pressure temporal evolution situation, reach ± 1mb of pressure precision;
Temperature monitoring system comprises high-precision temperature sensing probe and is arranged on the temperature demonstration logging software in computing machine, temperature sensing probe is placed in reflection tank, the data line of temperature sensing probe is received on computer with temperature data in the real time record reflection tank, and temperature temporal evolution situation in the monitoring reflection tank, temperature accuracy reaches ± and 0.01 ℃;
Temperature control system comprises heating plate, the temperature feedback control circuit, pt100 temp probe and temperature display watch head, heating plate is enclosed in the reflection tank inwall, the pt100 temp probe wraps in the heating plate inboard with Real-Time Monitoring reflection tank surface temperature, the heating plate pre-heating temperature is set to 28 ℃, the temperature feedback control circuit is controlled the heating plate break-make according to the temperature of pt100 monitoring, the equal cut-in temperature control enclosure of pt100 temp probe and heating plate, the temperature display watch head is arranged in control enclosure, the temperature display watch head shows the actual temperature that heating-up temperature and pt100 monitoring are set in real time.
The CO of described device
2the carbon isotope infrared spectrum detection method, it is characterized in that: at first reflection tank is pumped into to fixing low pressure, then input gas circuit by Standard Gases and be filled with high pure nitrogen to 1013mb in reflection tank, repeat above process 3 times, after high pure nitrogen in reflection tank remains on 1013mb constant pressure, 28 ℃ of steady temperatures, utilize infrared light supply to the reflection tank irradiating infrared light, and utilize infrared eye to gather high pure nitrogen spectrum spectrum as a setting, as the background of quantitative test;
When having gathered background spectrum, will be pumped into fixing low pressure in reflection tank, then by Standard Gases, input gas circuit and be filled with known δ
13cO
2the standard C O of value
2standard Gases, to 1013mb, repeats above process 3 times, treats reflection tank internal standard CO
2gas utilizes infrared light supply to the reflection tank irradiating infrared light after remaining on 1013mb constant pressure, 28 ℃ of steady temperatures, and utilizes infrared eye to gather standard C O
2gaseous spectrum, by background spectrum and standard C O
2the gaseous spectrum inverting obtains standard C O
2the δ of gas
13cO
2inverting value, by the δ of inverting
13cO
2inverting value and standard C O
2the δ of gas reality
13cO
2value compares and obtains calibration factor, as the foundation of following gas calibration to be measured;
Finally by gas input gas circuit to be measured, in reflection tank, be filled with gas CO to be measured
2to 1013mb constant pressure, 28 ℃ of steady temperatures, utilize infrared light supply to the reflection tank irradiating infrared light, and utilize infrared eye to gather gas infrared spectrum to be measured, obtained the δ of gas to be measured by background spectrum and gas infrared spectrum to be measured inverting
13cO
2inverting value, then in conjunction with calibration factor the δ to gas to be measured
13cO
2inverting value correction obtains the δ of gas to be measured
13cO
2measured value.
Described CO
2the carbon isotope infrared spectrum detection method is characterized in that: the infrared light through interferometer modulation forms interference signal, and infrared light is through reflection tank, by interference signal, carries out the Absorption Characteristics that spectrogram that Fourier transform obtains has characterized the reflection pool gas.
Described CO
2the carbon isotope infrared spectrum detection method is characterized in that: at CO
2will in carbon isotope ratio quantitative inversion
12cO
2with
13cO
2as two kinds independently component treat.
The present invention can realize in real time, online, unmanned measurement CO
2carbon isotope ratio, widened the application scope of infra-red sepectrometry.
The accompanying drawing explanation
Fig. 1 is structure principle chart of the present invention.
Embodiment
CO
2carbon isotope infrared spectrum pick-up unit, comprise reflection tank, reflection tank light inlet place is provided with infrared light supply, off-axis parabolic mirror, interferometer, and reflection tank light-emitting window place is provided with the infrared eye be connected with computing machine, and the reflection tank air intake opening has access to input by T-valve and contains CO
2gas input gas circuit to be measured and the known δ of input of gas gas to be measured
13cO
2the standard C O of value
2the Standard Gases input gas circuit of gas, the infrared light supply radiation has the infrared light of continuous infrared waves, infrared light enters reflection tank by the light inlet of reflection tank successively after off-axis parabolic mirror collimation, interferometer modulation, and in reflection tank through repeatedly toward after interflection by the outgoing of reflection tank light-emitting window to infrared eye.
