CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to United States Provisional Application No.

62/406,537, filed 11 October 2016, the contents of which is incorporated herein by reference in its entirety.

BACKGROUND

[0002] 1. Field of the Art

[0003] The present disclosure relates to methods of reducing saturated fatty acids in a fatty acid mixture, e.g., Tall Oil Fatty Acids (TOFA), and methods of producing a petroleum product.

[0004] 2. Description of Related Art

[0005] Sulfur acts as a natural lubricant in fuel. Mandates to decrease or remove sulfur from diesel fuel have resulted in the need for additional lubricating additives to be incorporated into fuel, such as diesel fuel. Fatty acid mixtures, e.g., Tall Oil Fatty Acids (TOFA), could be used as a lubricant additive to diesel fuel. Fatty acid mixtures, however, have a tendency to precipitate in petroleum products, e.g., in fuel tanks or fuel lines, which can result in the plugging of, e.g., fuel lines. The source or grade of fatty acid mixtures used as an additive determines at what temperature precipitation of the fatty acid mixture occurs (e.g., in diesel or jet fuel).

[0006] The amount of saturated fatty acid, specifically palmitic acid and stearic acid, present in the fatty acid mixture has a significant effect on the temperature at which precipitation is observed. Saturated fatty acids solidify at a higher temperature than unsaturated acids.

Although precipitation in petroleum can be measured by many methods, it is typically measured/examined by cloud point (e.g., ASTM method D2500-99) or titer point (ASTM method D1982-13). The ASTM D1982-13 is a method that measures the solidification temperature of a sample containing both unsaturated and saturated fatty acids by cooling the specimen and measuring the temperature at which solidification occurs (titer point). As such, a fatty acid mixture with higher levels of saturated fatty acids has a higher titer (solidification temperature) than fatty acid mixtures with lower levels of saturated fatty acids. [0007] Many methods have been tried and proven ineffective at decreasing the precipitation (i.e., lowering the cloud point, the titer point, or both) of fatty acid mixtures (e.g., as a lubricity agent) in petroleum products, e.g., diesel, gasoline or jet fuel. U.S. Patent Application No. 2,705,723 A describes a method to separate oleic acid from stearic and palmitic acids.

However, the describe method does not deal with general TOFA separation where linoleic acid is present, and the conditions described therein are not suitable for general TOFA separation. U.S. Patent No. 2,293,676 describes a method of separating fatty acids in tallow, brown grease and garbage grease, where organic solvents were mixed with water and using a multi-stage cooling process to separate saturated fatty acids from unsaturated ones. Clathrate separation of TOFA with urea (see, e.g., U.S. Patent Nos. 2,785,151 and 5,078,920) is both costly and not practical as a commercial process.

[0008] Therefore, there exists a need for an efficient and cost effective method, e.g. a solvent treatment, to reduce precipitation of fatty acid mixtures in petroleum products (e.g., reducing the amount of stearic and palmitic acids).

SUMMARY

[0009] The present description relates to a method of reducing the amount of saturated fatty acids in a fatty acid mixture (i.e., a mixture that comprises both saturated and unsaturated fatty acids), e.g., Tall Oil Fatty Acids (TOFA). In certain aspects, the method includes admixing an organic nitrile and a fatty acid mixture comprising saturated and unsaturated fatty acids, thereby forming a fatty acid-nitrile mixture; adding a co-solvent (e.g., organic co-solvent) to the fatty acid-nitrile mixture; and isolating the treated fatty acids. The present disclosure further relates to compositions and methods of preparing or producing a petroleum product comprising a fatty acid composition reduced in saturated fatty acids as described herein.

[0010] An aspect of the present disclosure provides a method of reducing the amount of saturated fatty acids in a fatty acid mixture, wherein the fatty acid mixture comprises saturated and unsaturated fatty acids. The method comprising: admixing the fatty acid mixture, and an organic nitrile, e.g., acetonitrile, acrylonitrile, benzonitrile, phthalonitrile, isobutyronitrile, aromatic nitriles, thereby forming a fatty acid-nitrile mixture; adding a co-solvent (such as an organic co-solvent) to the fatty acid-nitrile mixture; and isolating the treated fatty acids. [0011] In some embodiments, the saturated fatty acids are at least one of stearic acid, palmitic acid, or a combination thereof.

