MODIFIED TERPENE FORMULATION FOR REMOVING PETROLEUM OILS FROM CONTAMINATED SOILS, MODIFIED TERPENE-BASED CONCENTRATED OIL-IN-WATER EMULSION AND USE OF A MODIFIED TERPENE-BASED FORMULATION FOR CLEANING CONTAMINATED SOILS

Abstract

The present invention relates to a modified terpene-based formulation for removing petroleum oils from contaminated soils, which contains between 90 and 98% by weight d-limonene, between 0.1 and 2% by weight isomeric forms of carveol, between 0.01 and 1% by weight carvone, between 0.01 and 1% by weight limonene oxide and between 0.01 and 2% by weight alpha-terpineol. A modified terpene-based oil-in-water emulsion containing the abovementioned formulation and at least one non-ionic surfactant and a carrier is described, as well as use of said modified terpene formulation for cleaning contaminated soils.

Claims

1-15. (canceled)

16. Formulation of modified terpenes for removing petroleum-derived oil from contaminated soil, comprising the following ingredients: between 90 and 98% by weight of D-limonene; between 0.1 and 2% by weight of isomeric forms of carveol, consisting of cis-carveol, trans-carveol or mixtures thereof; between 0.01 and 1% by weight of carvone; between 0.01 and 1% by weight of limonene oxide and between 0.01 and 2% by weight of alpha-terpineol.

17. The formulation according to claim 16, wherein D-limonene is present in the range of 94-98% of the total weight of the formulation.

18. The formulation according to claim 16, wherein carveol in the cis or trans forms or mixtures thereof is present in the range of 0.1-0.4% of the total weight of the formulation.

19. The formulation according to claim 16, wherein carvone is present in the range of 0.05-0.25% of the total weight of the formulation.

20. The formulation according to claim 16, wherein limonene oxide is present in the range of 0.05-0.2% of the total weight of the formulation.

21. The formulation according to claim 16, wherein alpha-terpineol is present in the range of 0.15-0.4% of the total weight of the formulation.

22. A concentrated modified terpene-based oil-in-water emulsion, comprising the formulation of modified terpenes according to claim 16, at least one nonionic surfactant, and a carrier.

23. The concentrated oil-in-water emulsion according to claim 22, the emulsion consisting of: between 0.5% and 70% by weight of a formulation of modified terpenes, said formulation comprising between 90 and 98% by weight of D-limonene; between 0.1 and 2% by weight of isomeric forms of carveol, consisting of cis-carveol, trans-carveol or mixtures thereof; between 0.01 and 1% by weight of carvone; between 0.01 and 1% by weight of limonene oxide and between 0.01 and 2% by weight of alpha-terpineol; between 0.1% and 50% by weight of at least one food grade nonionic surfactant; and between 0.1% and 99.4% of a carrier.

24. The concentrated oil-in-water emulsion according to claim 22, the emulsion consisting of: between 4% and 32% by weight of a formulation of modified terpenes, the said formulation comprising between 90 and 98% by weight of D-limonene; between 0.1 and 2% by weight of isomeric forms of carveol, consisting of cis-carveol, trans-carveol or mixtures thereof; between 0.01 and 1% by weight of carvone; between 0.01 and 1% by weight of limonene oxide and between 0.01 and 2% by weight of alpha-terpineol; between 5% and 20% by weight of at least one food grade nonionic surfactant; and between 48% and 91% of a carrier.

25. The concentrated emulsion according to claim 22, further comprising 5-10% ethanol.

26. The concentrated oil-in-water emulsion according to claim 22, wherein the food grade nonionic surfactant comprises between 1 and 20 carbon atoms selected from the group consisting of: ethoxylated alcohols, polyethylene or polyol esters, alkyl polyglucosides, ethoxylated polyol esters, polysorbates, and mixtures thereof.

27. The concentrated oil-in-water emulsion according to claim 22, wherein the carrier is water.

28. Use of a formulation of modified terpenes according to claim 16, wherein the formulation of modified terpenes is intended for the preparation of a product for the cleanup of contaminated soil by petroleum derivatives.

29. The use according to claim 28, wherein the active component of various soil cleanup methods is selected from the group consisting of: hydraulic containment; Pump-and-treat; multi-phase extraction; chemical oxidation; soil vapor extraction; Air sparging; Air stripping; Biopiles; Bioremediation; Soil flushing; Bioventing; natural attenuation; Biosparging; thermal desorption; and phytoremediation.

