RU2781053C1 - Method for marking oil and products of its processing - Google Patents

Abstract

FIELD: oil products marking.

SUBSTANCE: invention relates to methods for marking oil and products of its processing. A method for marking oil and products of its processing is described, characterized by the introduction of 10-100 ppm. derivatives of cyanuric acid, in which the hydrogen atom of the hydroxyl group is replaced by alkyl radicals, both identical and different, in the preparation of which primary alcohols C₁-C₈, isopropyl alcohol, alcohols C₁-C₈are used, in which hydrogen atoms, partially or completely, replace atoms fluorine, isopropyl alcohol, in which hydrogen atoms, partially or completely, replace fluorine atoms.

EFFECT: marking of oil and products of its processing for identification and quality control of products.

1 cl, 4 dwg, 3 tbl, 6 ex

Description

Technical field

The invention relates to the field of labeling oil and oil products, namely the use of nitrogen-containing organic compounds for labeling and can be used to monitor the transport of oil and oil products, in particular to control oil flows in oil pipelines, control motor transport with hydrocarbon products, for timely detection of leaks and theft of products, as well as to localize the consequences of the incident.

State of the art

Currently, in the oil and related industries, there are increased requirements for quality control and control over the circulation of oil and oil products.

The tightening of environmental standards for the content of impurities in oil and oil products is a real challenge for the oil market and imposes increased requirements on the quality of oil products. To comply with these requirements, it is necessary to be able to identify oil and oil products from various suppliers along the entire route of their movement in order to quickly respond to changes in the quality of transported products. The use of marking means makes it possible to establish the presence of such changes.

The problem of theft of oil and oil products (with subsequent clandestine processing) is also relevant, which brings multibillion-dollar losses to both oil market companies and the state budget. The use of marking means will help criminalists to establish the true owner of the seized oil or oil product.

The technology of individual labeling of suppliers of oil and oil products is available on the market, but it is expensive and, as a rule, belongs to foreign companies.

Identification of new compounds suitable for use as marking agents for oil and oil products will allow developing competitive technologies for marking oil and oil products using domestic raw materials and components.

The analysis of scientific and technical literature, normative and technical documentation and other available materials shows that the choice of markers for oil and oil products depends on the purpose pursued by the labeling. Also, the choice of a marker is determined by the nature and properties of the material being marked. All marking methods are inextricably linked with the nature of the marker and the marked material, which determines, in addition, the method of identification, or the qualitative and (or) quantitative isolation of the marker from the marked material.

As compounds used for labeling oil and products of its processing, various organic molecules are often used, which, as a rule, differ in structure from those contained in oil products. These connections can be either visible to the naked eye or invisible.

The use of invisible markers is gaining relevance due to the fact that the color dye can be washed with salts and acids to avoid identification. As a result, according to experts, the use of illegal diesel fuel in 2014 amounted to from 12 to 13% of the market share in Northern Ireland and about 2% in the rest of the UK [New marker to tackle fuel fraud. URL: https://www.gov.uk/government/news/new-marker-to-tackle-foel-fraud. Date of access: 05/25/20.]. The new marker (Accutrace fuel marker developed by Dow Chemical) cannot be easily removed and can be detected at low concentrations, preventing illegal resale and fuel dilution [Chemistry too complex for fuel fraudsters: novel detection systems for laundered fuels succeed where dyes alone are failing. URL: http://www.dow.com/-/media/dow/business-units/dow-us/pdf/319-01108.ashx. Date of access: 26.05.20.; Croud V.V. et al. Criminal of fuel removal markers by distillation // Fuel processing technology. - 2016. - T. 144. - C. 341-347.].

As markers, hydroxyl-containing compounds of the aromatic series can be used, in which the hydroxyl group is connected directly to the aromatic nucleus selected from the series of resorcinol, 4-hexylresorcinol or β-naphthol [Bolotin B. M. Marking agents for oil and oil products as a means of protection against committing illegal acts // Encyclopedia of Forensic Science. - 2019. - No. 1 (20). - S. 76-86, RF Patent 2630689. IPC C07C 39/08, C07C 39/14, G01N 31/22, C10L 1/183. 09/12/2017].

