CA2170774C - A method and apparatus for determining the concentration of a component present in a fluid stream in dispersed form - Google Patents
A method and apparatus for determining the concentration of a component present in a fluid stream in dispersed form Download PDFInfo
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- CA2170774C CA2170774C CA 2170774 CA2170774A CA2170774C CA 2170774 C CA2170774 C CA 2170774C CA 2170774 CA2170774 CA 2170774 CA 2170774 A CA2170774 A CA 2170774A CA 2170774 C CA2170774 C CA 2170774C
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- 239000012530 fluid Substances 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000005259 measurement Methods 0.000 claims abstract description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- 230000000694 effects Effects 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 239000000356 contaminant Substances 0.000 claims description 12
- 230000003595 spectral effect Effects 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 4
- 230000005855 radiation Effects 0.000 claims description 2
- 239000000523 sample Substances 0.000 description 24
- 239000003921 oil Substances 0.000 description 22
- 229930195733 hydrocarbon Natural products 0.000 description 12
- 150000002430 hydrocarbons Chemical class 0.000 description 12
- 239000004215 Carbon black (E152) Substances 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007619 statistical method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
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- 239000008240 homogeneous mixture Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 150000007524 organic acids Chemical class 0.000 description 1
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- 231100000719 pollutant Toxicity 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 238000011867 re-evaluation Methods 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000012883 sequential measurement Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
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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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3577—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing liquids, e.g. polluted water
Abstract
A method and apparatus for determining the concentration of a component present in a fluid stream in dispersed form wherein the following steps are carried out: (a) emitting a light beam in a predetermined range of wavelengths to a fluid sample to be analyzed, said sample flowing through a measurement cell; (b) selecting a number of different wavelengths in said predetermined range; (c) measuring a number of light intensities while sample fluid is flowing through the measurement cell and deriving therefrom a number of measurement sets which each consists of a number of measured light intensities at said different wavelengths; (d) measuring a number of light intensities, while reference fluid is flowing through the measurement cell and deriving therefrom a number of reference fluid measurement sets which each consists of a number of measured reference light intensities at said different wavelengths; (e) deriving from the data, thus obtained, information on the concentration of dispersed components in the fluid stream.
Description
~1~~~~4 A METHOD AND APPARATUS FOR DETERMINING THE CONCENTRATION
OF A COMPONENT PRESENT IN A FLUID STREAM IN DISPERSED FORM
The invention relates in general to a method and apparatus for determining the concentration of a first fluid which is finely divided in a second fluid. Generally, a system wherein a first fluid is finely divided in a second fluid is defined a dispersed system, i.e. the first fluid (dispersed phase) is wandering about the second fluid (dispersing medium) in a finely divided form.
As known to those skilled in the art, dispersed systems can be sub-divided as follows: dependent on the diameter of the dispersed phase particles, a dispersed system can be a solution (homogeneous mixture in which no settling occurs and in which solute particles are at the molecular or ionic state of subdivision); a colloidal system (an intermediate kind of mixture in which the solute-like particles are suspended in the solvent-like phase and in which the particles of the dispersed phase are small enough that settling is negligible and large enough to make the mixture appear cloudy); or a suspension (a clearly heterogeneous mixture in which solute-like particles immediately settle out after mixing with a solvent-like phase).
In particular, the present invention relates to a method and apparatus for determining the concentration of a contaminant in a fluicl stream in dispersed form.
More in particular, the invention relates to detecting and measuring the concentration of dispersed hydrocarbon (oil) and/or particulate materials in a water stream.
The continuous on-line measurement of oil-in-water concentration is becoming increasingly important in order to meet future effluent quality standard.
A variety of instruments is known for measuring the oil present in water streams and is installed to monitor produced water discharges.
, These known instruments have inherent problems when applied to mixed pollutant waste streams and cannot discriminate between the oil contamination of interest and the presence of other materials.
Concern over the impact of industrial activities on the environment, often heightened by public concern and legislative requirements, has led to a re-evaluation of the wastes and discharges which routinely occur.
Historically, produced water has been disposed of to the environment after treatment, either by release to surface waters or by re-injection into suitable aquifiers or the production formations themselves. Strict quality levels are imposed by statutory authorities and these vary from maximum dispersed oil concentrations of 5 mg/1 for discharge to fresh water systems, to dispersed oil concentrations of 40 mg/1 for water streams discharged to the open sea. Current trends will result in reduction of these levels within the foreseeable future. New limits of 30 mg/1 have been proposed.
This will call for the on-line measurement of the discharge streams, and closer/improved control of the water treatment facilities, if the new standards are to be met.
Statutory measurement methods differ significantly throughout the world. However, the principle methods are based on infra-red measuring techniques in the 3.2 to 3.5 fun wavelength range. This requires the sampling of the water discharge, laboratory extraction of the oil present in a water sample by a suitable solvent, and the 2~ subsequent measurement of the oil concentration. In known solvent based instruments for determining oil concentrations water is to be separated from the oil, e.g. by means of halogenated solvents, and subsequently an infra-red (3.5 )un) analysis is carried out.
These methods have been shown to be time-consuming and inaccurate in practice. Changes in international convention will prohibit the use of the solvents used. Numerous commercial on-line monitors are available, based on a variety of detection principles e.g. (visible) light scattering, I.R.-absorption and the like. None have proved satisfactory for use in oil industry applications.
It ~s an object of the invention to provide a method and r. arv...nre..."n,.w.aMYn~..r~~~,.adwls.M.raN.ww.a...w.4rr, apparatus for determining the concentration of a dispersed component e.g. a contaminant in a fluid stream, based upon short wavelength measurement enabling the accurate detection and measurement of (low) concentration of hydrocarbon and/or other contaminants present in a fluid stream, concurrently and independently.
