RU2798683C1 - Method for detecting fluorescent and alcohol tracers in their joint presence in formation waters during tracer interwell surveys - Google Patents

Abstract

FIELD: analytical chemistry.

SUBSTANCE: invention can be used in the field of the oil industry, in particular in the study of wells and interwell space. A method for detecting fluorescent and alcohol tracers in their joint presence in formation waters during tracer cross-well surveys, including analysis of a composition of indicators for geophysical surveys in formation water with their joint presence, separation of the studied sample of formation water from oil, purification of the sample from fine and organic impurities by clarification with a coagulant in an alkaline medium and centrifugation, dividing the sample into several portions, adding additional reagents to each portion of the sample to improve the quality of the analysis, carrying out sequential to quantitative analysis of the composition of indicators in the formed portions of the sample using fluorescence spectroscopy methods and chromato-mass spectrometry. The indicator composition consists of sulfosalicylic acid, 4-methylumbelliferone, tinopal CBS-x, sodium fluorescein, eosin B, rhodamine C, safranin T, methylene blue, monoethanolamine, diethanolamine, propylene glycol, 2-ethoxyethanol, ethylene glycol, diethylene glycol, isopropanol, glycerine, whereas fluorescent tracers are analysed at the pH of the medium in which they exhibit the most intense luminescence properties, taking into account the intersection of the luminescence spectra of tracers with a close arrangement of emission peaks, and tracers based on alcohols with a wide boiling temperature range of 82.4 - 290°C are analysed under optimal conditions for the flow rate of the carrier gas and the temperature sweep of the chromatograph column.

EFFECT: increased accuracy of the quantitative determination of tracers and reduced error in taking spectra.

1 cl, 2 dwg, 3 tbl

Description

The invention relates to analytical chemistry and can be used in the field of the oil industry, in particular in the study of wells and interwell space in the development of oil fields for the quantitative determination of sixteen tracers (sulfosalicylic acid, 4-methylumbelliferone, tinopal CBS-x, sodium fluorescein, eosin B, rhodamine C, safranin T, methylene blue, monoethanolamine, diethanolamine, propylene glycol, 2-ethoxyethanol, ethylene glycol, diethylene glycol, isopropanol, glycerin) in formation waters using a minimum number of sample preparation steps and analysis methods.

At the moment, a method is known for determining the concentrations of tracers in the joint presence (sodium fluorescein, potassium thiocyanate, carbamide) in formation waters using a calibration experiment and using spectrophotometric analysis (patent RU No. 2275619, IPC G01N 21/17, publ. 27.04.2006 , Bull. No. 12). Formation water sample is separated from oil in a separating funnel and cleaned from fine solid impurities using paper filters. Clarification of the sample occurs by adding coagulant and alkali, and then the resulting solid particles are removed by centrifugation. Next, the sample is divided into several equal parts according to the number of tracers being studied. Additional reagents and fixed additives are introduced into each portion to improve the accuracy of the analysis in the presence of tracers. As a result of three optical measurements by the interpolation method of each part of the sample, data are obtained on the quantitative content of tracers in them. The technical result is to increase the accuracy of optical changes in the nonlinear region of the dependence of the signal on the concentration due to the linearization of the plot of the dependence at the measurement point between two fixed additives.

The disadvantage of this method is the need to know the approximate concentration of the tracer in the sample to add the exact amount of fixed additives, as well as a small number of tracers quantified in the joint presence.

Another method for determining the concentration of tracers (sodium fluorescein, potassium nitrate, potassium thiocyanate and urea) in their joint presence in the formation water sample from an oil refinery well (patent RU No. 2301409, IPC G01J 3/00, publ. 06/20/2007, Bull No. 17). Formation water samples are physically separated from oil, filtered to remove solid impurities and clarified with coagulant agents in an alkaline environment, followed by centrifugation until visible opalescence disappears. The sample is divided into several equal parts according to the number of tracers. Quantitative determination of tracers in each sample is carried out using three optical measurements: one measurement for the prepared sample, and the other two for model solutions artificially prepared from formation water with a fixed addition of sodium fluorescein in the same amount as in the test sample, and tracers to be determined.

The technical result is to increase the accuracy of the quantitative determination of all tracers, with the exception of sodium fluorescein, as well as to reduce the error in taking spectra by subtracting its signal.

The disadvantage of this method is the long preparation of model solutions, the absence of a method for the quantitative determination of sodium fluorescein in the joint presence with other tracers in the initial sample, as well as a small number of tracers quantified in the joint presence.

