WO2001040779A1 - Method and device for determining the quality of fluids - Google Patents

Method and device for determining the quality of fluids Download PDF

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Publication number
WO2001040779A1
WO2001040779A1 PCT/EP2000/011525 EP0011525W WO0140779A1 WO 2001040779 A1 WO2001040779 A1 WO 2001040779A1 EP 0011525 W EP0011525 W EP 0011525W WO 0140779 A1 WO0140779 A1 WO 0140779A1
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WIPO (PCT)
Prior art keywords
fluid
measuring
aging
chemiluminescence
oxygen
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PCT/EP2000/011525
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German (de)
French (fr)
Inventor
Bernhard Kirsch
Hagen MÜLLER
Manfred Pahl
Original Assignee
Hydac Filtertechnik Gmbh
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hydac Filtertechnik Gmbh filed Critical Hydac Filtertechnik Gmbh
Priority to AU18581/01A priority Critical patent/AU1858101A/en
Priority to JP2001542194A priority patent/JP2003515741A/en
Priority to EP00981278A priority patent/EP1240502A1/en
Publication of WO2001040779A1 publication Critical patent/WO2001040779A1/en

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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
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/76—Chemiluminescence; Bioluminescence

Definitions

  • the invention relates to a method for determining the quality, in particular the aging state, of fluids which contain hydrocarbons which form free radicals and hydroperoxides under the action of oxygen.
  • Fluids such as hydraulic fluids, consist predominantly of chemically relatively stable hydrocarbons.
  • additives for the thermal stability and aging stability of the fluid, additives in the form of antioxidants have proven to be particularly important which influence the reactivity of the fluid.
  • the aim of the invention is therefore to remove the hydroperoxides that may be present in the fluid in order to be able to deduce the remaining service life of the hydraulic oil by determining the amount of the preliminary products, in order to obtain a conclusion on the amount of the expected degradation products of the oil by determining the amount of the preliminary products before it the actual formation of aging products has occurred.
  • Another object of the invention is to carry out the aging determination in question online, i.e. with flowing fluids.
  • an apparatus for performing the method is to be provided.
  • chemiluminescence occurs during the formation thereof, ie light emission occurs in the fluid as a result of the chemical reaction that occurs.
  • the light emission can take place with ultraviolet, visible or infrared light below the glow temperature of the fluid substances involved.
  • the relevant chemiluminescence from organisms is also known as bioluminescence and is known, among other things, from the fireflies.
  • the basis of the measuring methods described below is the fact that as long as effective additives, such as antioxidants, are present in the fluid, the free amount of hydroperoxide reacts preferentially with the antioxidants, so that the rate of the chain reaction, which leads to the aging of the fluid, is much slower.
  • the hydroperoxide formed sets in motion a chain reaction that produces a large amount of aging products that decay when emitted by light. It is therefore possible to directly infer the speed of the aging reaction by measuring the light emission. It is also possible to infer different oil states, such as oxidation stability, peroxide and antioxidant content, by varying the measurement procedure.
  • FIG. 1 shows the basic structure of the measuring and evaluation device with evaluation diagrams
  • the basic construction of the measuring and evaluation device shown in FIG. 1 has a measuring chamber 10.
  • the fluid or oil sample to be examined is applied to a slide 12, for example in the form of a glass slide.
  • the measuring chamber 10 is sealed light-tight from the environment by means of a housing 14.
  • the housing 14 consists in particular of an upper housing part which is detachably connected to a plate-like lower housing part in order to allow an operator access to the interior of the housing 14 in this way.
  • the measuring chamber 10 is surrounded on the edge by an insulating plate 16 and has an exit point 18 for light detection by a sensor device 20 in the form of a photomultiplier.
  • the photomultiplier receives the light quanta emitted by the sample at a defined solid angle.
  • the photomultiplier referred to represents a so-called cascode, which is also called a photon counter. Due to the external photo effect, the incident light quantum knocks an electron out of the Photocathode. This primary electron generates an avalanche of secondary electrons in the subsequent cascaded electrodes, which can be measured as a defined amount of charge at the outlet of the cascode. The amount of charge generated is proportional to the energy of the light quantum captured; the number of charge pulses therefore corresponds to a constant fraction of the emitted light quanta.
  • the cascode within the photomultiplier 20 is located together with the sample in the light-tight housing chamber 14.
  • a movable shutter shutter
  • the shutter 22 consists of a rotatably mounted cylinder, in the longitudinal axis of which the photomultiplier 20 with its cascode circuit is arranged. There is a translucent opening in the cylinder, which can be rotated by means of an electric drive, so that the optical path between the cascode and the sample is periodically interrupted or released as the cylinder rotates. If the shutter 22 interrupts the optical path, the error-related background noise can be detected by means of the measuring and evaluation device, and after the optical sensor device of the photomultiplier 20 has been released, the light quanta emitted by the sample are actually measured. The measuring and evaluation device then subtracts the background noise from the actually obtained measured values and determines it such as the amount of light actually emitted. Erroneous measurements can thus be excluded with certainty.
  • the shutter 22 one can also use a lens system for collecting the light (condenser) in combination with a movable mirror (scanner) and a spectrometer (all components not shown).
  • the measuring chamber 10 can be heated by means of a heating device 24.
  • a temperature sensor 28 is arranged in a base plate 26 for the heating device 24.
  • a cooling device 30, in particular in the form of a fan is arranged inside the housing 14 and spatially separated from the heating device 24 via the insulating plate 16, in particular in the form of a fan, which cools the heat-sensitive electronic components, for example within the photomultiplier 20 , takes over.
  • the photomultiplier 20 is electrically connected to a voltage source 32 and, together with the temperature sensor 28, the sensor device 20 transmits its measurement data to a measurement data acquisition and evaluation designated as a whole as 24, which according to the image representation according to FIG. 1 shows an oscilloscope 36 and an A. / D converter 38 has for the evaluation of the chemiluminescence signal 40 and a temperature signal 42 in the form of a curve.
  • a connection 44 is available, which is in the otherwise closed measuring chamber 10 opens.
  • a modern microprocessor can also be used for the measurement data evaluation.