A set of hydrocarbons can also be used that are not specific to the oil, but can be identified and identified.

A method of labeling a liquid petroleum product with a marker is known, including adding from about 1 to about 100 ppm to the liquid petroleum product. a marker that is 1-alkyl (C ₁ -C ₆ )-amino-4-hydroxy-9,10 anthracenediones and 1-alkoxyamino (-O-(C ₁ -C ₃ -))-4-hydroxy-9, 10 anthracenediones or mixtures thereof. [US Patent No. 5205840. IPC C10L 1/22. 04/27/1993.].

A known method of hidden marking of substances, materials, products, carried out by introducing n-alkanes C ₁₆ -C ₂₆ or mixtures thereof directly into the composition of the marked substances [RF Patent 2199574. IPC C10L 1/00, C10M 171/00, C07C 9/22, G01N 33/00. February 27, 2003].

There is a method in which aliphatic monohydric alcohols with the number of carbon atoms in molecules from three to five or more or mixtures thereof are used as volatile markers, and an inert gas stream saturated with volatile compounds (alcohol markers and oil hydrocarbons). The use of aliphatic monohydric alcohols with the number of carbon atoms in the molecules from three to five normal and isostructure and mixtures thereof allows you to get 33 different labeling options [RF Patent 2537468. IPC G01N 30/00. 01/10/2015].

In patents [Patent Canada 2281213, IPC SW 67/22; С09В 67/44; C10L 1/00; C10L 1/223; C10L 1/226. 05/09/2000.; Australian Patent 700391. IPC C10L 1/00; G01N 21/80; G01N 31/22; G01N 21/29; (IPC1-7): B01D 15/04. 01/07/99] for invisible marking, a marker is added to motor fuel, which contains a suspension of carbon nanomaterial (CNM) and surface-active substances (surfactants). The CNM suspension may contain Taunit-M carbon nanomaterial as a solid dispersed phase, and liquid hydrocarbons as a liquid dispersion medium. Marked oil may contain a marker in a concentration of 10 ^-4 wt. %.

In the patent [Patent Canada 2281213, IPC SW 67/22; С09В 67/44; C10L 1/00; C10L 1/223; C10L 1/226. 05/09/2000.] for the invisible marking and subsequent identification of various liquid petroleum hydrocarbons, such as crude oil, diesel fuel, fuel oil, kerosene, lubricating oils, waxes, jet fuel and, in particular, gasoline, one or more dyes are used, having an absorption maximum in the visible wavelength range of 550-700 nm, in such low concentrations that they cannot be visually detected by the human eye. However, these markers can be identified in a relatively fast and simple manner that requires minimal tools, creates no waste, and allows highly accurate determination of the dye concentration in the field.

Phosphors as chemical markers have the greatest practical application. As a rule, this is a small group of organic compounds that, under the influence of UV radiation, glow blue, green, yellow or red. In this case, the phosphor acts as a converter of higher-energy invisible ultraviolet light into visible light with lower photon energy.

Most often, the identification of luminescent markers involves only visual confirmation under the influence of a UV source. This feature of them has both positive aspects (simplicity, speed and low cost of identification) and disadvantages (relative ease of detection and imitation). With fluorescent markers, quantitative determinations can be made by comparing the intensity of fluorescence emitted by a test sample against a set of standards that will indicate the approximate degree of dilution or falsification. A significant disadvantage of phosphors is also a partial or complete loss over time or from the impact of objects for marking properties valuable for quantitative and qualitative determination (luminescence).