[0012] In certain embodiments, the organic nitrile is at least one of acetonitrile, acrylonitrile, benzonitrile, phthalonitrile, isobutyronitrile, aromatic nitriles or a combination thereof. In certain embodiments, the organic nitrile is acetonitrile.

[0013] In certain embodiments, isolating the treated fatty acids comprises cooling the fatty acid-nitrile-co-solvent mixture, and filtering the cooled mixture to separate (e.g., retain) a formed precipitate enriched in saturated fatty acids from a filtrate enriched in unsaturated fatty acids.

[0014] In an embodiment, the treated fatty acid filtrate or the unsaturated portion of the fatty acid mixture has an increased percent of unsaturated fatty acids and a reduced percent of saturated fatty acids relative to the untreated fatty acid mixture.

[0015] In some embodiment, the co-solvent is selected from the group consisting of an alcohol, methanol, acetone, ethyl acetate, dichloromethane, hexane, or a combination thereof.

[0016] In other embodiments, the treated fatty acid filtrate has at least one of the following: a reduced titer point, a reduced cloud point, or a combination thereof.

[0017] In certain embodiments, the fatty acids mixture is selected from the group consisting of TOFA, vegetable oil, mineral oil, rapeseed oil, coconut oil, palm oil, corn oil, sunflower seed oil, soya oil, and linseed oil.

[0018] In some particular embodiments, the TOFA are selected from the group consisting of Altapyne™ L-5, Altapyne™ M-28B, Altapyne™ 1483, Altapyne™ L-l, Altapyne™M-15, Altapyne™ M-38, and Altapyne™ M-50B (Ingevity, South Carolina).

[0019] Another aspect of the present disclosure provides a method of producing a petroleum mixture including a fatty acid composition having a reduced propensity to precipitate in the petroleum mixture. The method comprises: admixing a composition comprising the treated fatty acid filtrate of the present disclosure and the petroleum product, wherein the resultant mixture has reduced propensity for fatty acid precipitation in the petroleum product (i.e., lower cloud point, titer point or both) relative to the untreated fatty acid mixture (e.g., TOFA).

[0020] In certain embodiments, the petroleum product is selected from the group consisting of diesel fuel, diesel oil, kerosene, gasoline, jet fuel. [0021] An additional aspect of the present disclosure provides a petroleum product comprising a low cloud point fatty acid composition that has been treated according to the methods described herein.

[0022] The preceding general areas of utility are given by way of example only and are not intended to be limiting on the scope of the present disclosure and appended claims.

Additional objects and advantages associated with the compositions, methods, and processes of the present disclosure will be appreciated by one of ordinary skill in the art in light of the instant claims, description, and examples. For example, the various aspects and embodiments of the present disclosure may be utilized in numerous combinations, all of which are expressly contemplated by the present description. These additional advantages, objects and embodiments are expressly included within the scope of the present disclosure. The publications and other materials used herein to illuminate the background of the disclosure, and in particular cases, to provide additional details respecting the practice, are incorporated by reference in their entirety for all purposes.

BRIEF DESCRIPTION OF THE DRAWINGS

[0023] The accompanying drawings, which are incorporated into and form a part of the specification, illustrate several embodiments of the present disclosure and, together with the description, serve to explain the principles of the disclosure. The drawings are only for the purpose of illustrating an embodiment of the disclosure and are not to be construed as limiting the present disclosure. Further objects, features and advantages of the disclosure will become apparent from the following detailed description taken in conjunction with the accompanying figures showing illustrative embodiments of the present disclosure, in which:

[0024] Figure 1A shows Altapyne™ L-5 and Altapyne™ M-28B at room temperature; and

[0025] Figure IB shows Altapyne™ L-5 and Altapyne™ M-28B after 1 hour at 5°C cooling.

DETAILED DESCRIPTION

[0026] The following is a detailed description provided to aid those skilled in the art in practicing the present disclosure. Those of ordinary skill in the art may make modifications and variations in the embodiments described herein without departing from the spirit or scope of the present disclosure. All publications, patent applications, patents, figures and other references mentioned herein are expressly incorporated by reference in their entirety.

