CN106053428A - F-P optical signal enhancement-based sensing device for measuring online gas content in petrochemical hydrogen-carrying pipe - Google Patents
F-P optical signal enhancement-based sensing device for measuring online gas content in petrochemical hydrogen-carrying pipe Download PDFInfo
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- CN106053428A CN106053428A CN201610353564.2A CN201610353564A CN106053428A CN 106053428 A CN106053428 A CN 106053428A CN 201610353564 A CN201610353564 A CN 201610353564A CN 106053428 A CN106053428 A CN 106053428A
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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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
Abstract
The invention provides an optical enhancing cavity and sensing device for measuring online gas content in a petrochemical hydrogen-carrying pipe. The sensing device comprises a sample cell provided with a gas inlet and a gas outlet; left and right ends of the sample cell are provided with a first reflector and a second reflector respectively, wherein both the first reflector and the second reflector comprise a spherical face, the middle of which is a circular plane; the first reflector is provided with a laser inlet for incoming of laser; the side of the sample cell is provided with a window glass plate connected with a Raman signal collecting unit for transmitting light. The optical enhancing cavity is composed of special reflectors, a double F-P cavity structure of the spherical face and circular plane is formed, laser power is greatly enhanced, which is unreachable for other devices, Raman signal light is enhanced by multiple orders of magnitude so that sensitivity and precision are very high, all-optical measurement is achieved on the petrochemical pipe, intrinsic safety is achieved, and online real-time measurement is also achieved.
Description
Technical field
The present invention relates to petrifaction gas body burden fields of measurement, be specifically related to a kind of petrochemical industry strengthened based on F-P optical signalling
Carry the sensing device of hydrogen pipeline gas content on-line measurement.
Background technology
Carry hydrogen technique to be widely used in petrochemical industry, under the conditions of suitable temperature, density of hydrogen and air pressure etc., generate one
The chemical products such as hydro carbons or the alcohols of determining molecular weight.Ethylene hydrogen is used for the device such as hydrocracking unit and wax oil hydrogenation
In, if ethylene hydrogen purity reduces, the system hydrogen partial pressure of above-mentioned hydrogenation plant will be reduced, be unfavorable for hydrogenation reaction, can shadow
Ring product quality.In order to keep enough hydrogen partial pressure, hydrogenation plant also needs to discharge the gas of low density of hydrogen, adds hydrogen
The consumption of gas.The ethylene hydrogen that many enterprises are used is outsourcing, and the ethylene hydrogen containing impurity component can increase cost of material.
If ethylene hydrogen purity reduces (methane, CO, CO2Impurity content rises), it is following unfavorable to will result in:
(1) impurity content rises, then hydrogen content relative drop can cause gas cost to increase.
(2) hydrogen that ethylene hydrogen and refinery hydrogen preparing device produce is mostly used in hydrocracking unit and wax oil hydrogenation dress
Putting, remaining hydrogen is for the old hydrogenation plant in refinery.If ethylene hydrogen purity reduces, by reduce above-mentioned hydrogenation plant it is
System hydrogen partial pressure, unfavorable to hydrogenation reaction, affect product quality.
(3) CO and CO2Under hydrogen atmosphere, it may occur that methanation reaction, release big calorimetric at beds, cause bed
Layer overtemperature, affects product quality.
Therefore, petrochemical industry is in the urgent need to the ethylene hydrogen purity monitoring technology of a safety.
At present, the method measuring gas purity mainly has three kinds: electrochemistry type, electricity type and optical type；But due to hydrogen
Etc. belonging to flammable explosive gas, use electrical sensor danger very big, if the most now for the sensor main light of petrochemical industry
Learn sensor.Gas chromatographic analysis is the other optical detection method of a kind of separation determination multicomponent mixture, based on not jljl
Matter relative motion biphase in there is different partition coefficients, when these materials with flowing phase shift time, the most between the two phases
Carry out repeated multiple times distribution, make original partition coefficient only have each Component seperation of fine difference, be sequentially sent to detector and measure, enter
And reach to separate the purpose analyzing each gas component.Various gases after separation successively flow into different special the most respectively again along with carrier gas
The gas detector levied carries out data acquisition and comprehensive analysis.The method need specific gas or liquid as flowing carrier,
Carry the sample into chromatographic column to be analyzed, add the complexity of system, improve operating cost, intermittent analysis can only be used
Mode.
