EP0042789B1 - Procédé de mesure de grande sensibilité des concentrations de gaz et produits volatils in situ et en continu et appareil de mise en oeuvre - Google Patents
Procédé de mesure de grande sensibilité des concentrations de gaz et produits volatils in situ et en continu et appareil de mise en oeuvre Download PDFInfo
- Publication number
- EP0042789B1 EP0042789B1 EP81400967A EP81400967A EP0042789B1 EP 0042789 B1 EP0042789 B1 EP 0042789B1 EP 81400967 A EP81400967 A EP 81400967A EP 81400967 A EP81400967 A EP 81400967A EP 0042789 B1 EP0042789 B1 EP 0042789B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- chamber
- expansion chamber
- gases
- enclosure
- concentrations
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims description 14
- 238000011065 in-situ storage Methods 0.000 title description 5
- 239000007789 gas Substances 0.000 claims abstract description 37
- 238000005259 measurement Methods 0.000 claims abstract description 23
- 239000000523 sample Substances 0.000 claims abstract description 15
- 238000012544 monitoring process Methods 0.000 claims abstract description 7
- 238000012545 processing Methods 0.000 claims abstract description 7
- 238000004458 analytical method Methods 0.000 claims description 21
- 238000005086 pumping Methods 0.000 claims description 4
- 230000035945 sensitivity Effects 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 claims 1
- 238000012423 maintenance Methods 0.000 claims 1
- 238000005070 sampling Methods 0.000 abstract description 3
- -1 more particularly Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 1
- 239000008246 gaseous mixture Substances 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000001514 detection method Methods 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000010365 information processing Effects 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 206010037844 rash Diseases 0.000 description 2
- 230000009897 systematic effect Effects 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 230000000135 prohibitive effect Effects 0.000 description 1
- 229910052704 radon Inorganic materials 0.000 description 1
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/24—Vacuum systems, e.g. maintaining desired pressures
Definitions
- the invention relates to a method of highly sensitive measurements carried out in situ and continuously of the concentrations of gases and volatile products as well as to apparatuses for implementing the method.
- such devices although having abundance detection thresholds of the order of 50 ppm when the measurement is made in situ and from 15 to 20 ppm in the laboratory, are still insufficient especially in the case of forecasts of '' volcanic eruptions because they can neither detect very small differences in concentrations nor the presence of a new element at very low concentration.
- a detection is essential to detect and measure the contributions of elements from leaks from the lower layers located for example at a depth of thirty kilometers and which can be disturbed by the atmosphere and the waters in cycles which cannot be establish the evolution only by systematic and continuous measurements over a long period.
- the object of the present invention is a method of measurement, high sensitivity, gas concentrations and volatile products from natural sites or not and regardless of the pressures and flow rates since these pressures are greater than 10- 2 bars, by means of an access pipe connected to a mass spectrometer via an expansion chamber, pumps simultaneously maintaining the pressures at optimal values in the expansion chamber and an analysis chamber, characterized in that the gases and volatile products are sampled for which it is desired to know the variations in concentrations, by establishing a permanent passage between the expansion chamber and the access pipe and maintaining the pressure of the expansion chamber at a value determined constant, on the order of magnitude from 10- 1 to 10- 2 mbar, by all of the automatic adjustments of the flow rate of access to the expansion chamber, the output flow of this expansion chamber and the pumping e of the latter in order to obtain a constant pressure.
- Such a method has the advantage of being able to measure with an accuracy of the order of 2 ppm and continuously the concentrations of gaseous or volatile elements originating from any emergence, whether it be very small emanations or leaks at high flow rates, pressures up to 5 bar for example.
- Another object of the invention and an apparatus for implementing the process thus defined characterized in that it comprises a semi-flexible stainless metal probe, connected by a low-flow conduit to an expansion chamber connected on the one hand to a gas transfer pump, on the other hand to a pressure gauge of said chamber, a controlled inlet valve controlling the flow rate accessing said chamber, a piezoelectric valve connecting said expansion chamber to the analysis chamber a mass spectrometer, said piezoelectric valve being controlled by an ion gauge for controlling the pressure of the analysis chamber or by the spectrometer itself.