[0027] Presently described are methods of producing/making a fatty acid composition with reduced/decreased amounts or levels of saturated fatty acids (e.g., stearic acid, palmitic acid, or a combination thereof) from a fatty acid mixture feedstock, such as Tall Oil Fatty Acids (TOFA), which comprises both saturated and unsaturated fatty acids. As described herein, following treatment and separation, the treated fatty acid filtrate has reduced amounts of saturated fatty acids. The description also provides methods that utilize the low saturated fatty acid filtrate. For example, the present disclosure provides for a method of producing a petroleum product comprising the low saturated fatty acid filtrate composition produced according to the methods described herein, which have a reduced propensity for precipitation in the petroleum mixture; i.e., lower cloud point, titer point or both.

[0028] Where a range of values is provided, it is understood that each intervening value, to the tenth of the unit of the lower limit unless the context clearly dictates otherwise (such as in the case of a group containing a number of carbon atoms in which case each carbon atom number falling within the range is provided), between the upper and lower limit of that range and any other stated or intervening value in that stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges is also encompassed within the invention, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either both of those included limits are also included in the invention.

[0029] The following terms are used to describe the present disclosure. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. The terminology used in the description is for describing particular embodiments only and is not intended to be limiting of the invention.

[0030] The articles "a" and "an" as used herein and in the appended claims are used herein to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article unless the context clearly indicates otherwise. By way of example, "an element" means one element or more than one element. [0031] The phrase "and/or," as used herein in the specification and in the claims, should be understood to mean "either or both" of the elements so conjoined, i.e., elements that are conjunctively present in some cases and disjunctively present in other cases. Multiple elements listed with "and/or" should be construed in the same fashion, i.e., "one or more" of the elements so conjoined. Other elements may optionally be present other than the elements specifically identified by the "and/or" clause, whether related or unrelated to those elements specifically identified. Thus, as a non-limiting example, a reference to "A and/or B", when used in conjunction with open-ended language such as "comprising" can refer, in one embodiment, to A only (optionally including elements other than B); in another embodiment, to B only (optionally including elements other than A); in yet another embodiment, to both A and B (optionally including other elements); etc.

[0032] As used herein in the specification and in the claims, "or" should be understood to have the same meaning as "and/or" as defined above. For example, when separating items in a list, "or" or "and/or" shall be interpreted as being inclusive, i.e., the inclusion of at least one, but also including more than one, of a number or list of elements, and, optionally, additional unlisted items. Only terms clearly indicated to the contrary, such as "only one of or "exactly one of," or, when used in the claims, "consisting of," will refer to the inclusion of exactly one element of a number or list of elements. In general, the term "or" as used herein shall only be interpreted as indicating exclusive alternatives (i.e., "one or the other but not both") when preceded by terms of exclusivity, such as "either," "one of," "only one of," or "exactly one of."

[0033] In the claims, as well as in the specification above, all transitional phrases such as

"comprising," "including," "carrying," "having," "containing," "involving," "holding,"

"composed of," and the like are to be understood to be open-ended, i.e., to mean including but not limited to. Only the transitional phrases "consisting of and "consisting essentially of shall be closed or semi-closed transitional phrases, respectively, as set forth in the United States Patent Office Manual of Patent Examining Procedures, Section 2111.03.

[0034] As used herein in the specification and in the claims, the phrase "at least one," in reference to a list of one or more elements, should be understood to mean at least one element selected from anyone or more of the elements in the list of elements, but not necessarily including at least one of each and every element specifically listed within the list of elements and not excluding any combinations of elements in the list of elements. This definition also allows that elements may optionally be present other than the elements specifically identified within the list of elements to which the phrase "at least one" refers, whether related or unrelated to those elements specifically identified. Thus, as a non-limiting example, "at least one of A and B" (or, equivalently, "at least one of A or B," or, equivalently "at least one of A and/or B") can refer, in one embodiment, to at least one, optionally including more than one, A, with no B present (and optionally including elements other than B); in another embodiment, to at least one, optionally including more than one, B, with no A present (and optionally including elements other than A); in yet another embodiment, to at least one, optionally including more than one, A, and at least one, optionally including more than one, B (and optionally including other elements); etc.