The most famous of the currently used fluorescent markers is produced by the English company John Hogg Technical Solutions Ltd of the Dyeguard brand, which after development becomes green. The disadvantage of this marking label is the need to use it in significant concentrations (the concentration of the label in gasoline is 100 g or more per 1000 liters (or >100 ppm)). Marks of John Hogg Technical Solutions Ltd are protected by patents [UK Patent 2344599. IPC C10L 1/233; G01N 21/63; G01N 21/76.14.06.2000, UK Patent 2535179. IPC C09B 67/00; С09В 67/22; C10L 1/16; C10L 1/198; C10L 1/226. 08/17/2016., UK patent 2354070. IPC C10L 1/00; C10L 1/232; C10L 1/24; C10L 1/30; G01N 21/64. March 14, 2001]. The disadvantage of this label is the need to use in high concentrations.

In the patent [US Patent 4209302. IPC C07D 295/13; C10L 1/00; C10L 1/223; C10L 1/233. 24.06.80.] given the requirements for fuel markers that are relevant to the present, which can be extended to markers of oil and petroleum products:

1. The marker should not have a structure similar to the substances that make up the fuel;

2. Can be supplied as liquids with high solubility in petroleum fuels.

3. Must not have color.

4. Should not change the quality characteristics of the fuel.

5. Should be easily removed from the marked fuel.

6. When removed from a labeled fuel, should be easily identifiable by a simple on-site test that is not affected by fuel components.

7. Identification can be confirmed by laboratory methods if necessary.

Not all markers used meet the above requirements, however, this discrepancy can be justified by higher rates of other requirements.

Disclosure of the essence of the invention

The technical problem to be solved by the claimed invention is to improve the efficiency of control over the quality of oil and oil products due to the fact that the proposed markers do not have a similar structure with the substances that make up oil and oil products.

The technical result of the claimed invention is the possibility of marking oil and products of its processing for identification and quality control of products, due to the addition of nitrogen-containing organic compounds that differ in composition from nitrogen-containing compounds contained in the composition of oil and products of their processing.

The technical result of the claimed invention is achieved by the proposed method for marking oil and products of its processing by adding relatively small amounts of 10-100 ppm. derivatives of cyanuric acid, in which the hydrogen atom of the hydroxyl group is replaced by alkyl radicals, both identical and different, in the preparation of which primary alcohols C ₁ -C ₈ , isopropyl alcohol, alcohols C ₁ -C ₈ are used, in which hydrogen atoms are partially or completely, replace fluorine atoms, isopropyl alcohol, in which hydrogen atoms, partially or completely, replace fluorine atoms.

The combination of the above essential features leads to the fact that:

triazine-based markers have a structure that can be easily modified, which is a significant advantage and makes it possible to combine the radicals R ₁ , R ₂ and R ₃ resulting in dozens of individual labels unique in their characteristics.

the use of triazine compounds as markers suggests a simple identification method based on extraction and concentration of the label and subsequent analysis of the sample by high performance liquid chromatography (HPLC);

realized the possibility of obtaining a large number of diverse structures (individual labels) unique in their characteristics due to the ability to combine the radicals R ₁ , R ₂ and R ₃ ;

elongation or branching of the carbon chain of the alkoxy group, preferably by increasing the solubility of markers in organic non-polar liquid media, in particular in oil and oil products, contributes to the uniform distribution of the label throughout the volume of the labeled products, however, an excessive increase leads to an increase in the time spent on extracting the marker from samples;

the sim-triazine compounds proposed as markers do not have a similar structure to the substances that make up oil and oil products, they have good solubility in typical organic solvents without changing their color;

the proposed method of using symtriazine compounds as markers involves a simple identification method based on the extraction and concentration of the label and subsequent analysis of the sample by HPLC;

Sym-triazine-based markers can be detected in low concentrations (10-100 ppm), which will ensure that they do not affect the performance properties of the marked objects (oil and oil products).

Brief description of the drawings

The present invention is illustrated by figures.

