CN1399719A - Method and device for determining quality of fluids - Google Patents
Method and device for determining quality of fluids Download PDFInfo
- Publication number
- CN1399719A CN1399719A CN 00816191 CN00816191A CN1399719A CN 1399719 A CN1399719 A CN 1399719A CN 00816191 CN00816191 CN 00816191 CN 00816191 A CN00816191 A CN 00816191A CN 1399719 A CN1399719 A CN 1399719A
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- China
- Prior art keywords
- liquid
- measurement
- chemiluminescence
- analytical equipment
- oxygen
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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
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
Technical field
The present invention relates to a kind of method that is used for quality, the especially ageing state of definite liquid, liquid is included in the following hydrocarbon that forms group and hydroperoxide of effect of oxygen.
Background technology
Liquid for example hydraulic fluid mainly is made up of the metastable hydrocarbon of chemical property.In order to improve the utilizability of these liquid, also will be a small amount of other substance dissolves therein, especially adopt the form of so-called adjuvant.With regard to the thermal stability and ageing stability of liquid, the proof form is that adjuvant antioxidant, that influence liquid reactions is even more important.
The common ground of all these liquid is, have oxygen such as atmosphere in oxygen and have chemical process to take place under the operating high-temperature condition of liquid appearing at such as meeting, its quality of getting off for a long time to these liquid has a negative impact.People also are called the aging of liquid to these processes that liquid quality is had a negative impact.In the multistage aging reaction that carries out, be formed with temporary transient or middle oxygen intergrade, the so-called intermediate of containing.They then react with other material or with self according to its reactivity.The quantity of these intermediates and decomposition rate are the standards that is used to weigh the liquid ageing state.
Oil deterioration, more precisely the oxidation of its hydrocarbon component is to be undertaken by the free radical chain mechanism process that forms hydroperoxide.Although the bad product that pre-determines in the aging reaction that is undertaken by group forms, superoxide always at first forms aging initial product.The subsequent products of aging reaction can be included into product group ethanol, ester, carboxylic acid, aldehyde etc.Though can not precognition can form what ageing prod in becoming chain reaction, superoxide always at first forms the initial product by the aging ethanol that forms, ketone, condensate etc.And, the objective of the invention is to determine the hydroperoxide that exists in the liquid, so that judge the remaining term of life of hydraulic fluid, and before having formed ageing products actually, determine that the quantity of initial product draws the conclusion of relevant liquid metathesis product quantity by the amount of determining initial product.Another object of the present invention is promptly to carry out relevant aging mensuration when liquid flow in on-line operation.In addition, the device that is used to carry out this method will be made effectively.
During the hydroperoxide as the aging reaction initial level forms, chemiluminescence can appear, that is to say, because chemical reaction takes place, have the light emission in the liquid.
Light is transmitted in and can be attended by ultraviolet ray, visible light or infrared ray under the luminance temperature of related liquid substance and takes place.Here it is luminous that the chemiluminescence of the biosome of mentioning is also referred to as biosome, but be different from the luminous of firefly.
Summary of the invention
The basis of the measuring method that describes below is such fact, promptly, as long as comprise effective additives such as antioxidant in the liquid, the hydroperoxide of freely measuring preferably reacts with antioxidant, causes the speed of the aging one-tenth chain reaction of liquid just to descend greatly like this.If but antioxidant exhausts, the hydroperoxide of Xing Chenging just begins to be carried out to chain reaction so, the ageing products that has decomposed when having formed the light emission therein in large quantities.In addition, can directly draw the conclusion of relevant aging reaction speed by the measuring light emission.Also can draw the conclusion of the various states of relevant liquid by changing measuring operation such as oxidation stability, peroxide level and oxidation preventive content.
Description of drawings
Device to method of the presently claimed invention and this method of execution is elaborated with reference to the accompanying drawings, the accompanying drawing not drawn on scale, wherein:
Fig. 1 shows the basic structure of measurement and analytical equipment;
Fig. 2 shows and relates to the measurement curve that the antioxidant equivalent is measured;
Fig. 3 shows the ratio of aging speed between aging liquid (top measurement curve) and the new liq (bottom measurement curve) with the form of measuring curve;
Fig. 4 is for being condition, T with the qualified relation between T and the t
1＞T
2And t
1＞t
2The oxygenated atmosphere environment in oxidation resistant survey sheet, T=f (t) or T are constant, wherein
T
2(ageing oil) and T
1(unaged oil)
t
2(ageing oil) and t
1(unaged oil)
L/V be light intensity, T be Celsius temperature, t in hour time.
