UA141641U - METHOD OF LABELING LIQUID CARBOHYDRATES WITH FLUORESCENT MARKER - Google Patents

Abstract

The method of marking liquid hydrocarbons with a fluorescent marker consists in dissolving in a liquid hydrocarbon a fluorescent marker - a concentrated solution of a long-wavelength phosphor in an organic solvent. Square acid derivatives are used as a long-wave phosphor.

Description

A useful model belongs to the area of problems of the fuel and energy complex and the development of chemical technologies, methods of "hidden" labeling of liquid hydrocarbons, such as, for example, fuels of different types (gasoline, diesel fuel, marine fuel, boiler fuel) and different manufacturers, lubricants (motor, transmission and special oils, mineral lubricants, plastic lubricants), petroleum-based liquids, using phosphors emitting light in the long-wave range of the spectrum. A useful model can be used to create a system for protecting fuel of various types and purposes against falsification, counterfeiting or theft.

Currently, Ukraine does not have its own means of protecting liquid fuel or fuel-lubricating materials against any types of counterfeiting (forgery and dilution) and smuggling (unauthorized import, export, transportation and unauthorized deliveries to gas stations).

Existing methods of laboratory control of fuels make it possible to detect only their compliance with accepted standards in terms of composition and content of impurities, but do not allow to establish the origin of these materials, that is, whether they were imported into Ukraine or produced in Ukraine on legal grounds, or whether they are contraband or counterfeit goods. They try to solve this problem by introducing special additives (labels or markers) into the fuel, the presence and concentration of which can be established only with the help of laboratory analyzes in specialized laboratories or with the help of special devices. Markers solve two problems at the same time: identification of the type of fuel and detection of the fact of its dilution. So, for example, in Great Britain, the color of the dye Boimepi Way 24 in combination with quinizarin, which acts as an antioxidant, was chosen to indicate the type of fuel to which a low tax is applied. On the territory of Europe, the so-called "EpgotagKeg" is necessarily introduced into the fuel, which is sold at a reduced tax. This marker has a yellowish color (also called

Zoimepi MePYom/ 124), which is not immediately visible to the naked eye when adding the necessary diluted concentration to the fuel, but which can be detected by adding an acid solution and short-term boiling if necessary. Blue dye is similarly applied to kerosene in the UK to distinguish jet fuel from diesel. Other dyes used for visual marking of liquid hydrocarbons include:

Zoimepi Way 24, Boimepi Way 19, Boimepi Viye 36, apa BoImepi Step 3. In some countries, along with

Along with the visual labeling of fuel, hidden labels are also used, which are detected when certain reagents are used or when extracted into an alkaline or acidic medium.

The visibility of the coloring has certain disadvantages, as it allows criminal groups to detect and remove the dye and sell subsidized fuel at a higher cost, resulting in reduced tax revenues. Therefore, the protective materials (labels) that are added must work in very low concentrations, that is, easily and reliably determined using special devices, but, at the same time, not be detected visually (by the color of the liquid) or using traditional means of recognizing protective signs (for example, with the help of ultraviolet currency detectors). In addition, they must not affect the operational properties of the fuel, be inert in relation to the parts of machines and engines, be non-toxic after use or combustion in the engine and not pollute the environment. Solving this task is also complicated by the fact that fuel components and metal surfaces of tanks and pipelines in which fuel is stored or transported can aggressively act on the label and destroy it, while the label must remain stable and not reduce its concentration in the fuel during entire storage period.

All of the above factors determine the urgency of creating new materials for inconspicuous, i.e., "hidden" marking of liquid fuels for various purposes.

The largest number of "hidden" markers is revealed by the formation of color when using certain reagents or during extraction in an alkaline or acidic environment and belongs to the class of azo or diazo dyes.

The known synthesis of fuel markers based on the reaction of p-alkylaniline with the diazo salt of aniline derivatives (5. Zimaprgazor "Reigoiyesht tagKege vzupipevzizei iliyot p-aikuIreplepe apa apiipe depmayimev", Ipa. Epa. Snet. Vez., 2003. - 42. - R. 5054-5059). These markers are invisible in diesel fuel, and the color appears during extraction with a solution of 1,2-diaminoethane in propane-1,3-diol and methanol.