[0035] It should also be understood that, in certain methods described herein that include more than one step or act, the order of the steps or acts of the method is not necessarily limited to the order in which the steps or acts of the method are recited unless the context indicates otherwise.

[0036] The present disclosure provides a process that results in a fatty acid composition or mixture of fatty acids with the surprising and unexpected characteristics of having decreased propensity to precipitate (e.g., a reduced temperature at which fatty acids precipitate) from a solution (e.g., a petroleum product). The method is a simpler and more efficient (e.g., cost effective) way to produce a fatty acid composition with the above-described characteristics. Previous techniques require substantially more solvents, as well as substantial heating steps.

[0037] In an aspect, the present disclosure provides a method of reducing the amount of saturated fatty acids in a fatty acid mixture. The method includes: admixing a fatty acid mixture and an organic nitrile, e.g., e.g., acetonitrile, acrylonitrile, benzonitrile, phthalonitrile, isobutyronitrile, aromatic nitriles, thereby forming a fatty acid-nitrile mixture; adding (e.g., mixing) a co-solvent (e.g., at least one of an organic co-solvent, an alcohol, methanol, ethanol, propanol, acetone, ethyl acetate, dichloromethane, hexane or combinations thereof) to the fatty acid-nitrile mixture; and isolating the treated fatty acids. Unless the context suggests otherwise, the term "fatty acid mixture" generally refers to a crude fatty acid mixture comprising unsaturated fatty acids and saturated fatty acids in amounts higher than in the fatty acid filtrate resulting from treatment according to the methods described herein (i.e., "treated fatty acid filtrate"). [0038] In an embodiment, the isolated substantially unsaturated portion of the fatty acids mixture or the filtrate of the filtered cooled mixture (fatty acid filtrate) has at least one of: an increased percent of unsaturated fatty acids relative to the untreated fatty acids mixture, a reduced percent of saturated fatty acids relative to the untreated fatty acids mixture, or a combination thereof.

[0039] The saturated fatty acids can be at least one of stearic acid, palmitic acid, or a combination thereof. In a particular embodiment, the co- solvent is selected from the group consisting of an alcohol, methanol, ethanol, propanol, acetone, ethyl acetate, dichloromethane, hexane, or a combination thereof. In other embodiments, the co- solvent is added in an amount sufficient to cause the mixture of the nitrile, e.g., acetonitrile, and the fatty acid mixture (i.e., the fatty acid- acetonitrile mixture) to turn clear.

[0040] In certain embodiments, a ratio of nitrile, e.g., acetonitrile, to co-solvent (e.g., alcohol) is about 5: 1 to about 9: 1. For example, the ratio of nitrile, e.g., acetonitrile, to co- solvent (e.g. alcohol) is about 6: 1 to about 8: 1, or about 7: 1

[0041] In further embodiments, a ratio of nitrile, e.g., acetonitrile, to the fatty acids mixture is about 1: 1 to about 4: 1. For example, the ratio of acetonitrile to the fatty acids mixture is about 1.5: 1 to about 3: 1, or about 2: 1.

[0042] In other embodiments, the method further comprises, after adding the co-solvent, cooling the mixture. For example, the mixture may be cooled at about 10°C to about 15°C. In certain embodiments, the mixture is cooled at or to about -10°C to about 15°C, about -10°C to about 10°C, about -10°C to about 5°C, about -10°C to about 0°C, about -10°C to about -5°C, about -5°C to about 15°C, about -5°C to about 10°C, about -5°C to about 5°C, about -5°C to about 0°C, about 0°C to about 15°C, about 0°C to about 10°C, about 0°C to about 5°C, about 5°C to about 15°C, about 5°C to about 10°C, or 10°C to about 15°C.