Embodiment
Measurement that its basic structure is shown in Figure 1 and analytical equipment have one and measure chamber 10.In measuring chamber 10, liquid that be studied or oil samples for example are placed to that form is on the thing frame 12 of microslide.Measure chamber 10 and covered the light sealing by shell 14 with respect to external environment.Shell 14 particularly is made of a top component that removably is connected on the tabular bottom part, so that can allow the operator contact the inside of shell 14.Measure chamber 10 and surround, and have an outlet position 18, being that the sensing device 20 of photomultiplier carries out light and detects by form at the distolateral plate 16 that is insulated.
Photomultiplier receives by the light quantum that limits the sample emission in the solid angle.Described photomultiplier comprises a device that is called cascode, also is called photon counter.Since the existence of external photoelectric effect, the electronics that the photon collision of incident comes out from photocathode.This simple electronics produces a large amount of secondary electrons in cascade electrode subsequently, it can be measured as the quantity of electric charge that limits at the output terminal of cascode.The quantity of electric charge that produces and the photon energy of collection are proportional; The number of charge pulse is also corresponding with the constant portion of ballistic phonon.
Cascode in the photomultiplier 20 is arranged in the outer shell cavity 14 that covers light with sample.And, a movably dimmer is arranged in the shell 14, this dimmer has been arranged, sample in measuring chamber 10 and the light path between the photomultiplier 20 just can be interrupted or connect.Thereby, the light quantum and the destructive phenomenon of sample emission can be distinguished, for example radioactivity background radiation, it can trigger the electronics in the cascode equally; This is called background noise.
The dimmer 22 that is not shown specifically is made of a kind of right cylinder of the supporting that can be pivoted of particular form, and it has the photomultiplier 20 that has shaded place, grid ground amplifying circuit on the longitudinal axis.In this right cylinder that can rotate by driven by power, have a translucent opening, like this along with cylindrical rotation, the light path between cascode and the sample is just interrupted termly and is connected.When dimmer 22 interrupts light paths, measure and analytical equipment can detect and causes the background noise of makeing mistakes, after the optical sensor arrangement of photomultiplier 20 was opened, just the light quantum that sample is launched carried out the measurement of reality.Then, measurement and analytical equipment deduct background noise from the measured value that reality obtains, thereby determine the light quantity of actual transmission.Thereby got rid of wrong measurement reliably.Can adopt a lens combination to replace dimmer 22, so that movably mirror (scanner) and a spectrometer come together to collect light (collector lens) (not shown whole elements) with one.
Be formation and the decomposition that encourages described sample intermediate, can utilize 24 pairs of heating arrangements to measure chamber 10 and heat.Heating arrangement 24 for example can be formed by resistive heating system etc., and when when the direction of observation of Fig. 1 is seen, it is positioned at the below of measuring chamber 10.In order to write down the temperature of sample, in the base plate 26 of heating arrangement 24, has a temperature sensor 28.Except heating arrangement 24, have a cooling device 30 in the upper area that in shell 14 and by insulcrete 16 and heating arrangement 24, separates, its form is a desk fan especially, is used for the heat-sensitive electronic components in the photomultiplier 20 are for example cooled off.
Photomultiplier 20 is electrically connected with voltage source 32, and it is 34 measurement data acquisition and analytic system that this sensing device 20 and temperature sensor 28 send its measurement data to label together, this system has an oscillograph 36 and an analog to digital converter 38 in the view of Fig. 1, be used for the chemiluminescence signal 40 and the temperature signal 42 of analytic curve form.For liquid, oxygen, nitrogen, the hydroperoxide that will be studied is provided selectively, to there be a kind of web member 44 at least, it leads to the measurement chamber of closing in other cases 10.Also can adopt a Modern microprocessor that is used for the measurement data analysis to replace described computer unit 34.
Utilize described hardware measurement mechanism that method of the presently claimed invention is described in detail below with reference to the measurement curve in Fig. 2 and 3.
Measure the measurement that curve relates to the antioxidant equivalent that is used for the commercial liquid hydraulic fluid for shown in Figure 2 two, horizontal ordinate is represented the number percent that the hydrogen peroxide amount is shared among the figure, and ordinate is represented chemiluminescnet light quantity.When each measurement point of representing when etui interconnects mutually along with the formation of mean value, just formed the measurement curve I of solid line.As long as the measurement curve I value of moving in the horizontal direction is 0.0064 place, just do not form light quantity, that is to say that the hydroperoxide of increase is balanced by the antioxidant in the hydraulic fluid.As long as antioxidant does not consume, liquid does not just begin to wear out, and described chemiluminescence just is suppressed.On the other hand, if antioxidant is consumed, be under the situation of boundary value 0.0064 at the shared number percent of hydrogen peroxide amount, the ratio of hydroperoxide increases because wear out, and just can begin to have measured chemiluminescence.If boundary value reaches during chemiluminescence in beginning, just the ratio of the antioxidant in the molar ratio of so corresponding hydroperoxide and the liquid is suitable.