Known latent markers based on azo- or diazo-dyes for fuel marking (US Pat.

MO 6514917, С0О9В 29/08 and US patent MO 8257975, С101М 33/26). These markers are practically colorless in the fuel, but are obtained during extraction (acidic or alkaline) and/or with the use of a developing agent.

Phthalenes (US patent Mo 6002056, С10Й 1/00 and US patent Mo 6482651, Сб070 307/88) and anthraquinone-based dyes (US patent Mo 5205840, СО9В 1/00) are known for marking petroleum products, the color of which appears after extraction in alkaline environment.

However, multi-step detection procedures for latent markers, including extraction or development with reagents, tend to complicate the detection process and are inconvenient for field use. In addition, visual identification or the use of absorption spectroscopy as an identification method have certain disadvantages, among which are the low sensitivity of these methods, as well as the need to introduce high concentrations of the dye (on average, 10-100 ppt). A large amount of tracer added can have a bad effect on engine parts or the environment, so it is advisable to reduce the tracer concentration to 1 ppm or less.

Fluorescent measurement methods are currently one of the most sensitive and, at the same time, cheap methods of analysis, which allows you to significantly reduce the concentration of the label added to fuel, increase the "hiddenness" and reliability of labeling, and reduce the cost of protection and detection. Fluorescent methods of analysis can be easily automated, and detection can be implemented both on standard spectral equipment in the presence of appropriate methods of analysis, and with the help of specialized (specially designed to solve this task) devices, including in a compact portable or field version.

Known phosphors for use in liquid hydrocarbons (US patent Mo 6991914, C120 1/44 and US patent Mo 9469717, 201M 21/76) that emit light in the region up to 550 nm.

It is known that due to the content of condensed aromatic hydrocarbons, liquid petroleum products have absorption and fluorescence that interfere with identification by means of short-wave markers, the "region of transparency" in this case starts from 550 nm. Therefore, the use of known phosphors for labeling liquid hydrocarbons is not convenient due to overlap with the fuel's own fluorescence.

For "hidden" marking, it is appropriate to use long-wave phosphors that glow in the red or near-infrared region of the spectrum.

A known method of labeling liquid hydrocarbons with squaraine-based markers,

From crocon, phthalo- and naphthalocyanine dyes (US patent No. 5525516, C101 1/232), the maximum absorption wavelengths of which are greater than 600 nm.

Known squaraine markers based on benzindolenine derivatives cover a rather narrow range of absorption wavelengths (650-690 nm), which limits their use as a source of fluorescence excitation in the narrow zone of 650-680 nm. In addition, the phthalocyanines and naphthalocyanines claimed in this patent contain metal or silicon atoms in their structure, which will lead to the formation of a solid residue during combustion in the engine and rapid wear of engine materials and parts.

As the closest analogue in terms of the number of common features, we have chosen the last of the above analogues.

The task of a useful model is to develop a simple method of labeling liquid hydrocarbons with fluorescent markers based on long-wavelength phosphors that have high solubility and photostability in hydrocarbons, do not contain metal atoms in their structure, and cover a wide spectral range of absorption, which allows their emission to be excited by a large set of various light sources .

The problem is solved by the fact that in the method of labeling liquid hydrocarbons with a fluorescent marker, which consists in dissolving a fluorescent marker in a liquid hydrocarbon - a concentrated solution of a long-wave phosphor in an organic solvent, according to a useful model, derivatives of the square acid of the general formula I or the general formula are used as a long-wave phosphor II, or the general PP formula: de te 7E Teh J mes de V SCHO tu ; where A is 50, -5, -M-Ba, -C(B2)(Bg), and, No, B? and Ве are -СОВЕ, -СМ, -СОМ(VU)(VU), -

SOOVNVI, moreover, VU, Ve, V! and VK is independently -H, a branched or linear aliphatic group, which may contain as substituents -OH, -ОВ89, -СОВК, -СМ, -СОМ(ВУ(Бе), -СООВ! groups, where ВZ is a branched or linear aliphatic group, or aromatic group;

0 - this-oh,-57;

U and E are O, 5, B, M-B" and C(B)(VI); Where B" is -H, an aliphatic, alicyclic or aromatic group; IN! and VI - aliphatic groups, alicyclic groups, aromatic groups or B! and VI form a cycle;