[0043] Isolating the treated fatty acid filtrate, e.g. an unsaturated fatty acid portion of the fatty acid mixture, can comprise filtering the cooled fatty acid-nitrile-co-solvent mixture to separate or retain a treated fatty acid precipitate, which is enriched in saturated fatty acids, wherein the unsaturated fatty acids are present in the filtrate. Filtering can be performed with any suitable known method/filter. For example, a coarse filter, a medium filter, or a fine filter, such as a fritted funnel, may be utilized. Filtering can be performed at 10°C to about 21°C. In certain embodiments, filtering is performed at about -10°C to about 15°C, about -10°C to about 10°C, about -10°C to about 5°C, about -10°C to about 0°C, about -10°C to about -5°C, about - 5°C to about 21°C, about -5°C to about 15°C, about -5°C to about 10°C, about -5°C to about 5°C, about -5°C to about 0°C, about 0°C to about 21°C, about 0°C to about 15°C, about 0°C to about 10°C, about 0°C to about 5°C, about 5°C to about 21°C, about 5°C to about 15°C, about 5°C to about 10°C, 10°C to about 21°C, 10°C to about 15°C, or 15°C to about 21°C.

[0044] In another embodiment, the method further comprises removing nitrile, e.g., acetonitrile, from the treated fatty acid filtrate, such as evaporating or nitrogen sparging the treated fatty acid filtrate. For example, evaporating can be performed with a rotary evaporator, a vacuum evaporator, a centrifugal evaporator, a vapor-compression evaporator, or a circulation evaporator. For example, evaporating can be performed with a rotary evaporator at about 55° C to about 90° C (e.g., about 65° C to about 75° C) and/or at about 5 mmHg to about 30 mmHg (e.g., about 5 mmHg to about 20 mmHg or about 10 mmHg). In some other embodiments, evaporating is performed with a rotary evaporator for at least about 30 minutes (e.g., about 30 minutes to about 3 hours, about 30 minutes to about 2 hours, about an hour to about 2 hours, about an hour to about 3 hours, or about 1 hour). Sparging can be performed at a temperature of at least 95°C, at least 100°C, or at least 105°C.

[0045] In additional embodiments, a yield of the treated fatty acids, e.g., fatty acids in the treated fatty acid filtrate, is at least about 65% (e.g, at least 75%, at least 80%, or about 80%, or more than about 80%).

[0046] In other embodiments, the fatty acids in the treated fatty acid filtrate have at least one of the following: a reduced titer point, a reduced cloud point, or a combination thereof.

[0047] In an embodiment, the fatty acids mixture is selected from the group consisting of

TOFA (e.g., TOFA from the Kraft process), vegetable oil, mineral oil, rapeseed oil, coconut oil, palm oil, corn oil, sunflower seed oil, soya oil, linseed oil, or a combination thereof.

[0048] In certain embodiments, the fatty acids mixture is selected from the group consisting of Altapyne™ L-5, Altapyne™ M-28B, Altapyne™ 1483, Altapyne™ L-l,

Altapyne™M-15, Altapyne™ M-38, and Altapyne™ M-50B (Ingevity, South Carolina, USA).

[0049] Another aspect of the present disclosure provides a method of producing a petroleum mixture comprising a fatty acid composition having a reduced propensity to precipitate in a petroleum mixture (e.g., a fatty acid composition that requires a lower temperature to precipitate relative to an untreated fatty acids mixture), i.e., a low precipitating petroleum-fatty acids mixture. The method comprises: admixing a petroleum product (e.g., diesel, diesel fuel, diesel oil, kerosene, gasoline, jet fuel, or a combination thereof) and a treated fatty acid filtrate as described herein, wherein the resultant mixture has a reduced or a decreased propensity for fatty acid precipitation in the petroleum product relative to untreated fatty acids, e.g., an untreated fatty acid mixture. For example, the treated fatty acid filtrate as described herein has a reduced or decreased propensity or ability to precipitate in the petroleum product or when part of a petroleum mixture.

[0050] In some embodiments, the petroleum product is selected from the group consisting of diesel fuel, diesel oil, kerosene, gasoline, jet fuel or a combination thereof.

[0051] In other embodiments, fatty acids from the treated fatty acid filtrate are present in an amount in a range of about 2% to about 20% of the petroleum mixture. For example, the fatty acids from the treated fatty acid filtrate are present in a range of about 2% to about 15%, about 2% to about 10%, about 2% to about 5%, about 5% to about 20%, about 5% to about 15%, about 5% to about 10%, about 10% to about 20%, or about 10% to about 15%.

