HYDROPHOBIC FLUORESCENT CARBON QUANTUM DOT FOR MARKER APPLICATION IN HYDROCARBON LIQUIDS AND PROCESS OF PREPARATION THEREOF

Abstract

The present invention relates to a process for preparation of metal free, nontoxic, hydrocarbon fuel compatible fluorescent carbon quantum dots (CQD), which act as marker as well as lubricity improver. CQDs are highly stable in non-polar hydrocarbons, at ppm level exhibit distinct fluorescent color upon irradiation with light of specific wavelength and exhibit distinct spectral properties compared to non-polar base hydrocarbons.

Claims

1. A process comprising: mixing a carbon source compound and a nitrogen containing non-polar solvent to obtain a solution, wherein the nitrogen containing non-polar solvent has a boiling point above 175° C.; and autoclaving or heating the solution at a temperature in a range of 180-220° C. for an overnight, followed by cooling to room temperature to obtain carbon quantum dots (CQD), wherein the CQDs are hydrophobic, and fluorescent, and wherein the process is a one step process.

2. The process as claimed in claim 1, wherein the CQDs have a size in a range of 2-7 nm.

3. The process as claimed in claim 1, wherein the carbon source compound is selected from the group consisting of citric acid, carbohydrate, amino acid, ascorbic acid, phenyl diamine, cyclic it-bond containing organic molecules and a mixture thereof, and wherein the cyclic it-bond containing organic molecules comprise naphthoic acid, phthalic acid, and dihydroxy biphenyl.

4. The process as claimed in claim 1, wherein the nitrogen containing non-polar solvent is selected from the group consisting of oleyl amine, octyl amine, dodecyl amine, Octa decyl amine.

5. The process as claimed in claim 1, wherein the hydrophobic, and fluorescent carbon quantum dots are stable upon adding to non-polar hydrocarbon-based fuels or oils.

6. The process as claimed in claim 5, wherein adding the CQDs to the non-polar hydrocarbon-based fuels reduces wear scar diameter (WSD) by about 30%.

7. The process as claimed in claim 5, comprises adding the CQDs to the non-polar hydrocarbon-based fuels in an amount ranging from 10 to 200 ppm to improve lubricity.

8. The process as claimed in claim 1, wherein the hydrophobic, fluorescent carbon quantum dots are stable upon adding to synthetic and mineral base oils (Gr I-Gr IV).

9. The process as claimed in claim 1, wherein the carbon source compound is ascorbic acid and the nitrogen containing non-polar solvent is oleyl amine.

10. The process as claimed in claim 5, wherein the non-polar hydrocarbon-based fuels are selected from the group consisting of motor spirit, ethanol blended motor spirit, diesel, biodiesel, synthetic base oils, mineral base oils, and a mixture thereof.

11. The process as claimed in claim 1, further comprising adding 10 to 200 ppm of the CQDs to a hydrocarbon-based fuel sample to yield an additized fuel; and irradiating the additized fuel with a light having a wavelength in a range of 450-500 nm for determining adulteration of the hydrocarbon-based fuel sample.

12. The process as claimed in claim 11, wherein the hydrocarbon-based fuel sample is selected from the group consisting of motor spirit, ethanol blended motor spirit, diesel, biodiesel, synthetic base oils, mineral base oils, and a mixture thereof.

13. The process as claimed in claim 11, wherein the additized fuel and un additized fuel exhibit different color emission under irradiation.

14. The process as claimed in claim 11, the additized fuel emits greenish yellow color.

15. The process as claimed in claim 5, wherein the non-polar hydrocarbon-based fuels comprising 2-100 ppm CQDs emit a greenish yellow light, when irradiated with a laser of wavelength 450-500 nm.

16. The process as claimed in claim 5, wherein the non-polar hydrocarbon-based fuels comprising 10-50 ppm CQDs emit a greenish yellow light, when irradiated with a light of wavelength with 480 nm light.