Superoxide and antioxidant are with stoichiometric proportion generation elimination reaction.According to the principle that superoxide increases and carry out simultaneously the chemiluminescence measurement gradually, also can measure indirectly the content of antioxidant in the liquid.Therefore, by increasing superoxide gradually, just can determine the equivalent amount of antioxidant in the liquid reliably, because chemiluminescence also becomes stoichiometric proportion with the concentration of superoxide.The equivalent amount one of antioxidant is fixing, has just shown the quality of aging performance with the liquid that will be studied.
The chemiluminescence effect can and improve through the sample heating in 24 pairs of measurements of heating arrangement chamber 10.In addition,, just can improve quantum efficiency, also just increase light intensity if use fluorophore during measuring.Particularly suitable fluorophore is 9, the amino fluoranthene of 10-dibromoanthracene or 3-.Measurement Resolution improves along with the increase of light intensity, and can carry out fluid analysis more accurately.Measure curve II among Fig. 2 and shown coherence effect, wherein fluorophore is added in the fluid sample.The light emission of here observing in the chemiluminescence has strengthened 5-20 doubly.Another kind of possibility is in the light path between sample and photomultiplier the fluoroscopic assist agent to be placed on the microslide etc.Operate under circulation pattern if measure the chamber, on-line measurement when liquid continuous flow just, maintaining static of fluorophore is particularly advantageous so.
In order to determine so-called liquid oxidation stability, under the aerobic situation, heat, and definite temperature and time that begins oxidation until liquid.Can will cause the formation of aging superoxide and decompose the initial oxidation of measuring liquid as chemiluminescnet emission.For not aged liquid, this temperature is longer than the time that continues in aging liquid, because not aged liquid comprises the antioxidant (comparison diagram 4) that resists oxidation (formation of hydroperoxide).
Oxygen in the oxygen especially atmosphere can be removed external the determining of peroxide level in the oil that carry out.Consideration item during according to oil degradation draws such conclusion, that is, have only when antioxidant and no longer do the time spent in oil, and superoxide just is formed in the oil.Therefore, the existence of the shortage of antioxidant and superoxide has shown oil deterioration.Particularly, utilized information that chemiluminescence method confirms, that evidence that be formed on the superoxide in the liquid through wearing out has produced relevant liquid ageing state.The concentration of measuring the stable state superoxide is equivalent to measure the aging speed of liquid.The state that is used for measuring continuously aging speed and express liquid based on On-line Measuring Method this point, that have temperature control flow measurement position.
The information relevant with ageing state and aging speed can obtain by alternately select oxygen and the nitrogen path on liquid under constant temperature.Relevant measurement curve is shown in Figure 3, measures curve III and represents commercial fresh oil, represents the commercial ageing oil that uses already and measure curve IV.Use O
2And N
2The measurement range of segmentation relates to the process of delivering oxygen and nitrogen in measuring the chamber.In addition, here chemiluminescnet amplitude and the phasing degree that provides with relative light intensity is a standard that is used for weighing hydrocarbon ageing state in the non-aqueous solution, wherein, the aging speed that is compared marks with double-head arrow along measuring the time shaft t shown in curve III and the IV, and double-head arrow not only refers to used oil but also refer to fresh oil.Particularly advantageous is even if can analyze signal little in the noisy environment by add the alternation rhythm and pace of moving things to aging speed, thereby can differentiate little aging speed.
Measuring method of the presently claimed invention has been arranged, just might form a kind of like this measurement and analytical equipment, that is, its structure is very compact, can be connected on the spot on the hydraulic system of a work done machine for example.If as chemiluminescence indicated, oil has the ageing state that need change, this measurement and analytical equipment just can send to control desk with caution signal on the spot in on-line operation so.
Claims (11)
1. the method for the quality of definite liquid, especially ageing state, liquid are included in the hydrocarbon that forms group and hydroperoxide under the oxygen effect, it is characterized in that, by chemiluminescence, determine the content of superoxide in the liquid with a measurement and analytical equipment.
2. the method for claim 1 is characterized in that, gets rid of oxygen by heating, by chemiluminescent measurement, determines the ageing state of liquid.
3. method as claimed in claim 1 or 2 is characterized in that, oxygen is being provided and with especially providing in the alternating sequence of nitrogen except it, is utilizing chemiluminescent intensity to determine the aging speed of liquid.
