CN108318591A - Laser micro-area ablation product component and isotope parallel analysis device and method - Google Patents
Laser micro-area ablation product component and isotope parallel analysis device and method Download PDFInfo
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- CN108318591A CN108318591A CN201711456305.3A CN201711456305A CN108318591A CN 108318591 A CN108318591 A CN 108318591A CN 201711456305 A CN201711456305 A CN 201711456305A CN 108318591 A CN108318591 A CN 108318591A
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- 238000004458 analytical method Methods 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000002679 ablation Methods 0.000 title abstract 4
- 238000001514 detection method Methods 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 42
- 239000012159 carrier gas Substances 0.000 claims description 33
- 238000005070 sampling Methods 0.000 claims description 26
- 230000004907 flux Effects 0.000 claims description 10
- 230000003287 optical effect Effects 0.000 claims description 10
- 238000012360 testing method Methods 0.000 claims description 8
- 238000000608 laser ablation Methods 0.000 claims description 6
- 230000000593 degrading effect Effects 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 3
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- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
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Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
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- General Health & Medical Sciences (AREA)
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Abstract
The invention provides a laser micro-area ablation product component and isotope parallel analysis device and a method, wherein the device comprises a laser micro-area ablation system, a sample introduction system, a temperature control system and an analysis detection system; the product trapping device in the sample introduction system is used for condensing and enriching gaseous products discharged from the laser micro-area ablation system and releasing the gaseous products through heating treatment of the temperature control system under specified conditions; the gas path shunting device in the analysis detection system is used for shunting the compounds separated by the chromatograph according to a certain proportion and then respectively introducing the compounds into the mass spectrometer and the isotope analyzer; the sample introduction temperature of the sample is controlled by a temperature control system arranged outside the chromatograph. The scheme provided by the invention can realize the on-line parallel analysis of the components of the laser micro-area denudation product and the monomer hydrocarbon isotope, ensure the comprehensiveness and accuracy of experimental data and improve the experimental efficiency.
Description
Technical field
The invention belongs to petroleum geology exploration fields, and in particular to a kind of laser microcell degrades product component with isotope simultaneously
Row analytical equipment and method.
Background technology
Traditional pyrolysis experiment can help geochemistry worker to Type of hydrocarbon source rock and its hydrocarbon potentiality etc. into
Row exploratory development, but this kind of experiment still has several drawbacks, includes mainly：(1) system structure and performance of instrument itself
The reason of aspect, is only capable of being detected the sample that a part of thermodynamic properties are consistent, to affect high structural polarity sample
Gas-chromatography resolution ratio；(2) experimental implementation link is more, and experimental result disturbing factor is more；(3) place before sample need to crush etc.
Reason, cannot do the positioning analysis of miniature scale scope.Paul Greenwood etc. since the 1990s laser fine fisssure
The research of (Laser Micropyrolysis) is solved, laser microprobe wavelength can reach 193nm at present, and analysis sample is not only
Further include reservoir bitumen, coal petrography, polymer, oil shale, kerogen, the soil organism and microfossil including fluid inclusion.
Laser microcell degrades the defect of system enhancement conventional pyrolytic, has the characteristics that：(1) there is higher sensitivity, Ke Yi
Biomarker, including carbon skeleton composition and position of functional group are detected in complicated deposition organic matter；(2) online point is taken
Analysis can carry out in-situ study to sample, reduce the influence factor of complex experiment link under line；(3) laser facula can essence
Really to 2 μ ms, in-situ study can be carried out to Individual fluid inclusion.
But the conventional laser microcell system of degrading can only individually carry out component analysis to degrading product or individually carry out same
Position element analysis.Since laser bombardment experiment is destructive test, after carrying out laser bombardment to sample surfaces or inclusion enclave sample, nothing
Method carries out other analyses again, and therefore, component analysis and isotope analysis can only be tested respectively.But it this tests respectively
Mode exist due to for be not the same laser bombardment product after all, reliability is difficult to verify.
Invention content
To solve the above problems, the purpose of the present invention is to provide a kind of laser microcells to degrade product component and isotope simultaneously
Row analytical equipment.
Another object of the present invention is to provide a kind of product component and isotope are degraded using above-mentioned apparatus laser microcell
The method of parallel parsing.