Description

BRIEF DESCRIPTION OF THE FIGURES

[0035] FIG. 1it displays the process of separating a petroleum-derived oil from the soil, and both the thick and thin cuts of soil can be decontaminated: (a) shows soil contaminated with 15% of heavy oil containing 7,253 mg of Total Petroleum Hydrocarbon (TPH) per Kg of soil and 20,000 mg of Oil and Grease (O&G) per Kg of soil; (b) shows thick cut after washing containing 304 mg of TPH per Kg of soil and 250 mg of O&G per Kg of soil; and (c) shows thin cut of soil after washing containing 506 mg of TPH per Kg of soil.

[0036] FIG. 2Chart comparing the emulsification capability of the following developed fractions: FPetro Soil and FPetro Env, with pure D-limonene and commercial products #1 and #2 for cleaning petroleum derivatives, all of them exhibiting 0.75% (m/m) of dilution concentrations, wherein the FPetro Env fraction of modified terpenes comprises 0.5% of oxidized terpenes produced according to the method disclosed by PI 0903082-4; the FPetro Soil fraction of modified terpenes comprises 0.1% of oxidized terpenes produced according to the method disclosed by PI 0903082-4; commercial product #1 contains an amount of oxidized ingredients with a large apolar fraction obtained through a catalyst's modified process; and commercial product #2 consists of a product having a 10% concentration of modified terpenes.

DETAILED DESCRIPTION OF VARIOUS EMBODIMENTS

[0037] The present invention consists of a modified terpene-based formulation for removing petroleum-derived oil from soil.

[0038] The claimed formulation consists of a mixture of terpenes and/or terpenoids produced by oxidizing D-limonene as recited in PI 0903082-4 by the same applicant.

[0039] We could notice that a certain solvent fraction of the mixture of terpenes and/or terpenoids obtained in accordance with the process disclosed by patent application PI 0903082-4 when in specific amounts is able to remove petroleum-derived oil from soil in a safe, simple and effective manner.

[0040] The process described in patent application PI 0903082-4 comprises essentially preparing mixtures of terpene and/or terpenoid derivatives by oxidizing D-limonene in the presence of an acid catalyst, at concentrations ranging between 0.1% and 10% of the mass of the reacting raw material, in a gas-liquid system, by making air flow at a rate ranging between 2 L/min and 8 L/min, per kg of raw material, under stirring and heating conditions, at temperatures ranging from 25 C. to 180 C.; and by washing the product of the reaction with water or alkaline solution, to reach a neutral pH and by vacuum drying the washed neutral product.

[0041] The resulting composition is a mixture of terpenes and/or terpenoids comprising: D-limonene, D-carveol, l-carveol carvone, limonene oxide, limonene epoxide, phellandrene, terpendiol, terpineol, dihydroxy-carvone etc.

[0042] The mixture of terpenes and/or terpenoids obtained according to the process described by PI 0903082-4 may also comprise D-limonene, their isomers and/or their oxygenated derivatives.

[0043] Of the mixture of terpenes and/or terpenoids produced by oxidizing D-limonene, we noticed that a certain solvent fraction promotes decontamination of soil contaminated with petroleum derivatives, thus providing an optimized cleaning effect.

[0044] Therefore, one of the objectives of the invention consists in providing a formulation of modified terpenes that can be applied to any type of soil contaminated with petroleum derivatives.

[0045] The types of contaminated soil to be decontaminated by the formulation in question includebut are not limited tothose contaminated by petroleum derivatives as the result of various activities. Petroleum derivatives relate to BTEXs (benzene, toluene, ethylbenzene and xylene), PAHs (polycyclic aromatic hydrocarbons), MTBE (methyl tert-butyl ether) or CHCs (chlorinated hydrocarbons) impregnated in the soil.

[0046] The present formulation can also be used for decontaminating various surfaces involving leak or contamination by petroleum derivatives.

[0047] The present formulation removes the petroleum derivative from soil and forms an emulsion which facilitates the removal and further separation of the formulation from the petroleum derivative for reuse of both.