4. as each described method among the claim 1-3, it is characterized in that, by adding form to liquid especially is the hydroperoxide of cumene hydroperoxide thing, form excessive superoxide and determine the equivalent amount of antioxidant in the liquid, so just can therefrom measure liquid condition and remaining term of life thereof.
5. as each described method among the claim 1-4, it is characterized in that the quality of liquid is at high temperature especially determined with the form of hydrocarbon in the non-aqueous solution.
6. as each described method among the claim 1-5, it is characterized in that,, add fluorophore to liquid, or the fluorophore on making liquid and being fixed on body surface contacts for raising is formed on light quantity in the chemiluminescence.
7. as each described method among the claim 1-6, it is characterized in that,, in low-speed cinematography, observe the aging of liquid, therefrom can measure the antioxygen stability under the variable concentrations by means of chemiluminescence by heating liquid under the aerobic situation.
8. carry out as the measurement and the analytical equipment of method as described in each among the claim 1-7, it is characterized in that, for record is formed on light quantity in the chemiluminescence, has a sensing device (20), especially photomultiplier, its sensing data form that is sent to that will be used for further analyzing especially is the computer unit of microprocessor (34).
9. measurement as claimed in claim 8 and analytical equipment, it is characterized in that, liquid preferably runs to one and measures in the chamber (10) in circulation, this measurement chamber is used for being detected the outlet position (18) of light by sensing device (20) except one, covers the light sealing with respect to external environment.
10. measurement as claimed in claim 9 and analytical equipment is characterized in that, this measures chamber (10) by a heating arrangement (24) heating, and this sensing device has one and is used to improve the sensor (22) of measuring quality.
11., it is characterized in that having the selectivity web member (44) that is used to provide with discharge liquid, oxygen, nitrogen and hydroperoxide as each described measurement and analytical equipment among the claim 8-10.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1999157212 DE19957212A1 (en) | 1999-11-27 | 1999-11-27 | Method for determining the quality of fluids and device for carrying out the method |
| DE19957212.7 | 1999-11-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1399719A true CN1399719A (en) | 2003-02-26 |
| CN1180241C CN1180241C (en) | 2004-12-15 |
Family
ID=7930605
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB008161917A Expired - Fee Related CN1180241C (en) | 1999-11-27 | 2000-11-20 | Method and device for determining quality of fluids |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP1240502A1 (en) |
| JP (1) | JP2003515741A (en) |
| CN (1) | CN1180241C (en) |
| AU (1) | AU1858101A (en) |
| DE (1) | DE19957212A1 (en) |
| WO (1) | WO2001040779A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH698784B1 (en) * | 2006-06-22 | 2009-10-30 | Acl Instr Ag | Chemiluminescence analyzer. |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4350495A (en) * | 1980-12-08 | 1982-09-21 | Broutman L J | Chemiluminescence apparatus and method for determining the oxidative stability of polymers |
| US4793977A (en) * | 1987-04-09 | 1988-12-27 | Cape Cod Research, Inc. | Colorimetric detector for monitoring oil degradation |
| DE69127196T2 (en) * | 1990-06-12 | 1998-01-02 | British Tech Group | ANTIOXIDANT TEST |
| US5472878A (en) * | 1992-11-16 | 1995-12-05 | Microbiomed Corp. | Fluorescent method for monitoring oil degradation |
| RU2110788C1 (en) * | 1993-08-27 | 1998-05-10 | Валерий Никитович Петров | Method of determination of remaining service life of lubricating oil and device intended for its realization |
| JP3765626B2 (en) * | 1996-09-03 | 2006-04-12 | 出光興産株式会社 | Method for judging the degree of deterioration of lubricating oil |
| US5818599A (en) * | 1997-03-28 | 1998-10-06 | Atlas Electric Devices Co. | Apparatus and method for accelerated testing of materials |
-
1999
- 1999-11-27 DE DE1999157212 patent/DE19957212A1/en not_active Withdrawn
-
2000
- 2000-11-20 CN CNB008161917A patent/CN1180241C/en not_active Expired - Fee Related
- 2000-11-20 WO PCT/EP2000/011525 patent/WO2001040779A1/en not_active Application Discontinuation
- 2000-11-20 JP JP2001542194A patent/JP2003515741A/en active Pending
- 2000-11-20 EP EP00981278A patent/EP1240502A1/en not_active Withdrawn
- 2000-11-20 AU AU18581/01A patent/AU1858101A/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| WO2001040779A1 (en) | 2001-06-07 |
| EP1240502A1 (en) | 2002-09-18 |
| DE19957212A1 (en) | 2001-06-07 |
| CN1180241C (en) | 2004-12-15 |
| AU1858101A (en) | 2001-06-12 |
| JP2003515741A (en) | 2003-05-07 |
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