In FIG. 1 shows the structural formula of sim-triazines

In FIG. 2 shows the scheme for obtaining sim-triazines

In FIG. 3 shows chromatograms of labels for constructing a calibration graph

In FIG. 4 shows chromatograms of an oil extract containing the labels C ₁ , C ₅ and C ₆

Implementation and examples of the invention

The proposed method for labeling oil and oil products is to use sim-triazines Fig. 1, 2 when labeling petroleum products with subsequent isolation and qualitative and/or quantitative determination of the content of markers by HPLC. FIG. 3 and 4. The method is part of a process that includes:

1) Obtaining sym-triazine labels FIG. 2

2) marking of oil and oil products

3) determination of the qualitative and quantitative content of the label in the labeled sample by HPLC FIG. 3 and 4.

1) Process for preparing the sim-triazine compounds of FIG. 2 consists in adding small portions of metallic sodium in an amount of 3-3.3 mol to 4.3-4.6 mol of dry С ₁ -С ₈ alcohol per 1 mol of cyanuric chloride, in a volume of benzene equal to the volume of alcohol, followed by aging at room temperature for 30 minutes and boiling for 8 hours. To this mixture, cooled to room temperature, is added a solution of 1 mol of cyanuric chloride in a quantity of dry benzene sufficient to dissolve it. Then boiled for 1 hour and cooled to room temperature, acidified with acetic acid, washed with water, filtered and the organic layer is separated. Dry over anhydrous magnesium sulfate and evaporate the solvents. The various alkyl cyanurates of FIG. 1, suitable for marking oil and products of its processing.

2) The following procedure is used to label oil or oil products: dissolve the calculated amount of sym-triazine in a mixture of petroleum ether and benzene in a ratio of 4:1 and add to the oil. The mixture is shaken. The procedure for adding a marker to the fuel is quite simple (dissolve the marker in the same fuel) and differs slightly from similar solutions, for example, US Patent No. 5156653 Silent markers for petroleum, method of tagging, and method of detection (1992), US Patent 5980593 Silent fluorescent petroleum markers 1999 or RF Patent 2630689 Marking label for gasoline (2007)

3) To identify the label to labeled to one volume of oil, to facilitate extraction, add 3 volumes of petroleum ether grade 40-70. Next, a solution containing sulfuric acid (1/100 volume of the mixture volume), acetic acid (1/20 volume of the mixture volume) and water (1/80 volume of the mixture volume) is added to this mixture, and the resulting emulsion is stirred on a magnetic stirrer 1 hour. The acid layer is separated, the oil layer is extracted in a similar way three more times. The acid extracts are combined, water is added (1/100 of the volume of the mixture of oil and petroleum ether) and neutralized by cooling with 10% sodium hydroxide solution to pH=6-7. The neutralizate is extracted with chloroform four times with a volume equal to 1/20 of the volume of the initial mixture of oil and petroleum ether). The combined extracts of chloroform are dried with 4A zeolite granules or anhydrous magnesium sulfate, the solvent is distilled off, the residue is dissolved in a mixture of 20 ml of acetonitrile and 10 ml of methanol. The sample is injected into an Agilent 1290 HPLC, C18 column (250 x 4.6), eluents MeCN:MeOH (2:1 with gradient transition to 100% MeOH for 40 minutes) or a similar chromatograph that allows you to work in the same modes.

The modes of preparation of symtriazine compounds (markers) and implementation of the labeling process discussed above were selected experimentally.