And B" is -H, a branched or linear aliphatic group, an alicyclic or aromatic group, which can contain -OH, -OH»8, -SOVK, -CM, -SOM(VU)(Vg), -SOOV! groups;

IN? and B? - is independently -Н, -СМ, -СОМ(ВУ(Бе), -СООВИ, -МО», -ОН»e, an aliphatic, alicyclic or aromatic group, part of a condensed aromatic or heterocyclic ring, which in turn can be replaced by -SM, -SOM(VU(Ve), -SOOVI, -MO», -ONEa or aliphatic groups; sHE TE in ozhZho still still SneE dennu and and not I r. and where A is 50, -5, - M-Ba, -С(В2)(Вг), moreover, Не, В? and Ве are -СОВЕ, -СМ, -СОМ(ВУ)(ВУ),

SOOVNVI, moreover, VU, Ve, V! and VK is independently -H, a branched or linear aliphatic group, which may contain as substituents -OH, -OH", -SOVK, -СМ, -СОМ(ВНУ(Ве), СООВИ: groups where Не is a branched or linear aliphatic group, or aromatic group;

ХУ and У are О, 5, бе, М-В" and С(В)ОС(ВИ); where В" is -Н, an aliphatic, alicyclic or aromatic group; IN! and V! - aliphatic groups, alicyclic groups, aromatic groups or B! and VU form a cycle;

В'Ii A" is -H, a branched or linear aliphatic group, an alicyclic or aromatic group, which may contain as substituents -OH, -OH»8, -SOVK, -CM, -СОМ(ВУ)(Вг), - SOOV! groups;

IN? and B? - is independently H, -СМ, -СОМ(ВУ)(Бе), -СООВИ, MO», -ОН»e, an aliphatic, alicyclic or aromatic group, part of a condensed aromatic or heterocyclic ring, which in turn can be substituted - СМ, -СОМ(ВУ)(Ве), -СООВИ, -МО», -ОВ9 or aliphatic groups; ; TI where A is 0, -5, -M-Ba, -C(B2)(Bg), moreover, No, B? and Ве are -СОВЕ, -СМ, -СОМ(VU)(VU), -

SOOVNVI, moreover, VU, Ve, V! and VK is independently -H, a branched or linear aliphatic group, which may contain as substituents -OH, -OH", -SOVK, -SM, -"СОМ(НУ)(Ве), СООВИ: groups where Ве is a branched or linear aliphatic group or an aromatic group;

Ko) p - is-O,-5;

ВІІ VT is -H, a branched or linear aliphatic group;

B2 and B2 are independently Н, -СМ, -СОМ(ВУ(Ве), -СООВ, МО», -ОН», -Щ(ВУ)(Ве), an aliphatic, alicyclic or aromatic group, part of a condensed aromatic or heterocyclic rings, which in turn can be replaced by -СМ, -СОМ(ВУ)(Ве), -СООВ!, -МО», -ОВе or aliphatic groups.

The marker is a concentrated dye solution used for marking fuel and lubricant materials for the purpose of its subsequent detection and/or quantitative determination.

Long-wavelength phosphors claimed as liquid hydrocarbon markers have absorption and fluorescence maxima in the range 530 to 760 nm and, as a result, can be easily detected by appropriate instruments that measure the fluorescence of solutions. At the same time, there is a visually imperceptible change in the color of the marked sample, which allows for "hidden" marking.

In addition, long-wavelength phosphors, which are claimed as markers of liquid hydrocarbons, are characterized by high solubility in liquid hydrocarbons subject to labeling (this makes it easy to obtain a hook concentration of the phosphor, which is reliably detected by fluorescence methods), have chemical stability for long-term storage of the labeled product in relation to sunlight, water, oxygen, temperature, etc. and chemical inertness to all components of the liquid to be marked (dyes, additives, etc.).

It should be noted that the luminescence intensity of the marker should be sufficient for its reliable detection. The increase in the intensity of the analytical signal is facilitated by the high brightness of the phosphor, which is the product of the multiplication of the extinction coefficient by the quantum yield.