Infrared detection technique is another gas-monitoring means that application is wide, and infrared absorption spectroscopy is to utilize material
Absorption intensity to a certain wavelength, reflects the concentration of material, methane gas based on infrared absorption spectroscopy method detection skill
Art is full-fledged, but this technology exists bigger difficulty to the detection of mixed gas.
Compared with above-mentioned optical detector technology, Raman spectroscopy can realize in real time, carry out material composition exactly
Detection.Raman scattering spectrum system and device is simple, and sample do not requires pretreatment, and lossless, to analyze speed fast, can meet existing
The detection of field real-time on-site.During detection of gas is analyzed, utilize Raman spectroscopy that the laser of single-frequency can be used to swash simultaneously
Send the raman scattering spectrum of multiple gases composition, in the Raman detection system of gas, owing to gas molecule is to exciting light
Wavelength does not has selectivity, Raman spectroscopy to can be applicable to the detection of many gas components, and infrared spectrum the most just cannot
Realize.It can analyze 8 kinds of components, the most common H simultaneously2、CO、CO2、O2、N2、CH4、CxHy、H2O.Detection range is several from ten
PPM to 100%, response time is extremely short.Therefore, Raman spectrum is purity and the on-line monitoring of impurity content of a kind of ethylene hydrogen
Powerful measure.
The principle of Raman technology detection is to utilize the laser of a certain frequency to be irradiated to body surface gas molecule can be made to occur
Raman scattering, every kind of gas molecule can produce specific Raman shift.So, it is irradiated in mixed gas when a certain frequency laser
Time, every kind of gas molecule will produce specific Raman shift spectral line, and Raman spectrum spectral line is analyzed just can knowing by we
The composition of road mixed gas, simultaneously as optic spectrum line intensity and gas concentration are directly proportional, therefore has only to analyze to be detected
Spectral line corresponding to gas molecule, just can obtain the levels of gas to be measured.And survey gas content with Raman technology at present
Subject matter is the long-pending several orders of magnitude fewer than its absorption cross-section of raman scattering cross section of gas molecule, comparatively speaking, gas
The absorption spectrum of molecule is easier to obtain, and the detection of Raman spectrum is much more difficult.In view of Raman light intensity with excite
Laser power is directly proportional, and therefore putting forward highly excited laser power is the effective means solving this problem, for gas,
The method of surface enhanced and resonant check is the most inapplicable, the most all uses the method that chamber strengthens.
CN1584555A discloses a kind of Quick detector for petroleum product quality based on low resolution Raman spectrum, this dress
Putting mainly for detection of petroleum oil product quality, its feature is low cost, and volume is little, it is simple to carry, but its resolution is the highest, does not has
There is design Raman scattering to strengthen system, be not suitable for petrochemical industry gas detecting.
CN1645106A discloses a kind of Detection Ssytem of Dissolved Gases in Power Transformer Oil Base analytical equipment based on Raman technology, this dress
Put and use nearly concentric cavity optical system as Raman scattering intensifier, improve sensitivity relative to other devices, but should
Laser instrument, sample cell and optical system are fixed on an installing plate by device, inevitably use power supply, are unfavorable for peace
It is contained in the inflammable and explosive gas pipelines such as petrochemical industry ethylene hydrogen on-the-spot, and the potentiation of this optical system is limited.
At present, the measurement system of Raman on-line monitoring of the flammable explosive gas such as petrochemical industry ethylene hydrogen it is applied in state
The most rare, the problem of gas molecule Raman spectrum detection difficult to be overcome, also to ensure to be arranged on scene is
Bulk cargo is put and is not used electricity etc. and may cause the equipment of potential safety hazard, it is also contemplated that the sealing problem of sample cell simultaneously.
Summary of the invention
The technical problem to be solved in the present invention is: provide a kind of petrochemical industry strengthened based on F-P optical signalling to carry hydrogen pipeline gas
The sensing device of body burden on-line measurement, it is achieved that the enhancing of the several order of magnitude of Raman signal light, thus have the highest sensitive
Degree and degree of accuracy, achieve Full-optical simultaneously in pipelines and petrochemical pipelines and measure operation, essential safety, and it is real-time to can be implemented in line
Measure.