The invention therefore provides a method for determining the concentration of a component present in a fluid stream in dispersed form comprising the steps of a) emitting a light beam in a predetermined range of wavelengths to a fluid sample to be analyzed, said sample flowing through a measurement cell; b) selecting a number of different wavelengths in said predetermined range; c) measuring a number of light intensities while sample fluid is flowing through the measurement cell and deriving therefrom a number of measurement sets which each consist of a number of measured light intensities at said different wavelengths; d) measuring a number of light intensities, while reference fluid is flowing through the measurement cell and deriving therefrom a number of reference fluid measurement sets; e) deriving from the data, thus obtained, information on the concentration of dispersed components in the fluid stream, characterized in that said reference fluid measurement sets each consist of a number of measured reference light intensities at said different wavelengths, and that step e) comprises calculating normalized light intensity differences for each of the sample fluid measurement sets by subtracting and subsequently dividing by the reference light intensity at the corresponding wavelength, and fitting the said normalized light intensity differences to form a linear combination of a determined number of relative spectral responses which take into account the manner in which the said normalized light ., , .~.~,*.,.~...." , **,...».,~"..~.,~.H, .
OF A COMPONENT PRESENT IN A FLUID STREAM IN DISPERSED FORM
The invention relates in general to a method and apparatus for determining the concentration of a first fluid which is finely divided in a second fluid. Generally, a system wherein a first fluid is finely divided in a second fluid is defined a dispersed system, i.e. the first fluid (dispersed phase) is wandering about the second fluid (dispersing medium) in a finely divided form.
As known to those skilled in the art, dispersed systems can be sub-divided as follows: dependent on the diameter of the dispersed phase particles, a dispersed system can be a solution (homogeneous mixture in which no settling occurs and in which solute particles are at the molecular or ionic state of subdivision); a colloidal system (an intermediate kind of mixture in which the solute-like particles are suspended in the solvent-like phase and in which the particles of the dispersed phase are small enough that settling is negligible and large enough to make the mixture appear cloudy); or a suspension (a clearly heterogeneous mixture in which solute-like particles immediately settle out after mixing with a solvent-like phase).
In particular, the present invention relates to a method and apparatus for determining the concentration of a contaminant in a fluicl stream in dispersed form.
More in particular, the invention relates to detecting and measuring the concentration of dispersed hydrocarbon (oil) and/or particulate materials in a water stream.
The continuous on-line measurement of oil-in-water concentration is becoming increasingly important in order to meet future effluent quality standard.
A variety of instruments is known for measuring the oil present in water streams and is installed to monitor produced water discharges.
, These known instruments have inherent problems when applied to mixed pollutant waste streams and cannot discriminate between the oil contamination of interest and the presence of other materials.
Concern over the impact of industrial activities on the environment, often heightened by public concern and legislative requirements, has led to a re-evaluation of the wastes and discharges which routinely occur.
Historically, produced water has been disposed of to the environment after treatment, either by release to surface waters or by re-injection into suitable aquifiers or the production formations themselves. Strict quality levels are imposed by statutory authorities and these vary from maximum dispersed oil concentrations of 5 mg/1 for discharge to fresh water systems, to dispersed oil concentrations of 40 mg/1 for water streams discharged to the open sea. Current trends will result in reduction of these levels within the foreseeable future. New limits of 30 mg/1 have been proposed.
This will call for the on-line measurement of the discharge streams, and closer/improved control of the water treatment facilities, if the new standards are to be met.
Statutory measurement methods differ significantly throughout the world. However, the principle methods are based on infra-red measuring techniques in the 3.2 to 3.5 fun wavelength range. This requires the sampling of the water discharge, laboratory extraction of the oil present in a water sample by a suitable solvent, and the 2~ subsequent measurement of the oil concentration. In known solvent based instruments for determining oil concentrations water is to be separated from the oil, e.g. by means of halogenated solvents, and subsequently an infra-red (3.5 )un) analysis is carried out.
These methods have been shown to be time-consuming and inaccurate in practice. Changes in international convention will prohibit the use of the solvents used. Numerous commercial on-line monitors are available, based on a variety of detection principles e.g. (visible) light scattering, I.R.-absorption and the like. None have proved satisfactory for use in oil industry applications.
It ~s an object of the invention to provide a method and r. arv...nre..."n,.w.aMYn~..r~~~,.adwls.M.raN.ww.a...w.4rr, apparatus for determining the concentration of a dispersed component e.g. a contaminant in a fluid stream, based upon short wavelength measurement enabling the accurate detection and measurement of (low) concentration of hydrocarbon and/or other contaminants present in a fluid stream, concurrently and independently.
The invention therefore provides a method for determining the concentration of a component present in a fluid stream in dispersed form comprising the steps of a) emitting a light beam in a predetermined range of wavelengths to a fluid sample to be analyzed, said sample flowing through a measurement cell; b) selecting a number of different wavelengths in said predetermined range; c) measuring a number of light intensities while sample fluid is flowing through the measurement cell and deriving therefrom a number of measurement sets which each consist of a number of measured light intensities at said different wavelengths; d) measuring a number of light intensities, while reference fluid is flowing through the measurement cell and deriving therefrom a number of reference fluid measurement sets; e) deriving from the data, thus obtained, information on the concentration of dispersed components in the fluid stream, characterized in that said reference fluid measurement sets each consist of a number of measured reference light intensities at said different wavelengths, and that step e) comprises calculating normalized light intensity differences for each of the sample fluid measurement sets by subtracting and subsequently dividing by the reference light intensity at the corresponding wavelength, and fitting the said normalized light intensity differences to form a linear combination of a determined number of relative spectral responses which take into account the manner in which the said normalized light ., , .~.~,*.,.~...." , **,...».,~"..~.,~.H, .
intensity at each wavelength changes proportional to other wavelengths for certain effects responsible for the measured light intensity differences, in order to give sets of proportionality constants which are indicative for the certain effects in question; and multiplying at least one of said proportionality constants by a calibration factor to obtain an absolute value of the concentration of dispersed components in the fluid stream.