17. The process as claimed in claim 5, wherein fluorescence intensity of the CQDs dispersed in the non-polar hydrocarbon-based fuels increases with an increasing amount of the CQDs.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0035] Exemplary embodiments of the present disclosure are illustrated by way of example in the accompanying drawings.

[0036] FIG. 1: Illustrates (a) UV-Vis, (b) PL spectrum and (c) TEM image of as synthesized CQDs.

[0037] FIG. 2: Illustrates digital images of CQD dispersion in fuel (a) and oil (b). PL spectra and maximum fluorescence intensity of CQD dispersion in fuel (b,c) and oil (e,f) at different time points.

[0038] FIG. 3: Illustrates digital fluorescence images of CQD dispersion in BSVI diesel and motor spirit under 480 nm light.

[0039] FIG. 4: Illustrates digital fluorescence images of CQDs dispersion in Gr II & III base oil (a, b) and transmission oil (c) under 480 nm light.

[0040] FIG. 5: Illustrates fluorescence spectrum of various concentration CQDs in diesel (a) and motor spirit (b).

DETAILED DESCRIPTION OF THE INVENTION

[0041] For the purpose of promoting an understanding of the principles of the invention, reference will now be made to the embodiments in the specific language will be used to describe the same. It will nevertheless be understood that no limitation of the scope of the invention is thereby intended, such alterations and further modifications in the illustrated process, and such further applications of the principles of the invention as illustrated therein being contemplated as would normally occur to one skilled in the art to which the invention relates. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skilled in the art to which this invention belongs. The composition, process, and examples provided herein are illustrative only and not intended to be limiting.

[0042] The articles “a”, “an” and “the” are used to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article.

[0043] The terms “comprise” and “comprising” are used in the inclusive, open sense, meaning that additional elements may be included. It is not intended to be construed as “consists of only”.

[0044] Throughout this specification, unless the context requires otherwise the word “comprise”, and variations such as “comprises” and “comprising”, will be understood to imply the inclusion of a stated element or step or group of element or steps but not the exclusion of any other element or step or group of element or steps.

[0045] The present invention provides a one step process for preparing oil dispersible highly fluorescent carbon quantum dots without any further modification.

[0046] In another aspect of the present invention, provides metal free, non-toxic, fluorescent CQD as a marker for non-polar hydrocarbon matrix.

[0047] In another embodiment, the present invention provides a process for preparation of color emitting hydrophobic CQDs by mixing of carbon source and a hydrophobic solvent, followed by solvothermal treatment of the mixture at temperature in a range of 180-220° C.

[0048] In another embodiment, the present invention, provides a greenish yellow color emitting hydrophobic CQDs, prepared by mixing ascorbic acid as a carbon source in an oleyl amine. Followed by transferring the solution into an autoclave and at a temperature of 200° C. Reaction is continued overnight and cooled down to room temperature. Optionally, the reaction can be carried out under normal heating at specific temperature under simple closed conditions below the boiling point of solvent, as long as the temperature is above the reaction temperature range of 180-220° C. Finally, obtained CQDs greenish yellow emission, is collected and stored for further characterization and use. It is to note that the reaction also can be carried out without an autoclave until unless the boiling point of the solvent used is higher than the reaction range of 180-220° C.

[0049] In another embodiment of the present invention, CQDs are prepared by mixing carbon source such as citric acid, carbohydrate, amino acid, cyclic it-bond containing organic molecules such as naphthoic acid, phthalic acid, dihydroxy biphenyl etc., and octyle amine, dodecyl amine, octadecyl amine as medium/solvent to carry out reaction. CQDs are not limited to greenish yellow emission. Other color emission CQDs are synthesized by changing the amount of carbon source, solvent, and temperature.

[0050] In another preferred embodiment of the present invention, CQDs are prepared by solvothermal treatment of the carbon source and nitrogen containing solvent at higher temperature of 180-220° C. CQDs are synthesized by changing the amount of carbon source, solvent, and temperature. Other carbon source such as citric acid, carbohydrate, amino acid, cyclic n-bond containing organic molecules can be used in synthesis of various color emitting hydrophobic CQDs.

