A sustainable fuel digital tracking system

Abstract

This invention discloses a sustainable fuel digital tracer system, comprising at least two chemical tracers added at predetermined concentration ratios, which constitute a unique identification code for each batch of fuel. The at least two chemical tracers are selected from methoxyacrylate compounds, or at least one is selected from methoxyacrylate compounds, with the remainder selected from at least one of benzoate compounds, p-hydroxybenzoate compounds, and sorbate compounds. The tracers of this invention are all pure organic small molecules free of metals and halogens, achieving "harmless passage" to the engine after combustion. This system can accurately decode fuel at low concentrations, possesses excellent cross-fuel versatility, and cleverly meets the shelf-life requirements of marine fuels, achieving low-cost, high-precision fuel authenticity verification and accurate traceability.

Description

Technical Field

[0001] This invention relates to a fuel tracer, and more specifically to a sustainable fuel digital tracer system. Background Technology

[0002] To achieve accurate traceability and identification of fuel origin, batch, and authenticity, adding tracers to sustainable fuels to give them a unique "identity fingerprint" has become an essential technical means that urgently needs to be implemented in the industry. Currently, existing fuel traceability technologies have significant limitations. On the one hand, traditional physicochemical index testing (such as density and acid value) is easily affected by raw materials and processes, and cannot uniquely identify a specific batch; while conventional single-tracer technologies, after fuel dilution or blending, can only reflect the "presence" of the fuel, failing to accurately reconstruct the original batch information and blending ratio. On the other hand, existing technologies struggle to ensure applicability across fuels; differences in polarity lead to insufficient solubility or poor stability of conventional tracers in different fuels (such as biodiesel and alcohol fuels).

[0003] To address more complex tracer coding requirements, existing technologies have attempted to introduce polyethylene glycol (PEG) or metal / halogen-based compounds as tracer systems. However, in practical applications, these technologies have revealed serious risks of secondary pollution and engine damage. For example, the ether bonds of PEG tracers are easily broken under high temperature or oxidizing conditions, leading not only to inaccurate quantitative detection, but also to incomplete combustion products generated by thermal degradation depositing as gum on the combustion chamber and fuel injectors. Metal-based / halogen tracers (such as sodium, potassium, copper, or bromoalkanes) not only act as catalysts, accelerating fuel deterioration and poisoning the engine aftertreatment system, but the solid metal particles and corrosive hydrogen halide gases produced after combustion can easily cause fuel injector coking, severe cylinder wear, and even the generation of highly toxic substances such as dioxins. Furthermore, existing tracers exhibit large quantitative errors at low concentrations (e.g., metal-based tracers have a deviation of 30-40% at the ppb level) and heavily rely on expensive and limited-access detection equipment (such as Raman spectrometers or ICP-MS).

[0004] In addition, the stringent storage environment in the marine biofuel sector places special demands on tracer technology. Under the high temperatures of ship cabins, the shelf life of the most common marine biodiesel (such as B20 to B30) is significantly shortened. Long-term research and monitoring show that this type of fuel faces a serious risk of microbial contamination after one month of storage, and irreversible oxidative degradation occurs after 3-6 months, producing large amounts of corrosive acids and gum deposits that cause injectors to stick. Therefore, in actual ship operations, the handling of marine biodiesel must strictly adhere to the "3-month golden rule," ensuring that the fuel is completely consumed within 3 months of refueling and avoiding long-term storage. This objective law indicates that marine fuel tracer systems do not need to possess indefinite resistance to oxidation and degradation; they only need to maintain chemical stability within the 3-month shelf life before substantial oxidative rancidity occurs. Therefore, developing a digital tracer system suitable for sustainable fuels based on the characteristics of marine biofuels is an urgent problem to be solved. Summary of the Invention

[0005] To address the aforementioned issues, this invention discloses a sustainable fuel digital tracer system. This system comprises at least two chemical tracers added at predetermined concentration ratios, which constitute a unique identification code for each batch of fuel. The tracers in this invention are all pure organic small molecules free of metals and halogens, ensuring "harmless passage" to the engine after combustion. This system can accurately decode fuel at low concentrations, possesses excellent cross-fuel versatility, and cleverly meets the shelf-life requirements of marine fuels, achieving low-cost, high-precision fuel authenticity verification and accurate traceability.

[0006] Specifically, the present invention provides a sustainable fuel digital tracer system, which includes at least two chemical tracers. The at least two chemical tracers are added to the sustainable fuel in a predetermined concentration ratio, wherein the concentration ratio constitutes the identification code of the batch of sustainable fuel. The at least two chemical tracers are all selected from methoxyacrylate compounds, or at least one is selected from methoxyacrylate compounds, and the remainder is selected from at least one of benzoate compounds, p-hydroxybenzoate compounds, and sorbate compounds.