  • the two measurement curves according to FIG. 2 relate to the measurement of the antioxidant equivalent in a commercially available hydraulic oil, the amount of light achieved during chemiluminescence being plotted over the mass fraction of hydroperoxide.
  • the solid line of the measurement curve I results when the individual measurement points, which are shown as boxes, are connected with one another to form average values.
  • the measurement curve I runs horizontally up to the value 0.0064, there is no amount of light, i.e. added hydroperoxides are compensated for by the antioxidants in the hydraulic oil.
  • the antioxidant has not been used up, the oil does not age and the chemiluminescence mentioned does not occur.
  • the antioxidants are used up, in the present case at a threshold value of 0.0064 mass fraction hydroperoxide, the hydroperoxide proportion increases due to aging and the chemiluminescence begins to be measured. If the threshold is reached by the onset of chemiluminescence, the mole fraction of hydroperoxide in question represents an equivalent for the antioxidant components in the fluid.
  • the elimination reaction of the peroxides by the antioxidants takes place in a stoichiometric ratio.
  • An indirect measurement of the antioxidant content in oils can also be based on the principle of the gradual addition of peroxides and simultaneous chemiluminescence measurement. consequences.
  • By gradually adding peroxides it is possible to reliably determine the equivalent amount of antioxidants in the oil, because chemiluminescence is also in a stoichiometric ratio to the peroxide concentration. The determination of the equivalent amount of antioxidants then provides evidence of the aging situation or the quality of the fluid to be examined.
  • the chemiluminescent effect can be improved by heating the sample in the measuring chamber 10 via the heating device 24. Furthermore, the quantum efficiency and thus the light intensity can be increased if fluorophores are used in the measurement. Particularly suitable fluorophores are 9, 10-dibromoanthracene or 3-aminofluoranthene. With the increase in light intensity, an increase in the measurement resolution is possible and therefore a more precise oil analysis.
  • the measurement curve II in FIG. 2 shows the relevant effect, the fluorophores being added to the oil samples. An increase of 5 to 20 times the light emission during chemiluminescence has been observed. Another possibility is to put the fluoroscent additives on a glass support or the like. in the optical path between the sample and the photomultiplier. Immobilization of the fluorophores is particularly advantageous if you want to operate a measuring chamber in flow mode, i.e. with the possibility of online measurement with continuously flowing fluids.
  • oxidation stability of an oil it is heated in the presence of oxygen and the temperature or the time until the oil begins to oxidize.
  • the onset of oxidation of the fluid can be measured as the emission of chemiluminescent light based on the aging-related peroxide formation and decomposition. For unaged oils this temperature is higher than in the case of oils which have already aged, since unaged oils contain antioxidants which counteract oxidation (hydroperoxide formation) (cf. FIG. 4).
  • the peroxide content in the oil can also be determined in the absence of oxygen, in particular atmospheric oxygen. From the considerations regarding the aging of oils which have already been mentioned, it can be seen that peroxides in oil only form when there are no longer any antioxidants in the oil. The absence of antioxidants and the presence of peroxides suggests an aged oil. In particular, the detection of peroxides formed in the fluid by aging using the chemiluminescence method allows a statement to be made about the aging state of the fluid. The measurement of the stationary peroxide concentration is equivalent to the aging rate of the oil. An online measuring method based on this with a temperature-controlled flow measuring point serves for the continuous measurement of the aging rate and display of the fluid state.
  • a statement about the state of aging and the rate of aging can also be achieved by alternately passing oxygen and nitrogen over the fluid at a constant temperature.
  • the relevant measurement curves are shown in FIG. 3, with measurement curve III showing a commercially available new oil and measurement curve IV showing a commercially available used oil.
  • the measuring ranges subdivided with 0 2 and N 2 relate to the process of supplying oxygen to the measuring chamber or supplying nitrogen to the same.
  • the amplitude and phase position of the chemiluminescence which is given here with relative light intensity, is therefore a measure of the aging state of hydrocarbon compounds in non-aqueous solutions, the aging conditions to be compared speeds along the specified time axis t in the measurement curves III and IV are indicated with a double arrow both for the old oil and for the new oil.
  • a double arrow both for the old oil and for the new oil.
  • the measuring method according to the invention it is possible to create a measuring and evaluation device which has a very compact structure and which can be connected on site to work machines, for example, to their hydraulics.
  • the measuring and evaluation device is then able to transmit a warning signal to a control center or the like on site in online operation. to be given, provided that the oil shows an aging state due to the chemiluminescence, which makes its replacement appear necessary.

Abstract

The invention relates to a device and a method for determining the quality, in particular the state of aging of fluids containing hydrocarbons which form radicals and peroxides in the presence of oxygen. A result on the state of aging of a given fluid can be obtained based on the determination of the presence of the content of peroxides in fluids in a chemiluminescence assay by means of a measuring and evaluation device.

Description

HYDAC Filtertechnik GmbH, Industriegebiet, 66280 Sulzbach/Saar HYDAC Filtertechnik GmbH, industrial area, 66280 Sulzbach / Saar
VERFAHREN UND VORRICHTUNG ZUR ERMITTLUNG DER QUALITÄT VON FLUIDENMETHOD AND DEVICE FOR DETERMINING THE QUALITY OF FLUIDS
Die Erfindung betrifft ein Verfahren zur Ermittlung der Qualität, insbesondere des Alterungszustandes von Fluiden, die Kohlenwasserstoffe enthalten, die unter Einwirkung von Sauerstoff Radikale und Hydroperoxide bilden.The invention relates to a method for determining the quality, in particular the aging state, of fluids which contain hydrocarbons which form free radicals and hydroperoxides under the action of oxygen.
Fluide, wie beispielsweise Hydraulikflüssigkeiten, bestehen überwiegend aus chemisch relativ stabilen Kohlenwasserstoffen. Um die Gebrauchsfähigkeit dahingehender Fluide zu verbessern, sind in diesen noch geringe Mengen anderer Stoffe gelöst, insbesondere in Form sog. Additive. Für die thermische Stabilität und Alterungsstabilität des Fluids haben sich dabei als be- sonders wichtig Additive in Form von Antioxidantien erwiesen, die die Reaktionsfähigkeit des Fluids beeinflussen.Fluids, such as hydraulic fluids, consist predominantly of chemically relatively stable hydrocarbons. In order to improve the usability of these fluids, small amounts of other substances are still dissolved in them, especially in the form of so-called additives. For the thermal stability and aging stability of the fluid, additives in the form of antioxidants have proven to be particularly important which influence the reactivity of the fluid.
