EP1036312A1 - Dispositif pour mesurer la pression partielle de gaz dissous dans des liquides - Google Patents
Dispositif pour mesurer la pression partielle de gaz dissous dans des liquidesInfo
- Publication number
- EP1036312A1 EP1036312A1 EP97928234A EP97928234A EP1036312A1 EP 1036312 A1 EP1036312 A1 EP 1036312A1 EP 97928234 A EP97928234 A EP 97928234A EP 97928234 A EP97928234 A EP 97928234A EP 1036312 A1 EP1036312 A1 EP 1036312A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- measuring
- light
- gas
- membrane
- partial pressure
- 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.)
- Ceased
Links
- 239000007789 gas Substances 0.000 title claims abstract description 64
- 230000036961 partial effect Effects 0.000 title claims abstract description 48
- 239000007788 liquid Substances 0.000 title claims abstract description 37
- 239000012528 membrane Substances 0.000 claims abstract description 47
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 66
- 239000000523 sample Substances 0.000 claims description 56
- 238000005102 attenuated total reflection Methods 0.000 claims description 38
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 31
- 239000001569 carbon dioxide Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 26
- 238000005259 measurement Methods 0.000 claims description 22
- 239000012530 fluid Substances 0.000 claims description 19
- 230000003287 optical effect Effects 0.000 claims description 16
- 238000000855 fermentation Methods 0.000 claims description 10
- 230000004151 fermentation Effects 0.000 claims description 10
- 238000010521 absorption reaction Methods 0.000 claims description 9
- 230000005855 radiation Effects 0.000 claims description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 235000013361 beverage Nutrition 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229910052594 sapphire Inorganic materials 0.000 claims description 4
- 239000010980 sapphire Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- GGYFMLJDMAMTAB-UHFFFAOYSA-N selanylidenelead Chemical compound [Pb]=[Se] GGYFMLJDMAMTAB-UHFFFAOYSA-N 0.000 claims description 2
- 238000004065 wastewater treatment Methods 0.000 claims description 2
- 230000001276 controlling effect Effects 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- 230000002829 reductive effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 11
- 239000013307 optical fiber Substances 0.000 description 8
- 238000009530 blood pressure measurement Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 230000001954 sterilising effect Effects 0.000 description 7
- 238000004659 sterilization and disinfection Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000004020 luminiscence type Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000000875 corresponding effect Effects 0.000 description 4
- 238000010276 construction Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
- 150000004770 chalcogenides Chemical class 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- YBNMDCCMCLUHBL-UHFFFAOYSA-N (2,5-dioxopyrrolidin-1-yl) 4-pyren-1-ylbutanoate Chemical compound C=1C=C(C2=C34)C=CC3=CC=CC4=CC=C2C=1CCCC(=O)ON1C(=O)CCC1=O YBNMDCCMCLUHBL-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000012092 media component Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000001139 pH measurement Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000007793 ph indicator Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- 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
- G01N21/84—Systems specially adapted for particular applications
- G01N21/85—Investigating moving fluids or granular solids
- G01N21/8507—Probe photometers, i.e. with optical measuring part dipped into fluid sample
-
- 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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/55—Specular reflectivity
- G01N21/552—Attenuated total reflection
-
- 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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/59—Transmissivity
- G01N21/61—Non-dispersive gas analysers
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/0004—Gaseous mixtures, e.g. polluted air
- G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
- G01N33/0011—Sample conditioning
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M41/00—Means for regulation, monitoring, measurement or control, e.g. flow regulation
- C12M41/30—Means for regulation, monitoring, measurement or control, e.g. flow regulation of concentration
- C12M41/32—Means for regulation, monitoring, measurement or control, e.g. flow regulation of concentration of substances in solution
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M41/00—Means for regulation, monitoring, measurement or control, e.g. flow regulation
- C12M41/40—Means for regulation, monitoring, measurement or control, e.g. flow regulation of pressure
Definitions
- the present invention relates to a novel device for measuring the gas partial pressure in liquid media according to P 4445 68.9.
- This process causes a change in pH in the electrolyte solution, which is measured using the pH probe.