The invention further provides an apparatus for l0 determining the concentration of a component present in a fluid stream in dispersed form, comprising means for emitting a light beam in a predetermined range of wavelengths to a fluid sample to be analyzed, said sample flowing through a measurement cell; means for selecting a number of different wavelengths in said predetermined range;
means for measuring a number of light intensities while sample fluid or reference fluid is flowing through the measurement cell and means for deriving from said number of light intensities a number of measurement sets which each consist of a number of measured light intensities at different wavelengths; and a number of reference liquid measurement sets, which each consist of a number of measured reference light intensities at said different wavelengths;
and means for deriving from the data, thus obtained, information on concentration of dispersed components in the fluid stream, characterized in that said reference liquid measurement sets each consist of a number of measured reference light intensities at said different wavelengths, and that means are present for calculating normalized light intensity differences for each of the sample fluid measurement sets by subtracting and subsequently dividing by the reference light intensity at the corresponding wavelength, and fitting the said normalized light intensity . ,N. ", ~....~.",",~,. ".,~,~"",",,~.~"..,.,."u"
- 4a -differences to form a linear combination of a determined plurality of relative spectral responses which take into account the manner in which the said normalized light intensity at each wavelength changes proportional to other wavelengths for certain effects responsible for the measured light intensity differences, in order to give sets of proportionality constants which are indicative for the relative spectral response in question; and multiplying at least one of said proportionality constants by a calibration factor to obtain an absolute value of dispersed components in the fluid stream.
Advantageously, the said predetermined range of wavelengths is in the near-infra-red range (1.0-2.5 ~cm).
The invention is based upon the application of a short wavelength, optical principle, based upon multiple wavelength measurement, comparison of differently treated samples of a test fluid, and statistical methods, which can detect and analyse small spectral differences between the samples caused by the presence of contaminants at different concentrations. The principle is based upon a combination of the scattering, and absorption properties which are related to refractive index and size distribution of the contaminants.
Further, the invention combines the principles of light scattering (sensitive to suspended components) and light absorption (sensitive to dissolved components).
Advantageously, visible light (0.4-1 um) can be emitted simultanesouly with the near infra-red radiation and at least one wavelength is selected in the said visible light range.
.., .~". ",..,"."m",.~w"w".m,.,...r.4.w.~..,W.r....,.~.1.~.....
- 4b -In particular, the invention is further based upon a differential measurement system to take two separate measurements under different sample conditions and allow comparison of the differences between them.
It is remarked that WO-A-85/04478 discloses an oil-in-water measurement wherein a reference sample is applied.
However, this measurement is only based upon absorption in the 3.4 to 3.5 ~,m wavelength range and the specific technique of the present invention has neither been disclosed nor suggested.
Further, FR-A-2685775 discloses a method for providing the polycyclic aromatics content in a hydrocarbon mixture using near-infra-red spectro photometric analysis in the 0.8-2.6 um wavelength range and DE-A-3633916discloses a method for determining concentrations using absorption of light in the infra-red to ultraviolet range.
However, the specific technique of the invention based upon the combination of scattering and absorption has not been disclosed.
The invention will now be described in more detail by way of example by reference to the accompanying drawings, in which:
fig. 1 represents schematically the principle of a prior art oil-in-water measuring instrument;
fig. 2 represents schematically the principle of the present invention.
Referring to fig. 1 a block scheme of a prior art oil-in-water analyzer is shown.
~.....". ,.,.~.,..,..,."...,w.,""".,...",,,~"~.~,~yy.~..,a,"""~,."......
Block 1 represents the oil-in-water sample to be analyzed.
Usually oils comprise hydrocarbons and are not water-soluble.
R'O 95/068y3 PGT/EP94/02956 ~ ~~~74 The hydrocarbons comprise CH-chains. Each of these chains has a different energy-absorption band in the 3.4-3.5 Eun range of the infra-red absorption spectrum.
It will be appreciated by those skilled in the art that, when measuring the infra-red absorption of an oil sample between 3.4 and 3.5 Vim, the absorption is related to the oil concentration in the sample. As water also absorbs energy in the infra-red band between 3.4 and 3.5 dun, it is virtually impossible to determine low oil concentrations in a water Sample. For this purpose the oil present in the water should be separated prior to measurement.
Halogenated solvents supplied in any way suitable for the purpose via line 2 are suitable to separate oil from water for the , subsequent infra-red analysis 3 as a) these solvents are virtually insoluble in water;
b) they have a specific gravity higher than water:
c) they dissolve easily all volatile or non-volatile organic compounds; and d) they do not absorb infra-red energy in the range of 2-4.5 dun.
After processing (block 4) of the infra-red analysis data 3, infoz-motion (block 5) on the oil concentration is derived.
In fig. 2 the principle of the invention will be described in more detail. No solvent is applied and advantageously a predetermined number of wavelengths in the optical range, e.g. near-infra-red (1.0-2.5 Eun) is used.
Light is emitted from any suitable light source 1' via any suitable optical system 2' to a sample or measurement cell 3'.