The closest in technical essence is the method for analyzing formation water, which includes a composition of nine tracers: sodium fluorescein, rhodamine C, thiourea, urea, ammonium thiocyanate, sodium nitrate, isopropanol, propanol, and tert-butanol (patent RU No. 2762994, IPC G01N 21/17, published 04.11.2020, Bull. No. 36). This method of analysis includes separating the studied sample of formation water from oil, clarification by filtration through a hydrophilic membrane filter, separation of indicators, passing the sample through hydrophobized silica gel with grafted C8 octal groups, separating the eluate into portions, adding appropriate reagents for the analysis of ionic indicators and measuring absorption at characteristic for each wavelength indicator, the quantitative determination of sodium fluorescein and rhodamine C by the luminescent method is carried out by desorption from the sorbent with a mixture of methanol and water in a volume ratio of 80:20, a borate buffer with pH = 9.18 is added and measurements are taken, aliphatic alcohols are determined by the gas chromatographic method by analyzing the vapor phase with the addition of a salting out agent. The quantitative determination of individual indicators is carried out according to a separately constructed calibration on formation water that does not contain indicators.

The disadvantages of this method are the duration and complexity of the implementation of the analysis due to the large number of sample preparation steps, as well as a small number of jointly determined tracers, which limits the possibility of using this method in the analysis of large oil and gas fields.

Currently, to study the structure of the reservoir and conduct appropriate geophysical tests, the simultaneous use of a larger number of indicators (usually 12-16) is required.

The essence of the claimed invention is the development of a simple, sensitive and selective method for the quantitative determination of sixteen tracers (sulfosalicylic acid, 4-methylumbelliferone, tinopal CBS-x, sodium fluorescein, eosin B, rhodamine C, safranin T, methylene blue, monoethanolamine, diethanolamine, propylene glycol, 2 -ethoxyethanol, ethylene glycol, diethylene glycol, isopropanol, glycerin) in formation waters using a minimum number of sample preparation steps and analysis methods.

A method for detecting fluorescent and alcohol tracers in their joint presence in formation waters during tracer interwell studies, including analysis of a composition of indicators for geophysical studies in formation water in their joint presence, separation of the studied formation water sample from oil, purification of the sample from fine and organic impurities by clarification with a coagulant in an alkaline medium and centrifugation, dividing the sample into several portions, adding additional reagents to each portion of the sample to improve the quality of the analysis being carried out, carrying out a sequential quantitative analysis of the composition of indicators in the formed portions of the sample by the methods of fluorescence spectroscopy and chromato-mass spectrometry.

What is new is that the indicator composition consists of sulfosalicylic acid, 4-methylumbelliferone, tinopal CBS-x, sodium fluorescein, eosin B, rhodamine C, safranin T, methylene blue, monoethanolamine, diethanolamine, propylene glycol, 2-ethoxyethanol, ethylene glycol, diethylene glycol, isopropanol, glycerin, while fluorescent tracers are analyzed at the pH of the medium in which they exhibit the most intense luminescence properties, taking into account the intersection of the luminescence spectra of tracers with a close arrangement of emission peaks, and tracers based on alcohols with a wide boiling temperature range of 82.4 - 290 ° C analyzed under the optimal selection of conditions for the flow rate of the carrier gas and the sweep of the temperature of the chromatograph column.

The technical result of this invention consists in the use at the stage of analysis of the property of additivity of fluorescence signals of tracers based on fluorescent dyes, as well as in the selection of optimal conditions for the analysis of tracers based on alcohols by gas chromatography-mass spectroscopy using a programmable temperature sweep, at which it is possible to simultaneously determine both low-boiling and high-boiling polar organic compounds, which makes it easy, without additional costs for sample preparation, to simultaneously determine eight fluorescent and eight polar organic tracers in one sample while maintaining the accuracy of the studies at an acceptable level and using only two methods of analysis.

In FIG. 1 shows the excitation spectra of tracers 1-8 according to the numbering in table 1.

In FIG. Figure 2 shows tracer emissions 1-8 according to the numbering in Table 1.

An example of a specific implementation of the method

Within the framework of this method, a Hitachi_F-7000 fluorescent spectrophotometer is used for the analysis of fluorescent indicators; for the analysis of alcohols, a GCMS 2010 Plus Shimadzu Chromatography-Mass Spectrometer (Japan) is used using a Zebron non-polar capillary column (30 m - length, 0.25 mm - diameter , phase layer thickness - 1 μm, carrier gas - helium) and electron ionization of the samples. The identification of components is carried out using the NIST-11 mass spectrum library, which includes 212961 individual compounds.