Allen diesen angesprochenen Fluiden ist gemeinsam, daß unter Anwesenheit von Sauerstoff, wie Luftsauerstoff, und bei erhöhten Temperaturen, wie sie bei Betrieb des Fluids auftreten können, chemische Prozesse ablaufen, die langfristig den Einsatz dieser Fluide beeinträchtigen. Man bezeichnet dahingehende, die Qualität des Fluids beeinträchtigende Prozesse auch als Alterung des Fluids. Bei den mehrstufig ablaufenden Alterungsreaktionen entstehen vorübergehend oder intermediär sauerstoffhaltige Zwischenstu- fen, sog. Intermediate. Aufgrund ihrer Reaktivität reagieren diese in der Folge mit anderen Substanzen bzw. mit sich selbst. Die Menge und die Zerfallsrate dieser Intermediate ist dabei ein Maß für den Alterungszustand des Fluids.All these fluids addressed have in common that in the presence of oxygen, such as atmospheric oxygen, and at elevated temperatures, which can occur during operation of the fluid, chemical processes take place which impair the use of these fluids in the long term. Processes that impair the quality of the fluid are also referred to as aging of the fluid. In the multi-stage aging reactions, temporary or intermediate oxygen-containing intermediate stages fen, so-called intermediate. Because of their reactivity, they subsequently react with other substances or with themselves. The amount and the rate of decay of these intermediates is a measure of the aging condition of the fluid.
Die Alterung von Ölen, genauer die Oxidation ihrer Kohlen Wasserstoff be- standteile, verläuft über einen Radikalkettenmechanismus, in dessen Verlauf es zur Bildung von Hydroperoxiden kommt. Obwohl die Produktbildung in radikalisch ablaufenden Alterungsreaktionen nicht vorherbestimmt ist, kommt es doch immer erst zur Bildung von Peroxiden als Vorprodukt der Alterung. Nachfolgeprodukte der Alterungsreaktion lassen sich den Produktgruppen Alkohol, Ester, Carbonsäuren, Aldehyde etc. zuordnen. Obwohl es sich nicht vorhersagen läßt, welche Alterungsprodukte während der Radikalkettenreaktion entstehen, kommt es doch immer erst zur Bildung von Peroxiden als Vorprodukt der durch Alterung entstehenden Alkohole, Ketone, Polymere etc.. Ziel der Erfindung ist es mithin, die eventuell vorhandenen Hydroperoxide im Fluid zu bestimmen, um auf die noch zu erwartende Reststandzeit des Hydrauliköls schließen zu können, indem man die Menge der Vorsprodukte bestimmt, um derart einen Rückschluß auf die Menge der noch zu erwartenden Abbauprodukte des Öles zu erhalten, indem man die Menge der Vorprodukte bestimmt bevor es zur eigentlichen Bildung von Alterungsprodukten gekommen ist. Ein weiteres Ziel der Erfindung ist, die dahingehende Alterungsbestimmung im Online-Betrieb durchzuführen, d.h. bei strömenden Fluiden. Des weiteren soll eine Vorrichtung zum Durchführen des Verfahrens bereitgestellt werden.The aging of oils, more precisely the oxidation of their carbon components, hydrogen, takes place via a radical chain mechanism, in the course of which hydroperoxides are formed. Although the formation of products in radical aging reactions is not predetermined, the formation of peroxides as a preliminary product of aging always occurs. Successor products of the aging reaction can be assigned to the product groups alcohol, esters, carboxylic acids, aldehydes etc. Although it cannot be predicted which aging products arise during the radical chain reaction, the formation of peroxides always occurs as a preliminary product of the alcohols, ketones, polymers etc. resulting from aging. The aim of the invention is therefore to remove the hydroperoxides that may be present in the fluid in order to be able to deduce the remaining service life of the hydraulic oil by determining the amount of the preliminary products, in order to obtain a conclusion on the amount of the expected degradation products of the oil by determining the amount of the preliminary products before it the actual formation of aging products has occurred. Another object of the invention is to carry out the aging determination in question online, i.e. with flowing fluids. Furthermore, an apparatus for performing the method is to be provided.
Bei der Hydroperoxidbildung als Vorstufe der Alterungsreaktionen kommt es bei der Bildung derselben zur Chemilumineszenz, d.h. infolge der auftretenden chemischen Reaktion findet eine Lichtemission bei dem Fluid statt. Die Lichtemission kann mit ultraviolettem, sichtbarem oder infrarotem Licht unterhalb der Glühtemperatur der beteiligten Fluidsubstanzen erfolgen. Die dahingehende Chemilumineszenz von Organismen wird auch als Biolumineszenz bezeichnet und ist unter anderem von den Glühwürmchen her bekannt.In the formation of hydroperoxides as a precursor of the aging reactions, chemiluminescence occurs during the formation thereof, ie light emission occurs in the fluid as a result of the chemical reaction that occurs. The light emission can take place with ultraviolet, visible or infrared light below the glow temperature of the fluid substances involved. The relevant chemiluminescence from organisms is also known as bioluminescence and is known, among other things, from the fireflies.