Table 1 shows the spectral characteristics of typical dyes of square acid derivatives of the general formula I, II, 1 (Atakhiaye absorption maxima)) and fluorescence (Htakhet), C as well as the extinction coefficients and quantum yields of squaraine dyes, which allow us to evaluate the efficiency of the phosphor as a fluorescent marker by its brightness.

Table 2 shows the obtained data on changes in the fluorescence intensity (Ifl) of solutions of compounds 24 and 26 (see Table 1) in diesel fuel during 1, 2, 3, 6, and 12 months of their storage (average data based on the results of fluorescence measurements of two of parallel prepared solutions for each point, three parallel measurements were performed for each solution).

In Fig. 1 shows the fluorescence spectra of some markers (Table 1, compounds 26, 24 and 22).

In Fig. 2 shows changes in the fluorescence spectra of some markers (Table 1, compounds 26, 24): (a) - in diesel fuel over time; (b) - their stability curves.

For the practical use of a fluorescent dye as a fuel marker, high stability of the dye and its spectral characteristics regarding long-term storage of the marked product in relation to sunlight, water, oxygen, temperature, components (additives) is necessary.

The method of marking liquid hydrocarbons with a fluorescent marker consists in adding to the liquid hydrocarbon being marked a fluorescent marker - a long-wavelength phosphor of formula I or formula II or formula PI in an amount from 1 mg/g to 1000 mg/t.

Due to the fact that the markers dissolve well in the fuel and lubricant, their distribution is uniform. Markers are injected into the fuel in small concentrations, detected using a light source with a wavelength in the region of 500-750 nm by their luminescence, and their presence is identified by determining the maximum and intensity of luminescence in the region of 550-850 nm of a sample of marked fuel, which is examined by the method of fluorescence

From spectroscopy. It is also possible to excite fluorescence in labeled liquids with a semiconductor laser or a semiconductor diode. A particular advantage is the use of a semiconductor laser or a semiconductor diode with a wavelength of maximum emission in the spectral range from Xtakh-100 nm to Xtakhn20 nm (where Xtakh is the wavelength of the maximum absorption of the marking substance). The maximum emission wavelength is 550-850 nm. The fluorescent light obtained in this way can be registered visually for rapid identification of the marker in the fuel, for example in the field.

Marking does not lead to visually noticeable changes in the fuel, namely changes in color, transparency, etc. In addition, the fuel marked with labels keeps all the necessary indicators within the limits of regulated regulatory documents and does not represent a threat to the environment or engine parts.

In order to minimize the cost of marking, to minimize the possible interactions of fuel markers with any of its ingredients, to ensure invisibility in marked fuel, the number of markers is set as small as possible. The total (mass) concentration of the phosphor in the liquid to be labeled is chosen in the range from 1 mg/t to 1000 mg/t. Another reason to reduce the number of markers as much as possible can be to overcome their damaging effect (if any), for example, on the parts of combustion engines or the exhaust pipe, and to reduce the amount of dye emissions into the external environment.

Organic liquids such as aliphatic or aromatic hydrocarbons (pentane, hexane, heptane, octane, isooctane, petroleum ether, toluene, xylene, ethylbenzene, tetralin, decalin, dimethylnaphthalene, test gasoline) can be labeled with the above compounds of formula I or formula II or formula NP ), mineral oils, gasoline, kerosene, diesel and boiler fuel, natural or synthetic motor, hydraulic or transmission oils (for example, oils for automobile engines or sewing machines).

Examples of implementation and use of the proposed technical solution are given below.

Example 1. Preparation of a comparison solution of a fluorescent marker (see Table 1, compound 24) in gasoline.

To a sample of 4.0 mg of compound 24 in a glass cone, add 10 ml of methyl tert-butyl ether with a 10 ml glass pipette, sucking the liquid with the help of a rubber bulb, close the 60 cone with a glass stopper and mix by shaking until a true solution is obtained.

The resulting solution has an intense blue color and a red fluorescence that can be observed visually. This concentrated solution is added to the fuel for marking. For this, 10 ml of a fluorescent label with a concentration of 400 mg/dm" of the compound 24 marker is added to 100 l of fuel. After thorough mixing, a reference solution with a concentration of 40 mg/m3 of compound 24 in the fuel is obtained. 10 ml of the reference solution is hermetically sealed in a transparent glass container glass and stored in a dark place at a temperature not higher than 2576.