- the device used still makes it possible, because of the access valves, to avoid the use of long capillary tubes intended to lower the pressure to a predetermined level but the use of which increases the response times of the devices to which they are connected.
- Another feature of the invention is a device of this type, the mass spectrometer of which is a quadrupole spectrometer so that the whole of the device and the pumps for emptying and establishing low pressures is easily inserted into a sealed housing of small dimensions, the measurements provided by the mass spectrometer being transmitted by cables or radio to any station far from the place of measurement.
- the single figure represents in schematic form the whole of the measuring device in its enclosure and of the connected elements.
- the enclosure shown in 1, can take any desired shape depending on the easements of use but is preferably in a parallelepiped shape, rainproof and of reduced dimensions due to the methods and means of implementation adopted. .
- Access to the various organs can be obtained by any known means by means of a station 2 outside the enclosure.
- This general control and command station 2 is connected to the electrical supply device 3 by the multiple link cable 4, the device 3 supplying voltage to the various elements of the device.
- a probe for sampling gases and volatile products has been shown diagrammatically in 5.
- This probe is permanently introduced into an appropriate vent.
- the sample thus collected is preferably channeled by a semi-flexible stainless steel tube 6 whose upstream end provided with a breather comprises a filter 7, optionally followed by any device for trapping water and carbon dioxide shown diagrammatically at 8
- the assembly can also be brought to a high temperature, 120 ° C. for example.
- a connection 9 brings in the gases and volatile products sampled at the inlet 10 of the device, this inlet being connected to an expansion chamber 11.
- a valve 12 for example a needle valve or any slaved valve, makes it possible to adjust the flow of gases and volatiles removed to maintain a certain pressure of 10- 2 to 10- 1 mbar for example in the expansion chamber 11 in order to ensure the reproducibility of measurements.
- the chamber 11 is connected to the pump 13 by the conduit 14.
- This pump is preferably a two-stage vane pump with a flow rate of 4.5 m 3 per hour or less depending on the applications.
- the gases exit from the enclosure 1 takes place via the conduit 15, the end of which is directed towards the ground.
- a pressure gauge 16, of the “Pirani for example” type, supplied by the cable 17 provides the value of the pressure on the indication 18 of the control and command station 2.
- This station may also include a means for adjusting the valve. 12, the manual or automatic adjustment being performed to maintain a constant pressure in the range of 10- 2 to 10- 1 mbar in the chamber 11.
- the expansion chamber 11 is connected to the analysis chamber 19 of the mass spectrometer 20 by the pipe 21 and under the control of the piezoelectric valve 22.
- This valve is automatically controlled by the ion gauge 23 connected to the chamber d analysis 19 by means of the metal fitting 24 or even directly controlled by the spectrometer itself.
- the ion gauge 23 and the piezoelectric valve 22 are supplied by the electric cable 25 and the devices 26 and 27, the device 27 being a reaction circuit directly controlling the piezoelectric valve 22.
- the reaction circuit 27 has been shown schematically, this circuit can be of any known type.
- the adjustment and control of the reaction circuit 27 as a function of the pressure of the analysis chamber 19 are such that they make it possible to vary the flow rate of the volatile products and of the expanded gases from the chamber 11 towards the analysis chamber 19 in order to maintain a stable pressure of 10- 8 to 10- 7 mbar. They can also cause the valve 22 to cut off all communication between the two chambers 11 and 19 in order to obtain perfect safety of the apparatus, in particular in the event of an operating incident liable to affect the filament of the spectrometer 20.
- the valve 22 also remains closed when the device is in the standby position between the measurements if they are done discontinuously.
- the analysis chamber 19 is emptied by means of a primary pump 28, of the same type as the pump 13, provided with an outlet pipe 29 and the connector 30 connected to the outlet of the ultra-fast pump 31 which is preferably an oil diffusion pump or a turbomolecular pump.
- the pump is surmounted by a baffle 32, the cooling of the pump being ensured by forced ventilation.
- This pumping can also be provided by any other known means, such as a turbo pump for example.