- the disadvantage of this measuring principle is the fact that carbon dioxide is not measured directly, but its ionic form. Since the proportion of the ionic form is less than 0.1%, this method is not sufficiently precise. Apart from this, other volatile acidic or basic gases interfere with the pH measurement. Furthermore, a very high level of maintenance is required.
- pCO2 optodes are known from the prior art. This is also a membrane-covered sensor system (SPIE Vol. 798 Fiber Optic Sensors II (1987) pp. 249-252; Anal. Chim. Acta 160 (1984) pp. 305-309; Proc. Int. Meeting on Chemical Sensors, Fukuoka, Japan, Elsevier, pp. 609-619, 1983, Talanta 35 (1988) 2 p.109-112, Anal.Chem. 65 (1993) pp. 331-337, Fresenius Z. Anal. Chem. 325 (1986) pp. 387-392).
- pH indicators which change their absorption or fluorescence properties as a function of the proton concentration are used as the indicator phase (Anal. Chem. 52 (1980), pp. 864-869, DE-OS 3 343 636 and 3 343 637, U.S. Pat. Appl. 855,384).
- gases for example carbon dioxide
- Such carbon dioxide optodes work analogously to the Severinghaus electrodes.
- the disadvantages of optical pH and therefore pCO2 measurements lie in the very limited analytical measuring range and the dependence on ionic strength. The wide use of the optodes is also opposed by the disadvantages already mentioned with regard to the Severinghaus electrodes.
- a differential pressure measuring device for the determination of carbonic acid is known from German laid-open specification 2435493.
- this device can only be used in flowing media. It is therefore particularly unsuitable for use in conventional stirred or fixed bed reactors, as are used in particular in the fermentation industry.
- a device for the continuous measurement of the content of dissolved carbon dioxide in liquids is known from German Offenlegungsschrift 2926138.
- the measuring principle is based on the determination of the conductivity difference.
- the device is equipped with a membrane which is flown on one side by the liquid containing dissolved carbon dioxide and on the other side by a neutral or basic measuring liquid.
- One conductivity sensor each is arranged in the conduit of the measuring liquid before and after the permeable membrane.
- the disadvantage of the measurement is that it is not suitable for liquids whose chemical and physical properties change.
- a division into two beam paths is already known from GB 2194333. With this method, only one light beam is passed through the material to be measured. The rest of the radiation is used as a reference light to also increase the accuracy.
- the measurement takes advantage of the phenomenon of the formation of evanescent waves or surface waves at the interface of two optically differently dense media.
- a light beam at the interface to an optically thinner medium is reflected back into the optically denser medium if the angle between the incident light beam and the solder on the interface exceeds the critical angle of total reflection.
- Some of the light waves penetrate a few wavelengths into the surrounding thinner medium and are only reflected back from there into the optically denser medium. If there are light-absorbing substances in the area of this short light path, the reflected portion of the light is reduced. This weakening can be detected and correlated with the amount of the absorbent.
- a large number of configurations for the use of this light absorption phenomenon are state of the art today.
- ATR devices contain crystals, mostly trapezoid cut prisms.
- the simplest geometric shapes for the ATR element are described in German Offenlegungsschrift DE 42 27 813.
- a cube corner reflector in the form of a triple prism is used in German Offenlegungsschrift DE 44 18 180.
- the advantage of this arrangement is its compact construction.
- the light emitted is thereby redirected around 1800.
- This enables an arrangement in a thin rod.
- the supply of the light to be radiated and the removal of the residual light is solved constructively by the use of optical fibers.
- the German published patent application DE 4038354 describes an ATR probe with no prisms, lenses or other components.
- the light is also transported via light guides.
- the incoming and outgoing light guides and the actual ATR sensor consist a common optical fiber.
- the jacket of the light guide has been removed.
- the optical waveguide is mechanically supported and arranged in a probe body in a measuring room so that it is in contact with the medium to be examined.
- a sapphire ATR (attenuated total reflection) crystal is arranged in a flow measuring cell for fluid substances, for example beer, perpendicular to the direction of flow.