A reference solution is used to determine the presence of a fluorescent marker in the fuel samples under investigation.

Example 2. Preparation of a comparison solution of compound 24 in diesel fuel.

To a portion of 4.0 mg of compound 24 in a glass cone, add 10 ml of 1-octanol with a 10 ml glass pipette, sucking the liquid with the help of a rubber bulb, close the cone with a glass stopper and mix by shaking until a true solution is obtained. The resulting solution has an intense blue color and a red fluorescence that can be observed visually.

This concentrated solution is added to the fuel for marking. For this, 10 ml of fluorescent label with a concentration of 400 mg/dm3 of compound 24 is added to 100 l of fuel. After thorough mixing, a comparison solution with a concentration of 40 mg/m3 of compound 24 in fuel is obtained. 10 ml of the comparison solution is hermetically sealed in a glass container made of transparent glass and stored in a dark place at a temperature not higher than 25 "С. The comparison solution is used to determine the presence of a fluorescent marker in the fuel samples under investigation.

Example 3. Detection of compound 24 in gasoline (field conditions).

The fuel under investigation is placed in a glass tube, irradiated with a diode laser with light with a wavelength of 635-650 nm and the color of the beam in the liquid is compared with that obtained for a comparison solution based on gasoline (see Example 1). In unmarked diesel fuel, the beam has practically no color, and in marked - there is a red color of the beam.

Example 4. Detection of compound 24 in diesel fuel (field conditions).

The fuel under investigation is placed in a glass test tube, irradiated by a diode laser with light with a wavelength of 635-650 nm, and the color of the beam in the liquid is compared with that obtained

Zo for the comparison solution based on diesel fuel (see Example 2). In unmarked diesel fuel, the beam has practically no color, and in marked - there is a red color of the beam.

Example 5. Detection of a fluorescent marker (see Table 1, compound 24) in industrial lubricant I-20 (laboratory conditions).

Fluorescence spectra of the lubricant sample under investigation are measured at room temperature using a Magap Sagu Esiirse spectrofluorimeter in standard 1-cm quartz cuvettes with the following device settings: excitation wavelength - 600 nm, spectrum measurement range - 605-750 nm, optical wavelength slits excitation and emission - 5 nm each, the voltage on the photomultiplier - 800 V. The emission maxima are determined with an accuracy of 0.5 nm based on the result of three parallel measurements. The value of fluorescence intensity is determined with an accuracy of 25 y. at. rluorescence. Three parallel measurements are made for each solution, and the result is calculated as the arithmetic mean of these three fluorescence intensity values at the wavelength of the maximum fluorescence (647 nm for compound 24).

Example 6. Detection of a fluorescent marker (see Table 1, compound 26) in diesel fuel (laboratory conditions).

Fluorescence spectra of the diesel fuel sample under investigation are measured at room temperature using a Maiap Sagu Esiirze spectrofluorimeter in standard 1-cm quartz cuvettes with the following device settings: excitation wavelength - 550 nm, spectrum measurement range - 550-750 nm, optical slits of lengths excitation and emission waves are 5 nm each, the voltage on the photomultiplier is 700 V. The emission maxima are determined with an accuracy of 0.5 nm based on the result of three parallel measurements. The value of the fluorescence intensity is determined with an accuracy of 5 y. at. rluorescence. Three parallel measurements are made for each solution, and the result is calculated as the arithmetic mean of these three fluorescence intensity values at the wavelength of the maximum fluorescence (575 nm for compound 26).

Example 7. Determination of the stability of compounds 24 and 26.

To study the stability of marker solutions in fuel over time, an experiment was conducted comparing the fluorescence of solutions of compounds 24 and 26, which were just prepared, and solutions with the same concentration, which were stored for different periods of time.

The concentration of the markers was chosen to be that used in the labeling fuel, namely 40 mg/m3 for compound 24 and 80 mg/m3 for compound 26.

The stability of the spectral characteristics of compounds 24 and 26 in fuel is sufficiently high. Namely, during three months of storage in diesel fuel, the fluorescent signal of compounds 24 and 26 decreases by no more than 6 95, and in 12 months it loses no more than 10 95, which is sufficient for their practical use.