The present invention solves that the technical scheme that above-mentioned technical problem is taked is: a kind of petrochemical industry load hydrogen pipeline gas that is used for contains
Amount on-line measurement optical enhancement cavity, it is characterised in that: it include sample cell, sample cell be provided with for be connected with gas to be measured
Industrial pipeline connect air inlet and gas outlet；
The left and right of sample cell is respectively arranged at two ends with the first reflecting mirror and the second reflecting mirror；Wherein the first reflecting mirror and second anti-
Penetrating the sphere that mirror all includes that focal length is f, the middle part of sphere is the disk of a diameter of l so that two spheres constitute a F-P and shake
Swinging chamber, two disks constitute the 2nd F-P vibration chamber；First reflecting mirror is provided with the laser entrance for incident laser；
Sample cell be laterally provided with the window slide being connected printing opacity with Raman signal collector unit.
By such scheme, the spacing d=4f-Δ d between the first described reflecting mirror and the second reflecting mirror, the scope of Δ d
For 0.2mm-0.4mm.
By such scheme, the diameter l of described disk is in the range of 3mm-4mm.
By such scheme, the first described reflecting mirror and the second reflecting mirror are coated with reflectance Gao Fanjie more than 99.5%
Plasma membrane.
By such scheme, between described air inlet and gas outlet and industrial pipeline, it is provided with ring flange and sealing ring.
A kind of petrochemical industry strengthened based on F-P optical signalling carries the sensing device of hydrogen pipeline gas content on-line measurement, and it is special
Levy and be: it includes optical enhancement cavity, also include that the demodulation of laser instrument, laser light incident unit, Raman signal collector unit, signal is single
Unit and signal processing unit；Wherein,
The laser that described laser instrument sends enters sample through laser light incident unit laser entrance from the first reflecting mirror
Pond；
Described Raman signal collector unit includes the broadband mirrors being arranged on sample cell side, and is arranged on sample cell
The Raman probe of opposite side；Raman light is received by Raman probe through window slide, and transmission to signal demodulation unit is demodulated into electricity
Signal, is transmitted further to signal processing unit.
By said apparatus, described laser light incident unit includes optoisolator, the standard set gradually along laser propagation direction
Straight battery of lens and reflectance plane high reflective mirror more than 99.5%, also include the angle adjustment for adjusting plane high reflective mirror angle
Frame.
By said apparatus, described Raman probe includes that the first focusing set gradually along the direction of propagation of Raman light is saturating
Mirror, optical filter, notch filtering light sheet and the second condenser lens.
By said apparatus, described broadband mirrors is coated with the high reflectance broadband medium film that reflectance is more than 95%.
The invention have the benefit that
1, optical enhancement cavity uses special reflecting mirror composition, constitutes the double F-P chambers structure of sphere and disk, significantly
Enhancing excitation light power, this is that other devices are not reached, it is achieved that the enhancing of the several order of magnitude of Raman signal light, thus
There is the highest sensitivity and degree of accuracy, in pipelines and petrochemical pipelines, achieve Full-optical simultaneously measure operation, essential safety, and can
To realize On-line sampling system.
2, laser light incident unit can realize the adjustment to laser incident angle and beam quality.
3, Raman collection unit uses bigbore spherical reflector, plates high inverse medium film, it is ensured that Raman signal light
Collect on a large scale, use the nearly heart to design simultaneously, improve collection angle, it is achieved that Raman signal light is collected to greatest extent.
4, air inlet and gas outlet use flange and seal washer to be attached with industrial pipeline, it is ensured that measure gas and
The real concordance of industrial gases, it is achieved that on-line monitoring truly.Whole device uses laser remote input and draws
The long-range way of output of graceful signal can avoid electrical part to wait gas pipeline near inflammable and explosive, detects safe and reliable, can be used for easily
Fire the explosive on-line monitoring waiting gas.
Accompanying drawing explanation
Fig. 1 is the apparatus structure schematic diagram of one embodiment of the invention.