Detention takes place via any suitable optical system 4' by any suitable detector 5' which is suitably connected e.g. via an amplifier 6' and A/D converter 7' to a computer 8' for data processing purposes. A set of measured light intensities is provided which are processed further in a data processing step Which leads to the measurement of the concentration of contaminant in the fluid.
The sample or measurement cell 3' is connected in any suitable manner to a flow selection means 9'; reference numerals 10', 11' represent suitable filters. A and B represent an inlet for contaminated fluid and a drain respectively.
In the optical system 2' wavelength selection is suitably achieved by narrow band interference filters. These are e.g. mounted on a rotating disc assembly (filter wheel), forming a light beam chopper, and allowing sequential wavelength measurement of the measuring system and fluid sample within the measurement cell 3', under identical conditions. Such sequential measurements can be carried out at relatively high speed (e. g. 500 r.p.m.). It is also possible to apply a number of separate light sources, each having a different wavelength, rather than a filter wheel. The reference and sample fluids are controlled and fed through the measurement cell (3') (e. g. 0.6 mm wide) by e.g. electrically controlled valves, with fluid flowing continuously through the measurement cell to ensure temperature stability and representative water conditions.
The complete device (not shown in detail for reasons of clarity) comprises a detector assembly, light source, chopper/filter, test cell, water control valves, and infra-red detector/amplifier. The reference fluid stream is produced from the contaminated fluid by a suitable filter assembly, to produce a fluid stream free of dispersed oil andlor other contamination. Any filter suitable for the purpose can be applied, as will be appreciated by those skilled in the art. E.g. a filter having a pore size < O.OOl~un is applied in case of dissolved contaminants, whereas in case of other dispersed contaminants a filter having a pore size of 0.001-1Nm is suitably applied.
Advantageously, in case of oil-in-water monitoring, both the concentration of the dissolved and of other dispersed hydrocarbon components, if any, can be determined by a sequence of two differential measurements, which differ only by the type of filter applied to create the reference water stream from the contaminated water stream. The concentration of dissolved contaminants can be determined by comparing the contaminated water stream with a , dissolved component-free water stream, which is created by feeding the contaminated water through a suitable filter, e.g. pore size 0.001-1 Eun. The said filter filters out all other dispersed companents but does not filter out the dissolved components. Next, the concentration of dissolved components can be determined by comparing the said dispersed-free water stream with a water stream free from both dissolved and said other dispersed components, which is created by feeding the contaminated water through a suitable filter (pore size < 0.001 Eun). In the following the general differential method will be described.
The operation of the invention is as follows:
In case of oil-in-water-monitoring, the hydrocarbon concentration, as determined by the hydrocarbon-in-water monitor, is obtained after a sequence of data processing steps on the measured light intensities. This sequence uses values taken from two measuring steps. These basic measuring steps and the subsequent data processing will be described here.
In the first measuring step, during a number of rotations (e. g.
100) of the filter wheel light intensities im are measured while sample water is flowing through the test cell. For each rotation of the filter wheel a measurement set im~~ is measured, which consists of a number of measured light intensities at different wavelengths ~, (corresponding to the number of filters (e.g. 8) mounted in the filter wheel). In this example, in total, 100 measurements sets im~~~n with n = 1-100) are collected, giving 800 measurement values. The large amount of measurements taken allows statistical analysis to improve the accuracy of the instrument. From e.g. 100 measurement sets, e.g. the 10 measurement sets which have the largest deviation from the average light intensity, are rejected. Thus, 90 sample water measurement sets remain for further processing.
In the second measuring step, again during e.g. 100 rotations of the filter wheel, light intensities are measured, but now while reference water is flowing through the test cell. Again, after rejecting e.g. 10~ of the measurements with largest deviation, this gives 90 reference water measurement sets. From these values, at each wavelength 7~, the averaged light intensity is calculated, giving the reference light intensity ix~~ at 8 wavelengths.
.. ...,..~ "". ,.e.."~"~~..~..~,~,w"",~,y~",~"",.kn,....
_ g _ Then, the normalized light intensity differences d~,,n are calculated for each of the 90 sample water measurement sets by subtracting and subsequently dividing by the reference light intensity at the corresponding wavelength, using Zm,~.,n Zx,~
dRn -Zx,A
Different effects are responsible for the measured light intensity differences. The ones considered here are the temperature difference between sample water and l0 reference water, the oil concentration in the sample water and the particle concentration in the sample water. Now, from calibration experiments it is known how for these effects the normalized lights intensity at each wavelength changes proportional to other wavelengths. This proportionality for a certain effect k is termed a relative spectral response yk,a. Therefore, with the same measurement principle it is possible to address effects from a very different physical origin.
Next, in the data processing, for each measurement set of the wavelengths (e. g. 8) the normalized light intensity differences are fitted using three proportionality constants P'k to form a linear combination of the three relative spectral responses, given by (2) d R,n - ~ .vk,~. ~ p k,n -~Y~.,n k=1 The fitting is done such that the squares of the residual differences r~,between measured light intensitites and the linear combination of relative spectral responses is minimized (least squares fitting). In this example, in total, 90 least square fits are performed giving 90 sets ....." .....~~.",.~,,..,",.~..~",.,""."w, _ - 8a -of 3 proportionality constants, which are indicative for the temperature difference, hydrocarbon concentration, and particle concentration.
To obtain absolute values Pk for the temperature difference, hydrocarbon concentration, and particle concentration, the proportionality constants obtained from the fitting procedure are multiplied by calibration factors Ck. using _ g _ Pk. n = Ck ~ fkn ( 3 ) These calibration factors are determined (e. g. experimentally, using a predetermined oil-in-water mixture, e.g. created by an accurate oil-injection). In this example, in total, 90 values for the 'temperature difference, oil concentration, and particle concentration are obtained. Finally, from these values the average oil and particle concentration together with their respective standard deviation are calculated.
