UA127869C2 - THE METHOD OF LABELING LIQUID HYDROCARBONS WITH A FLUORESCENT MARKER - Google Patents

Abstract

The invention relates to a method of labeling liquid hydrocarbons with a fluorescent marker, which includes the addition of a fluorescent marker - a solution of a long-wave phosphor in an organic solvent, and as a long-wave phosphor, derivatives of square acid of the general formula are used: , where A is =O, =S, =N-Ra, = C(Rb)(Rc), wherein Ra, Rb, and Rc are -CORk, -CN, -CON(Rd)(Re), -COORf, wherein Rd, Re, Rf, and Rk are, independently, -H, a branched or linear aliphatic group, which may contain as substituents -OH, -ORg, -CORk, -CN, -CON(Rd)(Rc), COORf-groups, where Rg is a branched or linear aliphatic group, or an aromatic group; Y and Y' - O, S, Se, N-Rh and C(Rі)(Rj); where Rh is -H, an aliphatic, alicyclic or aromatic group; Ri and Rj - aliphatic groups, alicyclic groups, aromatic groups, or Ri and Rj form a cycle; R1 and R1' are -H, a branched or linear aliphatic group, an alicyclic or an aromatic group, which may contain -OH, -ORg, -CORk, -CN, -CON(Rd)(Re), -COORf groups as substituents ; R2 and R2' are, independently, -H, -CN, -CON(Rd)(Re), -COORf, NO2, -ORe, an aliphatic, alicyclic or aromatic group, part of a fused aromatic or heterocyclic ring, which, in their respectively, can be substituted by -CN, -CON(Rd)(Re), -COORf, -NO2, -ORg or aliphatic groups.

Description

in A in in E zi (5)Usn b- C / in M M in?

M o a l 62 oh Mare ve de A is 20, -5, M-Va, -C(B2)(VU), and Va, V? and V: - these are -SOVK, -SM, -"SOM(VU)(Ve), -SOOVI, and KU, Ve, V! and ЭХ is, independently, -Н, a branched or linear aliphatic group, which may contain as substituents -ОН, -ОНя, -СОВкЕ -СМ, -СОМ(ВУ(Бе), СООВgroups, where BK9 is a branched or linear aliphatic group , or an aromatic group;

MU and x- 0, 5, 5e, MAV! ii S(K) (VI); where B" is -H, aliphatic, alicyclic or aromatic group;

IN! and VI - aliphatic groups, alicyclic groups, aromatic groups, or KE! and B) form a cycle;

В'Й Кк" is -H, a branched or linear aliphatic group, an alicyclic or aromatic group, which may contain as substituents -OH, -OH»8, -SOVK, -CM, -"СОМ(Не)(Бе), - SOOV group;

IN? and 2 are, independently, - Н, -СМ, -"СОМ(ВУ)(Ве), -СООНВИ, МО", -ОВ-, aliphatic, alicyclic or aromatic groups, part of a condensed aromatic or heterocyclic ring, which, in in turn, they can be replaced by -СМ, -СОМ(ВУ(Ве), -СООВИ, -МО», -ОВ» or aliphatic groups.

The invention relates 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 various 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. The invention 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. For example, in Great Britain, the color of the dye Boimepi Way 24, combined with the antioxidant quinizarin, was chosen to indicate the type of fuel to which the low tax applies. 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

Zoymepi 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 visual marking of fuel, hidden labels are also used, which are detected when

From the use of certain reagents or during extraction in an alkaline or acidic environment.

The visibility of the coloring has certain disadvantages because 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 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 "Reigoiite tazheg5 5upipezizei yot p-aikuIreplepe apa apiipe degmaimev5", Ipa. Epa. Spet. Nez., 2003, 42, pp. 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 hidden markers based on azo or diazo dyes for marking fuel (US patent

Mo6514917, SO9B 29/08 and US patent Me8257975, (30 IM 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 Mob002056, С10Й 1/00 and US patent Mob482651, Сб070 307/88) and anthraquinone-based dyes (US patent Mo5205840, СО9В 1/00) are known for marking petroleum products, the color of which appears after extraction into an alkaline medium.

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 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 the fuel, increase the "hiddenness" and reliability of the marking, 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 Mob991914, C120 1/44 and US patent Me9469717, (301 M 21/76), which emit light in the region up to 55 Ohm.

It is known that due to the content of condensed aromatic hydrocarbons, liquid petroleum products have absorption and fluorescence that interfere with identification using short-wavelength markers, the "region of transparency" in this case starts at 550 nm. Therefore, the use of known phosphors for marking 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.