Fig. 2 is laser light incident cellular construction schematic diagram.
Fig. 3 is the partial structurtes schematic diagram of one embodiment of the invention.
In figure: 1, laser light incident unit, 2, sample cell, 2-1, air inlet, 2-2, gas outlet, 3, Raman signal collect single
Unit, 4, laser instrument, 5, signal demodulation module, 6, signal processing unit, 7, optoisolator, 8, collimation lens set, 9, plane high anti-
Mirror, 10, angular adjustment frame, the 11, first reflecting mirror, 11-1, laser entrance, the 12, second reflecting mirror, 13, broadband mirrors, 14,
First condenser lens, 15, optical filter, 16, notch filtering light sheet, the 17, second condenser lens.
Detailed description of the invention
Below in conjunction with instantiation and accompanying drawing, the present invention will be further described.
The present invention provides a kind of and carries hydrogen tube hydrogen and the optical enhancement cavity of impurity content on-line measurement for petrochemical industry, such as figure
Shown in 1 and Fig. 3, it includes that sample cell 2, sample cell 2 are provided with the air inlet for being connected with the industrial pipeline being connected with gas to be measured
Mouth 2-1 and gas outlet 2-2；The left and right of sample cell 2 is respectively arranged at two ends with the first reflecting mirror 11 and the second reflecting mirror 12；Wherein first
Reflecting mirror 11 and the second reflecting mirror 12 all include the sphere that focal length is f, and the middle part of sphere is the disk of a length of l so that two
Individual sphere constitutes a F-P vibration chamber, and two disks constitute the 2nd F-P vibration chambeies；First reflecting mirror is provided with for incidence
The laser entrance 11-1 of laser；Sample cell 2 be laterally provided with the window slide being connected printing opacity with Raman signal collector unit 3.
In the present embodiment, the described spacing d=4f-Δ d between the first reflecting mirror 11 and the second reflecting mirror 12, Δ d's
Scope is 0.25mm.The diameter l of described disk is in the range of about 3.5mm.First reflecting mirror 11 and the second reflecting mirror 12
It is coated with the high inverse medium film of reflectance more than 99.5%.
Preferably, it is provided with ring flange and sealing ring between described air inlet 2-1 and gas outlet 2-2 and industrial pipeline.This
In embodiment, air inlet 2-1 is connected by flange, gasket seal pipe other with measurement, and gas outlet 2-2 passes through flange, gasket seal
Pipe other with emptying is connected, it is ensured that measure gas and the concordance of pipelines and petrochemical pipelines gas and the sealing of device.
A kind of for petrochemical industry load hydrogen tube hydrogen and the sensing device of impurity content on-line measurement, as shown in figures 1 and 3,
It includes optical enhancement cavity, also includes laser instrument 4, laser light incident unit 1, Raman signal collector unit 3, signal demodulation unit 5
With signal processing unit 6；Wherein, the laser that described laser instrument 4 sends through laser light incident unit 1 from the first reflecting mirror 11
Laser entrance 11-1 enters sample cell 2；Described Raman signal collector unit 3 includes that the broadband being arranged on sample cell 2 side is anti-
Penetrate mirror 13, and be arranged on the Raman probe of sample cell 2 opposite side；Raman light is received by Raman probe through window slide, transmission
It is demodulated into the signal of telecommunication to signal demodulation unit 5, is transmitted further to signal processing unit 6.
As in figure 2 it is shown, described laser light incident unit 1 includes optoisolator 7, the standard set gradually along laser propagation direction
Straight battery of lens 8 and reflectance more than 99.5% plane high reflective mirror 9, also include that the angle for adjusting plane high reflective mirror 9 angle is adjusted
Whole frame 10.Its mounting means is as follows: optoisolator 7 and collimation lens set 8 synthesis probe, is installed along with plane high reflective mirror 9
On angular adjustment frame 10, angular adjustment frame 10 can around fixing point rotate adjust plane high reflective mirror 9 angle, laser through light every
Incide after device 7 and collimation lens set 8 on the fixing point of plane high reflective mirror 9, can be regulated instead by Plane of rotation high reflective mirror 9
Penetrate the shooting angle of laser to realize angle of light regulation.