As can be seen from the description of the application materials, the claimed fluorescent markers fluoresce under simple test conditions and at very low concentrations (less than 2 ppm), dissolve well and do not react with components of fuel or fuel-lubricating materials, and also remain fairly stable over time with long-term storage.

Fuel of various types (gasoline, diesel fuel) and manufacturers, lubricants (motor, transmission and special oils, mineral lubricants, plastic lubricants), petroleum-based liquids can be used as labeling objects.

Table 1

Compound Structure Solvent Atachiare), NM Htahat), NM (E, M" cm" (Fe, because it is

SYH p USHNY 65O9 1 or go Y y, i Chloroform 637 (151000) A and Dodrmnek den y V. ( ) pud y DK

Seh meh Shh and vn ts set, ; 2 neo a Chloroform 641 (103000) 566

En and ШЩ Ш (4)

ME SHCI iy bu beru Zo as

He "zh hu, 67Z (128000) 461 697

From "Me SHK Y |: in "U Chloroform | )

E Codes day x Z (42) (6) app. EK

Povz ba Sukukh o ikh 682 (196000) 381 che sl KO 4 shi s Chloroform | ) 701 (44) or a (38)

Scrolls will be

ME SCM

BU NYA her i zhi Be I to yo 5 B is svy i cho Chloroform 687 (134000) 708 (13) and h iy

OM and in sh and det

B Mu sha! and Chloroform 701 (130000) 722 (79)

Beny o byk she: ok chi sche che a 7 zh shk shvi Chloroform 728 (166000) 757 (46)

Seni ba 0 SeMe that shi o Shi 647 (104000 dk ke ШЕ озна loroform 7 и Pro rophor Y и (43)

Be I | and he

To be the boss

Continuation of table 1 that mk sa BOD

WHAT ARE YOU AND ARE YOU (22)

Cebu Jan 5

Co. and Chloroform 652 (177000) 672 (65)

Bek Che would not be OV

Ka X Khe 11th tires Chloroform 663 (125000) 684 (80) St. Z oh

Ни чи: 683 Toshen Che o s» povy shi glo That Her h zi yet 6 8 Z 7 o o o 13 k- Mys and Chloroform svi vyy E (183000) (45) dbvsve Dva 683 699 z se t» nka Ko And: 14 more months Chloroform (185000) (45)

Monu sho SUM» vv Zk y y pi ach Ve sh 688 v sh Chloroform (159000) tv

Sae Che ev x M U y dey Som 653 664

N i PC dek x Z 16 o shi shi Khporoform (165000) (22)

SUMU Ve skh zhu in VE o no vvv 625 17 a chu shy Chloroform (1 1 2000) (35) ve Zh y; shh

Sebo S, 18 Kr Khporoform 608 (214000) 619 (59) bene be 0 swie shih 661 676

Mebtsu bu Sov

Be vv Zh v v v

Kt ne - khz 6 2 4 6 6 9

M GeZa Mche ge shshi shi 633 bag bu AS un bak MeV o You 694 22 o x s u Chloro fo rm ( 12000 0) 712 (2 8)

Kk How Eh.

Continuation of table 1

NOT

23 Sayakh, FD, Vic» Chloroform 563 693 vt ho. not skl lk w-b and EE ( 6 Z o o o o ) (4 8 )

M v rya

M. Jan

In still and a hmm groove M and 24 Ov and. same M de Chloroform (100000) 663 (14)

In Z KNU

- iy Y v Xia (v 9 (v

From the tire Chloroform 660 (120000) (c)

SaVh b base

Sn; b well p y Z o i I i y

Eh V SYA x KN x I same vd

I vB1 v6 27 v SHE mb Chloroform (155000) (8) kosu ka Sak" - OKU CHE SKU

NIJ ne dum ach FO ME 23 sh; vl che Chloroform (135000) 647 (23) gave 00 ba

My tires are not 633

MK ex u x y vya 6 6 Z 31 y: shi she chloroform 678

EM. she s i i i pot 683 32 Ko nyu Chloroform 665 (270000) (9) nku H. Ya tav"

C3 and lower Chloroform 652 (160000)

Table 2

Sample Ifl., Ifl., Ifl., Ifl., Ifl., Ifl., fresh 1 month 2 months From month 6 months 12 months