There is a known method of marking liquid hydrocarbons with markers based on squaraine, crocon, phthalocyanine and naphthalocyanine dyes (US patent Mo5525516, C 10 1 1/232), the maximum absorption wavelengths of which are greater than 600 nm.

Known squaraine markers based on benzenedolenine derivatives overlap quite a bit

Because of the 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.

We chose the last of the above analogues as a prototype based on the number of common features.

The task of this invention is the development of 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 solution to the problem is achieved by the fact that in the method of labeling liquid hydrocarbons with a fluorescent marker, which includes the addition of a fluorescent marker - a solution of a long-wave phosphor in an organic solvent, according to the invention, derivatives of square acid of the general formula I are used as long-wave phosphors: 2 v A v v | There is

H sulten s- y

М M 2" 7 АХ 1 y), are l, y 2 in X Mav v where A is 0, -5, -М-На, -С(В)(Вг), and Ва, В? and Ве - it is -SOVK -SM, -SOM(VU)(VU), -

SOORNY, and NU, Ve, V! and VK is independently -H, a branched or linear aliphatic group, 5O0 which may contain as substituents -OH, -OH", -SOVK, -SM, -СОМ(ВУ(В8е), СООВИ!-groups, where Бе is a branched or linear aliphatic group or an aromatic group;

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

And Her A" is -H, a branched or linear aliphatic group, an alicyclic or aromatic group, which may contain as substituents -OH, -OH»8, -SOVK, -SM, -СОМ(ВУ) (Ве), -СООВИ --groups;

IN? and B are, independently, H, -CM, -"СОМ(ВУ(Ве), -СООВ, МО", -ОВ8, 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.

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 of 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 claimed as markers of liquid hydrocarbons are characterized by high solubility in liquid hydrocarbons subject to labeling (this makes it easy to obtain such a concentration of the phosphor that is reliably detected by fluorescence methods), have chemical stability for long-term storage of the labeled product relative to sunlight , water, oxygen, temperature, etc. and chemical inertness to all components of the liquid to be labeled (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 the most typical dyes - derivatives of square acid of the general formula | (absorption maxima (tachyye)) and fluorescence (Htakhet), as well as extinction coefficients and quantum yields of squaraine dyes, which

They allow us to evaluate the efficiency of the phosphor as a fluorescent marker based on its brightness).

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

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

Due to the fact that the markers dissolve well in the fuel and lubricant material, 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 labeled fuel, which is investigated by fluorescence spectroscopy . It is also possible to excite fluorescence in labeled liquids with a semiconductor laser or a semiconductor diode. A special advantage is the use of a semiconductor laser or a semiconductor diode with a wavelength of maximum emission in the spectral range from 100 nm to 20 nm (where Х is the wavelength of the maximum absorption of the tracer). The wavelength of the maximum emission 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 pose 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 phosphor in the liquid to be marked is chosen in the range from 1 to 1000 mg/t. Another 60 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.

The above compounds of formula I can be used to label such organic liquids as aliphatic or aromatic hydrocarbons (pentane, hexane, heptane, octane, isooctane, petroleum ether, toluene, xylene, ethylbenzene, tetralin, decalin, dimethylnaphthalene, test gasoline), mineral oils, gasoline, kerosene, diesel and boiler fuel, natural or synthetic motor, hydraulic or transmission oils (for example, oils for car engines or sewing machines).

The declared compounds show stability during 1, 2, 3, b and 12 months of their storage in hydrocarbons, in particular fuel and lubricant materials.

The implementation and use of the proposed technical solution is given below.

Example 1. Preparation of a comparison solution of a fluorescent marker in gasoline.

To a sample of 4.0 mg of the marker compound in a glass cone, add 10 ml of methyl tert-butyl ether with a 10 ml glass pipette, sucking the liquid with 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 a fluorescent label with a concentration of 400 mg/dm" of the marker is added to 100 liters of fuel. After thorough mixing, a comparison solution with a concentration of 40 mg/m3 of the marker compound in the 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 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 the claimed marker compounds in diesel fuel.

To a sample of 4.0 mg of the marker compound in a glass cone, add 10 ml of 1-octanol with a 10 ml glass pipette, sucking the liquid with 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

From a fluorescent label with a concentration of 400 mg/dm? marker compounds are added to 100 liters of fuel.