[0052] EXAMPLES

[0053] Separating TOFA with acetonitrile-methanol solvent. One-hundred (100) g of a fatty acid mixture (TOFA) was mixed with 175 g acetonitrile (CH ₃ CN), and methanol (MeOH) was added to the mixture until it became clear at room temperature, approximately 25 g. The mixture was then cooled to 5° C for one hour. The white precipitate that formed was filtered off with a coarse fritted funnel while keeping the filtration temperature at 10° C. The filtrate was placed on a rotary evaporator to remove solvents at 70° C at 10 mmHg for 1 hour to collect solvent treated TOFA (yield about 80%). The presence and amount of each fatty acid was determined by gas chromatography.

[0054] As shown in Table 1 below, the acetonitrile-methanol separating method lowers the titer point, as determined by ASTM method D 1982- 13, of Altapyne™ L-5 (a TOFA sold by Ingevity ^® Corporation, North Charleston, SC, USA) from approximately 10.5° C to - 0.1° C. The same treatment of Altapyne™ 1483 (a TOFA sold by Ingevity ^® Corporation, North

Charleston, SC, USA), reduces the titer point from 20° C to 12.5° C. A decrease in cloud point, as determined by ASTM method D2500-99, was also observed for acetonitrile-methanol treated Altapyne™ L-5 and 1483. As such, TOFA prepared with the acetonitrile-methanol separating method have decreased propensity to precipitated (e.g., when mixed with a petroleum product).

[0055] Table 1. Characteristics of acetonitrile-methanol separated TOFA.

[0056] Table 2. Extractions results of acetonitrile and mixed co-solvents that formed precipitate when cooled to 5° C (area percent based on GC analysis).

dichloro- ethyl-

ACN mixture I PA acetone ; ethyl acetate ! methane : carbonate H20/DMSO iACN 11/1 5C ACN/MeOH

L-5 S.M 81-2 S1--4 61 -S 61-6 fii-i? palm 6 4 3 3 2.9 3.1 4.7 4.56 3.35

; stearic 2 1 0.69 0.69 : 0.73 0.8 1.65 1.32 0.78 oleic 33 37.4 36.5 36.6 33.3 34.1 32.7 34.97 36.8 i linoleic 28.6 30.1 29.3 31.1 ; 28.8 29.7 24.3 25.1 31.5

[0057] Table 3. Extractions results of acetonitrile and mixed co-solvents that formed layers when cooled to 5° C (area percent based on GC analysis).

: with hexa ne : with hexane with hexane, i with hexa ne, ;

ACN mixture 1/1 1/1 5%MeOH ! 5% MeOH

L-5

pa lm 6 5.53 3.95 5.73 4.66

i stea ric 2 1.97 1.91 2.19 1.57

oleic 33 37.5 26.3 38.8 30.87

i linoleic \ 28.6 28.3 20.6 26 23.88

[0058] Table 4. Extraction results of acetonitrile and water co-solvents that precipitated when cooled to 5°C (area percent based on GC analysis). : rt cooling i 5°C cooling

\ ACN/H20 i ACN/H20 ACN/H20 \ ACN/H20 ;

ACN mixture ACN 6-1 6/1 3/1 5/1 2/1

L-l L-5 L-5 L-5 L-5 L-5

pa lm 2.46 4.46 4.74 4.77 2.22 2.41

i stea ric 2.24 1.3 1.45 1.6 0.41 0.54

oleic 45.75 32.23 ; 34.91 j 32.98 34.66 \ 33.41 !

i linoleic 28.6 \ 29.52 ! 26.99 27.27 33.07 \ 33.48 I

[0059] Urea Clathrate Inclusion Compound Comparative Example. Inclusion complexes, such as urea clathrates, can separate some isomers of fatty acids and thus improve titer and cloud point. Comparing the method of the present disclosure to the clathrate process, which requires urea and large excess amount of solvents (such as methanol or ethanol), the process of the present disclosure is simpler and more cost efficient. The following is a typical procedure (not including the regeneration of urea): 30 g urea and 200 mL methanol MeOH was mixed and heated to 50-60° C for 30 minutes till the solution became clear. Thirty (30) g of Altapyne™ L-5 was added and precipitate was observed. The solution was heated at the same temperature for an additional 10 minutes and the solution was cooled to room temperature.

