UA127870C2 - 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, -Η, a branched or linear aliphatic group, which may contain as substituents -OH, -ORg, -CORk, -CN, -CON(Rd)(Re), COORf-groups, where Rg is a branched or linear aliphatic group, or an aromatic group; D is -O-, -S; R1 and R1' are -H, a branched or linear aliphatic group; R2 and R2' are, independently, H, -CN, -CON(Rd)(Re), -COORf, NO2, -ORg, - N(Rd)(Re), an aliphatic, alicyclic or aromatic group, part of a condensed aromatic or a heterocyclic ring, which, in turn, can be substituted by -CN, -CON(Rd)(Re), -COORf, -NO2, -ORg or aliphatic groups.

Description

Kk A in 2 in tt M

M M , in in 2 in! oo k, where A is ХО, -5, -М-На, -С(В2)(Не), and На, Ре and Бе are -SOVK -СМ, -СОМ(НУ(Ве), -SOONI, and НУ, Бе, В! and ВК are, independently, -Н, a branched or linear aliphatic group, which can contain as substituents -ОН, -ОН9, -СОВК, -СМ, -СОМ(ВУ(Бе), СООВ groups , where No is a branched or linear aliphatic group or an aromatic group, 0 is C., -5;

Wherein B is -H, a branched or linear aliphatic group;

IN? and B? - is, independently, Н, -СМ, -СОМ(ВУ(Ве), -СООВИ, МО», -ОВ8, - Ш(ВУ)(Ве), aliphatic, alicyclic or aromatic groups, part of a condensed aromatic or heterocyclic ring, which, in turn, can be replaced by -СМ, -СОМ(ВУ(Ве), -СООВИ, -МО», -ОВ9 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

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, in addition to 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. Zimzhaprgazor "ReigoYiyesht taKeg5 5upipezized iyot p-aKuIreplepe apa apiipe degmaymev", Ipa. Epa. Snet. 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

Mob 6514917, СО9В 29/08 and US patent Mo 8257975, Sh401M 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.

Known phthalenes (US patent Mo 6002056, 0101 1/00 and US patent Mo 6482651, Сб070 307/88| and dyes based on anthraquinone (US patent Me 5205840, С0О9В 1/00| for marking oil products, the color of which appears after extraction in 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 Mo 6991914, 120 1/44 and US patent Mo 9469717, 01M 21/76) which 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 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-wavelength phosphors that glow in the red or near-infrared region of the spectrum.

There is a known method of labeling liquid hydrocarbons with markers based on squaraine, crocon, phthalo- and naphthalocyanine dyes (US patent Mo 5525516, C101I 1/2321, the maxima of which absorption wavelengths 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 the square acid of the general formula I are used as a long-wave phosphor: p2 A v2 v2 v2 - / 2 x o Y dk

Mu o v" where A is 0, -5, -M-Na, -С(В)(Вг), and Ва, В? and Ве are -SOVK -СМ, -СОМ(ВУ)(ВУ), -

SOORNY, and NU, Ve, V! and VEK is, independently, -H, a branched or linear aliphatic group, which may contain as substituents -OH, -ОВ89, -СОВЕ, -СМ, -СОМ(Б8У)(Бе), СООВ- groups, where Бе - is a branched or linear aliphatic group or an aromatic group;

BO r is-O,-5;

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

B2 and B2 are, independently, Н, -СМ, -СОМ(НУ) (Бе), -СООНВИ, МО», -ОНе, - М(ВУ)(Бе), an aliphatic, alicyclic or aromatic group, part of a condensed aromatic or a heterocyclic ring, which in turn can be replaced by -СМ, -СОМ(НУ(Бе), -СООВ -MO», -ОНе 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 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 a typical bis(dimethylpyrrolyl)squarine dye - a derivative of a square acid of the general formula (absorption maxima (Atakhia)) and fluorescence (Atakh(et))"

Table 2 shows data on the change in fluorescence intensity (IFl) of a solution of a typical bis(dimethylpyrrolyl)squarine dye in diesel fuel during 1, 2, 3, 6, and 12 months of storage (average data based on the results of fluorescence measurements of two solutions prepared in parallel are given for each point , three parallel measurements were performed for each solution).

In fig. 1 shows the fluorescence spectrum of a typical bis(dimethylpyrrolyl)squarine dye (E)-2-(3,5-dimethyl-1H-pyrrol-2-yl)-4-(3,5-dimethyl-2H-pyrrol-1-ium) -2-ylidene)-3-

From oxocyclobut-1-enolate).

In fig. 2 shows changes in the fluorescence spectrum of a typical bis(dimethylpyrrolyl)squarine dye: (a) - in diesel fuel over time; (b) - its stability curve.

For the practical use of a fluorescent dye as a fuel marker, a 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 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 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 Atakh 20 nm (where Atakh is the wavelength of the maximum absorption of the marking substance). 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 the phosphor in the liquid to be marked is chosen in the range from 17 to 1000 mg/t. Another reason for reducing 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 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 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 25 76.

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 of 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 Mapap Sagu Esirbze 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).

Fluorescence spectra of the I-20 lubricant sample under investigation are measured at room temperature using a Magpap Sagu Esirze 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 sn, o But what / d-o- nose M M sn with ХМ o / with | Toluene 559,574

N. N

Table 1

Fresh 1 month 2 months From the month 6 months months sleep. o not 7-0-h 1 ZO1zh7 49946. | 4933410 (|, | 48657 (| on (48228 (| on ne be, | ЗО8ж5 (decreases! on 1.895)| on 3095) | 4.395) | 5 95) non on 1.4 95) ' ' ' ' 80 mg/ m

Claims (1)

FORMULA OF THE INVENTION The method of marking 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 the long-wave phosphor uses square acid derivatives of the general formula: 2 А in 2 в: т / 2 х о И ИК 35 е and ee where A is 0, -5, -M-Na, -C(B)(Hg), and Na, Be and B: - are -SONVK, -SM, -SOM(NU (Be), -SOONI, and НУ, Ве, В! and ВК are, independently, -Н, a branched or linear aliphatic group, which may contain as substituents -ОН, -ОН8, -СОВХ -СМ, -СОМ(ВУ(Не), СООВ groups, where Be is a branched or linear aliphatic group, or an aromatic group; p is -o,-5; And Her B is -H, a branched or linear aliphatic group; B? and B? are, independently, H, -CM . SOM(VU)(Ve), -SOOVI, -MO", -ON" or aliphatic groups. Fig. 1 b