The proposed method for analysis of formation water samples is carried out as follows.

Produced water sample containing a composition of sixteen tracers (sulfosalicylic acid, 4-methylumbelliferone, tinopal CBS-x, sodium fluorescein, eosin B, rhodamine C, safranin T, methylene blue, monoethanolamine, diethanolamine, propylene glycol, 2-ethoxyethanol, ethylene glycol, diethylene glycol , isopropanol, glycerin) is subjected to primary purification from mechanical impurities by filtration through a paper filter (blue ribbon). Next, the sample is clarified using the FeCl ₃ coagulant in an alkaline medium. The resulting solution is filtered, settled for a day and re-filtered before further analysis.

The quantitative determination of individual indicators is carried out by groups using a pre-built calibration on formation water that does not contain indicators.

The calibration of fluorescent tracers, as well as their determination, is carried out at the pH of the medium corresponding to the most intense luminescence of the tracer under study.

4-methylumbelliferone, sodium fluorescein, safranin T, rhodamine C, methylene blue are better defined in an alkaline medium at pH ≈ 9; sulfosalicylic acid, tinopal CBS-x, eosin B - in neutral, and safrain T - in acid. Determination of the luminescence intensity is carried out using the Hitachi_F-7000 instrument, keeping the instrument settings, such as the power of the light source and the monochromator slits, the same between calibration and testing for the tracer being determined. By graduation, the coefficients are determined in a linear dependence of the indicator luminescence intensity on its concentration:

,

,

where y is the signal of the spectrophotometer or chromatograph;

x is the concentration of the studied indicator C _i , g/dm ³ ;

a and b - calibration dependence coefficients.

To build calibration dependencies, water of medium mineralization with a mass fraction of salt of 10% and situationally modulated pH using a glycine-based buffer is used.

The results of instrument calibration (No. 1) for individual tracers are shown in Table 1.

Table 1 - Instrument calibration results for sixteen tracers No. Tracer name Coefficients of calibration dependence No. 1 Coefficients of calibration dependence No. 2 a _I ± Δa _I
( _λex ; _λem ;pH) b _I ± ∆b _I
( _λex ; _λem ;pH) a _II ± Δa _II
( _λex ; _λem ;pH) b _II ± Δb _II
( _λex ; _λem ;pH) 1 Sulfosalicylic acid 4.23*10 ⁷
(300; 400; 7) 111.5 1.02*10 ⁶
(330; 450; 9) 351 2 Tinopal 1.98*10 ⁸
(360; 410; 7) 330 0.94*10 ⁸
(330; 450; 9) 349 3 4-methylumbelliferone 0.808*10 ⁸
(330; 450; 9) 348 0.75*10 ⁶
(360; 410; 7) 325 4 Fluorescein 8.34* ¹⁰⁸
(490; 513; 9) 123 - - 5 Eosin B 2.02*10 ⁸
(515; 535; 7) 142 0.97*10 ⁷
(518; 587; 3) 115 6 Rhodamine C 2.74*10 ⁸
(555; 580; 9) 113 7.07* ¹⁰⁷
(518; 587; 3) 110 7 Safranin T 1.31*10 ⁷
(518; 587; 3) 112 1.93*10 ⁶
(555; 580; 9) 111 8 methylene blue 0.74*10 ⁷
(666; 687; 9) 100 - - 9 propylene glycol 2.89*10 ⁷
(-;-;7) 244
(-;-;7) - - 10 Diethanolamine 1.15*10 ⁷
(-;-;7) 161
(-;-;7) - - Table 1 continued eleven diethylene glycol 1.83*10 ⁷
(-;-;7) 192
(-;-;7) - - 12 ethylene glycol 2.23*10 ⁷
(-;-;7) 213
(-;-;7) - - 13 Propanol 3.16* ¹⁰⁷
(-;-;7) 516
(-;-;7) - - 14 Isopropanol 9.34*10 ⁷
(-;-;7) 232
(-;-;7) - - 15 Glycerol 3.59* ¹⁰⁷
(- ;- ;7) 326
(-;-;7) - - 16 Monoethanolamine 4.25*10 ⁷
(- ;- ;7) 457
(-;-;7) - -

The luminescence spectra of 4-methylumbelliferone and tinopal CBS-x, as well as rhodamine C and safranin T intersect in pairs (Fig. 1, 2), the luminescence spectrum of eosin B partially overlaps the luminescence spectrum of safranin T, just as the luminescence of sulfosalicylic acid partially overlaps the luminescence of tinopal CBS-x, in connection with which, for each of these tracers, an additional calibration of the device (No. 2) is carried out under the conditions of recording the luminescence of the interfering indicator, which differ mainly in the wavelengths of excitation and emission, as well as the pH of the medium. The overlap of the luminescence spectra between the remaining tracers is negligible due to the large difference in their excitation wavelengths, which makes it possible to ignore their intersection.