In order to achieve the above objectives, product component is degraded the present invention provides a kind of laser microcell to fill with isotope parallel parsing
It sets, wherein the device includes that laser microcell degrades system, sampling system, temperature control system and analysis detecting system；
The laser microcell system of degrading includes laser emitter, microscopes optical path component, sample room, carrier gas line and production
Object draws pipeline；The first valve is provided in the carrier gas line；
The sampling system includes product capturing device and sample introduction control device；Wherein, the product capturing device enters
Mouth end is degraded the extraction pipeline of the product in system with laser microcell and is connected to, and outlet end is connected to analysis detecting system；The product is caught
The gaseous products that acquisition means are used to degrade laser microcell system discharge condense enrichment, and pass through temperature control under specified requirements
The heat treatment of system releases the gaseous products again；The sample introduction control device is provided with flowmeter and second for one
Valve and with the pipeline of extraneous unicom, be set to product capturing device and analyze on the pipeline that is connected to of detecting system；The sample introduction control
Device processed is used to detect the carrier gas flux into sampling system, and the folding by controlling the second valve will be drawn in sampling system
Gas discharge it is extraneous or introduce analysis detecting system；
The analysis detecting system includes chromatograph, mass spectrograph, stable isotope instrument and gas circuit part flow arrangement；Wherein, institute
It states the chromatographic column in chromatograph to be directly connected to the product capturing device in sampling system, chromatographic outlet end is provided with gas circuit
Part flow arrangement；The outlet end of the gas circuit part flow arrangement is connected to mass spectrograph and isotope instrument respectively, which uses
It is directed respectively into mass spectrograph and isotope instrument after the compound for detaching chromatograph shunts by a certain percentage；The sample introduction of the sample
Temperature is controlled by the temperature control system being set to outside chromatograph；The split ratio of the gas circuit part flow arrangement is (1.5:8.5)(2.5:
7.5), wherein small scale gas enters mass spectrograph.
The present invention provides scheme and may be implemented that laser microcell degrades the component of product and hydro carbon isotope divides parallel online
Analysis, ensure that the comprehensive and accurate property of experimental data, while improving conventional efficient.
Product component, which is degraded, in laser microcell provided by the invention passes through unique sample introduction with isotope parallel parsing device
System is successfully realized following two functions：(1) it is examined by sample introduction control device to entering analysis detecting system load volume
It surveys and effectively controls, to ensure subsequently to be carried out at the same time the carrier gas requirement of mass spectral analysis and isotope analysis.(2) it is caught by product
Acquisition means realize that laser microcell degrades the concentration capture of product and concentrates release.Moreover, in the analysis detecting system of the device
Gas circuit part flow arrangement passes through specific split ratio (1.5:8.5 to 2.5:7.5) Mass Spectrometer Method and isotope detection, can be made simultaneously
(laser ablation systematic sampling region is small, and it is few to degrade product, if being only simple same for requirement with good detection effect
When introduce isotope instrument and mass spectrograph, reliable detection data can not be obtained simultaneously, can not be detected sometimes or even at all
Go out).
In the art, due to the destructiveness and sample introduction feature of laser bombardment so that laser microcell degrades product analysis number
According to reliability demonstration it is more difficult.Especially for organic volumetric laser microcell of unripe standard sample and its method of calibration
Degrade the reliability demonstration of product analytical data.Further, due to matter in the parallel parsing system that is used in the present invention program
The testing conditions of spectrometer and isotope instrument are harsher so that conventional method of calibration is poor to the applicability of this programme.For this purpose,
Invention especially provides a kind of schemes that accurate calibration can be carried out to system.The program is that sample room is designed as double storehouses,
Specifically：Sample room includes mutually independent first sample cell and the second sample cell, and the first sample cell is used to place measuring samples,
Second sample cell is for injecting calibrating gas and/or placing standard sample.This double-chamber type can be designed so that device to sample
Product examine is detected and corrects to whole system before surveying, to ensure the accuracy of experiment.It has the characteristics that：(1) sample room
Being designed as double-chamber type can be to avoid the pipe leakage problem caused by one sample room of repeated disassembled and assembled；(2) it designs mutually independent
The first sample room for detecting sample and the second sample room for calibration can avoid standard sample and done to detection sample
It disturbs；There are a dual function in (3) second sample rooms, and one is that can inject calibrating gas, can be used for detecting isotope instrument and mass spectrometric
Stability and accuracy are sent into same position with detection sample with after laser ablation secondly for that can be put into standard sample with identical program
Plain instrument is detected with mass spectrograph, to demarcate testing result；Ensure that the accuracy of verification.Therefore, use provided by the invention
The sample room of double-chamber type design can not only solve on the basis of the precision of analysis result in can ensureing parallel system
The problem of to standard sample can not be injected after mass spectrograph and the transformation of isotope instrument injection port, and organic volumetric laser stripping can be solved
The problem of erosion detection can not carry out standard sample calibration.
