Patent Grant
8409504
This application is a §371 of International PCT Application PCT/FR2008/051977, filed Nov. 3, 2008.
1. Field of the Invention
The present invention relates to a device for analyzing a fluid and to a method of delivering at least one gas mixture especially to a fluid analyzer.
The analyzable fluids may be either gases or liquids. They may be obtained by direct sampling on an industrial process for the purpose of quality control or by sampling a given atmosphere, for example the ambient air, for monitoring or control purposes.
2. Related Art
The analyzers used for measuring small concentrations of chemical species in a fluid sample are sensitive to the characteristics of the pure gases and gas mixtures with which they are supplied. Pure gases or gas mixtures are used to convey the specimen right to the detector and to set a “zero” point during calibration, this being essential in the fluid analysis field. They may also serve to operate the device itself. These pure gases or gas mixtures are called instrumentation gases. For example, these instrumentation gases are helium, nitrogen, air or mixtures such as H2/He, H2/Ar, CH4/Ar, CO2/Ar and H2/N2.
The content of impurities present in these instrumentation gases and the specifications for producing them are parameters that have an influence on the sensitivity of the analyzers and the reproducibility of the analyses.
The levels and nature of the impurities contained in the instrumentation gases enable a quality equivalent to a purity of 99.999% to be achieved. The most frequently guaranteed impurities are moisture and hydrocarbons. Carbon oxides (CO and CO2) and oxygen may also form the subject of guarantees.
Because of ever more stringent regulations, analytical laboratories have to measure ever lower concentrations. The improvement in the performance of analyzers is consequently focused on their detection limit and their precision. The guarantees offered today in the case of instrumentation gases are no longer sufficient to meet these requirements, both in terms of purity and production precision. This is because the impurities present with too high a concentration disturb the background noise of analyzers, thus downgrading their sensitivity. The range of guaranteed impurities may be insufficient and become a source of interference in the measurements. For example, guaranteed impurities are moisture and oxygen, whereas those that are critical for analysis are hydrocarbons, an additional specification enabling interference on the analyses to be limited. Finally, the difference between the deviations in composition from one mixture to another, which is too high compared with the theoretically intended production of the proportions of the various components of the instrumentation gases, is a source of imprecision in the analytical results.
The particular example of a flame ionization detector (FID) as analyzer consists of a flame supplied with a hydrogen/helium mixture and with air, and a collecting plate. The specimen to be analyzed passes through a flame which decomposes the organic molecules and produces ions. These are recovered on a biased electrode and thus produce an electrical signal. An FID is extremely sensitive and provides a wide dynamic range. FIDs are used for detecting hydrocarbons, such as for example methane, ethane or even acetylene. The specimen to be analyzed is mixed beforehand with the combustible instrumentation mixture in a preheated zone. The ions and the electrons formed in the flame are collected and thus enable a current to flow in an external circuit. The current is proportional to the amount of ions, which depends on the concentration of hydrocarbons in the fluids to be analyzed. The current is detected by a suitable electrometer and is displayed on an analog output. Thus, an FID provides a rapid, precise (down to ppb) and continuous reading of the hydrocarbon concentration.
The FID is supplied with two gas mixtures, namely hydrogen/helium (H2/He) in well-defined respective proportions, for example 40% and 60%, and oxygen/nitrogen (O2/N2) in well-defined respective proportions, for example 20% and 80%. The variation in deviations relative to the theoretically intended production of the proportions of the various components from one mixture to another constitutes a source of uncertainty about the results of the analyses carried out using an FID. To improve the reliability of analyses carried out by FID, the H2/He and O2/N2 mixtures, called flame gases, must therefore have steady production precision levels from one mixture to another, thus enabling the influence of this parameter on the measurements to be limited. Furthermore, the content of impurities present in the instrumentation gases is also a factor to be taken into consideration, the more so when small amounts (less than or equal to one part per million) have to be analyzed by FID.
These specifications must therefore be improved in order to ensure reliability of the analyses.
For example in the case of FIDs, the flame gases today are delivered in bottle form with production precision levels between 1 and 2% absolute for the hydrogen content in the case of an H2/He mixture and between 0.5 and 1% absolute for the oxygen content in the case of an O2/N2 mixture. The variation in composition of these mixtures from one bottle to another is a source of error for the end customer. This is because a variation of 2% absolute in the H2 concentration in the H2/He mixture may generate up to a 30% variation in the FID signal obtained for analyzing hydrocarbons. Likewise, a 2% variation in the oxygen content in the O2/N2 mixture supplying the FID generates a 10% variation in the FID signal.