It will be appreciated that the reference water conditioning system can be selected in such a manner that it is possible to measure and calculate the concentration of the dissolved and the dispersed components. This will entail two reference water systems and applying the above-mentioned calculation technique of the desired concentrations in order to detect the presence of these materials from the measured data.
It will be appreciated by those skilled in the art that any optical wavelength and any number of wavelengths suitable for the purpose can be applied in the said predetermined range of wavelengths.
Advantageously, the number of wavelengths applied is four to ten and in particular eight, e.g. 1.3, 1.43, 1.5, 1.6, 1.73, 2.16, 2.23 and 2.29 Eun. It has appeared that advantageous effects of using such wavelengths are the following:
7i, = 1.43 ftm, especially sensitive to temperature ~, = 1.30 Eun, ~, = 2.29 Eun, the combination of these wavelengths is especially sensitive to dispersed oil ~, = 2.23 Hm, especially sensitive to total dissolved hydrocarbons ~. = 2.16 lun, especially sensitive to dissolved aliphatic hydrocarbons . ~. = 2.29 dun, especially sensitive to dissolved aromatic hydrocarbons.
Further, it will be appreciated that any number of rotations of the filter wheel and any suitable number of relative spectral responses can be applied. The measuring principle of the invention -Z1 ~
is capable of the detection of a large number of quality parameters of a discharge stream, such as salt concentration, alcohols and organic acids and similar contaminants.
Further, it will also be appreciated by those skilled in the art that the invention is not restricted to oil-in-water monitoring but can be applied for the measurement of a range of fluid based applications: e.g. dissolved hydrocarbons and other materials in water, fine dispersed materials in either aqueous or hydrocarbon streams, chemical quality analysis and the like.
10 Various modifications of the present invention will become apparent to those skilled in the art from the foregoing description.
Such modifications are intended to fall within the scope of the appended claims.
The invention further provides an apparatus for l0 determining the concentration of a component present in a fluid stream in dispersed form, comprising means for emitting a light beam in a predetermined range of wavelengths to a fluid sample to be analyzed, said sample flowing through a measurement cell; means for selecting a number of different wavelengths in said predetermined range;
means for measuring a number of light intensities while sample fluid or reference fluid is flowing through the measurement cell and means for deriving from said number of light intensities a number of measurement sets which each consist of a number of measured light intensities at different wavelengths; and a number of reference liquid measurement sets, which each consist of a number of measured reference light intensities at said different wavelengths;
and means for deriving from the data, thus obtained, information on concentration of dispersed components in the fluid stream, characterized in that said reference liquid measurement sets each consist of a number of measured reference light intensities at said different wavelengths, and that means are present for calculating normalized light intensity differences for each of the sample fluid measurement sets by subtracting and subsequently dividing by the reference light intensity at the corresponding wavelength, and fitting the said normalized light intensity . ,N. ", ~....~.",",~,. ".,~,~"",",,~.~"..,.,."u"
- 4a -differences to form a linear combination of a determined plurality of relative spectral responses which take into account the manner in which the said normalized light intensity at each wavelength changes proportional to other wavelengths for certain effects responsible for the measured light intensity differences, in order to give sets of proportionality constants which are indicative for the relative spectral response in question; and multiplying at least one of said proportionality constants by a calibration factor to obtain an absolute value of dispersed components in the fluid stream.
Advantageously, the said predetermined range of wavelengths is in the near-infra-red range (1.0-2.5 ~cm).
The invention is based upon the application of a short wavelength, optical principle, based upon multiple wavelength measurement, comparison of differently treated samples of a test fluid, and statistical methods, which can detect and analyse small spectral differences between the samples caused by the presence of contaminants at different concentrations. The principle is based upon a combination of the scattering, and absorption properties which are related to refractive index and size distribution of the contaminants.
Further, the invention combines the principles of light scattering (sensitive to suspended components) and light absorption (sensitive to dissolved components).
Advantageously, visible light (0.4-1 um) can be emitted simultanesouly with the near infra-red radiation and at least one wavelength is selected in the said visible light range.
.., .~". ",..,"."m",.~w"w".m,.,...r.4.w.~..,W.r....,.~.1.~.....
- 4b -In particular, the invention is further based upon a differential measurement system to take two separate measurements under different sample conditions and allow comparison of the differences between them.
It is remarked that WO-A-85/04478 discloses an oil-in-water measurement wherein a reference sample is applied.
However, this measurement is only based upon absorption in the 3.4 to 3.5 ~,m wavelength range and the specific technique of the present invention has neither been disclosed nor suggested.
Further, FR-A-2685775 discloses a method for providing the polycyclic aromatics content in a hydrocarbon mixture using near-infra-red spectro photometric analysis in the 0.8-2.6 um wavelength range and DE-A-3633916discloses a method for determining concentrations using absorption of light in the infra-red to ultraviolet range.
However, the specific technique of the invention based upon the combination of scattering and absorption has not been disclosed.
The invention will now be described in more detail by way of example by reference to the accompanying drawings, in which:
fig. 1 represents schematically the principle of a prior art oil-in-water measuring instrument;
fig. 2 represents schematically the principle of the present invention.
Referring to fig. 1 a block scheme of a prior art oil-in-water analyzer is shown.
~.....". ,.,.~.,..,..,."...,w.,""".,...",,,~"~.~,~yy.~..,a,"""~,."......