In above-mentioned laser microcell degrades product component and isotope parallel parsing device, it is preferable that first sample
The carrier gas line is accessed in pond after being connected to the carrier gas inlet of the second sample cell；The production of first sample cell and the second sample cell
The product is accessed after object outlet draws pipeline.
In above-mentioned laser microcell degrades product component and isotope parallel parsing device, it is preferable that second sample
Pond is additionally provided with the standard gas sample feeding pipe for injecting calibrating gas.Valve can be set on standard gas sample feeding pipe or carried out by blocking
Sealing.
In above-mentioned laser microcell degrades product component and isotope parallel parsing device, it is preferable that the product trapping
Device is U-tube cold-trap, and the cooling material in cold-trap is liquid nitrogen.
In above-mentioned laser microcell degrades product component and isotope parallel parsing device, it is preferable that the isotope instrument
Including carbon isotope analyser and hydrogen isotope analysis instrument.
In above-mentioned laser microcell degrades product component and isotope parallel parsing device, it is preferable that the gas circuit shunting
The split ratio of device ranging from (1.7:8.3)-(2.3:7.7).
In above-mentioned laser microcell degrades product component and isotope parallel parsing device, it is preferable that the temperature control system
Be additionally operable to control the sample room, product capturing device temperature.
In above-mentioned laser microcell degrades product component and isotope parallel parsing device, it is preferable that the temperature control system
It is additionally operable to the temperature of control chromatograph and mass spectrograph unicom pipeline.
In above-mentioned laser microcell degrades product component and isotope parallel parsing device, it is preferable that the Laser emission
Device is femto-second laser.Often it is excimer laser with laser since the conventional laser microcell for organism analysis degrades system
Device, but fuel factor phenomena impair sample analysis precision, current titanium sapphire femto-second laser are more applicable than excimer laser
In the laser micro-zone analysis of organism.When application scheme uses femto-second laser thus, maximum laser energy density and most
Big laser peak intensity can respectively reach 8J/cm2With 1.6 × 1014W/cm2, compared with excimer laser, femto-second laser pulse
Duration is short, peak value of pulse intensity is high, and it is non-thermal to degrade, and collateral damage is small, can effectively avoid fuel factor and shock wave, keep away
The element fractionation effect caused by fuel factor is exempted from.In conjunction with the sample room of above-mentioned point of storehouse design, organism laser can be made to shell
Erosion detection obtains higher precision.
Product component is degraded with isotope parallel parsing device in above-mentioned laser microcell, and necessity can be set on each pipeline
Valve or plugging device.
It carrying out laser microcell the present invention also provides a kind of using above-mentioned apparatus and degrades product component and divide parallel with isotope
The method of analysis, this approach includes the following steps：
The first valve that laser microcell degrades carrier gas line in system is opened, carrier gas is passed through to sample room；And pass through temperature control
Respective lines or unit temp are adjusted to preset value by system；
The second valve on sample introduction control device in sampling system is opened, detection enters the carrier gas flux of sampling system, and
The carrier gas flux entered in sampling system is adjusted to preset value by adjusting the first valve；
Open microscopes optical path system, using pulse laser by microscopes optical path system to oriented sample surfaces into
Row bombards, and the second valve is closed after end of bombardment；At this point, the product that degrades that bombardment generates is captured after the condensation of product capturing device
In device；
The refrigerating part for removing product capturing device, then will degrade product by the heat treatment of temperature control system and release
Come；
The product that degrades released enters chromatograph and is detached, and is then detached chromatograph by gas circuit part flow arrangement
Compound is directed respectively into mass spectrograph after shunting by a certain percentage and isotope instrument is detected；Split ratio is (1.5:8.5)-
(2.5:7.5), wherein small scale gas enters mass spectrograph.
In above-mentioned laser microcell degrades method of the product component with isotope parallel parsing, it is preferable that this method is also wrapped
The step of being calibrated using the second sample room is included, is specifically included：
Carrier gas is injected to second sample room, obtains background data；
Calibrating gas is injected to second sample room, in conjunction with the background data to isotope instrument and mass spectrometric stabilization
Property and accuracy are detected；
It is put into standard sample to second sample room, with the parameter and flow of preset detection sample to be tested, to standard
Sample carries out isotope instrument and the mass spectrometric detection of laser ablation and product；It obtains for the corresponding detection to sample to be tested
As a result the data demarcated.