The first condenser lens 14 that preferably, described Raman probe includes setting gradually along the direction of propagation of Raman light,
Optical filter 15, notch filtering light sheet 16 and the second condenser lens 17.
In the present embodiment, broadband mirrors 13 is diameter 70mm heavy caliber coquille, and minute surface plating high reflectance broadband is situated between
Plasma membrane, reaches more than 95% to the Raman light reaction rate of laser, and Raman probe uses the design of the nearly heart, the i.e. first condenser lens simultaneously
The focal length of 14 uses little focal length to be about 7.5mm, it is ensured that the collection angle that collecting lens is sufficiently large, so can ensure that to greatest extent
Collect the Raman signal light inspired；Optical filter 15 and notch filtering light sheet 16 are used for filtering the background such as laser and Rayleigh scattering light
Light, it is ensured that accept the signal to noise ratio of signal.
In the present embodiment, laser light incident unit 1 and optical enhancement cavity and Raman signal collector unit 3 are arranged on a level
On support, the laser of laser emitting to laser light incident unit 1, injects optical enhancement by optical cable transmission after beam treatment
Chamber excites Raman light, and Raman light enters optical cable transmission to signal demodulation module 5, signal after being collected by Raman signal collector unit 3
Demodulation module connects signal processing unit 6 by order wire and carries out signal processing.Air inlet 2-1 and gas outlet 2-2 passes through flange
It is connected with industrial pipeline with sealing gasket.
The present embodiment uses distance optical cable to carry out laser and the transmission of Raman signal light, it is achieved the full light knot of exploring block
Structure, essential safety is reliable.
Above example is merely to illustrate design philosophy and the feature of the present invention, its object is to make the technology in this area
Personnel will appreciate that present disclosure and implement according to this, and protection scope of the present invention is not limited to above-described embodiment.So, all depend on
The equivalent variations made according to disclosed principle, mentality of designing or modification, all within protection scope of the present invention.
Claims (9)
1. the optical enhancement cavity carrying hydrogen pipeline gas content on-line measurement for petrochemical industry, it is characterised in that: it includes sample
Pond, sample cell is provided with the air inlet for being connected and gas outlet with the industrial pipeline being connected with gas to be measured；
The left and right of sample cell is respectively arranged at two ends with the first reflecting mirror and the second reflecting mirror；Wherein the first reflecting mirror and the second reflecting mirror
All include that focal length isfSphere, the middle part of sphere is a diameter oflDisk so that two spheres constitute a F-P vibration
Chamber, two disks constitute the 2nd F-P vibration chamber；First reflecting mirror is provided with the laser entrance for incident laser；
Sample cell be laterally provided with the window slide being connected printing opacity with Raman signal collector unit.
The optical enhancement cavity carrying hydrogen pipeline gas content on-line measurement for petrochemical industry the most according to claim 1, its feature
It is: the spacing between the first described reflecting mirror and the second reflecting mirrord =4f -Δd, ΔdIn the range of 0.2mm-
0.4mm。
The optical enhancement cavity carrying hydrogen pipeline gas content on-line measurement for petrochemical industry the most according to claim 1, its feature
It is: the diameter of described disklIn the range of 3mm-4mm.
The optical enhancement cavity carrying hydrogen pipeline gas content on-line measurement for petrochemical industry the most according to claim 1, its feature
It is: the first described reflecting mirror and the second reflecting mirror are coated with the reflectance high inverse medium film more than 99.5%.
The optical enhancement cavity carrying hydrogen pipeline gas content on-line measurement for petrochemical industry the most according to claim 1, its feature
It is: between described air inlet and gas outlet and industrial pipeline, be provided with ring flange and sealing ring.
6. the petrochemical industry strengthened based on F-P optical signalling carries a sensing device for hydrogen pipeline gas content on-line measurement, its feature
Be: it includes the optical enhancement cavity in claim 1 to 5 described in any one, also include laser instrument, laser light incident unit,
Raman signal collector unit, signal demodulation unit and signal processing unit；Wherein,
The laser that described laser instrument sends enters sample cell through laser light incident unit laser entrance from the first reflecting mirror；
Described Raman signal collector unit includes the broadband mirrors being arranged on sample cell side, and be arranged on sample cell another
The Raman probe of side；Raman light is received by Raman probe through window slide, and transmission to signal demodulation unit is demodulated into the signal of telecommunication,
It is transmitted further to signal processing unit.