Analysis of the concentration of tracers is carried out in groups, built taking into account the most effective medium for determining the pH and the research method:

- 4-methylumbelliferone, sodium fluorescein, rhodamine C, methylene blue. To a certain aliquot of the test sample with a volume of 10 ml, add 1 ml of a glycine-based buffer solution with pH = 9 and a concentration of 1 g/l, thereby transferring the solution medium to the alkaline region. Luminescence is determined at excitation wavelengths λ _ex = 330 nm, 490 nm, 555 nm, 666 nm and emission wavelengths 446 nm, 513 nm, 580 nm, 687 nm for tracers 4-methylumbelliferone, sodium fluorescein, rhodamine C and methylene blue, respectively .

- Sulfosalicylic acid, tinopal CBS-x, eosin B. Some aliquot of the test sample is examined without additional modulation of the medium at pH = 7 - 8. Studies are carried out at excitation wavelengths λ _ex = 300 nm, 360 nm, 515 nm and emission wavelengths λ _em = 400 nm, 410 nm, 535 nm for tracers sulfosalicylic acid, tinopal CBS-x, eosin B.

- Safranin T. To some aliquot of the test sample with a volume of 10 ml, add 1 ml of a glycine-based buffer solution with pH = 3 and a concentration of 1 g / l, thereby transferring the solution medium to the acidic region, where the luminescence of Safranin T is more pronounced. Luminescence is determined at lengths excitation wavelengths _λex = 520 nm and emission wavelengths _λem = 587 nm for safranin T tracers, respectively.

- Monoethanolamine, diethanolamine, propylene glycol, 2-ethoxyethanol, ethylene glycol, diethylene glycol, isopropanol, glycerin. Some aliquot of the test sample is examined without additional modulation of the medium at pH = 7 - 8 by gas chromatography mass spectroscopy. At a temperature of 280 °C, 0.1 µl of a sample is introduced into the injector, which, at a carrier gas flow rate in the column (helium) - 1.5 ml/min, an initial column temperature of 40 °C with a heating rate of 10°C/min up to 250 °С, separation takes place on a non-polar capillary column "Zebron" 30 m long, 0.25 mm in diameter, phase layer thickness 1 μm with an electron-ion ionizer at an ion source temperature of 220 °С. The area of the peaks in the chromatogram determines the concentration of polar tracers.

Thus, eight luminescence parameters (I ₁ - I ₈ ) are determined, which allow the concentration of each fluorescent tracer to be determined individually. The values obtained must be within the linear concentration range for the tracer to be determined, which are listed in Table 2.

Table 2 - Linear concentration determination for tracers No. tracer Symbol for luminescence intensity Range of linear determination of concentration, g / dm ³ Sulfosalicylic acid I _SC 10 ^-5 - 10 ^-3 Tinopal I _T 10 ^-6 - 10 ^-4 4-methylumbelliferone I _4M 10 ^-6 - 10 ^-4 Fluorescein I _F 10 ^-6 - 10 ^-4 Eosin B I _E 10 ^-6 - 10 ^-4 Rhodamine C I _R 10 ^-6 - 10 ^-4 Safranin T I _ST 10 ^-5 - 10 ^-3 methylene blue I _MS 10 ^-5 - 10 ^-3 propylene glycol - 10 ^-3 - 1 Diethanolamine - 10 ^-3 - 1 diethylene glycol - 10 ^-3 - 1 ethylene glycol - 10 ^-3 - 1 Propanol - 10 ^-3 - 1 Isopropanol - 10 ^-3 - 1 Glycerol - 10 ^-3 - 1 Monoethanolamine - 10 ^-3 - 1

The concentrations of tracers based on sulfosalicylic acid, sodium fluorescein, eosin B, methylene blue, as well as monoethanolamine, diethanolamine, propylene glycol, 2-ethoxyethanol, ethylene glycol, diethylene glycol, isopropanol, glycerin are determined by formula (1) with known coefficients a _I and b _I , previously determined by calibration, having previously multiplied the luminescence values for sodium fluorescein and methylene blue by a factor of 1.1 in order to take into account dilution when setting pH.

