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EA-053303-B1 - METHOD FOR SAMPLING AND AUTHENTICATION OF MARKERS IN LIQUEFIED HYDROCARBON PRODUCTS UNDER PRESSURIZATION

EA053303B1EA 053303 B1EA053303 B1EA 053303B1EA-053303-B1

Abstract

The present invention relates to methods for sampling marked liquefied petroleum products under pressure (PLHP). The methods comprise the steps of collecting PLHP containing at least one marker in a first gas cylinder; transferring at least a portion of said PLHP to a second gas cylinder; transferring a mixture of PLHP, at least one marker, and a solvent to a receiving container, and allowing the PLHP to evaporate. Subsequently, the PLHP can be authenticated by an additional step of determining the concentration of an analyte and/or an analyte functional group of at least one marker using an analytical method. After authentication, the PLHP can be assessed for quantitatively determining its adulteration by an additional step of calculating the concentration of at least one marker in the PLHP and comparing the calculated concentration with a given concentration of at least one marker in the PLHP.

Inventors

  • Лопес Гехо Хуан
  • Маркес Давид
  • Стрингари Паоло
  • Рива Мауро

Assignees

  • СИКПА ХОЛДИНГ СА

Dates

Publication Date
20260504
Application Date
20241007
Priority Date
20231011

Claims (8)