In above-mentioned the step of being calibrated using the second sample room, the calibrating gas used can be to be commonly used in laboratory
Standard gas.The standard sample used can be conventional or homemade.In one embodiment of the present invention, using certainly
The standard specimen of system evaporates into dry deuterated alkane standard sample on copper sheet.
In addition, this system part is more for the control of temperature, as sample room needs to be arranged in a suitable temperature, with true
The sample protected after laser bombardment smoothly volatilizees but is unlikely to be pyrolyzed；Sampling system and isotope instrument junction need high temperature with
Ensure that sample introduction is gasified totally.For this purpose, providing following preferred temperature parameter：
Preferably, the temperature preset value of sample room is 100-150 DEG C, preferably 120 DEG C.
Preferably, the temperature preset value that product draws pipeline is 230-260 DEG C, preferably 250 DEG C；It at this temperature, can be with
So that the laser microcell that sample room is drawn is degraded product and enters product capturing device as possible.
Preferably, in chromatograph, the preset value of the injector temperature of sample is 260-300 DEG C, preferably 280 DEG C.
Preferably, the temperature preset value for controlling chromatograph and mass spectrograph unicom pipeline is 260-300 DEG C, preferably 280 DEG C.
At this temperature, it is ensured that the sample after chromatograph separation is introduced into mass spectrograph in a gaseous form.
Preferably, in it will degrade the step of product releases by the heat treatment of temperature control system, heat treatment
Temperature is 230-260 DEG C, preferably 250 DEG C.
In above-mentioned laser microcell degrades method of the product component with isotope parallel parsing, it is preferable that carrier gas flux
Preset value is 180-220mL/min, preferably 200mL/min.
In above-mentioned laser microcell degrades method of the product component with isotope parallel parsing, it is preferable that swashed using pulse
The number that light bombards sample surfaces is 3-6 times.
Compared with prior art, the present invention tool has the advantage that：
(1) device in the present invention program can obtain and detect simultaneously the component and isotope ratio of same microcell sample online
Value Data；
(2) in the present invention program, laser may act on the sample of micro-meter scale, realize that the analysis of Individual fluid inclusion is surveyed
Examination；
(3) in the present invention program, using on-line analysis, the gaseous sample generated after laser bombardment sample surfaces is collected in line
And detect simultaneously, it ensure that the efficiently and accurately property of experiment.
(4) scheme provided by the invention that sample room is related to double-chamber type analyzes knot in it can ensure parallel system
On the basis of the precision of fruit；It can not only solve to standard sample can not be injected after mass spectrograph and the transformation of isotope instrument injection port
The problem of；And it can solve the problems, such as that the detection of organism laser ablation can not carry out standard sample calibration.
Description of the drawings
Fig. 1 is the structural schematic diagram that laser microcell degrades product component and isotope parallel parsing device in embodiment 1；
Fig. 2 is chromatography-Mass Spectrometer Method spectrogram that embodiment 1 obtains；
Fig. 3 is the isotope detection spectrogram that embodiment 1 obtains.
Specific implementation mode
In order to which technical characteristic, purpose and the advantageous effect to the present invention are more clearly understood, now to the skill of the present invention
Art scheme carry out it is described further below, but should not be understood as to the present invention can practical range restriction.
Embodiment 1
Product component and isotope parallel parsing device are degraded the present invention provides a kind of laser microcell and its utilize the dress
Set the method analyzed.
Laser microcell provided in this embodiment degrades product component, and (structural schematic diagram is shown in figure with isotope parallel parsing device
1), including laser microcell degrades system, sampling system, temperature control system and analysis detecting system；
The laser microcell system of degrading includes that laser emitter, microscopes optical path component, sample room, carrier gas line and product draw
Go out pipeline；The first valve is provided in carrier gas line (helium is 1.)；Wherein, sample room include mutually independent first sample cell and
Second sample cell, the first sample cell is for placing measuring samples, and the second sample cell is for injecting calibrating gas and/or placing standard
Sample；Carrier gas line is accessed after the connection of the carrier gas inlet of first sample cell and the second sample cell；First sample cell and the second sample
Access product draws pipeline after the product exit connection in pond；
Sampling system includes product capturing device and sample introduction control device；Wherein, the arrival end of product capturing device with swash
Light microcell, which degrades the product in system, draws pipeline connection, and outlet end is connected to analysis detecting system；The product capturing device is used
Enrichment, and the adding by temperature control system under specified requirements are condensed in the gaseous products that laser microcell is degraded to system discharge
Heat treatment releases the gaseous products again；Sample introduction control device be one be provided with flowmeter and the second valve and with the external world
The pipeline of unicom, is set to product capturing device and analyzes on the pipeline that detecting system is connected to；The sample introduction control device is for examining
The gas surveyed the carrier gas flux into sampling system, and will drawn in sampling system by controlling the folding of the second valve (helium is 2.)