[0051] In another embodiment, present invention provides compatible and dispersible CQDs, which are stable in various fuels and oils. CQDs in an amount of 1-1000 ppm is mixed with diesel, Motor spirit, base oils, formulated engine oil and/or transmission oil. The CQDs are highly stable in medium and show no agglomeration. As experimentally studied, even after 6 months, the fluorescence intensity remained steady, indicating stability.

[0052] In another preferred embodiment of the present invention, CQDs are doped in fuel to identify the products using fluorescent properties of CQDs. Fuel containing 2-100 ppm CQDs, particularly 10-50 ppm, when irradiated with a 450-500 nm laser, emitted a characteristic greenish yellow light.

[0053] In another embodiment, the present invention provides doping of CQD in base oils to identify the product using fluorescent properties of CQDs. By irradiating with 480 nm light, oils/fuels containing 2-100 ppm of CQD, especially 10-50 ppm, emits a characteristic greenish yellow emission. Under 480 nm light irradiation, specific transmission and engine oils containing CQD in the range of 2-100 ppm displays different emission and PL features as depicted in FIG. 3.

[0054] In another embodiment, the present invention provides that fluorescent intensity of CQD dispersion in fuels and oils varies with the amount of CQDs. Fluorescence intensity of CQD dispersed in fuel/oil increases as the amount of CQD increases.

[0055] In another embodiment, the present invention CQD improves lubricity of fuels/oils. Even without the use of a standard organic lubricity improver, the requisite lubricity is achieved when CQDs dispersed in diesel.

EXAMPLES

[0056] The following examples are included herein for illustrative purposes only. Those skilled in the art will appreciate that many modifications may be made in the invention without changing the essence of invention.

Example 1

[0057] Synthesis of Hydrophobic CQD

[0058] Hydrophobic fluorescent CQDs were synthesized via solvothermal method. The solvent for the synthesis is chosen carefully so that the CQDs are soluble or compatible to targeted non-polar hydrocarbons. In a typical reaction, 2-5 g ascorbic acid mixed with 70-100 mL oleyl amine. Next, the solution was transferred into an autoclave and temperature set at 200° C. Reaction continued overnight and cooled down to room temperature. It is to note that the reaction also can be carried out without an autoclave until unless the boiling point of the solvent used is higher than the reaction range of 180-220° C. Finally, product collected and stored for further characterization and use. It is to note that other amines such as octyle amine, dodecyl amine, octadecyl amine; polar base oils such as Naphthenic base oil, tertiary butyl phenyl phosphate, 2-methyl Naphthalene; ester based base oils such as di isodecyl adipate, neo polyol can be used as solvent. Suitable carbon source such as citric acid, carbohydrate, amino acid, Phenyl diamine, other cyclic it-bond containing organic molecules such as naphthoic acid, phthalic acid, dihydroxy biphenyl etc., may be used for preparation of these hydrophobic CQDs.

Example 2

[0059] Size, Shape, and Optical Properties of the Hydrophobic CQD

[0060] UV-Vis spectroscopy and Fluorescence spectrum of synthesized CQD diluted in hexane recorded to check absorption and emission properties of CQDs (FIG. 1). Absorption spectrum of CQDs did not show any significant absorption peak in visible region although the solution becomes yellowish in color (FIG. 1a). Photoluminescence (PL) spectrum of CQDs exhibit excitation dependent fluorescence and shows emission at 560 nm, when excited with 480 nm. (FIG. 1b). Such excitation dependent fluorescence property is common for CQDs nanoparticles and is dependent on the presence of various energy level associated with defect of hetero atom N and O in the nanoparticles. TEM microscopy technique was used to check the size and diversity of as synthesized CQD nanoparticles. TEM image of as synthesized CQD clearly shows formation of monodispersed spherical shape nanoparticles of size around 2-7 nm (FIG. 1c).