  1. 1. A method for sampling a liquefied petroleum product under pressure (PLHP), preferably selected from the group consisting of liquefied petroleum gases (LPG), natural gases (NG), liquefied natural gases (LNG), natural gases supplied through a pipeline (NPG), and mixtures thereof, containing at least one marker containing at least one analyte atom and/or at least one analyte functional group, wherein said sampling method comprises the steps of: A) collecting in a first gas cylinder a sample of a liquefied petroleum product under pressure (PLHP) containing at least one marker from a storage container; B) connecting the second gas cylinder to a vacuum pump for vacuuming the second gas cylinder; C) weighing the second gas cylinder; D) transferring a given volume of solvent into a second gas cylinder, wherein the boiling point (BP) of the solvent is equal to or greater than 60°C ± 5% and the miscibility in the liquefied petroleum product under pressure (PLHP) is in the range of 10 wt.% ± 5% to 90 wt.% ± 5%; E) weighing the second gas cylinder containing the solvent to obtain the exact mass and volume of the solvent; F) transferring at least a portion of the pressurized liquefied petroleum product (PLHP) containing at least one marker located in the first gas cylinder from the first gas cylinder to the second gas cylinder; - 12053303 G) weighing the second gas cylinder and calculating the amount of liquefied petroleum product under pressure (PLHP) containing at least one marker transferred into the second gas cylinder by subtracting the obtained mass value from the value obtained in step E; and H) transferring a pressurized liquefied petroleum product (PLHP) mixture of at least one marker and a solvent into a receiving container and allowing the pressurized liquefied petroleum product (PLHP) to evaporate; characterized in that the boiling point of at least one marker is equal to or exceeds 60°C ± 5% and the solubility of at least one marker in PLHP is in the range of 0.00001 wt.% ± 5% to 1 wt.% ± 5%, based on the total weight of the marker and PLHP, and the solubility of at least one marker in the solvent is from 0.0001 wt.% ± 5% to 10 wt.% ± 5%, based on the total weight of the solvent and the marker. 1) Average value of three measured samples; value calculated using the equation above. 1) Average value of three measured samples; value calculated using the equation above.
  2. 2. The method according to claim 1, characterized in that the solubility of at least one marker in the PLHP is in the range of from 0.0001 wt.% ± 5% to 1 wt.% ± 5%, preferably from 0.001 wt.% ± 5% to 1 wt.% ± 5%, more preferably from 0.01 wt.% ± 5% to 1 wt.% ± 5%, based on the total weight of the marker and the PLHP, and the solubility of at least one marker in the solvent is from 0.001 wt.% ± 5% to 10 wt.% ± 5%, preferably from 0.01 wt.% to 10 wt.% ± 5%, based on the total weight of the solvent and the marker. 2) Calculated for the received labeled synthetic LPG fuel. 2) Calculated for the received labeled synthetic LPG fuel. Extraction of marker from stored labeled LPG (according to the present invention) (Examples E5-E9) To evaluate the method's reproducibility over time, particularly during storage of labeled LPG fuel, the method according to the present invention was applied to a sample of labeled LPG fuel at various points in time between the fuel's labeling and the extraction and analysis processes. Table 2 shows the results of the analysis of labeled LPG fuel at various time intervals. Table 2 E5 E6 E7 E8 E9 Time 3) /days 0 7 14 36 42 A Y (solvent) /ml 10.4 11.0 10.3 10.9 10.6 IN m(LPG)/g 15 17.6 24.7 28.2 26 C Marker concentration (as measured by XRF analysis) / mg(Bg)/L x 100 256.1 258.3 259.2 257.9 260.6 D Expected concentration of bromine 2 ) / mg (Bg) / l x 100 259 259 259 259 259 E Difference between measurement 1.1% 0.66% 0.08% 0.81% 0.62% and calculation / %
  3. 3. The method according to claim 1 or 2 for additional authentication of a liquefied petroleum product under pressure (PLHP), wherein said method comprises: i) steps A-H of the sampling method according to claim 1 and ii) a step of determining the presence of at least one analyte atom and/or at least one analyte functional group of at least one marker using an analytical method. 3) The time interval between the marking of LPG fuel and the extraction and analysis of marked LPG fuel. As illustrated in Tables 1 and 2, the method disclosed in this document demonstrated acceptable accuracy, with the difference between the measured and calculated bromine concentrations ranging from 0.08 to 12.01%. The occasionally observed large difference between the measured and calculated bromine concentrations (e.g., in Examples E2 and E3) can be explained by manipulation of the cylinders during the process, in particular the connection and disconnection of the cylinders. CLAUSES OF THE INVENTION
  4. 4. The method according to claim 3 for further quantitative determination of adulteration of a liquefied petroleum product under pressure (PLHP), wherein said method comprises: i) steps A-H of the sampling method according to claim 1; ii) a step of determining the presence of at least one analyte atom and/or at least one analyte functional group according to claim 3; iii) the stage of calibration of the analytical instrument to enable the concentration to be obtained for the identified marker; iv) a step of calculating the concentration of at least one marker in the liquefied petroleum product under pressure (PLHP) and v) a step of comparing the concentration of at least one marker calculated in step iv) with a predetermined concentration of at least one marker in the liquefied petroleum product under pressure (PLHP).
  5. 5. The method according to any one of claims 1 to 4, characterized in that the method for taking samples additionally includes step I of shaking the second gas cylinder, wherein said step is carried out after step G and before step H.
  6. 6. The method according to claim 5, characterized in that the sampling method further includes the step J of holding the second gas cylinder in a vertical position for a time of at least 10 s, wherein said step is carried out after step I and before step H.
  7. 7. The method according to any one of claims 1 to 6, characterized in that the sampling method further includes the step K of heating and/or shaking the receiving container to accelerate the evaporation of the liquefied hydrocarbon product under pressure (PLHP), and said step is carried out after step H.
  8. 8. The method according to any one of claims 3 and 4, characterized in that the analytical method is selected from the group consisting of fluorescence spectroscopy, (surface-enhanced) Raman spectroscopy SERS, infrared (FT-IR) spectroscopy with Fourier transform, UV spectroscopy, UV spectroscopy in combination with HPLC, atomic absorption method using elemental analysis, atomic absorption method in combination with high-performance liquid chromatography (HPLC-AAS), mass spectrometry, mass spectrometry with inductively coupled plasma (ICP-MS), mass spectrometry with laser ionization (LIMS), gas chromatography in combination with mass spectrometry (GC-MS), high-performance liquid chromatography in combination with mass spectrometry (HPLC-MS), emission spectroscopy, mass spectrometry with inductively coupled plasma mass spectrometry (ICP-MS), inductively coupled plasma optical emission spectroscopy (ICP-OES), electron capture detection, electron capture detection coupled to gas chromatography (GC-ECD), flame ionization detection, flame ionization detection coupled to gas chromatography (GC-FID), X-ray fluorescence (XRF) spectroscopy and any combinations thereof, preferably selected from the group consisting of Fourier transform infrared (FT-IR) spectroscopy, laser ionization mass spectrometry LIMS, X-ray fluorescence (XRF) spectroscopy and combinations thereof. -