The concentrations of tinopal CBS-x and 4-methyllumbelliferone are determined from the following system of equations with two unknowns:

where 1.1 is the dilution factor of the 4-methyllumbelliferone sample when modulating the pH of the medium,

a _n(m) , b _n(m) - coefficients from the equation of the calibration line,

n - index indicating that the coefficient belongs to the calibration line of an individual tracer (coincides with the indices in the luminescence intensity symbol),

m - index defining the number of the used calibration dependence,

C _T , C _4M - concentrations of tinopal CBS-x and 4-methylumbelliferone, respectively.

The concentrations of tracers of rhodamine C and safranin T are determined from another system of equations with two unknowns:

where 1.1 is the dilution factor for samples of rhodamine C and safranin T when modulating the pH of the medium,

a _n(m) , b _n(m) - coefficients from the equation of the calibration line, n - index indicating that the coefficient belongs to the calibration line of an individual tracer (coincides with the index in the luminescence intensity symbol),

m - index that determines the number of the calibration dependence used,

C _ST , C _R - concentrations of safranin T and rhodamine C, respectively.

Experimental evaluation of the performance of the proposed method for determining the concentrations of sixteen indicators (sulfosalicylic acid, 4-methylumbelliferone, tinopal CBS-x, sodium fluorescein, eosin B, rhodamine C, safranin T, methylene blue, monoethanolamine, diethanolamine, propylene glycol, 2-ethoxyethanol, ethylene glycol, diethylene glycol , isopropanol, glycerin) in formation water was carried out using the example of the analysis of three mixtures of these indicators. The results of quantitative determination of indicators in formation water without sorption and with sorption are presented in Table 3.

The relative error in determining the concentration of the n-th indicator was determined by the formula:

where С _в is the tracer concentration introduced into the sample, g/dm ³ ,

C _n - certain concentration of tracer n in the sample, g/dm ³ .