Grundlage der nachfolgend beschriebenen Meßverfahren ist die Tatsache, daß, solange wirksame Additive, wie Antioxidatien, im Fluid enthalten sind, die freie Menge an Hydroperoxid mit den Antioxidantien bevorzugt rea- giert, so daß die Geschwindigkeit der Kettenreaktion, die zur Alterung des Fluids führt, wesentlich verlangsamt ist. Sind die Antioxidantien jedoch aufgebraucht, setzt entstehendes Hydroperoxid eine Kettenreaktion in Gang, bei der in hohem Maße Alterungsprodukte entstehen, die unter Aussendung von Licht zerfallen. Mithin ist es möglich, durch die Messung der Lichtemis- sion auch direkt auf die Geschwindigkeit der Alterungsreaktion zu schließen. Auch ist es möglich, durch Variation der Meßdurchführung auf verschiedene Ölzustände, wie Oxidationsstabilität, Peroxid- und Antioxidanti- engehalt, zu schließen.The basis of the measuring methods described below is the fact that as long as effective additives, such as antioxidants, are present in the fluid, the free amount of hydroperoxide reacts preferentially with the antioxidants, so that the rate of the chain reaction, which leads to the aging of the fluid, is much slower. However, once the antioxidants have been used up, the hydroperoxide formed sets in motion a chain reaction that produces a large amount of aging products that decay when emitted by light. It is therefore possible to directly infer the speed of the aging reaction by measuring the light emission. It is also possible to infer different oil states, such as oxidation stability, peroxide and antioxidant content, by varying the measurement procedure.
Im folgenden wird das erfindungsgemäße Verfahren sowie die Vorrichtung zum Durchführen des Verfahrens anhand der Zeichnung näher erläutert. Es zeigen in prinzipieller und nicht maßstäblicher Darstellung dieThe method according to the invention and the device for carrying out the method are explained in more detail below with reference to the drawing. They show the principle and not to scale
Fig.1 den grundlegenden Aufbau der Meß- und Auswerteeinrich- tung mit Auswertediagrammen;1 shows the basic structure of the measuring and evaluation device with evaluation diagrams;
Fig.2 Meßkurven betreffend die Messung des Antioxidantgleichwer- tes; Fig.3 in Form von Meßkurven das Verhältnis der Alterungsgeschwindigkeit zwischen bereits gealtertem Fluid (obere Meßkurve) und von neuem Fluid (untere Meßkurve);2 measurement curves relating to the measurement of the antioxidant equivalent; 3 shows, in the form of measurement curves, the ratio of the aging rate between fluid which has already aged (upper measurement curve) and new fluid (lower measurement curve);
Fig.4 eine Meßdarstellung der Oxidationsbeständigkeit in sauer- stoffhaltiger Atmosphäre bei T, > T2 bzw. t, > t2 mit der Bedingung eines definitiven Zusammenhanges zwischen T und t; T = f(t) bzw. T = konstant mit4 shows a measurement of the resistance to oxidation in an oxygen-containing atmosphere at T,> T 2 or t,> t 2 with the condition of a definite relationship between T and t; T = f (t) or T = constant with
T2 (gealtertes Öl) und T, (ungealtertes Öl), t2 (gealtertes Öl) und t, (ungealtertes Öl), wobei l/V die Lichtintensität, T die Temperatur in Grad Celsius und t die Zeit in Stunden ist.T 2 (aged oil) and T, (unaged oil), t 2 (aged oil) and t, (unaged oil), where l / V is the light intensity, T is the temperature in degrees Celsius and t is the time in hours.
Die in der Fig.1 von ihrem prinzipiellen Aufbau her dargestellte Meß- und Auswerteeinrichtung weist eine Meßkammer 10 auf. In der Meßkammer 10 ist auf einem Objektträger 12, beispielsweise in Form eines Glasträgers, die zu untersuchende Fluid- oder Ölprobe aufgebracht. Die Meßkammer 10 ist lichtdicht gegenüber der Umgebung mittels eines Gehäuses 14 abgeschlossen. Das Gehäuse 14 besteht insbesondere aus einem Gehäuseoberteil, das lösbar mit einem plattenartigen Gehäuseunterteil verbunden ist, um derart einer Bedienperson den Zugang in das Innere des Gehäuses 14 zu ermöglichen. Die Meßkammer 10 ist randseitig von einer Isolierplatte 16 umgeben und weist eine Austrittsstelle 18 für die Lichterfassung durch eine Sensoreinrichtung 20 in Form eines Photomultipliers auf.The basic construction of the measuring and evaluation device shown in FIG. 1 has a measuring chamber 10. In the measuring chamber 10, the fluid or oil sample to be examined is applied to a slide 12, for example in the form of a glass slide. The measuring chamber 10 is sealed light-tight from the environment by means of a housing 14. The housing 14 consists in particular of an upper housing part which is detachably connected to a plate-like lower housing part in order to allow an operator access to the interior of the housing 14 in this way. The measuring chamber 10 is surrounded on the edge by an insulating plate 16 and has an exit point 18 for light detection by a sensor device 20 in the form of a photomultiplier.
Der Photomultiplier empfängt die von der Probe emittierten Lichtquanten in einem definierten Raumwinkel. Der angesprochene Photomultiplier stellt eine sog. Kaskode dar, die auch Photonenzähler genannt wird. Durch den äußeren Photoeffekt schlägt das einfallende Lichtquant ein Elektron aus der Photokathode aus. Dieses Primärelektron erzeugt in nachfolgenden, kaska- dierten Elektroden eine Lawine aus Sekundärelektronen, welche am Ausgang der Kaskode als eine definierte Ladungsmenge meßbar sind. Die erzeugte Ladungsmenge ist proportional zur Energie des aufgefangenen Licht- quants; die Anzahl der Ladungspulse entspricht mithin einem konstanten Bruchteil der emittierten Lichtquanten.The photomultiplier receives the light quanta emitted by the sample at a defined solid angle. The photomultiplier referred to represents a so-called cascode, which is also called a photon counter. Due to the external photo effect, the incident light quantum knocks an electron out of the Photocathode. This primary electron generates an avalanche of secondary electrons in the subsequent cascaded electrodes, which can be measured as a defined amount of charge at the outlet of the cascode. The amount of charge generated is proportional to the energy of the light quantum captured; the number of charge pulses therefore corresponds to a constant fraction of the emitted light quanta.