- the infrared light which is fed to the crystal on one side, passes through the crystal and is totally reflected several times. With each reflection, the radiation enters the sample liquid by several ⁇ m and is weakened by the presence of carbon dioxide. The amount of residual light at the other end of the crystal is measured.
- the disadvantage of this method is that no partial pressures can be measured. On the other hand, with changing fluids, the results can be falsified by changing the reflective properties.
- the basic application P 4445 68.9 on which this application is based has set itself the task of providing a device for measuring the partial pressure of gases dissolved in liquids by means of optical methods which no longer has the disadvantages described of the devices known from the prior art and which in particular the gas partial pressure measurement with longer long-term stability of the device allows precise and changing chemical-physical composition in media as well as in clear, cloudy and changeable cloudy media.
- the device a) is separated from a measuring chamber, which is permeable to the gas to be determined by means of a gas-permeable membrane, from a sample space which contains the liquid with the gas to be determined therein, b) a light emission source for generating a light beam passing through the measuring chamber with a wavelength that is absorbed by the gas to be determined, and c) a measuring arrangement for determining the light beam leaving the measuring chamber.
- the measuring chamber, light emission source and measuring arrangement are arranged in a rod-shaped probe. If this is in the field of biotechnology, e.g. used in fermentations, beverage production or wastewater treatment, it is designed as a sterilizable device. Since the field of fermentation technology is mainly sterilized using steam, the probe materials must be adjusted to these conditions. That is why the membrane materials that have proven themselves in this area are primarily used. This primarily includes polytetrafluoroethylene (silicone and other fluoride polymers). Solubility membranes have proven successful as gas-selective membranes. When used in the sample chamber, these can establish a balance between the sample liquid and the inner mixture.
- the measuring chamber is preferably filled with a chemically and biologically inert fluid. This is selected so that it absorbs the gas to be determined, which diffuses through the membrane into the measuring chamber.
- a chemically and biologically inert fluid This is selected so that it absorbs the gas to be determined, which diffuses through the membrane into the measuring chamber.
- Suitable liquids or gases can be used for the same purpose. The type of fluids mentioned depends on the gases to be measured.
- Luminescent diodes are preferably used as the light emission source.
- the use of these devices has the following advantages:
- the emission is relatively narrow-band, i.e. the use of interference filters is not absolutely necessary to selectively determine the corresponding gas. Due to the relatively low power consumption, it is possible in principle to make the measurement setup portable with battery operation.
- a key advantage over conventional infrared sources is the high level of performance. Therefore, it may be possible to do without a comparison route or to set up compensation circuits without moving parts. Such a system is mechanically less sensitive. At the same time, the high level of performance guarantees long operation without recalibration.
- the luminescent diodes are dimensioned so small that the light can easily be coupled into the optical waveguide. The sensitive parts can thus be positioned externally and are not subject to the thermal-mechanical loads of steam sterilization.
- the detectors compatible with the luminescent diodes are also used.
- Photodiodes, photoresistors and lead selenide photodetectors are particularly suitable as such. The latter work predominantly in the infrared range and are particularly suitable for the determination of carbon dioxide.
- Optical fibers are used to guide the light waves from the light emission source to the measuring chamber. The same applies to the conduction of the light from the measuring chamber to the measuring arrangement for the determination of the non-absorbed light components.
- the measuring arrangement is preferably connected to a special circuit for evaluating, storing and displaying the signals. Because of this, the device is particularly suitable for the automation of systems. Using an integrated evaluation unit, all the data can be automatically recorded and fed to a control process.
- the possibility of a pressure-resistant design of the device is also advantageous. It is only necessary to adapt the housing construction of the probe accordingly. In this way, the device can be used at pressures of 200 bar.
- the probe is preferably used at pressures up to 20 bar. When used for fermentation processes, it is only necessary to ensure that the probe can withstand the increased pressures that occur under sterilization conditions.
- Another subject of P 4445 68.9 is a method for measuring the partial pressure of gases dissolved in liquids.
- the described device is immersed in the liquid present in the sample space in such a way that the membrane is completely wetted with sample liquid.
- the gas to be determined can now selectively diffuse through the membrane into the measuring chamber.