Body discharge is extraneous or introduces analysis detecting system；
It includes chromatograph, mass spectrograph, stable isotope instrument and gas circuit part flow arrangement to analyze detecting system；Wherein, chromatograph
In chromatographic column be directly connected to the product capturing device in sampling system, chromatographic outlet end be provided with gas circuit shunting dress
It sets；The outlet end of gas circuit part flow arrangement is connected to mass spectrograph and isotope instrument respectively, which is used for chromatograph
The compound of separation is directed respectively into mass spectrograph and isotope instrument after shunting by a certain percentage；The injector temperature of sample is by being set to color
Temperature control system control outside spectrometer；
The split ratio of gas circuit part flow arrangement is 2:8, wherein small scale gas enters mass spectrograph；
Product capturing device is U-tube cold-trap, and the cooling material in cold-trap is liquid nitrogen；
Temperature control system is additionally operable to control the sample room, product draws the temperature of pipeline；Meanwhile controlling chromatograph and mass spectrum
Having heaters is set on instrument unicom pipeline (transmission line).
In the present embodiment, sample room is specially：It is designed using double storehouses, is 5cm × 5cm, a height of 3cm by two surfaces
Blocky stainless steel sample cell constitute jointly, each sample pool surface carry a diameter of 2cm glass visual window.Double sample cells
For longitudinal arrangement, respectively the first sample cell and the second sample cell, it is not connected among two sample cells.Wherein, the first sample cell
Both sides are all connected to the hollow pipeline for including coating, the second sample cell mark that outer tape splicing blocks on the basis of No. 1 sample cell respectively
Quasi- gas sample feeding pipe.
In the present embodiment, the running parameter setting of chromatograph, mass spectrograph and isotope instrument is as follows respectively：
(1) chromatograph analysis condition：Chromatography capillary column is PONA columns (50m × 0.2mm × 0.5 μm), and flow rate of carrier gas is
1.5mL/min, injector temperature are 280 DEG C, 30 DEG C of post case initial temperature, and 70 DEG C are raised to 1.5 DEG C/min after constant temperature 15min,
130 DEG C are raised to 2.5 DEG C/min again, be then raised to 280 DEG C with 3.5 DEG C/min and constant temperature is kept to go out until all chromatographic peaks
It is complete.
(2) spectrometer analysis condition：The sources EI ionizing energy 70eV, 100 μ A of heater current, 280 DEG C of ion source temperature.
(3) isotope instrument analysis condition：
1. carbon isotope analysis：980 DEG C of furnace temperature is aoxidized, 640 DEG C of furnace temperature, ion source vacuum degree 2.6 × 10 are restored- 6MBar, ion source voltage 3.07kV；
2. hydrogen isotope analysis：1450 DEG C of Pintsch process furnace temperature, ion source vacuum degree 2.6 × 10-6MBar, ion source electricity
Press 9.51kV, the H of isotope instrument3 +Factor values<1.0×10-5And it keeps stablizing.
It can be summarized as using the method that above-mentioned apparatus carries out analysis test：Laser emitter can emit continuous type and impulse type
The laser of both of which, High Power Laser Pulses enter microscopes optical path system, and the sample surfaces to selecting microcell bombard, and lead to
It crosses helium gas jet gas is degraded into product and blow to the U-tube of liquid nitrogen frozen, gaseous products are enriched with by rapid condensation, then short
U-tube is warming up to 250 DEG C of captured gaseous products of release in time, band gas circuit part flow arrangement is then sent by sampling system
Chromatograph gaseous products are divided into two-way, be carried out at the same time component and isotope detection through mass spectrograph and isotope instrument respectively.