The petrochemical industry strengthened based on F-P optical signalling the most according to claim 6 carries hydrogen pipeline gas content on-line measurement
Sensing device, it is characterised in that: optoisolator that described laser light incident unit includes setting gradually along laser propagation direction,
Collimation lens set and the reflectance plane high reflective mirror more than 99.5%, also includes the angle for adjusting plane high reflective mirror angle
Adjust frame.
The petrochemical industry strengthened based on F-P optical signalling the most according to claim 6 carries hydrogen pipeline gas content on-line measurement
Sensing device, it is characterised in that: described Raman probe includes that the first focusing set gradually along the direction of propagation of Raman light is saturating
Mirror, optical filter, notch filter sheet and the second condenser lens.
The petrochemical industry strengthened based on F-P optical signalling the most according to claim 6 carries hydrogen pipeline gas content on-line measurement
Sensing device, it is characterised in that: described broadband mirrors is coated with reflectance high reflectance broadband medium film more than 95%.
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| CN201610353564.2A CN106053428B (en) | 2016-05-25 | 2016-05-25 | A kind of petrochemical industry based on the enhancing of F-P optical signallings carries the sensing device of hydrogen pipeline gas content on-line measurement |
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| CN201610353564.2A CN106053428B (en) | 2016-05-25 | 2016-05-25 | A kind of petrochemical industry based on the enhancing of F-P optical signallings carries the sensing device of hydrogen pipeline gas content on-line measurement |
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| CN106990091A (en) * | 2017-04-13 | 2017-07-28 | 重庆大学 | Frequency Locking V-type for gas Raman spectral detection signal enhancing strengthens chamber |
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| CN106990091A (en) * | 2017-04-13 | 2017-07-28 | 重庆大学 | Frequency Locking V-type for gas Raman spectral detection signal enhancing strengthens chamber |
| CN106990091B (en) * | 2017-04-13 | 2020-04-28 | 重庆大学 | Frequency locking V-shaped enhancement cavity for enhancing gas Raman spectrum detection signal |
| CN108303376A (en) * | 2017-12-15 | 2018-07-20 | 复旦大学 | The multi-chamber series connection gas sample cell of built-in reflective mirror |
| CN108344727B (en) * | 2018-04-27 | 2024-01-30 | 中国石油化工集团有限公司 | Raman signal collection system and method |
| CN108344727A (en) * | 2018-04-27 | 2018-07-31 | 中石化西南石油工程有限公司地质录井分公司 | A kind of Raman signal collection system and method |
| CN108426872A (en) * | 2018-06-13 | 2018-08-21 | 武汉理工大学 | A kind of gas concentration on-line measurement system and its method for Raman scattering optical fiber sensing |
| CN108767641A (en) * | 2018-08-29 | 2018-11-06 | 中山市禾统光电科技有限公司 | A kind of laser pump (ing) light extraction regulating system |
| CN108767641B (en) * | 2018-08-29 | 2024-04-02 | 中山市禾统光电科技有限公司 | Laser pumping light-emitting adjusting system |
| CN109507169A (en) * | 2018-12-29 | 2019-03-22 | 广州玉科仪器有限公司 | Gas analysis system and gas analysis auxiliary device |
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| CN109655445B (en) * | 2019-01-22 | 2021-08-24 | 重庆大学 | Multi-section circular multi-pass air chamber for improving gas Raman detection sensitivity |
| WO2020169808A1 (en) | 2019-02-21 | 2020-08-27 | Laser-Laboratorium Göttingen e.V. | Method and apparatus for identifying volatile substances using resonator-amplified raman spectroscopy under reduced pressure |
| CN111426677B (en) * | 2020-04-29 | 2023-09-19 | 中国工程物理研究院核物理与化学研究所 | Raman spectrum multi-site excitation structure and gas analysis method |
| CN111426677A (en) * | 2020-04-29 | 2020-07-17 | 中国工程物理研究院核物理与化学研究所 | Raman spectrum multi-site excitation structure and gas analysis method |
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