After thorough mixing, a comparison solution with a concentration of 40 mg/m3 of the marker compound in the 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 2576.

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

Example 3. Detection of marker compounds in gasoline (field conditions).

The fuel under investigation is placed in a glass tube, irradiated by a diode laser with light with a wavelength in the range of 580-700 nm (depending on the selected compound) and the color of the beam in the liquid is compared with that obtained for a reference 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 marker compounds in diesel fuel (field conditions).

The fuel under investigation is placed in a glass tube, irradiated by a diode laser with light with a wavelength in the range of 580-700 nm (depending on the selected compound) and the color of the beam in the liquid is compared with that obtained for a 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 marker compounds in diesel fuel (laboratory conditions).

Fluorescence spectra of the fuel sample under investigation are measured at room temperature using a Magpap Sago Esirzhe spectrofluorimeter in standard 1-cm quartz cuvettes with the following instrument settings: excitation wavelength range 550-730 nm and spectrum measurement - 565-800 nm (depending on the selected compounds), optical slits of excitation and emission wavelengths - 5 nm each. 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 sch-5 u.o. fluorescence. Three parallel measurements are made for each solution, and the result is calculated as the arithmetic mean of these three values of the fluorescence intensity at the wavelength of the fluorescence maximum.

Example 6. Detection of fluorescent markers in industrial lubricant I-20 (laboratory conditions).

The fluorescence spectra of the I-20 lubricant sample under investigation are measured at room temperature using a Magpap Sagu Esirzhe spectrofluorimeter in standard 1-cm quartz cuvettes with the following device settings: excitation wavelength range 550-730 nm and spectrum measurement - 565-800 nm ( depending on the selected compound), optical slits of excitation and emission wavelengths of 5 nm. 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 sch-5 u.o. fluorescence. Three parallel measurements are made for each solution, and the result is calculated as the arithmetic mean of these three values of the fluorescence intensity at the wavelength of the fluorescence maximum.

Example 7. Determination of the stability of the claimed compounds.

To study the stability of the solution of markers in fuel over time, an experiment was conducted comparing the fluorescence of a solution of compounds of formula I, which was just prepared, and a solution with the same concentration, which was stored for different periods of time.

The concentration of the marker is chosen as that used in the fuel for marking.

The stability of spectral characteristics of compounds of formula I in fuel is sufficiently high. Namely, during three months of storage in diesel fuel, the fluorescent signal of compounds 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

M nm (F

Shchi Structure Solvent |(Htahiarve), NM (is, M" cm") tet (Fe, o dl A Z xx

TK and 651 667 1 | m fr Chloroform in PO she rophor (155000) (8) o Sei /MASN SzNu» x Z ; oh in still Z shu

KO y 654 671 2 | Zh tk Chloroform por kiy still rophor (162000) (7) with SI and. Me Sen." ME" Sam, 7 pe

Claims (2)

FORMULA OF THE INVENTION The method of labeling liquid hydrocarbons with a fluorescent marker, which includes the addition of a fluorescent marker - a solution of a long-wave phosphor in an organic solvent, which differs in that derivatives of square acid of the general formula are used as a long-wave phosphor: 35 2 Kk A 2 1 and in Ye zy H s sn s- and M zh v2 in X More in where A is 50, -5, -M-Na, -С(В)(Нг), and Ka, Ve? and K-g are -SONVK, -SM, -SOM(NU (Ve), -SOONI, and KU, Ve, V! and EC is, independently, -H, a branched or linear aliphatic group, which may contain as substituents -ОН, -ОНя, -СОВХ -СМ, -СОМ(ВУ(Бе), СООВ groups, where B9 is a branched or linear aliphatic group, or aromatic group; In and are - 0, 5, be, M-B" and C(B)(VI); where B" is -H, aliphatic, alicyclic or aromatic group; V and VI! - aliphatic groups, alicyclic groups, aromatic groups, or PE. and B! form a cycle; А'Й КК" is -H, a branched or linear aliphatic group, an alicyclic or aromatic group, which may contain as substituents -OH, -OH", -SOVK, -SM, -SOM(VU (Ve), -СООНВ! -groups; B and Kg are, independently, - H, -SM, -ССОМ(НУ)(Бе), -СООНИ, MO», -ОНе, aliphatic, alicyclic or aromatic groups, part of a condensed aromatic or heterocyclic ring, which, in their in turn, can be replaced by -СМ, -СОМ(НУ)(Ве), -СООВИ, -МО», -ОН» or aliphatic groups.