Die Kaskode innerhalb des Photomultipliers 20 befindet sich zusammen mit der Probe in der lichtdichten Gehäusekammer 14. Außerdem befindet sich in dem Gehäuse 14 eine bewegliche Blende (Shutter), mit der man den optischen Weg zwischen der Probe innerhalb der Meßkammer 10 und dem Photomultiplier 20 unterbrechen oder freigeben kann. Damit ist man in der Lage, von der Probe emittierte Lichtquanten von störenden Ereignissen, wie zum Beispiel radioaktive Hintergrundstrahlung, zu unterscheiden, die ebenfalls in der Kaskode Elektronen auslösen können, was man mit Hintergrundrauschen bezeichnet.The cascode within the photomultiplier 20 is located together with the sample in the light-tight housing chamber 14. In addition, in the housing 14 there is a movable shutter (shutter) with which the optical path between the sample within the measuring chamber 10 and the photomultiplier 20 is interrupted or can release. This makes it possible to distinguish light quanta emitted by the sample from disturbing events, such as radioactive background radiation, which can also trigger electrons in the cascode, which is known as background noise.
Der im einzelnen nicht näher dargestellte Shutter 22 besteht in einer speziellen Ausführung aus einem drehbar gelagerten Zylinder, in dessen Längs- achse der Photomultiplier 20 mit seiner Kaskodenschaltung angeordnet ist. Im mittels eines elektrischen Antriebes drehbaren Zylinder befindet sich eine lichtdurchlässige Öffnung, so daß mit der Drehung des Zylinders periodisch der optische Pfad zwischen Kaskode und Probe unterbrochen bzw. freigegeben ist. Unterbricht der Shutter 22 den optischen Pfad, ist mittels der Meß- und Auswerteeinrichtung das fehlerbedingte Hintergrundrauschen erfaßbar und nach Freigabe der optischen Sensoreinrichtung des Photomultipliers 20 erfolgt die tatsächliche Messung der von der Probe emittierten Lichtquanten. Die Meß- und Auswerteeinrichtung subtrahiert dann von den tatsächlich erhaltenen Meßwerten das Hintergrundrauschen und ermittelt derart die tatsächlich emittierte Lichtmenge. Somit lassen sich fehlerhafte Messungen mit Sicherheit ausschließen. Anstelle des Shutters 22 kann man auch ein Linsensystem zum Sammeln des Lichtes (Kondensor) in Kombination mit einem bewegbaren Spiegel (Scanner) und einem Spektrometer (alle Komponenten nicht dargestellt) benutzen.In a special embodiment, the shutter 22, not shown in detail, consists of a rotatably mounted cylinder, in the longitudinal axis of which the photomultiplier 20 with its cascode circuit is arranged. There is a translucent opening in the cylinder, which can be rotated by means of an electric drive, so that the optical path between the cascode and the sample is periodically interrupted or released as the cylinder rotates. If the shutter 22 interrupts the optical path, the error-related background noise can be detected by means of the measuring and evaluation device, and after the optical sensor device of the photomultiplier 20 has been released, the light quanta emitted by the sample are actually measured. The measuring and evaluation device then subtracts the background noise from the actually obtained measured values and determines it such as the amount of light actually emitted. Erroneous measurements can thus be excluded with certainty. Instead of the shutter 22, one can also use a lens system for collecting the light (condenser) in combination with a movable mirror (scanner) and a spectrometer (all components not shown).
Um die Bildung und den Zerfall der angesprochenen Intermediate der Probe zu stimulieren, kann die Meßkammer 10 mittels einer Heizeinrichtung 24 beheizt werden. Die Heizeinrichtung 24 kann beispielsweise aus einer elektrischen Widerstandsheizung od.dgl. gebildet sein, die in Blickrichtung auf die Fig.1 gesehen unterhalb der Meßkammer 10 angeordnet ist. Zur Erfassung der Probentemperatur ist in einer Grundplatte 26 für die Heizeinrichtung 24 ein Temperatursensor 28 angeordnet. Neben einer Heizeinrichtung 24 ist innerhalb des Gehäuses 14 und räumlich von der Heizeinrich- tung 24 über die Isolierplatte 16 getrennt im oberen Bereich eine Kühleinrichtung 30, insbesondere in Form eines Ventilators, angeordnet, der die Kühlung der hitzeempfindlichen elektronischen Bauteile, beispielsweise innerhalb des Photomultipliers 20, übernimmt.In order to stimulate the formation and decay of the intermediates of the sample mentioned, the measuring chamber 10 can be heated by means of a heating device 24. The heating device 24 or the like, for example, from an electrical resistance heater. be formed, which is arranged as seen in the direction of Figure 1 below the measuring chamber 10. To detect the sample temperature, a temperature sensor 28 is arranged in a base plate 26 for the heating device 24. In addition to a heating device 24, a cooling device 30, in particular in the form of a fan, is arranged inside the housing 14 and spatially separated from the heating device 24 via the insulating plate 16, in particular in the form of a fan, which cools the heat-sensitive electronic components, for example within the photomultiplier 20 , takes over.
Der Photomultiplier 20 ist elektrisch an eine Spannungsquelle 32 angeschlossen und zusammen mit dem Temperatursensor 28 gibt die Sensoreinrichtung 20 ihre Meßdaten an eine als Ganzes mit 24 bezeichnete Meßdatenerfassung und -auswertung weiter, die gemäß der Bilddarstellung nach der Fig.1 ein Oszilloskop 36 sowie einen A/D-Wandler 38 aufweist für die Auswertung des Chemilumineszenzsignals 40 und einem Temperatursignal 42 in Kurvenform. Für das wahlweise Zuführen von zu untersuchendem Fluid, Sauerstoff, Stickstoff und Hydroperoxid steht mindestens ein Anschluß 44 zur Verfügung, der in die ansonsten abgeschlossene Meßkammer 10 mündet. Anstelle der angesprochenen Rechnereinheit 34 kann auch ein moderner Mikroprozessor für die Meßdatenauswertung eingesetzt werden.The photomultiplier 20 is electrically connected to a voltage source 32 and, together with the temperature sensor 28, the sensor device 20 transmits its measurement data to a measurement data acquisition and evaluation designated as a whole as 24, which according to the image representation according to FIG. 1 shows an oscilloscope 36 and an A. / D converter 38 has for the evaluation of the chemiluminescence signal 40 and a temperature signal 42 in the form of a curve. For the optional supply of fluid to be examined, oxygen, nitrogen and hydroperoxide, at least one connection 44 is available, which is in the otherwise closed measuring chamber 10 opens. Instead of the computer unit 34 mentioned, a modern microprocessor can also be used for the measurement data evaluation.