Furthermore, the impurity content is a critical parameter as regards analysis reliability. An impurity concentration of 40 ppb generates a 23% increment in the signal when a zero air sample is analyzed by total FID. However, at the present time the usually guaranteed level of impurities in a bottled mixture is between 50 and 100 ppbv. For example in the case of FIDs, the delivery of bottles of H2/He and O2/N2 mixtures for supplying FIDs therefore has the drawback of generating large uncertainties in the analytical results, which will be all the more critical the lower the contents to be analyzed. The delivery of such bottled mixtures therefore does not guarantee reproducibility over time, either in their composition or in their purity.
This guarantee corresponds to a method of preparing the containers and filling them with mixtures that enables a large number of products to be produced at economically viable costs. The change in requirements in terms of precision and guaranteed levels of impurity means that the production of these bottled mixtures would necessitate modifying the existing processes and plants, something which would incur a significant increase in production costs. Thus, it seems that, for these types of mixtures, the limits in production precision levels achieved by filling centers have today been reached, at the very least for manufacturing a large number of these mixtures. As regards impurities, the guaranteed levels fluctuate depending on the sources used, the process for producing the gas bottles and the method of filling these bottles.
One object of the present invention is to alleviate some or all of the abovementioned drawbacks.
For this purpose, the invention consists of a device for analyzing a fluid, comprising:
According to one embodiment of the invention, the system for supplying said analyzer with instrumentation gases further includes at least one purifier located upstream of at least one mixer.
The advantage of having a single purifier downstream of the mixer is that it simplifies the entire delivery process. However, the addition of a purifier upstream of the mixer makes it possible to remove specific impurities from at least one of the pure gases upon entry that it would not be possible to remove from the final mixture because of technical and/or safety constraints.
Moreover, embodiments of the invention may include one or more of the following features:
In one embodiment of the invention, said at least one purifier may also include an alarm or warning, such as an audible or visual signal, or another message indicating that the purifier has reached the end of its guaranteed lifetime. Such a device enables the user to be informed so that he can either change the purifier or switch to an emergency supply offering him the same specifications. As a variant, this alarm may be coupled to an automatic mixer shutoff in order to prevent erroneous analyses because of the deterioration in the performance of the purifier.
The emergency supply may either consist of a bottled gas of known composition or a switch to another purifier.
As an additional variant, the purification is provided by a self-regenerated purification means. Such a purification means is for example a PSA (pressure swing adsorption) or TSA (temperature swing adsorption) unit. In the latter two examples, two tanks are placed in parallel with the flow of the gas and are filled with an adsorbent (such as active carbon, activated alumina or a zeolite). When the first tank is enabling the gas to flow to the mixer, the second is in regeneration mode. This regeneration may take place by means of a change in pressure (PSA unit) or an increase in temperature under a stream of gas (TSA unit).
According to one embodiment of the invention, a pressure regulator is located downstream of said at least one purifier.
Another subject of the invention is a feed system for supplying a fluid analyzer with instrumentation gases, consisting of at least one mixer which generates said instrumentation gas combined with at least one purifier located downstream of said at least one mixer, said feed system being integrated into one and the same fluid analysis device.
Another subject of the invention is a feed system for supplying a flame ionization detector with instrumentation gases, formed by two mixers each generating an instrumentation gas mixture, each mixer being located upstream of a purifier.
Another subject of the invention is the use of a feed system as described above, for delivering at least one instrumentation gas mixture to a fluid analyzer.
Yet another subject of the invention is a method of delivering at least one gas mixture to a fluid analyzer, comprising the following steps:
Such a method may further include, prior to step a), a step of purifying at least one gas to be mixed.
Yet another subject of the invention is a method of delivering two gas mixtures to a flame ionization detector, comprising the following steps:
Other features and advantages will become apparent on reading the description below, given with reference to
The existing technologies for the mixer 7 or 8 allow mixtures 5 or 6 to be generated with an uncertainty not exceeding 0.5% absolute in the concentration of the minor component. It may involve mass flow rate regulators or sonic orifices or regulating valves.
The purifier 9 or 10 is used to reduce the content of impurities that are critical for the analysis. For example, the purifier may be a catalyst composed of metal oxides in order to convert hydrocarbons to CO2 and H2O. It may be combined with adsorbents for trapping these impurities in order to limit their impact on the measurement.
All this gas mixture delivery equipment enables precise mixtures having low impurity contents to be generated. The subject of the present invention, which constitutes an alternative to bottled mixtures, is a means for reducing the contribution played by analyzer supply mixtures to analytical uncertainty.
Pure gases, such as G1 and G2 (or G3 and G4), enter the mixer 7 (or alternatively 8), said mixer delivering a mixture G1/G2 flowing in a line 12 (or alternatively G3/G4 flowing in a line 13). The purifier 9 (or alternatively 10) serves to reduce the content of critical impurities of the mixture G1/G2 (or alternatively G3/G4) and thus deliver a mixture 5 (or alternatively 6). The mixtures 5 and 6 each represent an instrumentation gas for analyzing the fluid 2 coming from the reservoir 14. Said fluid 2 flows in a line 11 into the analyzer 3, into which the instrumentation gases also flow. According to one particular embodiment of the invention, the equipment 4 is made up of a single section. A section consists of a mixer 7, a purifier 9 and a line 12 in which the instrumentation gas 5 flows. A device according to the invention may also comprise equipment 4 consisting of more than two sections.