Block 1 represents the oil-in-water sample to be analyzed.
Usually oils comprise hydrocarbons and are not water-soluble.
R'O 95/068y3 PGT/EP94/02956 ~ ~~~74 The hydrocarbons comprise CH-chains. Each of these chains has a different energy-absorption band in the 3.4-3.5 Eun range of the infra-red absorption spectrum.
It will be appreciated by those skilled in the art that, when measuring the infra-red absorption of an oil sample between 3.4 and 3.5 Vim, the absorption is related to the oil concentration in the sample. As water also absorbs energy in the infra-red band between 3.4 and 3.5 dun, it is virtually impossible to determine low oil concentrations in a water Sample. For this purpose the oil present in the water should be separated prior to measurement.
Halogenated solvents supplied in any way suitable for the purpose via line 2 are suitable to separate oil from water for the , subsequent infra-red analysis 3 as a) these solvents are virtually insoluble in water;
b) they have a specific gravity higher than water:
c) they dissolve easily all volatile or non-volatile organic compounds; and d) they do not absorb infra-red energy in the range of 2-4.5 dun.
After processing (block 4) of the infra-red analysis data 3, infoz-motion (block 5) on the oil concentration is derived.
In fig. 2 the principle of the invention will be described in more detail. No solvent is applied and advantageously a predetermined number of wavelengths in the optical range, e.g. near-infra-red (1.0-2.5 Eun) is used.
Light is emitted from any suitable light source 1' via any suitable optical system 2' to a sample or measurement cell 3'.
Detention takes place via any suitable optical system 4' by any suitable detector 5' which is suitably connected e.g. via an amplifier 6' and A/D converter 7' to a computer 8' for data processing purposes. A set of measured light intensities is provided which are processed further in a data processing step Which leads to the measurement of the concentration of contaminant in the fluid.
The sample or measurement cell 3' is connected in any suitable manner to a flow selection means 9'; reference numerals 10', 11' represent suitable filters. A and B represent an inlet for contaminated fluid and a drain respectively.
In the optical system 2' wavelength selection is suitably achieved by narrow band interference filters. These are e.g. mounted on a rotating disc assembly (filter wheel), forming a light beam chopper, and allowing sequential wavelength measurement of the measuring system and fluid sample within the measurement cell 3', under identical conditions. Such sequential measurements can be carried out at relatively high speed (e. g. 500 r.p.m.). It is also possible to apply a number of separate light sources, each having a different wavelength, rather than a filter wheel. The reference and sample fluids are controlled and fed through the measurement cell (3') (e. g. 0.6 mm wide) by e.g. electrically controlled valves, with fluid flowing continuously through the measurement cell to ensure temperature stability and representative water conditions.
The complete device (not shown in detail for reasons of clarity) comprises a detector assembly, light source, chopper/filter, test cell, water control valves, and infra-red detector/amplifier. The reference fluid stream is produced from the contaminated fluid by a suitable filter assembly, to produce a fluid stream free of dispersed oil andlor other contamination. Any filter suitable for the purpose can be applied, as will be appreciated by those skilled in the art. E.g. a filter having a pore size < O.OOl~un is applied in case of dissolved contaminants, whereas in case of other dispersed contaminants a filter having a pore size of 0.001-1Nm is suitably applied.
Advantageously, in case of oil-in-water monitoring, both the concentration of the dissolved and of other dispersed hydrocarbon components, if any, can be determined by a sequence of two differential measurements, which differ only by the type of filter applied to create the reference water stream from the contaminated water stream. The concentration of dissolved contaminants can be determined by comparing the contaminated water stream with a , dissolved component-free water stream, which is created by feeding the contaminated water through a suitable filter, e.g. pore size 0.001-1 Eun. The said filter filters out all other dispersed companents but does not filter out the dissolved components. Next, the concentration of dissolved components can be determined by comparing the said dispersed-free water stream with a water stream free from both dissolved and said other dispersed components, which is created by feeding the contaminated water through a suitable filter (pore size < 0.001 Eun). In the following the general differential method will be described.
The operation of the invention is as follows:
In case of oil-in-water-monitoring, the hydrocarbon concentration, as determined by the hydrocarbon-in-water monitor, is obtained after a sequence of data processing steps on the measured light intensities. This sequence uses values taken from two measuring steps. These basic measuring steps and the subsequent data processing will be described here.
In the first measuring step, during a number of rotations (e. g.
100) of the filter wheel light intensities im are measured while sample water is flowing through the test cell. For each rotation of the filter wheel a measurement set im~~ is measured, which consists of a number of measured light intensities at different wavelengths ~, (corresponding to the number of filters (e.g. 8) mounted in the filter wheel). In this example, in total, 100 measurements sets im~~~n with n = 1-100) are collected, giving 800 measurement values. The large amount of measurements taken allows statistical analysis to improve the accuracy of the instrument. From e.g. 100 measurement sets, e.g. the 10 measurement sets which have the largest deviation from the average light intensity, are rejected. Thus, 90 sample water measurement sets remain for further processing.
In the second measuring step, again during e.g. 100 rotations of the filter wheel, light intensities are measured, but now while reference water is flowing through the test cell. Again, after rejecting e.g. 10~ of the measurements with largest deviation, this gives 90 reference water measurement sets. From these values, at each wavelength 7~, the averaged light intensity is calculated, giving the reference light intensity ix~~ at 8 wavelengths.
.. ...,..~ "". ,.e.."~"~~..~..~,~,w"",~,y~",~"",.kn,....