[0048] Modified terpenes are the selection of a certain solvent fraction from a mixture of terpenes and/or terpenoids obtained by oxidizing D-limonene as reported by patent application PI 0903082-4. Particularly, modified terpenes consist of specific amounts of D-limonene, cis- and trans-carveol, carvone, limonene oxide and alpha-terpineol.

[0049] More specifically, the modified terpene-based formulation of the present invention consists of the following solvent fraction: [0050] from 90 to 98% by weight of D-limonene [0051] between 0.1 and 2% by weight of isomeric forms of carveol, consisting of cis-carveol, trans-carveol or mixtures thereof [0052] between 0.01 and 1% by weight of carvone [0053] between 0.01 and 1% by weight of limonene [0054] between 0.01 and 2% by weight of alpha-terpineol

[0055] Preferably, the formulation of the present invention may comprise between 94 and 98% D-limonene, a mixture of 0.1 to 0.4 of cis- and trans-carveol, from 0.05 to 0.25% carvone, from 0.05 to 0.2% D-limonene oxide and from 0.15 to 0.4% alpha-terpineol.

[0056] The aforementioned formulation may contain impurities at concentrations below 0.05%.

[0057] The formulation for removing petroleum-derived oil must be preferably utilized by qualified professionals and can be applied according to many techniques of interest, such as, but not limited to: Hydraulic containment; Pump-and-treat; Multi-phase extraction; Chemical oxidation; Soil vapor extraction; Air sparging; Air stripping; Biopiles; Bioremediation; Soil flushing; Bioventing; Natural attenuation; Biosparging; Thermal desorption and Phytoremediation.

[0058] In an embodiment of the invention, the formulation of modified terpenes can be associated with surfactants and other carriers, forming an oil-in-water emulsion.

[0059] The surfactants that can be combined with the formulation of modified terpenes of the present invention include food grade nonionic surfactants having from 1 to 20 carbon atoms in the chain.

[0060] The carrier to be used in combination with the formulation of modified terpenes of the present invention preferably comprises water.

[0061] The concentrated oil-in-water emulsionthat comprises the formulation of modified terpenes, surfactant and carrierconsists of a biodegradable product for cleaning contaminated soil and has the following composition: [0062] between 0.5% and 70% by weight of a formulation of modified terpenes; [0063] between 0.1% and 50% by weight of at least one nonionic surfactant; and [0064] between 0.1% and 99.4% of a carrier.

[0065] In another embodiment of the present invention, 5-10% water-soluble ethanol can be added to facilitate the emulsion's flowdability when it appears viscous.

[0066] In a preferred embodiment of the concentrated oil-in-water emulsion a mixture of 4-32% of a mixture of modified terpenes, 5-20% by weight of at least one nonionic surfactant and 48-91% by weight of a carrier is produced.

[0067] The nonionic surfactant consists of food grade nonionic surfactants having from 1 to 20 carbon atoms in the chain, preferably selected from: ethoxylated alcohols, polyethylene or polyol esters, alkyl polyglucosides, ethoxylated polyol esters and polysorbates or mixtures thereof, but not limited thereto.

[0068] Out of the carriers that can be used in the emulsion, water is preferably utilized.

[0069] The present formulation of modified terpenes is stable and capable of emulsifying contaminating oil. Separation or decontamination occurs when the oil-in-water emulsion of the present invention and the contaminated oil are emulsified, thereby allowing for the recycling of the solvents and the contaminating oil. Decontamination is displayed by FIG. 1, where we can see that the formulation can remove even the contaminants from the thin cut of the soil, which poses an enormous challenge to the prior art due to its great adsorption capability.

[0070] Hence, the emulsions of the present invention produced by incorporating the formulation of modified terpenes can remove oil from contaminated soil without interfering in or producing effects on soil microorganisms and therefore do not leave residues in the soil for they are biodegradable.

EXAMPLES OF APPLICATION TESTS AND THEIR RESULTS

Example 1

[0071] Test on the emulsification capability of the formulation of modified terpenes of the present invention in comparison with that of regular terpenes.

[0072] The emulsification capability of five samples were tested and compared: pure commercial D-Limonene, the fraction of modified terpenes FPetro Env, the fraction of modified terpenes FPetro Soil, commercial product #1 and commercial product #2.

[0073] The pure commercial D-limonene sample comprises between 95% and 97% of D-limonene.