Example 3

[0061] Dispersion Stability of CQD in Hydrocarbon Matrices

[0062] Dispersion stability of CQDs in fuels and oils accessed by observing presence of any agglomeration and change in fluorescence of solution at different time point. In the digital images of CQDs in fuel (FIG. 2a) and oil (FIG. 2b) did not show any agglomeration in solution. Corresponding fluorescence spectrum and intensity of fluorescence of CQDs dispersion solution in fuels (FIG. 2b-c) and oil (FIG. 2e-f) showed that both the spectral pattern and intensity of fluorescence remain unchanged over several days' time. Thus, these results prove that CQDs in fuel and oil have high dispersion stability

Example 4

[0063] Fluorescence Imaging of CQD Doped Fuels

[0064] Various concentrations of CQD were added to various fuels to test the capacity of CQDs to identify the product using their fluorescence qualities. Next, 480 nm light was irradiated on CQD additized fuel solution and color of the solutions observed. Digital images of fluorescence of CQD dispersion in BS VI diesel & motor spirit fuel showed distinct greenish yellow color compared to solution without CQD. (FIG. 3).

Example 5

[0065] Fluorescence Imaging of CQD Doped Oils

[0066] To evaluate the feasibility of CQD fluorescence properties to identify oil, different amounts of CQDs were added to different base oils and created oils. Next, CQDs additized oils were kept under 480 nm light and emission color of CQDs in various solution examined. Digital fluorescence images of CQD additized base oil showed distinct yellowish emission compared to only base oils (FIG. 4 a, b). CQD additized transmission oil also exhibit significant greenish yellow emission under irradiation of 480 nm light (FIG. 4c).

Example 6

[0067] Effect of Concentration of CQD in Matrix on Intensity

[0068] Changes in fluorescence with the amount of CQD present in solution investigated by taking fluorescence spectrum of various concentration of CQD in fuel and oil. The fluorescence spectrum of various concentration CQD in BSVI diesel and motor spirit presented in FIG. 4. The results showed that fluorescence intensity decreases with decreasing the concentration of CQD in both fuels. This indicated that's present invention CQD protects the mother product from the mixing with other cheap product.

Example 7

[0069] Lubricity Study of Fuel Doped with CQD

[0070] CQD doped fuel prepared by adding different amount of CQDs stock solution and lubricity of the samples vis a vis base fuel was evaluated using HFRR technique. The outcome of the HFRR results of diesel is represented in table 1. Wear scar diameter (WSD) of the neat diesel without any lubricity improver or CQD is 590, which notably reduces to 411 microns after addition of CQD of concentration 30. The same value for commercial diesel (BS VI) containing organic lubricating additive is 425. Hence, the CQDs also works as lubricity improver in diesel fuel. We also studied effect of CQD on commercial diesel, which normally contains lubricity improver to compensate the lost lubricity with sulfur removal. With addition of 20 and 50 ppm of CQD, the WSD value decreases to 388 and 386 microns compare to WSD value of diesel (425 microns). Hence, the CQDs function in synergetic with the lubricity improver without any negative interaction. All these data demonstrated that CQD can be used as lubricating additive for diesel and also work in synergetic with lubricating additive for marker purpose.

TABLE-US-00001 TABLE 1 HFRR results of CQDs dispersion in diesel HFRR Lubricity Amount of WSD value Test Matrix Improver CQD in ppm in micron 1. Diesel (BS VI) No 0 590 2. Diesel (BS VI) No 30 411 3. Diesel (BS VI) No 60 405 4. Diesel (BS VI) Yes 0 425 5. Diesel (BS VI) Yes 20 388 6. Diesel (BS VI) Yes 50 386

Advantage of Present Invention

[0071] 1. Highly stable CQDs in non-polar hydrocarbon-based fuels (motor spirit, ethanol blended motor spirit, diesel, biodiesel etc.) and both in synthetic and mineral base oils (Gr I-Gr IV). [0072] 2. CQDs have distinct Fluorescence as compared to base oils and fuels. [0073] 3. CQDs as a lubricity improver in hydrocarbon-based fuels.