_ g _ Then, the normalized light intensity differences d~,,n are calculated for each of the 90 sample water measurement sets by subtracting and subsequently dividing by the reference light intensity at the corresponding wavelength, using Zm,~.,n Zx,~
dRn -Zx,A
Different effects are responsible for the measured light intensity differences. The ones considered here are the temperature difference between sample water and l0 reference water, the oil concentration in the sample water and the particle concentration in the sample water. Now, from calibration experiments it is known how for these effects the normalized lights intensity at each wavelength changes proportional to other wavelengths. This proportionality for a certain effect k is termed a relative spectral response yk,a. Therefore, with the same measurement principle it is possible to address effects from a very different physical origin.
Next, in the data processing, for each measurement set of the wavelengths (e. g. 8) the normalized light intensity differences are fitted using three proportionality constants P'k to form a linear combination of the three relative spectral responses, given by (2) d R,n - ~ .vk,~. ~ p k,n -~Y~.,n k=1 The fitting is done such that the squares of the residual differences r~,between measured light intensitites and the linear combination of relative spectral responses is minimized (least squares fitting). In this example, in total, 90 least square fits are performed giving 90 sets ....." .....~~.",.~,,..,",.~..~",.,""."w, _ - 8a -of 3 proportionality constants, which are indicative for the temperature difference, hydrocarbon concentration, and particle concentration.
To obtain absolute values Pk for the temperature difference, hydrocarbon concentration, and particle concentration, the proportionality constants obtained from the fitting procedure are multiplied by calibration factors Ck. using _ g _ Pk. n = Ck ~ fkn ( 3 ) These calibration factors are determined (e. g. experimentally, using a predetermined oil-in-water mixture, e.g. created by an accurate oil-injection). In this example, in total, 90 values for the 'temperature difference, oil concentration, and particle concentration are obtained. Finally, from these values the average oil and particle concentration together with their respective standard deviation are calculated.
It will be appreciated that the reference water conditioning system can be selected in such a manner that it is possible to measure and calculate the concentration of the dissolved and the dispersed components. This will entail two reference water systems and applying the above-mentioned calculation technique of the desired concentrations in order to detect the presence of these materials from the measured data.
It will be appreciated by those skilled in the art that any optical wavelength and any number of wavelengths suitable for the purpose can be applied in the said predetermined range of wavelengths.
Advantageously, the number of wavelengths applied is four to ten and in particular eight, e.g. 1.3, 1.43, 1.5, 1.6, 1.73, 2.16, 2.23 and 2.29 Eun. It has appeared that advantageous effects of using such wavelengths are the following:
7i, = 1.43 ftm, especially sensitive to temperature ~, = 1.30 Eun, ~, = 2.29 Eun, the combination of these wavelengths is especially sensitive to dispersed oil ~, = 2.23 Hm, especially sensitive to total dissolved hydrocarbons ~. = 2.16 lun, especially sensitive to dissolved aliphatic hydrocarbons . ~. = 2.29 dun, especially sensitive to dissolved aromatic hydrocarbons.
Further, it will be appreciated that any number of rotations of the filter wheel and any suitable number of relative spectral responses can be applied. The measuring principle of the invention -Z1 ~
is capable of the detection of a large number of quality parameters of a discharge stream, such as salt concentration, alcohols and organic acids and similar contaminants.
Further, it will also be appreciated by those skilled in the art that the invention is not restricted to oil-in-water monitoring but can be applied for the measurement of a range of fluid based applications: e.g. dissolved hydrocarbons and other materials in water, fine dispersed materials in either aqueous or hydrocarbon streams, chemical quality analysis and the like.
10 Various modifications of the present invention will become apparent to those skilled in the art from the foregoing description.
Such modifications are intended to fall within the scope of the appended claims.
Claims (15)
1. A method for determining the concentration of a component present in a fluid stream in dispersed form comprising the steps of a) emitting a light beam in a predetermined range of wavelengths to a fluid sample to be analyzed, said sample flowing through a measurement cell;
b) selecting a number of different wavelengths in said predetermined range;
c) measuring a number of light intensities while sample fluid is flowing through the measurement cell and deriving therefrom a number of measurement sets which each consist of a number of measured light intensities at said different wavelengths;
d) measuring a number of light intensities, while reference fluid is flowing through the measurement cell and deriving therefrom a number of reference fluid measurement sets;
e) deriving from the data, thus obtained, information on the concentration of dispersed components in the fluid stream, characterized in that said reference fluid measurement sets each consist of a number of measured reference light intensities at said different wavelengths, and that step e) comprises calculating normalized light intensity differences for each of the sample fluid measurement sets by subtracting and subsequently dividing by the reference light intensity at the corresponding wavelength, and fitting the said normalized light intensity differences to form a linear combination of a determined number of relative spectral responses which take into account the manner in which the said normalized light intensity at each wavelength changes proportional to other wavelengths for certain effects responsible for the measured light intensity differences, in order to give sets of proportionality constants which are indicative for the certain effects in question; and multiplying at least one of said proportionality constants by a calibration factor to obtain an absolute value of the concentration of dispersed components in the fluid stream.
b) selecting a number of different wavelengths in said predetermined range;
c) measuring a number of light intensities while sample fluid is flowing through the measurement cell and deriving therefrom a number of measurement sets which each consist of a number of measured light intensities at said different wavelengths;
d) measuring a number of light intensities, while reference fluid is flowing through the measurement cell and deriving therefrom a number of reference fluid measurement sets;
e) deriving from the data, thus obtained, information on the concentration of dispersed components in the fluid stream, characterized in that said reference fluid measurement sets each consist of a number of measured reference light intensities at said different wavelengths, and that step e) comprises calculating normalized light intensity differences for each of the sample fluid measurement sets by subtracting and subsequently dividing by the reference light intensity at the corresponding wavelength, and fitting the said normalized light intensity differences to form a linear combination of a determined number of relative spectral responses which take into account the manner in which the said normalized light intensity at each wavelength changes proportional to other wavelengths for certain effects responsible for the measured light intensity differences, in order to give sets of proportionality constants which are indicative for the certain effects in question; and multiplying at least one of said proportionality constants by a calibration factor to obtain an absolute value of the concentration of dispersed components in the fluid stream.