[0007] Preferably, the sustainable fuel is at least one or more of biodiesel, methanol fuel, and ethanol fuel.

[0008] Preferably, the chemical tracer can be qualitatively and quantitatively analyzed using gas chromatography-mass spectrometry (GC-MS) to decode the identity code of the sustainable fuel; and / or, when the sustainable fuel is biodiesel, the chemical tracer needs to be extracted with a solvent and then qualitatively and quantitatively analyzed using GC-MS; when the sustainable fuel is methanol or ethanol, the chemical tracer does not need to be extracted after dissolution and can be directly qualitatively and quantitatively analyzed using GC-MS to decode the identity code of the sustainable fuel.

[0009] Preferably, the shelf life of the chemical tracer is longer than that of the sustainable fuel.

[0010] Preferably, the chemical tracer remains stable for at least 3 months while the marine biodiesel is stored in the ship's hold.

[0011] Preferably, when the sustainable fuel is biodiesel, the total concentration of the chemical tracer added to the sustainable fuel is 1-600 ppm; and / or, when the sustainable fuel is methanol fuel or ethanol fuel, the total concentration of the chemical tracer added to the sustainable fuel is 10 ppb - 1 ppm.

[0012] Preferably, the methoxyacrylate compounds, benzoate compounds, p-hydroxybenzoate compounds, and sorbate compounds all have at least a corrosion-preventing function in the sustainable fuel.

[0013] Preferably, the methoxyacrylate compound is selected from at least one of azoxystrobin, pyraclostrobin, azoxystrobin, tebuconazole, or pyraclostrobin.

[0014] Preferably, the benzoate compound is selected from at least one of methyl benzoate, ethyl benzoate, propyl benzoate, isopropyl benzoate, butyl benzoate, isoamyl benzoate, or benzyl benzoate; the p-hydroxybenzoate compound is selected from at least one of methyl p-hydroxybenzoate, ethyl p-hydroxybenzoate, propyl p-hydroxybenzoate, isopropyl p-hydroxybenzoate, butyl p-hydroxybenzoate, or isobutyl p-hydroxybenzoate; and the sorbate compound is selected from at least one of methyl sorbate, ethyl sorbate, propyl sorbate, or butyl sorbate.

[0015] Compared with the prior art, the present invention has the following beneficial effects: First, this invention abandons the easily cracked single tracer and uses methoxyacrylates and other specific ester compounds in a preset concentration ratio to construct a "digital identity code." This not only has a huge information capacity and extremely strong anti-counterfeiting ability, but it can also be rapidly decoded using gas chromatography-mass spectrometry (GC-MS), which is standard equipment in most conventional fuel laboratories, without the need for additional investment in expensive equipment such as ICP-MS or Raman spectrometers. Real-world shipboard tests have proven that the detection value of the organic ester tracer in this application deviates from the expected value by less than 5% at extremely low concentrations (e.g., below 5 ppm), completely solving the fatal flaw of existing metal-based / halogen tracers, which have quantitative deviations as high as 30%-40% at low concentrations and cannot be used to deduce the true blending ratio. Furthermore, the selected ester combination does not cause phase separation or precipitation in non-polar biodiesel and polar alcohol fuels.

[0016] Secondly, existing technologies using polyethylene glycol (PEG) are prone to thermal degradation at high temperatures, generating deposited gum. Furthermore, metal-based / halogen tracers not only accelerate fuel deterioration and poison engine aftertreatment systems, but their combustion residues can also lead to injector coking, cylinder wear, and even the formation of highly toxic dioxins. In contrast, the four types of ester compounds selected in this application are all pure organic small molecules completely free of metal elements and halogen atoms. After fulfilling their identification function, they can be completely burned with the fuel in the engine cylinder, with the final products being only carbon dioxide and water, producing no ash or hard particles, achieving truly "harmless passage" for the engine and marine ecosystem. Simultaneously, many of these compounds are approved food or cosmetic additives with complete toxicological data, maximizing the long-term stable operation of expensive fuel systems under harsh conditions.

[0017] 3. It cleverly conforms to the "3-month golden rule" of marine fuel, combining high stability with the dual functions of a sacrificial agent.