Gas input gas circuit to be measured comprises drying tube, the gas meter of managing, be equipped with successively HE-3 type drying agent by gas thief hatch to be measured, the dust filter unit of pipeline connection, the Dewar tank that liquid nitrogen is housed, Nafion, gas to be measured enters gas to be measured input gas circuit from gas thief hatch to be measured, then filters dust, Dewar tank through filtrator successively and carry out that one-level drying, Nafion pipe are carried out secondary drying, drying tube that HE-3 type drying agent is housed carries out sending in reflection tank by T-valve after three-stage drying, gas meter metering.
Standard Gases input gas circuit comprises passes through Standard Gases air intake opening, the gas meter of pipeline connection successively, and Standard Gases is inputted gas circuit from Standard Gases air intake opening Engage of standard gas, then by T-valve, sends in reflection tank after the gas meter metering.
T-valve has the valve port of a, b, tri-directions of c, and T-valve a direction valve port is connected with the reflection tank air intake opening, T-valve b direction valve port access Standard Gases input gas circuit, and T-valve c direction valve port accesses gas input gas circuit to be measured,, T-valve a direction valve port normal open; When the reflection tank air inlet is Standard Gases, the ventilation of T-valve a-b direction valve implication road, a-c direction valve implication road closure; When the reflection tank air inlet is gas to be measured, T-valve a-b direction valve implication mouth closure, the ventilation of a-c direction valve implication road.
The reflection tank gas outlet is communicated with the Nafion pipe by flowrate control valve, and the dry gas that reflection tank is discharged is sent into the Nafion pipe by flowrate control valve, as the purge gas of Nafion pipe.
Infrared light supply, infrared eye, interferometer form Fourier transform infrared spectrometer, and its mid-infrared light source adopts Globar heating element, and infrared eye adopts indium antimonide detector, and interferometer is Michelson interferometer; Fourier infrared spectrograph and reflection tank are placed in seal box jointly, and described seal box has access to blow valve port, and seal box purges in real time high pure nitrogen with the 0.5l/min flow velocity in gathering spectroscopy procedure.
Also comprise pressure monitor system, temperature monitoring system, temperature control system, wherein:
Pressure monitor system comprises that high-precision pressure sensing probe and the pressure be arranged in computing machine show logging software, the pressure sensing probe is placed in reflection tank, the data line of pressure sensing probe is received on computing machine with real time record reflection tank internal pressure data, and monitoring reflection tank internal pressure temporal evolution situation, reach ± 1mb of pressure precision;
Temperature monitoring system comprises high-precision temperature sensing probe and is arranged on the temperature demonstration logging software in computing machine, temperature sensing probe is placed in reflection tank, the data line of temperature sensing probe is received on computer with temperature data in the real time record reflection tank, and temperature temporal evolution situation in the monitoring reflection tank, temperature accuracy reaches ± and 0.01 ℃;
Temperature control system comprises heating plate, the temperature feedback control circuit, pt100 temp probe and temperature display watch head, heating plate is enclosed in the reflection tank inwall, the pt100 temp probe wraps in the heating plate inboard with Real-Time Monitoring reflection tank surface temperature, the heating plate pre-heating temperature is set to 28 ℃, the temperature feedback control circuit is controlled the heating plate break-make according to the temperature of pt100 monitoring, the equal cut-in temperature control enclosure of pt100 temp probe and heating plate, the temperature display watch head is arranged in control enclosure, the temperature display watch head shows the actual temperature that heating-up temperature and pt100 monitoring are set in real time.