- a set of control and display means 33 of the control station 2 makes it possible to control each of the pumps 13, 28 and 31 supplied respectively by the electrical circuits 34, 35 and 36.
- the station 2 likewise allows the control of the ion gauge the spectrometer 20 and the reaction circuit 27 controlling the piezoelectric valve 22 as well as the Pirani gauge 16, its reaction circuit and the valve 12.
- the results of the mass spectrometer 20, which is of the quadrupole type supplied by the cable 37, are transmitted by the cable 39 to an information processing device 39 possibly connected by the cable 40 to the control and command station 2.
- the device 39 can be a digital or analog computing device and can be located at any station more or less away from the analysis site. It can be connected by means of the cable 43 to all auxiliary display 41 or print 42 devices.
- the enclosure 1 of reduced dimensions of the order for example of 40 ⁇ 50 ⁇ 60 cm at least, in the immediate vicinity of this site and to carry out measurements of very low gas concentrations with a view to detecting variations in elements such as H, He, CH 4 , NH 3 etc ... in a mass of H 2 0, CO z , N 2 , l apparatus thus produced having an abundance sensitivity of the order of 2 ppm.
- the apparatus being in the vicinity of the site, operating autonomously and being permanently controlled by the station 2 possibly slaved to the data processing system 39, it is possible, depending on the results obtained, to repeat the sampling cycles by the probed 5 and of introduction into the analysis chamber 19 by passing through the expansion chamber 11, according to variable frequencies.
- the data processing device 39 therefore makes it possible to control the frequency of repetition of the measurement cycles as a function of the values of the concentrations obtained independently of the pressures of the gases collected by the probe.
- the response time of the device can be very short since on the one hand its reduced dimensions lend themselves to a possibility of installation very close to the chosen vent and on the other hand, due to the controls of valves 12 and 22 it is not necessary to connect the device to the probe 5 by a capillary extending over the entire distance existing between probe and device.
- a single calculation device 39 can be connected to several enclosures 1, each of which permanently receives the emanations from a neighboring emergence.
- the device can also be used to control the gassing of geothermal boreholes and detect gas anomalies in geothermal energy or in mining research.
- the apparatus can then be coupled to a scintillation probe 44 for the detection and simultaneous measurement of the Radon.
- This usual type probe can be connected by any suitable expansion junction 11.
- the current supply to the probe has been shown diagrammatically by wire 45 and the output by wire 46.
- the station 2 for monitoring and controlling the elements contained in the enclosure 1 is then controlled by the results of the remote information processing device 39 supplied by the mass spectrometer 20 and by the scintillation probe 44 connected to the expansion chamber 11.
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Sampling And Sample Adjustment (AREA)
- Electron Tubes For Measurement (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT81400967T ATE15722T1 (de) | 1980-06-20 | 1981-06-17 | Verfahren zum in situ und ununterbrochenen messen mit hoher empfindlichkeit von gaskonzentrationen und fluechtigen produkten und vorrichtung zur ausfuehrung des verfahrens. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8013776 | 1980-06-20 | ||
FR8013776A FR2485201A1 (fr) | 1980-06-20 | 1980-06-20 | Procede de mesure de grande precision des concentrations de gaz et produits volatils en situ et en continu et appareil in situ en oeuvre |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0042789A1 EP0042789A1 (fr) | 1981-12-30 |