- a light beam is guided through the measuring chamber by the light emission source via optical waveguides.
- the non-absorbed part of the light beam is fed via an optical waveguide to the measuring arrangement for determining the gas partial pressure.
- storage and display devices can be determined and evaluated on the basis of the measurement of the non-absorbed light beam.
- Electromagnetic radiation generated by luminescent diodes is preferably used.
- the infrared range is very particularly preferred.
- the device and the method are particularly suitable for using the measurement of the carbon dioxide partial pressure.
- Carbon dioxide is a significant production factor in the food industry, particularly in the beverage industry. In the beverages themselves, carbon dioxide is responsible for the shelf life and the refreshing taste. Most determinations are made today via simultaneous pressure and temperature control.
- a carbon dioxide partial pressure measurement is also required for optimal process management of biotechnical processes.
- the supply of gases to the microorganisms and their inhibitory properties are a function of the corresponding partial pressures and not of the concentrations.
- the carbon dioxide partial pressure has not been sufficiently taken into account to date.
- a satisfactory solution to its determination has not yet been found.
- the main problems when choosing a suitable determination method are the lack of equipment and the high chemical stability of the carbon dioxide. Carbon dioxide is the highest oxidation state of carbon and is therefore very inert at room temperature. In solution, unlike other heterogeneous gases, it does not form hydrogen bonds.
- the measuring chamber is filled with a carrier fluid for carbon dioxide.
- This fluid must have a solubility for carbon dioxide.
- Another condition is that it is chemically and biologically inert.
- the fluid has a higher boiling point than the material to be measured, in order to largely avoid pressure fluctuations.
- the device is not limited to a specific carrier liquid. Rather, their composition and chemical nature depend on the type of gas to be measured and the conditions under which the probe is used.
- the present invention has for its object to provide a device for measuring the partial pressure of gases dissolved in liquids by means of optical methods, which no longer has the disadvantages described of the devices known from the prior art and which in particular the gas partial pressure measurement for a long time
- Long-term stability of the device allows precise chemical and physical composition changing in media as well as in clear, cloudy and changeably cloudy media.
- the device should have considerably shorter response times and, in particular, should also be usable at high partial pressures of the gas.
- a device which a) has a measuring location which is partially separated by means of a gas-permeable membrane which is permeable to the gas to be determined, b) a light emission source for generating a light beam with a wavelength which interacts with the liquid in the measuring location , which is absorbed by the gas to be determined, and c) includes a measuring arrangement for determining the light leaving the measuring location, and which is characterized in that d) the measuring location (15) is in contact with the interface of a light-conducting element, and e ) the light is guided through this element in such a way that attenuated total reflection occurs at the interface.
- the element showing the attenuated total reflection is referred to below as the "ATR element” (for "Attenuated Total Reflectance”).
- the ATR element, light emission source and measuring arrangement are arranged in a rod-shaped probe. If this is used in the field of biotechnology, it is designed as a sterilizable device. Since the field of fermentation technology is mainly sterilized using steam, the probe materials must be adjusted to these conditions.
- the type of light emission source, its arrangement, its use, the type of detectors, its arrangement, its use, the type of optical waveguide and the pressure-resistant design corresponds to P 4445 68.9 as described above.
- the ATR element can be chosen arbitrarily. This includes the use of prisms, lenses or optical fibers. For use under steam sterilization conditions, they must be able to withstand thermal loads.
- quartz glass is available for the UV to NIR range, and Sapphire for longer-wave light. If an optical waveguide is used, quartz glass fibers are suitable for the UV to NIR range, and chalcogenide, fluoride or silver halide fibers are particularly suitable for the longer-wave range.
- the membrane can be arranged in two different ways in relation to the ATR element. If the membrane material shows no or constant absorption for the wavelength range, the membrane can be applied directly to the ATR unit. If this is not the case, a gap in the order of a few wavelengths of light can be left between the membrane and the ATR element. This gap is then filled according to the invention with a chemically and biologically inert fluid. This is selected so that it absorbs the gas to be determined, which diffuses through the membrane into the gap. Suitable liquids or gases can be used for this purpose in the same way. The type of fluids mentioned depends on the gases to be measured.