Description

Field of technology to which the invention relates The present invention relates to a method for sampling marked liquefied petroleum liquids under pressure (LPHP) and detecting markers contained therein. The present invention also relates to a method for authenticating marked LPHP, i.e., detecting LPHP markers. If markers are present, the present invention also relates to quantifying the marker concentration in a sample of marked LPHP. The present invention also relates to a method for detecting and quantifying adulteration in LPHP. Prerequisites for the creation of the invention Liquefied petroleum gas (LPG) is a fuel gas containing a flammable mixture of hydrocarbon gases, specifically propane, propylene, butylene, isobutane, and n-butane. LPG is used as a fuel gas in heating systems, cooking appliances, and vehicles. It is also increasingly used as an aerosol propellant and refrigerant (as a replacement for chlorofluorocarbons to reduce ozone depletion). When used as a motor fuel, it is often called autogas or simply gas. Commercially available LPG varieties include mixtures consisting primarily of propane, predominantly of butane, and, most commonly, mixtures containing both propane and butane. Document WO 2009/017505 A1 discloses a device for detecting a marker pre-introduced into a hydrocarbon liquid under pressure, said device comprising a first valve, a vessel connected to the first valve, and a detector configured to be connected to the vessel, wherein the detector is configured to detect the presence or absence of a marker in the hydrocarbon liquid under pressure in the vessel. In particular, the device is suitable for the online detection of fluorescent markers in LPG under pressure. The device and detection method require the use of specialized equipment for analyzing the product under high pressure. Document WO 2011/040910 A1 discloses a method and device for marking LPG under pressure with a solution of a marker and a solvent, transporting the LPG, and subsequently determining the amount of marker in the LPG. The device is permanently installed in a pipeline for supplying hydrocarbon liquid under pressure such that the hydrocarbon liquid under pressure, flowing through the pipeline from a first location to a second location, passes through a detection system. The method and device also require special equipment, for example, an explosion-proof detection device installed in the pipeline such that a first portion of the hydrocarbon liquid under pressure, flowing through the pipeline from the first location to the second location, passes through the detection device, and an explosion-proof electronics unit connected to the detection device and the pipeline, wherein a second portion of the hydrocarbon liquid under pressure, flowing through the pipeline from the first location to the second location, passes through the electronics unit. Document EP 0 677 568 A1 discloses a method suitable for labeling LPG or NPG with nitro compound(s). However, the disclosed detection/authentication method is qualitative, not quantitative. Document US 5,980,593 discloses a method for extracting markers using a solvent from a marked hydrocarbon liquid for authentication of the marked liquid. The disclosed method can be applied to liquid hydrocarbon products, but not to liquefied hydrocarbon products under pressure. The literature describes numerous methods for labeling and authenticating liquefied petroleum products. Methods for labeling and authenticating pressurized liquefied petroleum products (PLHPs), such as liquefied petroleum gas (LPG), are considerably less common. The embedded detection methods disclosed in WO 2009/017505 A1 and WO 2011/040910 A1 require the installation and use of special equipment. There is a need for a sampling method, an authentication method, and a method for batch detection of markers in pressurized liquefied petroleum products (PLHPs). Specifically, there is a need for field sampling and authentication methods suitable for the qualitative and quantitative detection of markers in pressurized liquefied petroleum products (PLHPs). Brief description of the invention The present invention provides a method for sampling a pressurized liquefied petroleum product (PLHP), preferably selected from the group consisting of liquefied petroleum gases (LPG), natural gases (NG), liquefied natural gases (LNG), pipeline natural gases (NPG), and mixtures thereof, containing at least one marker, - 1 053303 containing at least one analyte atom and/or at least one analyte functional group, wherein said sampling method comprises the steps of: A) collecting in a first gas cylinder a sample of a liquefied petroleum product under pressure (PLHP) containing at least one marker from a storage container; B) connecting the second gas cylinder to a vacuum pump for vacuuming the second gas cylinder; C) weighing the second gas cylinder; D) transferring a given volume of solvent into the second gas cylinder; E) weigh