[0074] The fraction of modified terpenes FPetro Env of the present invention comprises 0.5% of oxidized terpenes produced according to the method described in patent PI 0903082-4.

[0075] The fraction of modified terpenes FPetro Soil of the present invention comprises 0.1% of oxidized terpenes produced according to the method described in patent PI 0903082-4.

[0076] Commercial product #1 consists of a product which amount of oxidized terpenes is unknown, having a large apolar fraction obtained from a catalyst's modified process.

[0077] Commercial product #2 consists of a product having a concentration of 10% modified terpenes.

[0078] Each of the samples above was added with polysorbate 80 in a ratio of 3:1 of terpenes to surfactant and then the samples were diluted in water in a ratio of 1:100, so as to remain with 0.75% terpenes in the final solution.

[0079] The test consisted in putting 20 mL of the solutions to be tested in a graduated cylinder and adding 5 mL of thinner (a petroleum derivative) thereto with a pipette, then sealing the graduated cylinder and turning it upside down and back to the initial position three times at intervals of 2 to 4 seconds for each move. It must then be noticed if phase separation occurred, which is evinced by the formation of bubbles and immediate separation of the solution; if not, more 5 mL of thinner are added to the solutions and then over and over again till phase separation is achieved.

[0080] All tests were carried out three times, and the average of the results thereof was utilized as final values in the analysis.

[0081] The values obtained were compared to an existing standard intended to compare the tested samples identified as compound S-600, comprising 10% of terpenes with 0.2% of oxidized terpenes, 13.4% of polysorbate 80 and 76.6% of water, and the best results are displayed in the table below.

TABLE-US-00001 TABLE 1 Best emulsification test results. Emulsification above the standard (ml) FPetro Soil with 0.75% 11.67 FPetro Env with 0.75% 10.42 Comm. Prod. #1 with 0.75% 9.17 D-Limonene with 0.75% 6.67 Comm. Prod. #2 with 0.75% 4.17

[0082] As it can be seen in table 1 above, formulation FPetro Soil of modified terpenes of the present invention has a cleaning content 30% superior to that of the commercial product exhibiting the best result, and 75% superior to the result of the conventional D-Limonene terpene.

[0083] FIG. 2 displays the result shown above in another way for better understanding thereof

Example 2Phase Separation Kinetics Test

[0084] For the Phase separation kinetics Test the same samples of the previous example were considered: pure commercial D-Limonene, the fraction of modified terpenes FPetro Env, the fraction of modified terpenes FPetro Soil, commercial product #1 and commercial product #2 at the same concentration of 0.75% terpenes.

[0085] The test consisted in adding 12.5 mL of a solution of thinner (a petroleum derivative), in a graduated cylinder, to 10 mL of the solutions intended for testing. After vigorous stirring, separation time was measured and recorded every time 1 mL of thinner was separated till the separation limit was reached.

TABLE-US-00002 TABLE 2 Separation kinetics test results Time to emulsify (in seconds): 4 mL 5 mL 6 mL D-Limonene 0.75% 48.00 58.00 68.00 FPetro Soil 42.00 47.00 53.00 FPetro Env 43.00 50.00 57.00 Comm. Prod. #1 44.00 50.33 57.33 Comm. Prod. #2 33.00 36.00 39.00

[0086] The best results were obtained from the FPetro Soil and Commercial product #2 samples with 0.75%, in which 6 mL were separated in 53.0 seconds and 39.0 seconds, respectively.

[0087] Analysis on the Emulsion vs Time results:

[0088] Although Commercial product #2 has exhibited the best result in the Separation kinetics test, it should be noted that it yielded the worst result in the emulsification capability test.

[0089] By considering the features of the FPetro Soil sample in both tests, we have a product exhibiting the best emulsification capability and good kinetics, i.e., the most suitable product for the treatment of soil contaminated with hydrocarbon.

[0090] At the same time, by comparing the results of the formulations with the said standard we could see that the said results do not follow a linear logic, and the increase in efficiency is not necessarily related to the increase in the concentration of terpenes, but rather to the ranges tested and established in this invention.

[0091] As the preferred examples of embodiments were herein described, it must be understood that the scope of the present invention encompasses other possible variations, being limited only by the content of the appended claims, including the possible equivalents.