A kind of CO
2the carbon isotope infrared spectrum detection method, at first reflection tank is pumped into to fixing low pressure, then input gas circuit by Standard Gases and be filled with high pure nitrogen to 1013mb in reflection tank, repeat above process 3 times, after high pure nitrogen in reflection tank remains on 1013mb constant pressure, 28 ℃ of steady temperatures, utilize infrared light supply to the reflection tank irradiating infrared light, and utilize infrared eye to gather high pure nitrogen spectrum spectrum as a setting, as the background of quantitative test;
When having gathered background spectrum, will be pumped into fixing low pressure in reflection tank, then by Standard Gases, input gas circuit and be filled with known δ
13cO
2the standard C O of value
2standard Gases, to 1013mb, repeats above process 3 times, treats reflection tank internal standard CO
2gas utilizes infrared light supply to the reflection tank irradiating infrared light after remaining on 1013mb constant pressure, 28 ℃ of steady temperatures, and utilizes infrared eye to gather standard C O
2gaseous spectrum, by background spectrum and standard C O
2the gaseous spectrum inverting obtains standard C O
2the δ of gas
13cO
2inverting value, by the δ of inverting
13cO
2inverting value and standard C O
2the δ of gas reality
13cO
2value compares and obtains calibration factor, as the foundation of following gas calibration to be measured;
Finally by gas input gas circuit to be measured, in reflection tank, be filled with gas CO to be measured
2to 1013mb constant pressure, 28 ℃ of steady temperatures, utilize infrared light supply to the reflection tank irradiating infrared light, and utilize infrared eye to gather gas infrared spectrum to be measured, obtained the δ of gas to be measured by background spectrum and gas infrared spectrum to be measured inverting
13cO
2inverting value, then in conjunction with calibration factor the δ to gas to be measured
13cO
2inverting value correction obtains the δ of gas to be measured
13cO
2measured value.
Infrared light through interferometer modulation forms interference signal, and infrared light is through reflection tank, by interference signal, carries out the Absorption Characteristics that spectrogram that Fourier transform obtains has characterized the reflection pool gas.
At CO
2will in carbon isotope ratio quantitative inversion
12cO
2with
13cO
2as two kinds independently component treat.
As shown in Figure 1.Fourier transform infrared spectrometer 18, detector 15, light source 17 and multiple reflecting pool 11 all are placed in seal box 13, in the spectra collection process, seal box purges with the high pure nitrogen of 0.5l/min flow velocity in real time, guarantees not contain unnecessary steam and CO on light path of optical spectrometer in seal box
2gas.When the a-b of T-valve 8 direction is closed, during the ventilation of a-c direction, on-the-spot gas to be measured is under the work of aspiration pump, first pass through the filtration of filtrator 2, filter out airborne dust, then tracheae can be removed a part of steam in gas to be measured through the condensation of Dewar tank 3 interior liquid nitrogen, through the gas to be measured of one-level drying successively again through Nafion pipe 4 and be equipped with the HE-3 high efficiency drier self-indicating drying tube 5 two, three-stage drying, then enter Multi reflection sample cell 11 through gas meter 7 and T-valve 8.When the a-c of T-valve 8 direction is closed, during the ventilation of a-b direction, calibrating gas enters reflection tank through gas meter 7 and T-valve 8.CO
2calibration every day of carbon isotope infrared spectrum pick-up unit once, during calibration, at first reflection tank is pumped into to fixing low pressure (<1mb), then be filled with high pure nitrogen to 1013mb, repeat above process 3 times, after high pure nitrogen in reflection tank remains on 1013mb, 28 ℃ of steady temperatures, pressure, gather high pure nitrogen spectrum as a setting spectrum as the background of later quantitative test; When having gathered background spectrum, low pressure (<1mb) will be pumped in reflection tank, then be filled with calibration gas to 1013mb, repeat above process 3 times, after reflection tank internal standard gas remains on 1013mb, 28 ℃ of steady temperatures, pressure, gather calibrating gas spectrum, inverting calibrating gas carbon isotope ratio is as the foundation of following gas calibration.Gather in spectroscopy procedure, every spectrum adopts 64scans scanning, at CO
2will in carbon isotope ratio quantitative inversion
12cO
2with
13cO
2as two kinds independently component treat.