Im folgenden wird nun das erfindungsgemäße Verfahren anhand der aufge- zeigten apparatetechnischen Meßvorrichtung unter Bezugnahme auf die Meßkurven in den Fig.2 und 3 näher erläutert.The method according to the invention will now be explained in more detail below with the aid of the apparatus-related measuring device with reference to the measuring curves in FIGS. 2 and 3.
Die beiden Meßkurven nach der Fig.2 betreffen die Messung des Antioxi- dantgleichwerr.es bei einem handelsüblichen Hydrauliköl, wobei über den Massenanteil an Hydroperoxid die erreichte Lichtmenge bei der Chemilumineszenz aufgetragen ist. Die durchgezogene Linie der Meßkurve I ergibt sich, wenn man die einzelnen Meßpunkte, die als Kästchen dargestellt sind, unter Bildung von Durchschnittswerten miteinander verbindet. Solange die Meßkurve I bis zu dem Wert 0,0064 waagerecht verläuft, entsteht dabei keine Lichtmenge, d.h. zugegebene Hydroperoxide werden durch die im Hydrauliköl befindlichen Antioxidantien kompensiert. Solange das Antioxi- dant nicht verbraucht ist, setzt auch noch keine Alterung des Öls ein und die angesprochene Chemilumineszenz unterbleibt. Sind die Antioxidantien hingegen aufgebraucht, im vorliegenden Fall bei einem Schwellenwert von 0,0064 Massenanteil-Hydroperoxid, nimmt alterungsbedingt der Hydroper- oxidanteil zu und die Chemilumineszenz setzt meßbar ein. Ist der Schwellenwert bis zum Einsetzen der Chemilumineszenz erreicht, so stellt der dahingehende Molanteil an Hydroperoxid ein Äquivalent für die im Fluid befindlichen Antioxidantanteile dar.The two measurement curves according to FIG. 2 relate to the measurement of the antioxidant equivalent in a commercially available hydraulic oil, the amount of light achieved during chemiluminescence being plotted over the mass fraction of hydroperoxide. The solid line of the measurement curve I results when the individual measurement points, which are shown as boxes, are connected with one another to form average values. As long as the measurement curve I runs horizontally up to the value 0.0064, there is no amount of light, i.e. added hydroperoxides are compensated for by the antioxidants in the hydraulic oil. As long as the antioxidant has not been used up, the oil does not age and the chemiluminescence mentioned does not occur. If, on the other hand, the antioxidants are used up, in the present case at a threshold value of 0.0064 mass fraction hydroperoxide, the hydroperoxide proportion increases due to aging and the chemiluminescence begins to be measured. If the threshold is reached by the onset of chemiluminescence, the mole fraction of hydroperoxide in question represents an equivalent for the antioxidant components in the fluid.
Die Eliminationsreaktion der Peroxide durch die Antioxidantien erfolgt in einem stöchiometrischen Verhältnis. Eine indirekte Messung des Antioxi- dantiengehaltes in Ölen kann also auch nach dem Prinzip der schrittweisen Zugabe von Peroxiden und gleichzeitiger Chemilumineszenzmessung er- folgen. Durch schrittweise Zugabe von Peroxiden ist es also möglich, die Äquivalentmenge an Antioxidantien im Öl verläßlich zu bestimmen, denn auch die Chemilumineszenz steht in stöchiometrischem Verhältnis zur Peroxidkonzentration. Das Feststellen der Äquivalentmenge an Antioxidantien erbringt dann den Nachweis über die Alterungssituation bzw. die Qualität des zu untersuchenden Fluids.The elimination reaction of the peroxides by the antioxidants takes place in a stoichiometric ratio. An indirect measurement of the antioxidant content in oils can also be based on the principle of the gradual addition of peroxides and simultaneous chemiluminescence measurement. consequences. By gradually adding peroxides, it is possible to reliably determine the equivalent amount of antioxidants in the oil, because chemiluminescence is also in a stoichiometric ratio to the peroxide concentration. The determination of the equivalent amount of antioxidants then provides evidence of the aging situation or the quality of the fluid to be examined.
Der Chemilumineszenzeffekt läßt sich durch Aufheizen der Probe in der Meßkammer 10 über die Heizeinrichtung 24 verbessern. Des weiteren läßt sich der Quantenwirkungsgrad steigern und mithin die Lichtintensität, sofern man bei der Messung Fluorophore einsetzt. Besonders geeignete Fluorophore ist dabei 9, 10-Dibromanthracen oder 3-Aminofluoranthen. Mit der Steigerung der Lichtintensität ist eine Vergrößerung der Meßauflösung möglich und mithin eine genauere Ölanalyse. Die Meßkurve II in der Fig.2 zeigt den dahingehenden Effekt, wobei die Fluorophore den Olproben zugesetzt werden. Es ist dabei eine Steigerung um das 5- bis 20-fache der Lichtemission bei der Chemilumineszenz beobachtet worden. Eine weitere Möglichkeit besteht darin, die fluoroszierenden Hilfsstoffe auf einem Glasträger od.dgl. in den optischen Weg zwischen Probe und Photomultiplier zu set- zen. Eine Immobilisierung der Fluorophore ist insbesondere dann vorteilhaft, sofern man eine Meßkammer im Durchflußbetrieb betreiben möchte, d.h. mit der Möglichkeit der Online-Messung bei kontinuierlich strömenden Fluiden.The chemiluminescent effect can be improved by heating the sample in the measuring chamber 10 via the heating device 24. Furthermore, the quantum efficiency and thus the light intensity can be increased if fluorophores are used in the measurement. Particularly suitable fluorophores are 9, 10-dibromoanthracene or 3-aminofluoranthene. With the increase in light intensity, an increase in the measurement resolution is possible and therefore a more precise oil analysis. The measurement curve II in FIG. 2 shows the relevant effect, the fluorophores being added to the oil samples. An increase of 5 to 20 times the light emission during chemiluminescence has been observed. Another possibility is to put the fluoroscent additives on a glass support or the like. in the optical path between the sample and the photomultiplier. Immobilization of the fluorophores is particularly advantageous if you want to operate a measuring chamber in flow mode, i.e. with the possibility of online measurement with continuously flowing fluids.