Before being detected to sample to be tested, is calibrated, specifically included first with the second sample room：
Carrier gas is injected to the second sample room, obtains background data；
Inject calibrating gas to the second sample room, in conjunction with the background data to isotope instrument and mass spectrometric stability and
Accuracy is detected；
It is put into standard sample to the second sample room, with the parameter and flow of preset detection sample to be tested, to standard sample
Carry out isotope instrument and the mass spectrometric detection of laser ablation and product；It obtains for the corresponding testing result to sample to be tested
The data demarcated.
It is to the detailed process that sample to be tested is detected：
(1) laser is opened, energy is adjusted and makes its stabilization；
(2) sample to be tested is put into the first sample room, opens microscope light source, adjusted objective table, mesh is found by eyepiece
Mark sample position；
(3) temperature control system is opened, the first sample room is warming up to 120 DEG C, sampling system is heated to chromatograph junction
280 DEG C, heating gas circuit part flow arrangement is to 280 DEG C；
(4) chromatograph, isotope instrument and mass spectrograph program parameter are set；
(5) it opens helium 1., opens helium 2. flow controller, carrier gas flux is turned up to 200ml/min；
(6) U-tube is immersed in liquid nitrogen；
(7) microscopes optical path system is opened, using pulse laser by microscopes optical path system to oriented sample table
Face is bombarded, and same sample repeats bombardment 3-4 times；
(8) it closes helium 2., is captured the sample that degrades generated after bombardment into U-tube rapidly with high velocity carrier gas stream；
(9) liquid nitrogen is removed, U-tube temperature is heated rapidly by temperature control system to 250 DEG C, discharges the gaseous sample of capture,
And blowed to sampling system by high velocity carrier gas, with 2 after chromatography post separation:8 ratio will degrade sample and be respectively fed to mass spectrum
Instrument and isotope instrument are detected；
(10) while starting mass spectrograph and isotope instrument linkage program；
(11) processing analysis is carried out to the component of acquisition and isotopic data.Obtained same sample chromatography-mass spectroscopy and same
The test result of the plain instrument in position is shown in Fig. 2 and Fig. 3 respectively.
By the data of Fig. 2 and Fig. 3 it is found that the component and monomer that laser microcell degrades product may be implemented in application scheme
The online parallel parsing of hydrocarbon isotope.And the experimental data obtained is comprehensive, and accuracy is high.
Claims (12)
1. a kind of laser microcell degrades product component and isotope parallel parsing device, which is characterized in that the device includes laser
Microcell degrades system, sampling system, temperature control system and analysis detecting system；
The laser microcell system of degrading includes that laser emitter, microscopes optical path component, sample room, carrier gas line and product draw
Go out pipeline；The first valve is provided in the carrier gas line；
The sampling system includes product capturing device and sample introduction control device；Wherein, the arrival end of the product capturing device
The extraction pipeline of the product in system is degraded with laser microcell to be connected to, outlet end is connected to analysis detecting system；Product trapping dress
It sets and condenses enrichment for laser microcell to be degraded to the gaseous products of system discharge, and pass through temperature control system under specified requirements
Heat treatment the gaseous products are released again；The sample introduction control device is provided with flowmeter and the second valve for one
And with the pipeline of extraneous unicom, be set to product capturing device and analyze on the pipeline that is connected to of detecting system；Sample introduction control dress
The gas set for detecting the carrier gas flux for entering sampling system, and will drawn in sampling system by controlling the folding of the second valve
Body discharge is extraneous or introduces analysis detecting system；
The analysis detecting system includes chromatograph, mass spectrograph, stable isotope instrument and gas circuit part flow arrangement；Wherein, the color
Chromatographic column in spectrometer is directly connected to the product capturing device in sampling system, and chromatographic outlet end is provided with gas circuit shunting
Device；The outlet end of the gas circuit part flow arrangement is connected to mass spectrograph and isotope instrument respectively, which is used for will
The compound of chromatograph separation is directed respectively into mass spectrograph and isotope instrument after shunting by a certain percentage；The injector temperature of sample is by setting
The temperature control system control being placed in outside chromatograph；The split ratio ranging from (1.5 of the gas circuit part flow arrangement:8.5)-(2.5:7.5),
Wherein, small scale gas enters mass spectrograph.
2. laser microcell according to claim 1 degrades product component and isotope parallel parsing device, which is characterized in that
The sample room includes mutually independent first sample cell and the second sample cell, and first sample cell waits for sample for placing
Product, second sample cell is for injecting calibrating gas and/or placing standard sample.