- the gas to be determined can diffuse out of the sample within a very short time. Partial pressure changes in the sample are therefore registered with an extremely short response time in the range from milliseconds to seconds. In contrast, the diffusion for a device according to P 4445 68.9 takes a time in the range of minutes.
- the device according to the invention is particularly suitable for the measurement of high partial pressures at which the measuring signal is absorbed too strongly in conventional systems.
- the arrangement of a fluid that absorbs the gas between the ATR element and the membrane means that very low partial pressures can also be measured, since the gas accumulates in this fluid.
- the membrane consists of steam sterilizable materials.
- Proven membrane materials are primarily used in this area. These include above all silicone, polytetrafluoroethylene and other fluorinated polymers. For application to fibers as an ATR element, these must be liquefiable or sprayable, in particular polytertrafluoroethylene.
- Another object of the present invention is a method for measuring the partial pressure of gases dissolved in liquids.
- the device according to the invention is immersed in the liquid present in the sample space in such a way that the membrane is completely wetted with sample liquid.
- the gas to be determined can now selectively enter the membrane in the event that the membrane is applied directly to the ATR element and in the event that a gap containing fluid is arranged between the ATR element and the membrane diffuse into the gap.
- Part is fed to the measuring arrangement for the determination of the gas partial pressure via an optical waveguide.
- Appropriate evaluation, storage and display devices can be used to determine and evaluate the gas partial pressure based on the measurement of the non-absorbed light beam.
- the device and the method according to the invention are particularly suitable for using the measurement of the carbon dioxide partial pressure.
- the specific problems of carbon dioxide partial pressure measurement described above are solved.
- a gap can be provided which is filled with a carrier fluid.
- the short response time and suitability for determining high partial pressures are particular advantages.
- Fig.2 shows the probe tip with gap
- Fig. 3 shows the probe tip with optical fiber as an ATR element without
- the device according to the invention in the form of a probe 1.
- the probe body is made of stainless steel. However, it is possible to manufacture from any other material. As a rule, however, these are corrosion-free substances.
- the probe 1 has a connection piece 2, which allows the probe 1 to be inserted pressure-tight into the pipeline or the wall 5 of a vessel.
- the connector 2 and the O-ring arrangement 3 allow the probe 1 to be fastened in a sealing manner in an access pipe 4 to the wall 5.
- the Access pipe 4 has the corresponding connector to connector 2.
- This construction gives the possibility to subject the probe head to steam sterilization and to use it in sterile operation.
- a light source 6 and a measuring arrangement 7 are present within the probe 1.
- the light source 6 is a luminescence diode and the measuring arrangement 7 is a photo receiver. Both parts of the device are connected to the electrical cables
- the luminescence diode 6 is supplied with current via the line 8.
- the photo receiver 7 transmits a signal pulse over the line
- the luminescence diode 6 and the photo receiver 7 are arranged outside the liquid space 10. They are used via the extrinsic optical waveguides 12 and 13, which are used to transmit the light 12 from the liminescence diode 6 and the non-absorbed light to the photo receiver 7.
- the optical waveguides can be made from any materials suitable for the transmission of light. In the example according to the invention, work is carried out in the infrared range. Therefore, light guides made of transparent material, e.g. from silver halides and chalcogenides. These fiber-optic cables can withstand thermal loads and are therefore suitable for use in steam-sterilizable environments.
- ATR element 14 is located at the tip of the head of probe 1. In the example according to the invention, this is a sapphire crystal.
- the ATR element 14 is separated from the sample space 10 via the gas-permeable membrane 11.
- the membrane 11 is a thermally stable membrane, which is made of steam sterilizable material is made.
- polytetrafluoroethylene or / and Teflon is preferred for this.
- the luminescence diode 6 emits narrow-band light, which is selectively absorbed by the gas to be determined.
- the wavelength can be in the UV / VIS as well as in the infrared range with respect to the gas to be examined. For carbon dioxide, this is preferably 4.3 ⁇ m.