Zur Bestimmung der sog. Oxidationsstabilität eines Öles wird dieses in Gegenwart von Sauerstoff erhitzt und die Temperatur bzw. die Zeit bis zur einsetzenden Oxidation des Öles bestimmt. Einsetzende Oxidation des Fluids ist anhand der alterungsbedingten Peroxidbildung und -Zersetzung als Emission von Chemilumineszenzlicht meßbar. Für ungealterte Öle liegt diese Temperatur zeithöher als bei schon gealterten Ölen, da ungealterte Öle Antioxidantien enthalten, die einer Oxidation (Hydroperoxidbildung) entgegenwirken (vgl. Fig. 4).To determine the so-called oxidation stability of an oil, it is heated in the presence of oxygen and the temperature or the time until the oil begins to oxidize. The onset of oxidation of the fluid can be measured as the emission of chemiluminescent light based on the aging-related peroxide formation and decomposition. For unaged oils this temperature is higher than in the case of oils which have already aged, since unaged oils contain antioxidants which counteract oxidation (hydroperoxide formation) (cf. FIG. 4).
Die Bestimmung des Peroxidgehaltes im Öl kann auch unter Ausschluß von Sauerstoff, insbesondere von Luftsauerstoff, erfolgen. Aus den bereits angesprochenen Überlegungen zur Alterung von Ölen geht hervor, daß es erst dann zur Bildung von Peroxiden in Öl kommt, wenn keine Antioxidantien im Öl mehr wirksam sind. Die Abwesenheit von Antioxidantien und Anwe- senheit von Peroxiden läßt mithin auf ein gealtertes Öl schließen. Insbesondere der nach der Chemilumineszenzmethode geführte Nachweis von im Fluid durch Alterung gebildeten Peroxiden erlaubt eine Aussage zum Alterungszustand des Fluids. Die Messung der stationären Peroxidkonzentration stellt ein Äquivalent zur Alterungsgeschwindigkeit des Öles dar. Ein hierauf basierendes online-Meßverfahren mit temperierter Durchflußmeßstelle dient der kontinuierlichen Messung der Alterungsgeschwindigkeit und Anzeige des Fluidzustandes.The peroxide content in the oil can also be determined in the absence of oxygen, in particular atmospheric oxygen. From the considerations regarding the aging of oils which have already been mentioned, it can be seen that peroxides in oil only form when there are no longer any antioxidants in the oil. The absence of antioxidants and the presence of peroxides suggests an aged oil. In particular, the detection of peroxides formed in the fluid by aging using the chemiluminescence method allows a statement to be made about the aging state of the fluid. The measurement of the stationary peroxide concentration is equivalent to the aging rate of the oil. An online measuring method based on this with a temperature-controlled flow measuring point serves for the continuous measurement of the aging rate and display of the fluid state.
Eine Aussage über den Alterungszustand und die Alterungsgeschwindigkeit läßt sich auch erreichen, indem bei konstanter Temperatur abwechselnd Sauerstoff und Stickstoff über das Fluid geführt wird. Die dahingehenden Meßkurven sind in der Fig.3 dargestellt, wobei die Meßkurve III ein handelsübliches Neuöl und die Meßkurve IV ein bereits im Gebrauch befindliches handelsübliches Altöl zeigt. Die mit 02 und N2 unterteilten Meßberei- ehe betreffen den Vorgang der Sauerstoffzufuhr in die Meßkammer bzw. die Stickstoffzufuhr in dieselbe. Die Amplitude und Phasenlage der Chemilumineszenz, die hier mit relativer Lichtintensität angegeben ist, ist mithin ein Maß für den Alterungszustand von Kohlenwasserstoffverbindungen in nicht wässrigen Lösungen, wobei die zu vergleichenden Alterungsge- schwindigkeiten entlang der vorgegebenen Zeitachse t in den Meßkurven III und IV mit einem Doppelpfeil sowohl für das Altöl als auch für das Neuöl angegeben sind. Von besonderem Vorteil ist die Möglichkeit, durch Einprä- gung eines alternierenden Rhythmuses der Alterungsgeschwindigkeit selbst kleine Signale in verrauschter Umgebung auswerten zu können, um so die Auflösung geringer Alterungsgeschwindigkeiten zu ermöglichen.A statement about the state of aging and the rate of aging can also be achieved by alternately passing oxygen and nitrogen over the fluid at a constant temperature. The relevant measurement curves are shown in FIG. 3, with measurement curve III showing a commercially available new oil and measurement curve IV showing a commercially available used oil. The measuring ranges subdivided with 0 2 and N 2 relate to the process of supplying oxygen to the measuring chamber or supplying nitrogen to the same. The amplitude and phase position of the chemiluminescence, which is given here with relative light intensity, is therefore a measure of the aging state of hydrocarbon compounds in non-aqueous solutions, the aging conditions to be compared speeds along the specified time axis t in the measurement curves III and IV are indicated with a double arrow both for the old oil and for the new oil. Of particular advantage is the possibility of being able to evaluate even small signals in a noisy environment by impressing an alternating rhythm of the aging rate, in order to enable the resolution of low aging rates.
Mit dem erfindungsgemäßen Meßverfahren ist es möglich, eine Meß- und- Auswerteeinrichtung zu schaffen, die sehr kompakt aufbaut und die vor Ort beispielsweise an Arbeitsmaschinen an deren Hydraulik anschließbar ist. Die Meß- und Auswerteeinrichtung ist dann in der Lage, vor Ort im Online- Betrieb ein Warnsignal an eine Leitstelle od.dgl. abzugeben, sofern durch die Chemilumineszenz angesagt das Öl einen Alterungszustand aufweist, das seinen Austausch notwendig erscheinen läßt. With the measuring method according to the invention, it is possible to create a measuring and evaluation device which has a very compact structure and which can be connected on site to work machines, for example, to their hydraulics. The measuring and evaluation device is then able to transmit a warning signal to a control center or the like on site in online operation. to be given, provided that the oil shows an aging state due to the chemiluminescence, which makes its replacement appear necessary.