Compound 82958 81657 80455 78555 76657 24 84854 (decreases by o o o o

Compound 50157 49956 (| on | 493.10 (| on 48657 48218 26 50855 (decreases on o o o o 80 mg/m 149 1.8 Fo) 3.0 Ob) (una4.3 96) | (|) on 5, 1 95)

Claims (1)

USEFUL MODEL FORMULA The method of labeling liquid hydrocarbons with a fluorescent marker, which consists in dissolving a fluorescent marker in a liquid hydrocarbon - a concentrated solution of a long-wave phosphor in an organic solvent, which differs in that as a long-wave phosphor, derivatives of square acid of the general formula are used | or the general formula II, or the general formula ІІ 2 v A v2 U t v U- c- (o: e M M v2 x o / 2 v" r v" and where A is 0, -5, -M-Na . , a branched or linear aliphatic group, which may contain as substituents -OH, -OH", -SOVK, -SM, -"СОМ(ВУ)(Вг), -СООВ! groups, where VZ is a branched or linear aliphatic group, or aromatic group; 0- is-o,-57; U and M are O, 5, b, M-B" and C(B)(B)); where B" is -H, aliphatic, alicyclic or aromatic group, B! and VI - aliphatic groups, alicyclic groups, aromatic groups or B! and VI form a CYCLE; V. and VI are -H, a branched or linear aliphatic group, an alicyclic or aromatic group, which may contain as substituents -OH, -OH", -SOVK, -SM, -SOM(VU (Ve), -SOOV! groups ; B2g and B are independently -H, -CM, -COM(NU) (Be), -SOONI, -MO», -OH», an aliphatic, alicyclic or aromatic group, part of a condensed aromatic or heterocyclic ring, which in their -СОМ, -СОМ(ВУ(Ве), -СООВИ, -МО», -ОНея or aliphatic groups can be substituted; in" x HER where A is 0, -5, -M-Na, -C(B)(Vg), and Na, Be and B: - are -SONVK, -SM, -SOM(NU (Be), -СООНИ, and НУ, Не, В: and ВК are independently -Н, a branched or linear aliphatic group, which may contain as substituents -ОН, -ОНе, -СОВК, -СМ, -СОМ(ВУ)(Ве), SOOV!: groups where z is a branched Zo or linear aliphatic group, or an aromatic group; M and U are O, 5, b, M-B" and C(B)(VI); where B" is - H, aliphatic, alicyclic or aromatic group; B! and VI - aliphatic groups, alicyclic groups, arom atic groups or B! and VI form a CYCLE; "V" is -H, a branched or linear aliphatic group, an alicyclic or aromatic group, which may contain as substituents OH, -OH9, -SOVK, -SM, -СОМ(ВУ)(Ве), -СООВ! groups; B? and B? are independently H, -CM, -"SOM(NU)(Be), -SOOVI, MO", -085, an aliphatic, alicyclic or aromatic group, part of a condensed aromatic or heterocyclic ring, which in in turn, they can be replaced by -СМ, -СОМ(ВУ)(Бе), -СООВИ, -МО", -ОВ9 or aliphatic groups; v2 A v v: v v m Kk x ! o / 2 v v v" A is XO, -5, -M-Na, -C(B2)(Vg), and Na, P? and V: - these are -SOVK, -SM, -"SOM(VU)(Ve), -SOONVI, and NU, Ve, V! and VK is independently -H, a branched or linear aliphatic group, which may contain as substituents -OH, -ОНВ85, -СОВК, -СМ, -СОМ(ВУ(Ве), СООВ! groups, where Ве is a branched or a linear aliphatic group, or an aromatic group; p is -o,-5; A' and B are -H, a branched or linear aliphatic group; B and B? are independently H, -CM, -SOM(NU)( Бе), -СООВ МО», -ОНе, -М(НУ) (Бе), aliphatic, alicyclic or aromatic group, part of a condensed aromatic or heterocyclic ring, which in turn can be replaced by -СМ, -СОМ(НУ(Бе ), -SOOV -MO", -ONE or aliphatic groups. ШЕ ! за : т Vo. и п за BO ryh z vo. Кк з ' ШЕ Shk НЙ B Я х бан A; M, - initials and і ; Oh, and the length of the book Fig. 1