- the emitted wavelength range can be limited by a heat radiator with an interference filter or preferably by a narrow-band luminescence diode.
- the particular advantage of using the luminescent diode is that the radiation can be modulated, which increases detection and minimizes effects such as DC drift.
- the emitted radiation is fed to the ATR element 14 via the optical waveguide 12.
- the gas present specifically attenuates the radiation emitted.
- the weakened light is partially received by the optical waveguide 13 and fed to the photo receiver 7. This measures the attenuated light and produces an electrical signal proportional to the attenuated light. If modulated light is used, the electrical signal can also be modulated.
- a device could be created from the arrangement according to FIG. 1 by removing the ATR element 14.
- a fluid-filled chamber would remain behind the membrane 11 through which the measuring light can be guided.
- Figure 2 shows the tip of the probe 1 in the event that the membrane 11 absorbs light at the corresponding wavelength.
- the ATR element 14 is not arranged flush with the probe head (as in FIG. 1), but rather is sunk somewhat so that a gap 15 is formed.
- the gas located in the sample space 10 then diffuses through the membrane 11 into the gap until equilibrium prevails and it can be determined without additional absorption through the membrane 11.
- the same arrangement is chosen for the case where there are low partial pressures.
- the gap is filled with a carrier fluid which has a high physical absorption capacity for the gas.
- This configuration can also be selected if the ATR element 14 consists of a stripped fiber and a gap is used.
- FIG 3 shows the configuration of the probe tip in the event that an optical fiber is used as an ATR unit and is operated without a gap.
- the incoming and outgoing optical fibers 12 and 13 and the ATR element 14 consist of one fiber.
- the actual ATR element 14 is an optical fiber stripped on this piece.
- a membrane 11 is applied to this.
- a cage 16 is attached to the tip of the probe.
- the advantages achieved by the invention consist in particular in the fact that, in particular in the case of carbon dioxide partial pressure measurement, separation of the measurement space from the sample space does not result from the presence of turbid and changing particles in their concentration. Furthermore, the implementation of the membrane guarantees the measurement of the partial pressure. In principle it is possible to convert concentration into partial pressures using Henry's law. But it requires the simultaneous knowledge of temperature and pressure as well as the media properties. The latter is particularly difficult when using fermentation media. Furthermore, the long-term stability, Accuracy and the measuring range compared to pH-sensitive partial pressure probes increased.
- the extremely short response time and the suitability for determining high partial pressures are particularly advantageous in the system according to the present invention.
- the probe structure is simplified since no separate light emitters and light receivers need to be arranged, in which problems with adjustment and sterilization can occur.
- the probe according to the invention can be used particularly well both in the beverage industry and in biotechnology.
- probes for measuring ranges of up to 10 bar can be created.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Immunology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Food Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
La présente invention concerne un dispositif pour mesurer la pression partielle de gaz dissous dans des liquides. Ce dispositif comporte (a) un point de mesure (15) qui est partiellement isolé par une membrane perméable aux gaz (11), laquelle est perméable au gaz à déterminer; (b) une source d'émission lumineuse (6) pour produire un faisceau lumineux assurant une interaction avec le liquide dans le point de mesure (15) et présentant une longueur d'onde qui est absorbée par le gaz à déterminer; et (c) un système de mesure (7) permettant de déterminer la lumière quittant le point de mesure (15). Ce dispositif est caractérisé en ce que (d) le point de mesure (15) est en contact avec l'interface d'un élément photoconducteur (14), et (e) la lumière est guidée à travers ledit élément (14) de telle manière que sa réflexion totale est affaiblie au niveau de l'interface.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19624844 | 1996-06-21 | ||