Table 3 - Results of quantitative determination of indicators in formation water without sorption and with sorption Tracer name Introduced concentration С _вв , g / dm ³ Certain concentration Calculation according to the calibration dependence of the tracer concentration Calculation using the additivity of the tracer luminescence signal C _n , μg / cm ³ Relative error δС, % C _n , μg / cm ³ Relative error δС, % Blend #1 Sulfosalicylic acid 6.00⋅10 ⁴ 5.92⋅10 ⁴ 1.28 5.92⋅10 ⁴ 1.28 Tinopal 5.00⋅10 ^{4 4.77⋅104} 4.53 5.01⋅10 ⁴ 0.19 4-methylum belliferone ^{2.00⋅105 2.57⋅105} 28.58 ^2.08⋅105 3.77 Fluorescein ^1.00⋅105 9.50⋅10 ⁶ 5.00 9.50⋅10 ⁶ 5.00 Eosin B ^{2.50⋅105 2.40⋅105} 3.89 ^2.40⋅105 3.88 Rhodamine C ^{1.50⋅105 1.47⋅105} 1.95 1.36⋅10 ⁵ 9.40 Safranin T ^4.00⋅104 4.22⋅10 ⁴ 5.39 3.73⋅10 ⁴ 6.65 methylene blue 5.00⋅10 ⁴ 4.67⋅10 ⁴ 6.62 4.67⋅10 ⁴ 6.62 propylene glycol 0.019 0.0194 2.11 - - Diethanolamine 0.066 0.0708 7.34 - - Table 3 continued Diethylene glycol 0.012 0.0131 8.87 - - ethylene glycol 0.027 0.0288 6.71 - - Propanol 0.035 0.0378 7.89 - - Isopropanol 0.019 0.0197 3.87 - - Glycerol 0.064 0.0687 7.36 - - Mono ethanolamine 0.044 0.0444 0.85 - - Blend #2 Sulfosalicylic acid 2.00⋅10 ^{4 2.16⋅104} 7.89 ^2.16⋅104 7.89 Tinopal ^{2.00⋅105 5.40⋅105} 170.04 ^1.86⋅105 7.23 4-methylum belliferone ^{3.00⋅105 3.17⋅105} 5.54 ^3.05⋅105 1.59 Fluorescein ^{2.00⋅105 1.92⋅105} 4.07 ^1.92⋅105 4.07 Eosin B ^{4.00⋅105 4.31⋅105} 7.74 ^4.31⋅105 7.74 Rhodamine C ^{3.00⋅105 2.89⋅105} 3.59 ^3.03⋅105 1.16 Safranin T 2.00⋅10 ⁴ 3.72⋅10 ⁴ 85.84 2.14⋅10 ⁴ 7.00 methylene blue 3.00⋅10 ^{4 3.19⋅104} 6.34 ^3.19⋅104 6.34 propylene glycol 0.043 0.0459 6.75 - - Table 3 continued Diethanolamine 0.048 0.0501 4.40 - - Diethylene glycol 0.005 0.0054 7.30 - - ethylene glycol 0.019 0.0192 0.79 - - Propanol 0.067 0.0720 7.42 - - Isopropanol 0.033 0.0350 6.18 - - Glycerol 0.065 0.0698 7.43 - - Mono ethanolamine 0.057 0.0609 6.85 - - Blend #3 Sulfosalicylic acid 8.00⋅10 ^{4 8.49⋅104} 6.12 ^8.49⋅104 6.12 Tinopal ^{7.00⋅105 8.50⋅105} 21.49 ^6.78⋅105 3.14 4-methylum belliferone ^{1.50⋅105 1.95⋅105} 29.77 ^1.48⋅105 1.18 Fluorescein ^5.00⋅105 5.12⋅10 ⁵ 2.37 5.12⋅10 ⁵ 2.37 Eosin B ^{1.50⋅105 1.46⋅105} 2.44 ^1.46⋅105 2.44 Rhodamine C ^{5.00⋅105 4.73⋅105} 5.46 ^4.74⋅105 5.30 Safranin T 7.00⋅10 ⁴ 8.46⋅10 ⁴ 20.88 6.65⋅10 ⁴ 4.96 methylene blue 8.00⋅10 ⁴ 7.58⋅10 ⁴ 5.26 7.58⋅10 ⁴ 5.26 Table 3 continued propylene glycol 0.020 0.0210 4.97 - - Diethanolamine 0.007 0.0075 7.64 - - Diethylene glycol 0.074 0.0786 6.27 - - ethylene glycol 0.026 0.0277 6.45 - - Propanol 0.021 0.0220 4.96 - - Isopropanol 0.032 0.0323 1.02 - - Glycerol 0.048 0.0513 6.83 - - Mono ethanolamine 0.012 0.0127 5.63 - -

Thus, the proposed method makes it possible to improve the sensitivity of determining fluorescent tracers with intersecting luminescence spectra relative to the well-known direct method of determination based on the proportionality of the luminescence signal intensity to concentration, and also makes it possible to determine polar tracers based on alcohols with a sufficiently low error in their simultaneous presence.

The use of the proposed method for detecting fluorescent and alcohol tracers in their joint presence in formation waters during tracer interwell studies allows, while maintaining the number of tracers involved, to avoid a long stage of sample preparation and the use of ionic compounds, the analysis of which, as a rule, is accompanied by significant errors due to their possible presence in the rock, and also makes it possible to increase the accuracy of determining fluorescent tracers by taking into account the superposition of their excitation and emission spectra at the determination parameters.

Claims (1)

A method for detecting fluorescent and alcohol tracers in their joint presence in formation waters during tracer interwell studies, including analysis of a composition of indicators for geophysical studies in formation water in their joint presence, separation of the formation water sample under study from oil, sample purification from fine and organic impurities by clarification with a coagulant in an alkaline medium and centrifugation, dividing the sample into several portions, adding additional reagents to each portion of the sample to improve the quality of the analysis being carried out, carrying out a sequential quantitative analysis of the composition of indicators in the formed portions of the sample using fluorescence spectroscopy and chromato-mass spectrometry, different the fact that the composition of indicators consists of sulfosalicylic acid, 4-methylumbelliferone, tinopal CBS-x, sodium fluorescein, eosin B, rhodamine C, safranin T, methylene blue, monoethanolamine, diethanolamine, propylene glycol, 2-ethoxyethanol, ethylene glycol, diethylene glycol, isopropanol, glycerin, while fluorescent tracers are analyzed at a pH of the medium in which they exhibit the most intense luminescence properties, taking into account the intersection of the luminescence spectra of tracers with a close arrangement of emission peaks, and tracers based on alcohols with a wide boiling temperature range of 82.4 - 290°C are analyzed at optimal selection of the conditions for the flow rate of the carrier gas and the sweep of the temperature of the chromatograph column.

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