Below the invention is illustrated by the following examples:

Example 1

In a 250 ml three-neck round-bottom flask, with a magnetic stirrer, addition funnel, argon inlet, thermometer, reflux condenser with argon outlet, 40 ml of dried benzene, 14.7 g (19 ml, 0.24 mol) of dry propanol-1 and 3.68 g (0.16 mol) of metallic sodium are added in small portions. Incubated for 30 minutes at room temperature, then heated and boiled for 8 hours. Cool to room temperature, add dropwise a solution of 10 g (0.054 mol) of cyanuric chloride in 100 ml of dry benzene. Heat and boil for 1 hour then cool, acidify with acetic acid (5 ml, 5.1 g), wash with water (50 ml), filter and separate. Wash with water again (50 ml). Dry over anhydrous magnesium sulfate and evaporate the solvents. The remaining alcohol is evaporated by drying in a vacuum oven at 120°C for 8 hours. 11.1 g of a light yellow substance are obtained, which crystallizes completely in the refrigerator. Yield: 81%

Elemental Analysis (%) Calculated: C: 56.5; H: 8.3; N: 16.5. Found: C 56.2; H: 8.1; N: 16.6.

Example 2

50 ml of dried benzene, 20.2 g (25.3 ml, 0.23 mol) of dry pentanol- 1 and add in small portions 3.91 g (0.17 mol) of metallic sodium. Incubated for 30 minutes at room temperature, heated and boiled for 8 hours. Cool to room temperature, add dropwise a solution of 10 g (0.054 mol) of cyanuric chloride in 100 ml of dry benzene. Heat and boil for 1 hour then cool, acidify with acetic acid (5 ml, 5.1 g), wash with water (50 ml), filter and separate. Wash with water again (50 ml). Dry over anhydrous magnesium sulfate and evaporate the solvents. The remaining alcohol is evaporated by drying in a vacuum oven at 120°C for 8 hours. 8.6 g of a light yellow substance are obtained, which crystallizes completely in the refrigerator. Yield: 75%

Elemental Analysis (%) Calculated: C: 63.7; H: 9.8; N: 12.4. Found: C 63.8; H: 9.3; N: 12.6.

Example 3

50 ml of dried benzene, 21.4 g (26.7 ml, 0.21 mol) of dry hexanol- 1 and add in small portions 4.14 g (0.18 mol) of metallic sodium. In this case, intensive gas evolution is observed, then foaming and heating, then the mass thickens strongly. Incubated for 30 minutes at room temperature, heated and boiled for 8 hours. Cool to room temperature, add dropwise a solution of 10 g (0.054 mol) of cyanuric chloride in 100 ml of dry benzene. Heat and boil for 1 hour then cool, acidify with acetic acid (5 ml, 5.1 g), wash with water (50 ml), filter and separate. Wash with water again (50 ml). Dry over anhydrous magnesium sulfate and evaporate the solvents. The remaining alcohol is evaporated by drying in a vacuum oven at 120°C for 8 hours. 12.3 g of a light yellow substance are obtained, which crystallizes completely in the refrigerator. Yield: 60%

Elemental Analysis (%) Calculated: C: 66.1; H: 10.3; N: 11.0. Found: C 66.0; H: 9.9; N: 11.4.

The procedure for obtaining the remaining derivatives of cyanuric acid is the same as in the examples described above, but instead of propanol-1 (C ₃ ) or pentanol-1 (C ₅ ) or hexanol-1 (C ₆ ), primary C ₁ - C ₂ , C ₄ , C ₇ -C ₈ alcohols, isopropyl alcohol, C ₁ -C ₈ alcohols, in which hydrogen atoms, partially or completely, replace fluorine atoms, isopropyl alcohol, in which hydrogen atoms, partially or completely, replace atoms fluorine.

Example 4

Extraction of labels With _1,3-8 from the model solution.

In a 500 ml conical flask, a solution containing 4 ml of sulfuric acid, 20 ml of acetic acid and 5 ml of water is added to a solution of 0.01 g of the C _3-8 label in a mixture of 70 ml of hexane and 30 ml of benzene. Label C ₁ is pre-dissolved in a mixture of 4 ml of petroleum ether and 1 ml of benzene. The resulting emulsion is stirred at room temperature for 1 hour. The acid layer is separated, and the hydrocarbon layer is washed with the same ratio of acids 3 more times for 1 hour. Next, the acid extracts are combined, 50 ml of water are added and neutralized by cooling with 10% sodium hydroxide solution pH=6-7. The neutralizate is extracted with chloroform four times in 20 ml. The combined extracts of chloroform are dried with zeolite 4A pellets or anhydrous magnesium sulfate, the solvent is distilled off, the residue is dissolved in a mixture of 20 ml of acetonitrile and 10 ml of methanol and solution No. 1 is obtained.