| DE19624844A DE19624844C2 (de) | 1994-12-21 | 1996-06-21 | Vorrichtung zur Messung des Partialdruckes von in Flüssigkeiten gelösten Gasen in Anlagen zur Durchführung von biotechnologischen oder lebensmitteltechnologischen Prozessen |
| PCT/EP1997/003177 WO1997049985A1 (fr) | 1996-06-21 | 1997-06-18 | Dispositif pour mesurer la pression partielle de gaz dissous dans des liquides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1036312A1 true EP1036312A1 (fr) | 2000-09-20 |
Family
ID=7797616
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP97928234A Ceased EP1036312A1 (fr) | 1996-06-21 | 1997-06-18 | Dispositif pour mesurer la pression partielle de gaz dissous dans des liquides |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP1036312A1 (fr) |
| JP (1) | JP2000512758A (fr) |
| AU (1) | AU732530B2 (fr) |
| CA (1) | CA2259275A1 (fr) |
| WO (1) | WO1997049985A1 (fr) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE59811266D1 (de) * | 1997-09-01 | 2004-06-03 | Buechs Jochen | Verfahren und Vorrichtung zur Ermittlung und Überwachung des physiologischen Zustandes mikrobieller Kulturen |
| DE10030920C2 (de) * | 2000-06-24 | 2003-01-02 | Glukomeditech Ag | Messvorrichtung zur gleichzeitigen refraktrometrischen und ATR-spektrometrischen Messung der Konzentration flüssiger Medien und Verwendung dieser Vorrichtung s |
| DE10214713A1 (de) * | 2002-04-03 | 2003-10-30 | C Cit Ag Waedenswill | Vorrichtung und Verfahren zur Durchführung und zur kontinuierlichen Überwachung von chemischen und/oder biologischen Reaktionen |
| DE10300957A1 (de) * | 2003-01-13 | 2004-07-22 | Ibidi Gmbh | Probenkammer für eine Flüssigkeit |
| FR2978547B1 (fr) * | 2011-07-29 | 2014-11-28 | Diafir | Capteur a fibre optique a ondes evanescentes |
| DE102020110349B4 (de) | 2020-04-15 | 2022-01-20 | Mettler-Toledo Gmbh | Sensoraufnahme zur Verwendung eines herkömmlichen Sensors mit einem Einwegbioreaktor unter Wahrung der Sterilität des Einwegbioreaktors |
| DE102024125365A1 (de) | 2024-09-04 | 2026-03-05 | Hamilton Bonaduz Ag | Membranbauteil für ein ATR-Messelement, ATR-Sensor mit einem solchen Membranbauteil und Verfahren zur Anordnung des Membranbauteils an einer ATR-Sensorbasisbaugruppe |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4201222A (en) * | 1977-08-31 | 1980-05-06 | Thomas Haase | Method and apparatus for in vivo measurement of blood gas partial pressures, blood pressure and blood pulse |
| US4800886A (en) * | 1986-07-14 | 1989-01-31 | C. R. Bard, Inc. | Sensor for measuring the concentration of a gaseous component in a fluid by absorption |
| NL8902238A (nl) * | 1989-09-06 | 1991-04-02 | Interconnection B V | Verwarmingselement en stelsel omvattende een dergelijk verwarmingselement. |
| DE4418180C2 (de) * | 1994-06-27 | 1997-05-15 | Emmrich Roland | Sondenanordnung zur Messung der spektralen Absorption in Flüssigkeiten, Gasen oder Feststoffen |
| DE4445668C2 (de) * | 1994-12-21 | 1997-05-15 | Euroferm Gmbh I Gr | Vorrichtung zur Messung des Partialdruckes von in Flüssigkeiten gelösten Gasen in Anlagen zur Durchführung von biotechnologischen oder lebensmitteltechnologischen Prozessen |
-
1997
- 1997-06-18 JP JP10502273A patent/JP2000512758A/ja active Pending
- 1997-06-18 AU AU32604/97A patent/AU732530B2/en not_active Ceased
- 1997-06-18 WO PCT/EP1997/003177 patent/WO1997049985A1/fr not_active Ceased
- 1997-06-18 EP EP97928234A patent/EP1036312A1/fr not_active Ceased
- 1997-06-18 CA CA002259275A patent/CA2259275A1/fr not_active Abandoned
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9749985A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2000512758A (ja) | 2000-09-26 |
| WO1997049985A1 (fr) | 1997-12-31 |
| AU3260497A (en) | 1998-01-14 |
| CA2259275A1 (fr) | 1997-12-31 |
| AU732530B2 (en) | 2001-04-26 |
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