EP0042789B1 true EP0042789B1 (fr) | 1985-09-18 |
Family
ID=9243343
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP81400967A Expired EP0042789B1 (fr) | 1980-06-20 | 1981-06-17 | Procédé de mesure de grande sensibilité des concentrations de gaz et produits volatils in situ et en continu et appareil de mise en oeuvre |
Country Status (7)
Country | Link |
---|---|
US (1) | US4442353A (ja) |
EP (1) | EP0042789B1 (ja) |
JP (1) | JPS5774656A (ja) |
AT (1) | ATE15722T1 (ja) |
CA (1) | CA1170079A (ja) |
DE (1) | DE3172323D1 (ja) |
FR (1) | FR2485201A1 (ja) |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4924097A (en) * | 1984-06-22 | 1990-05-08 | Georgia Tech Rss. Corp | Monodisperse aerosol generator for use with infrared spectrometry |
JPH0746074B2 (ja) * | 1984-11-27 | 1995-05-17 | 日電アネルバ株式会社 | 真空計 |
DE3510378A1 (de) * | 1985-03-22 | 1986-10-02 | Coulston International Corp., Albany, N.Y. | Verfahren zur analytischen bestimmung von organischen stoffen |
DE3631862A1 (de) * | 1986-09-19 | 1988-03-31 | Strahlen Umweltforsch Gmbh | Einrichtung zur analytischen bestimmung von organischen stoffen |
WO1987001205A1 (en) * | 1985-08-24 | 1987-02-26 | Analytical Security Systems Limited | Method and apparatus for detecting dangerous substances |
CA2058763C (en) * | 1989-06-06 | 1998-04-21 | Russell Drew | Miniaturized mass spectrometer system |
US5313061A (en) * | 1989-06-06 | 1994-05-17 | Viking Instrument | Miniaturized mass spectrometer system |
US5153433A (en) * | 1991-09-10 | 1992-10-06 | The United States Of America As Represented By The United States Department Of Energy | Portable mass spectrometer with one or more mechanically adjustable electrostatic sectors and a mechanically adjustable magnetic sector all mounted in a vacuum chamber |
US5525799A (en) * | 1994-04-08 | 1996-06-11 | The United States Of America As Represented By The United States Department Of Energy | Portable gas chromatograph-mass spectrometer |
JP2003344230A (ja) * | 2002-05-24 | 2003-12-03 | Hitachi Ltd | ガス導入装置とガス分析システム |
JP4218756B2 (ja) * | 2003-10-17 | 2009-02-04 | 株式会社荏原製作所 | 真空排気装置 |
US9518904B2 (en) * | 2011-12-07 | 2016-12-13 | Peter R. Bossard | System and method of quantifying impurities mixed within a sample of hydrogen gas |
US9091618B1 (en) | 2012-08-23 | 2015-07-28 | The Boeing Company | Gas sampling system |
CN105842404B (zh) * | 2016-05-12 | 2017-09-22 | 郑州光力科技股份有限公司 | 提高矿井火情气体监测实时性的控制系统和控制方法 |
CN109839654B (zh) * | 2017-11-27 | 2024-01-12 | 核工业西南物理研究院 | 一种家庭便携氡气测量仪 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2610300A (en) * | 1951-08-07 | 1952-09-09 | Wilson W Walton | Flow control |
US2721270A (en) * | 1951-08-14 | 1955-10-18 | Willard H Bennett | Leak primarily for mass spectrometers |
US3992626A (en) * | 1973-02-23 | 1976-11-16 | Honeywell Inc. | Test instrument |
US3895231A (en) * | 1973-04-30 | 1975-07-15 | Univ Colorado | Method and inlet control system for controlling a gas flow sample to an evacuated chamber |
US4201913A (en) * | 1978-10-06 | 1980-05-06 | Honeywell Inc. | Sampling system for mass spectrometer |
-
1980
- 1980-06-20 FR FR8013776A patent/FR2485201A1/fr active Granted
-
1981
- 1981-06-11 JP JP56090173A patent/JPS5774656A/ja active Pending
- 1981-06-17 AT AT81400967T patent/ATE15722T1/de not_active IP Right Cessation
- 1981-06-17 DE DE8181400967T patent/DE3172323D1/de not_active Expired
- 1981-06-17 EP EP81400967A patent/EP0042789B1/fr not_active Expired
- 1981-06-19 US US06/275,164 patent/US4442353A/en not_active Expired - Fee Related
- 1981-06-19 CA CA000380247A patent/CA1170079A/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
CA1170079A (en) | 1984-07-03 |
EP0042789A1 (fr) | 1981-12-30 |
ATE15722T1 (de) | 1985-10-15 |
DE3172323D1 (en) | 1985-10-24 |
JPS5774656A (en) | 1982-05-10 |
US4442353A (en) | 1984-04-10 |
FR2485201A1 (fr) | 1981-12-24 |
FR2485201B1 (ja) | 1984-03-09 |
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