[0018] Addressing the industry pain point of short lifespan of marine biodiesel in the harsh, high-temperature environment of ship cabins, this invention deeply integrates the design of the tracer system with the "3-month" shelf life of the fuel in actual operation. During the "non-deterioration" window of biodiesel, the system lacks reactive free radicals to trigger chain reactions, insufficient to trigger the decomposition of methoxyacrylate compounds, thus ensuring the long-term effectiveness of the tracer code. More ingeniously, the tracers in the tracer system provided by this invention can all serve as preservatives for sustainable fuels; their chemical integrity and the excellent quality of the fuel are mutually reinforcing and corroborating. This design not only meets the traceability requirements within the specified period but also successfully creates a new generation of digital tracer solution for sustainable fuels that highly adheres to the actual fuel usage patterns of ships and achieves closed-loop management of "low-cost addition, high-precision decoding, and zero residual damage." Compared with benzoic acid esters, parabens, and sorbates, methoxyacrylates have greater advantages in terms of recovery rate, GC-MS quantitative and qualitative analysis, and susceptibility to biodiesel background. They have higher recovery rates, single and easily identifiable quantitative and qualitative peaks, and are less affected by biodiesel background. Attached Figure Description

[0019] Figure 1 This is a chromatogram of biodiesel and three tracers in biodiesel in a 1:1:1 ratio, as tested in Example 4; Figure 2 The chromatograms are those of the three tracers in a 1:1:1 ratio in biodiesel, a 1:3 mixture of diesel, and a 1:3 mixture of biodiesel and diesel tested in Example 6. Figure 3 This is the chromatogram of the sample after 40 days of storage at room temperature, as tested in Example 7; Among them, the characteristic peaks of methyl benzoate (a 1-benzoate ester), propyl 2-hydroxybenzoate (a 2-hydroxybenzoate ester), pyrimethanil (a 3-methoxyacrylate ester), ethyl benzoate (a 4-benzoate ester), methyl sorbate (a 5-sorbate ester), and pyrimethanil (a 6-methoxyacrylate ester) are shown. Detailed Implementation

[0020] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0021] Example 1 This embodiment provides a digital tracer system for biodiesel, comprising three chemical tracers: a methoxyacrylate compound, methyl benzoate, a benzoate compound, and propylparaben, a paraben compound. The three tracers are mixed in a preset mass ratio of 1:1:1 and added to a batch of biodiesel, with a total addition of 600 ppm. This ratio "1:1:1" serves as the identification code for this batch of biodiesel and is recorded in the product traceability system.

[0022] Example 2 The difference between this embodiment and Example 1 is that the chemical tracers are selected from phenoxyacetic acid esters (a type of methoxyacrylate) and butylparaben (a type of paraben). The two tracers are mixed at a mass ratio of 7:3, with a total addition of 260 ppm, and added to the biodiesel. This ratio serves as the identification code for this batch of biodiesel for subsequent traceability verification.

[0023] Example 3 This example illustrates a solvent extraction method. Take 1 ml of biodiesel with a specific proportion of tracer added, add 2 ml of acetonitrile, vortex for 2 min; then add 2 ml of n-hexane, vortex for 1 min, allow to separate layers, and collect the supernatant; add 1 ml of acetonitrile, vortex for 1 min, allow to separate layers, and collect the supernatant; add 1 ml of acetonitrile, vortex for 1 min, allow to separate layers, and collect the supernatant. Collect the supernatant from all three extractions and place in a -20°C freezer for 8 hours to allow separation. Then, collect the supernatant and transfer it. Purge with nitrogen to 2 ml, add QuEChERS purifying agent, vortex for 1 min, centrifuge for 6-8 min, collect the supernatant; add 1 ml of acetonitrile, repeat; add another 1 ml of acetonitrile, repeat; purge with nitrogen to dryness, add 1 ml of n-hexane, and transfer to a 2 ml chromatographic vial for analysis.

[0024] Example 4 This embodiment illustrates a detection method. For the biodiesel sample with the tracer system added in Example 1, gas chromatography-mass spectrometry (GC-MS) was used for detection. The detection conditions were as follows: chromatographic column: HP-5MS (30 m × 0.25 mm × 0.25 μm); injection port temperature: 280℃; temperature program: initial temperature 50℃, held for 1 min; increased to 125℃ at 25℃ / min; then increased to 300℃ at 10℃ / min, held for 15 min. Mass spectrometry used an electron impact ionization (EI) source, with selected ion monitoring (SIM) mode for quantitative analysis of the characteristic ions of the three tracers. Results are as follows: Figure 1 As shown, after recovery rate correction, the proportions of the three tracers are consistent with the preset proportions, accurately realizing the identification of the identity code.