2. The method as claimed in claim 1, wherein from the values of the reference fluid measurement sets, at each wavelength the averaged light intensity is calculated, giving the reference light intensity at each of said wavelengths.
3. The method as claimed in any one of claims 1-2, wherein the number of wavelengths is 4-10.
4. The method as claimed in any one of claims 1-3, wherein at least 100 measurement sets are collected.
5. The method as claimed in any one of claims 1-4, wherein the fluid is water, and the said component is a contaminant comprising at least one of oil and particles.
6. The method as claimed in any one of claims 1-5, wherein the certain effects are temperature difference, oil concentration and particle concentration.
7. The method as claimed in any one of claims 1-6, wherein the said predetermined range of wavelengths is in the near-infra-red range.
8. The method as claimed in clam 7, wherein in step a) simultaneously visible light is emitted, and in step b) at least one wavelength in said visible light range is selected.
9. An apparatus for determining the concentration of a component present in a fluid stream in dispersed form, comprising means for emitting a light beam in a predetermined range of wavelengths to a fluid sample to be analyzed, said sample flowing through a measurement cell;
means for selecting a number of different wavelengths in said predetermined range; means for measuring a number of light intensities while sample fluid or reference fluid is flowing through the measurement cell and means for deriving from said number of light intensities a number of measurement sets which each consist of a number of measured light intensities at different wavelengths; and a number of reference liquid measurement sets, which each consist of a number of measured reference light intensities at said different wavelengths; and means for deriving from the data, thus obtained, information on concentration of dispersed components in the fluid stream, characterized in that said reference liquid measurement sets each consist of a number of measured reference light intensities at said different wavelengths, and that means are present for calculating normalized light intensity differences for each of the sample fluid measurement sets by subtracting and subsequently dividing by the reference light intensity at the corresponding wavelength, and fitting the said normalized light intensity differences to form a linear combination of a determined plurality of relative spectral responses which take into account the manner in which the said normalized light intensity at each wavelength changes proportional to other wavelengths for certain effects responsible for the measured light intensity differences, in order to give sets of proportionality constants which are indicative for the relative spectral response in question;
and multiplying at least one of said proportionality constants by a calibration factor to obtain an absolute value of dispersed components in the fluid stream.
means for selecting a number of different wavelengths in said predetermined range; means for measuring a number of light intensities while sample fluid or reference fluid is flowing through the measurement cell and means for deriving from said number of light intensities a number of measurement sets which each consist of a number of measured light intensities at different wavelengths; and a number of reference liquid measurement sets, which each consist of a number of measured reference light intensities at said different wavelengths; and means for deriving from the data, thus obtained, information on concentration of dispersed components in the fluid stream, characterized in that said reference liquid measurement sets each consist of a number of measured reference light intensities at said different wavelengths, and that means are present for calculating normalized light intensity differences for each of the sample fluid measurement sets by subtracting and subsequently dividing by the reference light intensity at the corresponding wavelength, and fitting the said normalized light intensity differences to form a linear combination of a determined plurality of relative spectral responses which take into account the manner in which the said normalized light intensity at each wavelength changes proportional to other wavelengths for certain effects responsible for the measured light intensity differences, in order to give sets of proportionality constants which are indicative for the relative spectral response in question;
and multiplying at least one of said proportionality constants by a calibration factor to obtain an absolute value of dispersed components in the fluid stream.
10. The apparatus as claimed in claim 9, wherein wavelength selection is achieved by narrow band interference filters, mounted on a rotating disc assembly.
11. The apparatus as claimed in claim 9 or 10, wherein means are present for calculating at each wavelength the averaged light intensity from the values of the reference fluid measurement sets, giving the reference light intensity at each of said number of wavelengths.
12. The apparatus as claimed in any one of claims 9-11, wherein the said predetermined range of wavelengths is in the near-infra-red range.
13. The apparatus as claimed in claim 12, wherein means are present for emitting visible light simultaneously with the said near-infra-red radiation, and means for selecting at least one wavelength in said visible light range.
14. The apparatus as claimed in any one of claims 9-13, wherein the fluid is water, and the component is a contaminant comprising at least one of oil and particles.
15. The apparatus as claimed in claim 9 or 14, wherein the certain effects are temperature difference, oil concentration and particle concentration.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP93306972.6 | 1993-09-03 | ||
| EP93306972 | 1993-09-03 | ||
| PCT/EP1994/002956 WO1995006873A1 (en) | 1993-09-03 | 1994-09-01 | A method and apparatus for determining the concentration of a component present in a fluid stream in dispersed form |
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| Publication Number | Publication Date |
|---|---|
| CA2170774A1 CA2170774A1 (en) | 1995-03-09 |
| CA2170774C true CA2170774C (en) | 2005-11-01 |
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| CA 2170774 Expired - Fee Related CA2170774C (en) | 1993-09-03 | 1994-09-01 | A method and apparatus for determining the concentration of a component present in a fluid stream in dispersed form |
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| CN112763450A (en) * | 2020-12-14 | 2021-05-07 | 中国原子能科学研究院 | Method for simultaneously determining concentrations of aluminum nitrate and nitric acid in aqueous solution |
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