Claims

P a t e n t a n s p r ü c h e Patent claims
1 . Verfahren zur Ermittlung der Qualität, insbesondere des Alterungszustandes von Fluiden, die Kohlenwasserstoffe enthalten, die unter Einwirkung von Sauerstoff Radikale und Peroxide bilden, dadurch gekennzeichnet, daß mittels Chemilumineszenz eine Bestimmung des Gehaltes von Peroxiden im Fluid mittels einer Meß- und Auswerteeinrichtung durchgeführt wird.1 . Method for determining the quality, in particular the aging condition, of fluids which contain hydrocarbons which form radicals and peroxides under the action of oxygen, characterized in that the content of peroxides in the fluid is determined by means of chemiluminescence by means of a measuring and evaluation device.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, daß durch Aufheizen unter Ausschluß von Sauerstoff anhand der Messung der Chemilumineszenz der Alterungszustand des Fluids bestimmt wird.2. The method according to claim 1, characterized in that the aging state of the fluid is determined by heating with the exclusion of oxygen based on the measurement of chemiluminescence.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß in alternierender Abfolge unter Zuführen von Sauerstoff sowie seinem Ausschluß, insbesondere durch Zuführen von Stickstoff, anhand der Intensität der Chemilumineszenz die Alterungsgeschwindigkeit des Fluids bestimmt wird.3. The method according to claim 1 or 2, characterized in that the aging rate of the fluid is determined in an alternating sequence with the addition of oxygen and its exclusion, in particular by adding nitrogen, based on the intensity of chemiluminescence.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß durch die Zugabe von Hydroperoxid, insbesondere in Form von Cumolhydroperoxid, in das Fluid ein Peroxidüberschuß zur Bestimmung der Äquivalentmenge der im Fluid vorhandenen Antioxidantien eingebracht wird, so daß hieraus ein Maß für den Fluidzustand und seine Restgebrauchsdauer abgeleitet werden kann.4. The method according to any one of claims 1 to 3, characterized in that by adding hydroperoxide, in particular in the form of cumene hydroperoxide, an excess of peroxide is introduced into the fluid to determine the equivalent amount of the antioxidants present in the fluid, so that a measure of this the fluid state and its remaining service life can be derived.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Qualität des Fluids insbesondere in Form von Kohlenwasser- Stoffverbindungen in nicht wässrigen Lösungen bei erhöhten Temperaturen bestimmt wird.5. The method according to any one of claims 1 to 4, characterized in that the quality of the fluid in particular in the form of hydro- Compounds in non-aqueous solutions at elevated temperatures is determined.
6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß zur Erhöhung der bei der Chemilumineszenz entstehenden Lichtmenge dem Fluid Fluorophore zugesetzt werden oder daß das Fluid mit an Werkstoffoberflächen immobilisierten Fluorophoren in Kontakt gebracht wird.6. The method according to any one of claims 1 to 5, characterized in that fluorophores are added to the fluid to increase the amount of light produced during chemiluminescence, or that the fluid is brought into contact with fluorophores immobilized on material surfaces.
7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß durch Aufheizen des Fluids in Anwesenheit von Sauerstoff mittels Chemilumineszenz das Altern des Fluids im Zeitraffer beobachtet wird, aus dem ein Maß für die Stabilität gegen Sauerstoff in verschiedenen Konzentrationen abgeleitet werden kann.7. The method according to any one of claims 1 to 6, characterized in that by heating the fluid in the presence of oxygen by means of chemiluminescence, the aging of the fluid is observed in time-lapse, from which a measure of the stability against oxygen in different concentrations can be derived.
8. Meß- und Auswerteeinrichtung zum Durchführen des Verfahrens nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß zur Erfassung der bei der Chemilumineszenz entstehenden Lichtmenge eine Sensoreinrichtung (20), insbesondere ein Photomultiplier, vorhanden ist, der seine Sensordaten für die weitere Auswertung an eine Rechnereinheit (34), insbesondere in Form eines Mikroprozessors, weiterleitet.8. Measuring and evaluation device for carrying out the method according to one of claims 1 to 7, characterized in that for detecting the amount of light generated during chemiluminescence, a sensor device (20), in particular a photomultiplier, is present, which its sensor data for further evaluation to a computer unit (34), in particular in the form of a microprocessor.
9. Meß- und Auswerteeinrichtung nach Anspruch 8, dadurch gekennzeichnet, daß das Fluid vorzugsweise im Durchfluß in eine Meßkammer (10) gelangt, die lichtdicht gegenüber der Umgebung abgeschlossen ist bis auf eine Austrittsstelle (18) für die Lichterfassung durch die Sensoreinrichtung (20). 9. Measuring and evaluation device according to claim 8, characterized in that the fluid preferably flows through in a measuring chamber (10) which is light-tight to the environment except for an exit point (18) for light detection by the sensor device (20) ,
0. Meß- und Auswerteeinrichtung nach Anspruch 9, dadurch gekennzeichnet, daß die Meßkammer (10) mittels einer Heizeinrichtung (24) beheizt ist und daß die Sensoreinrichtung zur Erhöhung der Qualität der Messung einen Shutter (22) aufweist.0. Measuring and evaluation device according to claim 9, characterized in that the measuring chamber (10) is heated by means of a heating device (24) and that the sensor device has a shutter (22) to increase the quality of the measurement.
1. Meß- und Auswerteeinrichtung nach einem der Ansprüche 8 bis 10, dadurch gekennzeichnet, daß wahlweise Anschlüsse (44) vorhanden sind für die Zu- und Abfuhr von Fluid, Sauerstoff, Stickstoff und Hydroperoxid. 1. Measuring and evaluation device according to one of claims 8 to 10, characterized in that optional connections (44) are provided for the supply and removal of fluid, oxygen, nitrogen and hydroperoxide.
PCT/EP2000/011525 1999-11-27 2000-11-20 Method and device for determining the quality of fluids WO2001040779A1 (en)

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