[0025] Example 5: Detection effect of different addition amounts The tracer combination from Example 1 was added to biodiesel at total concentrations of 1 ppm, 100 ppm, and 600 ppm, respectively, and analyzed using the detection method described in Example 3. The results showed that all three tracers exhibited good linear responses (R²>0.999) in the 1-600 ppm range, with a detection limit of 0.01 ppm and a quantitation limit of 0.05 ppm. This indicates that the tracer system can stably detect different concentrations, meeting the requirements of practical applications.

[0026] Example 6: Anti-interference test Biodiesel with the tracer system added in Example 1 was mixed with commercially available ordinary diesel at volume ratios of 1:1, 1:3, and 3:1 to simulate adulteration. Extraction was performed using the extraction method of Example 3 (with both solvent volume and vortex shaking time doubled), and detection was performed using the detection method of Example 4. The results are as follows: Figure 2 As shown, even in mixed samples, the proportions of the three tracers can still be accurately identified, and the identification code is unaffected, indicating that the tracer system has good anti-interference ability.

[0027] Example 7 This embodiment illustrates a tracer lifetime experiment, comparing biodiesel stored at room temperature for 40 days with added three chemical tracers to a freshly prepared control. The three tracers are a methoxyacrylate compound pyrimethanil, a benzoate compound ethyl benzoate, and a sorbate compound methyl sorbate. The three tracers were added in a predetermined mass ratio of 1:2:1, with a total addition of 400 ppm. Figure 3 As shown, the tracer system remained effective after being stored at room temperature for 40 days.

[0028] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Those skilled in the art can make various improvements and modifications without departing from the spirit and principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A sustainable fuel digital tracking system, characterized in that, It includes at least two chemical tracers, which are added to sustainable fuel in a predetermined concentration ratio, the concentration ratio constituting the identification code of the batch of sustainable fuel; The at least two chemical tracers are selected from methoxyacrylate compounds, or at least one is selected from methoxyacrylate compounds, and the remainder is selected from at least one of benzoate compounds, p-hydroxybenzoate compounds, and sorbate compounds.

2. The sustainable fuel digital tracking system of claim 1, wherein, The sustainable fuel includes at least one or more of biodiesel, methanol, and ethanol.

3. The sustainable fuel digital tracing system according to claim 1, characterized in that, The chemical tracer can be qualitatively and quantitatively analyzed using gas chromatography-mass spectrometry (GC-MS) to decode the identity code of the sustainable fuel; and / or, when the sustainable fuel is biodiesel, the chemical tracer needs to be extracted with solvent and then qualitatively and quantitatively analyzed using GC-MS; when the sustainable fuel is methanol or ethanol, the chemical tracer does not need to be extracted after dissolution and can be directly analyzed qualitatively and quantitatively using GC-MS to decode the identity code of the sustainable fuel.

4. The sustainable fuel digital tracing system according to claim 1, characterized in that, The shelf life of the chemical tracer is longer than that of the sustainable fuel.

5. The sustainable fuel digital tracking system of claim 1, wherein, The chemical tracer remains stable for at least 3 months while the sustainable fuel is stored in the ship's hold.

6. The sustainable fuel digital tracking system of claim 1, wherein, When the sustainable fuel is biodiesel, the total concentration of the chemical tracer added to the sustainable fuel is 1-600 ppm; and / or, when the sustainable fuel is methanol or ethanol, the total concentration of the chemical tracer added to the sustainable fuel is 10 ppb - 1 ppm.

7. The sustainable fuel digital tracking system of claim 1, wherein, The methoxyacrylate compounds, benzoate compounds, p-hydroxybenzoate compounds, and sorbate compounds all have at least anti-corrosion properties in the sustainable fuel.

8. The sustainable fuel digital tracking system of claim 1, wherein, The methoxyacrylate compound is selected from at least one of azoxystrobin, pyrimethanil, azoxystrobin, fenpyroxime, pyrimethanil, fenpyroxime, pyrimethanil, and phenoxystrobin.

9. The sustainable fuel digital tracking system of claim 1, wherein, The benzoic acid ester compound is selected from at least one of methyl benzoate, ethyl benzoate, propyl benzoate, isopropyl benzoate, butyl benzoate, isoamyl benzoate, phenyl benzoate, or benzyl benzoate; the p-hydroxybenzoic acid ester compound is selected from at least one of methyl p-hydroxybenzoate, ethyl p-hydroxybenzoate, propyl p-hydroxybenzoate, isopropyl p-hydroxybenzoate, butyl p-hydroxybenzoate, or isobutyl p-hydroxybenzoate; the sorbic acid ester compound is selected from at least one of methyl sorbate, ethyl sorbate, propyl sorbate, or butyl sorbate.

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