3. laser microcell according to claim 2 degrades product component and isotope parallel parsing device, which is characterized in that
The carrier gas line is accessed after the connection of the carrier gas inlet of first sample cell and the second sample cell；First sample cell and
The product, which is accessed, after the product exit connection of two sample cells draws pipeline.
4. laser microcell according to claim 1 degrades product component and isotope parallel parsing device, which is characterized in that
The split ratio ranging from (1.7 of the gas circuit part flow arrangement:8.3)-(2.3:7.7).
5. laser microcell according to claim 1 degrades product component and isotope parallel parsing device, which is characterized in that
The temperature control system be additionally operable to control the sample room, product capturing device or chromatograph unicom pipeline temperature.
6. laser microcell according to claim 1 degrades product component and isotope parallel parsing device, which is characterized in that
The laser emitter is femto-second laser.
It carrying out laser microcell 7. a kind of using any one of claim 1-6 described devices and degrades product component and divide parallel with isotope
The method of analysis, which is characterized in that this approach includes the following steps：
The first valve that laser microcell degrades carrier gas line in system is opened, carrier gas is passed through to sample room；And pass through temperature-controlling system
Respective lines or unit temp are adjusted to preset value；
The second valve on sample introduction control device in sampling system is opened, detection enters the carrier gas flux of sampling system, and passes through
It adjusts the first valve and the carrier gas flux entered in sampling system is adjusted to preset value；
Microscopes optical path system is opened, oriented sample surfaces are banged by microscopes optical path system using pulse laser
It hits, the second valve is closed after end of bombardment；At this point, the product that degrades that bombardment generates is trapped in dress after the condensation of product capturing device
In setting；
The refrigerating part for removing product capturing device, then will degrade product by the heat treatment of temperature control system and release；
The product that degrades released enters chromatograph and is detached, the chemical combination for then being detached chromatograph by gas circuit part flow arrangement
Object is directed respectively into mass spectrograph after shunting by a certain percentage and isotope instrument is detected；Split ratio is (1.5:8.5)-(2.5:
7.5), wherein small scale gas enters mass spectrograph.
8. the method that laser microcell according to claim 7 degrades product component and isotope parallel parsing, feature exist
In this method further includes the step of calibration using the second sample room, being specifically included before being detected to sample to be tested：
Carrier gas is injected to second sample room, obtains background data；
Inject calibrating gas to second sample room, in conjunction with the background data to isotope instrument and mass spectrometric stability and
Accuracy is detected；
It is put into standard sample to second sample room, with the parameter and flow of preset detection sample to be tested, to standard sample
Carry out isotope instrument and the mass spectrometric detection of laser ablation and product；It obtains for the corresponding testing result to sample to be tested
The data demarcated.
9. the method that laser microcell according to claim 7 degrades product component and isotope parallel parsing, feature exist
In the temperature preset value of sample room is 100-150 DEG C, preferably 120 DEG C；The temperature preset value that product draws pipeline is 230-
260 DEG C, preferably 250 DEG C；The preset value of the injector temperature of sample is 260-300 DEG C, preferably 280 DEG C；Control chromatograph and
The temperature preset value of mass spectrograph unicom pipeline is 260-300 DEG C, preferably 280 DEG C.
10. the method that laser microcell according to claim 7 degrades product component and isotope parallel parsing, feature exist
In in it will degrade the step of product releases by the heat treatment of temperature control system, the temperature of heat treatment is 230-260
DEG C, preferably 250 DEG C.
11. the method that laser microcell according to claim 7 degrades product component and isotope parallel parsing, feature exist
In the preset value of carrier gas flux is 180-220mL/min, preferably 200mL/min.