If the analyzer 3 is a flame ionization detector, the instrumentation gas supply system or equipment 4 comprises a first purifier 9 located downstream of a first mixer 7, which generates a hydrogen (G1)/helium (G2) mixture 5 flowing in the line 12. A second purifier 10 is located downstream of a second mixer 8, which generates an oxygen (G3)/nitrogen (G4) mixture 6 flowing in the line 13. This purifier 10 is located upstream of the analyzer 3 intended to analyze the fluid 2 coming from the specimen 14, said fluid flowing in the line 11 into the analyzer 3 via the inlet 17.
The mixtures 5 and 6 supply the analyzer 3 via the inlets 15 and 16 and conduct the fluid 2 of the specimen 14 into that part of the analyzer 3 in which the measurements will be carried out. These flame gases 5 and 6 also serve to set a “zero” point when calibrating the analyzer 3.
In general, the solution proposed by the present invention therefore consists, on the one hand, of a mixer allowing on-site generation of the instrumentation gases and, on the other hand, of a purifier placed downstream of the mixer and upstream of the analyzer. These two components are combined and constitute a single piece of equipment.
The mixer makes it possible to ensure that the composition of the mixture is stable over time. It may be made up either of mass flow rate regulators or sonic orifices, depending on the flow dynamics desired by the customer. The purifier serves to remove the critical impurities, for example hydrocarbons, by converting them to CO2 and H2O, for example using a catalytic process. This purifier may also comprise an adsorbent in successive beds for trapping these impurities, for example a sieve first bed for trapping H2O and a zeolite second bed for trapping CO2.
The components of the mixer make it possible to achieve a mixture production precision in the concentration of the minor component of 0.5% absolute or better. Production on the customer's site obviates potential fluctuations in the concentrations of the mixtures forming the instrumentation gases. For example in the case of an FID, production on the customer's site obviates potential fluctuations of the hydrogen concentration in the H2/He mixture or the oxygen concentration in the O2/N2 mixture. By guaranteeing this precision, reproducibility of the customer's analyses is improved.
The purifier enables a level of hydrocarbon impurities to be achieved upstream of the analyzer that is below that disturbing its analysis. Its continuous operation enables the “background noise” of the analyzer to be maintained at satisfactory levels for analyzing low hydrocarbon contents. In the case of FIDs, the critical impurities are hydrocarbons—for analysis of 100 ppbv of hydrocarbons, the purifier must achieve hydrocarbon contents below 10 ppbv.
The complete equipment provides the customer with a guarantee that the composition of the mixture is stable over time, thanks to the precision of the mixer, and that the purity delivered at the point of use is constant, thanks to the performance of the purifier. This solution therefore has the advantage of providing the customer with a mixture having essential characteristics that are stable over the course of time. Thus the proposed solution helps to reduce the contribution played by the analyzer feed gases to the uncertainty of the analyses. Furthermore, combining mixer and purifier offers the customer greater ease of use and faster operation compared with bottled delivery.
It should be obvious that the present invention allows for embodiments in many other specific forms without it departing from the field of application of the invention as claimed. Consequently, the present embodiments must be considered as illustrations, but they may be modified within the field defined by the scope of the appended claims, and the invention should not be limited to the details given above.
It will be understood that many additional changes in the details, materials, steps and arrangement of parts, which have been herein described in order to explain the nature of the invention, may be made by those skilled in the art within the principle and scope of the invention as expressed in the appended claims. Thus, the present invention is not intended to be limited to the specific embodiments in the examples given above.
| Number | Date | Country | Kind |
|---|---|---|---|
| 07 59342 | Nov 2007 | FR | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/FR2008/051977 | 11/3/2008 | WO | 00 | 5/27/2010 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2009/068767 | 6/4/2009 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 5214952 | Leggett et al. | Jun 1993 | A |
| 5524473 | Haskell | Jun 1996 | A |
| 6562088 | Ukai et al. | May 2003 | B2 |
| 20010032668 | Doty et al. | Oct 2001 | A1 |
| Number | Date | Country |
|---|---|---|
| 1883783 | Dec 2006 | CN |
| 19 842 413 | Oct 1999 | DE |
| 6 194353 | Jul 1994 | JP |
| 8 262000 | Oct 1996 | JP |
| 2000 516713 | Dec 2000 | JP |
| Entry |
|---|
| PCT/FR2008/051977 Written Opinion dated May 12, 2009. |
| PCT International Search Report for PCT/FR2008/051977. |
| Number | Date | Country | |
|---|---|---|---|
| 20100310419 A1 | Dec 2010 | US |