The remaining layer of hexane and benzene was washed with 20 ml of 10% sodium hydroxide solution, dried with 4A zeolite granules or anhydrous magnesium sulfate. After drying, the solvents are distilled off, the residue is dissolved in a mixture of 20 ml of acetonitrile and 10 ml of methanol and solution No. 2 is obtained.

Solutions No. 1 and No. 2 analyzed by HPLC. The content of the label in the phases is determined by correlating the areas of the peaks; the information is presented in Table 1.

Example 5

Extraction of C _{1,3-6 labels} from a 100 g oil sample.

In a conical flask for 500 ml of oil weighing 100 g is dissolved in 300 ml of petroleum ether brand 40-70. To the resulting solution is added a solution of the label in petroleum ether (label C ₁ in a mixture of petroleum ether and benzene in a ratio of 4:1). Next, a solution containing 4 ml of sulfuric acid, 20 ml of acetic acid and 5 ml of water is added to the mixture, and the resulting emulsion is stirred on a magnetic stirrer for 1 hour. The acid layer is separated, the oil layer is extracted in a similar way three more times. Acid extracts are combined, 50 ml of water are added and neutralized with cooling with 10% sodium hydroxide solution to pH=6-7. The neutralizate is extracted with chloroform four times in 20 ml. The combined extracts of chloroform are dried with 4A zeolite granules or anhydrous magnesium sulfate, the solvent is distilled off, the residue is dissolved in a mixture of 20 ml of acetonitrile and 10 ml of methanol.

Example 6

Extraction of labels C _1,3-6 from a sample of oil weighing 200 g.

In a 2 L flat-bottomed flask, 200 g of oil is dissolved in 600 ml of 40-70 grade petroleum ether. To the resulting solution is added a solution of the label in petroleum ether (label C ₁ in a mixture of petroleum ether and benzene in a ratio of 4:1). Next, a solution containing 8 ml of sulfuric acid, 40 ml of acetic acid and 10 ml of water is added to the mixture, and the resulting emulsion is stirred on a magnetic stirrer for 1 hour. The acid layer is separated, the oil layer is extracted in a similar way three more times. Acid extracts are combined, 100 ml of water are added and neutralized with cooling with 10% sodium hydroxide solution to pH=6-7. The neutralizate is extracted with chloroform four times in 20 ml. The combined extracts of chloroform are dried with 4A zeolite granules or anhydrous magnesium sulfate, the solvent is distilled off, the residue is dissolved in a mixture of 20 ml of acetonitrile and 10 ml of methanol. Table 3 shows the minimum concentration of the label (the volume of labeled oil is 200 ml). Sample preparation for HPLC is carried out by passing 1.5 ml of the resulting solution through a syringe filter.

Thus, the claimed method makes it possible to mark oil and oil products by adding nitrogen-containing organic compounds (sim-triazines) that differ in composition from nitrogen-containing compounds contained in the composition of oil and their products and to detect them by this method at concentrations of 10-100 ppm .

Claims (1)

A method for marking oil and products of its processing, characterized by the addition of 10-100 ppm derivatives of cyanuric acid, in which the hydrogen atom of the hydroxyl group is replaced by alkyl radicals, both identical and different, in the preparation of which primary alcohols C ₁ -C ₈ , isopropyl alcohol, alcohols C ₁ -C ₈ are used, in which hydrogen atoms are partially or completely, replace fluorine atoms, isopropyl alcohol, in which hydrogen atoms, partially or completely, replace fluorine atoms.

Images