12. the method that laser microcell according to claim 7 degrades product component and isotope parallel parsing, feature exist
In the number bombarded sample surfaces using pulse laser is 3-6 times.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109187137A (en) * | 2018-09-20 | 2019-01-11 | 中国石油天然气股份有限公司 | Device and method for preparing organic fluid standard sample for laser micro-area ablation system |
| CN109297800A (en) * | 2018-11-05 | 2019-02-01 | 中国工程物理研究院材料研究所 | A kind of laser ablation purging pond and its application method |
| CN110176386A (en) * | 2019-06-12 | 2019-08-27 | 大连理工大学 | Improve the mass spectrometric resolution device of flight time mass spectrum measurement laser ablation ionic species |
| CN110895268A (en) * | 2018-09-13 | 2020-03-20 | 株式会社岛津制作所 | Thermal conductivity detector and gas chromatograph provided with same |
| CN111272917A (en) * | 2020-03-30 | 2020-06-12 | 中国科学院地质与地球物理研究所 | Element isotope analysis system and method for analyzing sulfur isotope in trace sulfate sample and application thereof |
| CN112816598A (en) * | 2021-03-12 | 2021-05-18 | 浙江浙能技术研究院有限公司 | Nanosecond laser fast pyrolysis analysis device |
| CN116399661A (en) * | 2023-03-31 | 2023-07-07 | 中国地质科学院矿产资源研究所 | Femtosecond ultraviolet laser ablation-gas isotope mass spectrometry sulfide tetrasulfur isotope micro-region in-situ analysis system and method |
| CN116399660A (en) * | 2023-03-31 | 2023-07-07 | 中国地质科学院矿产资源研究所 | Femtosecond laser probe silicate silicon oxygen isotope micro-region in-situ analysis system and method |
| CN117110175A (en) * | 2023-09-02 | 2023-11-24 | 上海凯来仪器有限公司 | Femtosecond laser ablation mass spectrum flow type all-in-one machine and application method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101726556A (en) * | 2008-10-24 | 2010-06-09 | 中国石油化工股份有限公司 | Device and method for analyzing hydrocarbon component of monomer oil gas inclusion |
| CN202196016U (en) * | 2011-09-14 | 2012-04-18 | 河北工业大学 | Device for testing infrared emission performance of mineral materials |
-
2017
- 2017-12-28 CN CN201711456305.3A patent/CN108318591A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101726556A (en) * | 2008-10-24 | 2010-06-09 | 中国石油化工股份有限公司 | Device and method for analyzing hydrocarbon component of monomer oil gas inclusion |
| CN202196016U (en) * | 2011-09-14 | 2012-04-18 | 河北工业大学 | Device for testing infrared emission performance of mineral materials |
Non-Patent Citations (3)
| Title |
|---|
| HERBERT VOLK等: "First on-line analysis of petroleum from single inclusion using ultrafast laser ablation", 《ORGANIC GEOCHEMISTRY》 * |
| 苏奥等: "东海盆地丽水凹陷油气成因、来源及充注过程", 《石油勘探与开发》 * |
| 袁伟等: "《科技基础共享平台运行服务模式创新与实践》", 31 August 2015 * |
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| CN109187137A (en) * | 2018-09-20 | 2019-01-11 | 中国石油天然气股份有限公司 | Device and method for preparing organic fluid standard sample for laser micro-area ablation system |
| CN109297800A (en) * | 2018-11-05 | 2019-02-01 | 中国工程物理研究院材料研究所 | A kind of laser ablation purging pond and its application method |
| CN109297800B (en) * | 2018-11-05 | 2021-02-02 | 中国工程物理研究院材料研究所 | Laser ablation purging pool |
| CN110176386A (en) * | 2019-06-12 | 2019-08-27 | 大连理工大学 | Improve the mass spectrometric resolution device of flight time mass spectrum measurement laser ablation ionic species |
| CN111272917A (en) * | 2020-03-30 | 2020-06-12 | 中国科学院地质与地球物理研究所 | Element isotope analysis system and method for analyzing sulfur isotope in trace sulfate sample and application thereof |
| CN112816598A (en) * | 2021-03-12 | 2021-05-18 | 浙江浙能技术研究院有限公司 | Nanosecond laser fast pyrolysis analysis device |
| CN116399661A (en) * | 2023-03-31 | 2023-07-07 | 中国地质科学院矿产资源研究所 | Femtosecond ultraviolet laser ablation-gas isotope mass spectrometry sulfide tetrasulfur isotope micro-region in-situ analysis system and method |
| CN116399660A (en) * | 2023-03-31 | 2023-07-07 | 中国地质科学院矿产资源研究所 | Femtosecond laser probe silicate silicon oxygen isotope micro-region in-situ analysis system and method |
| CN116399660B (en) * | 2023-03-31 | 2023-09-19 | 中国地质科学院矿产资源研究所 | Femtosecond laser probe silicate silicon oxygen isotope micro-region in-situ analysis system and method |
| CN116399661B (en) * | 2023-03-31 | 2023-11-24 | 中国地质科学院矿产资源研究所 | Femtosecond ultraviolet laser ablation-gas isotope mass spectrometry sulfide tetrasulfur isotope micro-region in-situ analysis system and method |
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