Precipitate settled at the bottom and the top liquid (yellow) was then decanted to another beaker and bottom solid was left in the original beaker. Filtrate yield after vacuum strip was about 80%

[0060] Winterization Comparative Example. Altapyne™ L-5 and Altapyne™ M-28B are low viscosity, clear liquids at room temperature. See Figure 1A. After being cooled to 5° C for 1 hour, both became waxy solids that are difficult to filter. See figure 1A. As such, separating saturated and unsaturated fatty acids by this method, known as winterization, without a solvent is very difficult.

[0061] SPECIFIC EMBODIMENTS:

[0062] According to an aspect, a method of reducing the amount of saturated fatty acids in a fatty acids mixture is provided. The method comprises: admixing a fatty acid mixture and an organic nitrile, e.g., acetonitrile, acrylonitrile, benzonitrile, phthalonitrile, isobutyronitrile, or aromatic nitriles; adding a co-solvent to the fatty acid-nitrile mixture; and isolating treated fatty acids.

[0063] In any aspect or embodiment disclosed herein, the saturated fatty acids are at least one of stearic acid, palmitic acid, or a combination thereof. [0064] In any aspect or embodiment disclosed herein, the co-solvent (e.g., an organic co- solvent) is added in an amount sufficient to cause the fatty acid-nitrile, e.g., acetonitrile, mixture to turn clear.

[0065] In any aspect or embodiment disclosed herein, the nitrile, e.g., acetonitrile, and the co-solvent are present in a ratio of about 5: 1 to about 9: 1.

[0066] In any aspect or embodiment disclosed herein, the nitrile, e.g., acetonitrile, and the co-solvent are present in a ratio of about 6: 1 to about 8: 1.

[0067] In any aspect or embodiment disclosed herein, the nitrile, e.g., acetonitrile, and the co-solvent are present in a ratio of about 7: 1.

[0068] In any aspect or embodiment disclosed herein, wherein a ratio of the nitrile, e.g., acetonitrile, to the fatty acids mixture is about 1: 1 to about 4: 1.

[0069] In any aspect or embodiment disclosed herein, the ratio of the nitrile, e.g., acetonitrile, to the fatty acids mixture is about 1.5: 1 to about 3: 1.

[0070] In any aspect or embodiment disclosed herein, the ratio of the nitrile, e.g., acetonitrile, to the fatty acids mixture is about 2: 1.

[0071] In any aspect or embodiment disclosed herein, the method further comprises, after adding the co-solvent, cooling the mixture.

[0072] In any aspect or embodiment disclosed herein, the mixture is cooled to about 10°

C to about 15° C.

[0073] In any aspect or embodiment disclosed herein, the isolating the treated fatty acids comprises filtering the cooled mixture to separate a formed precipitate and a filtrate.

[0074] In any aspect or embodiment disclosed herein, filtering is performed with a coarse filter.

[0075] In any aspect or embodiment disclosed herein, the filtering is performed at about

10° C to about 21° C.

[0076] In any aspect or embodiment disclosed herein, the method further comprises removing nitrile, e.g., acetonitrile, from the treated fatty acids, e.g., the precipitate or filtrate from filtering the cold mixture.

[0077] In any aspect or embodiment disclosed herein, removing nitrile, e.g., acetonitrile, comprises evaporating or nitrogen sparging the treated fatty acids, e.g., precipitate or the filtrate from filtering the cold mixture. [0078] In any aspect or embodiment disclosed herein, evaporating is performed with a rotary evaporator.

[0079] In any aspect or embodiment disclosed herein, evaporating is performed at about

55° C to about 90° C.

[0080] In any aspect or embodiment disclosed herein, evaporating is performed at about

65° C to about 75° C.

[0081] In any aspect or embodiment disclosed herein, evaporating is performed at about

5 mmHg to about 30 mmHg.

[0082] In any aspect or embodiment disclosed herein, evaporating is performed at about

5 mmHg to about 20 mmHg.

[0083] In any aspect or embodiment disclosed herein, evaporating is performed at about

10 mmHg.

[0084] In any aspect or embodiment disclosed herein, evaporating is performed for a period of time sufficient to obtain treated fatty acids with no greater than 0.5% nitrile, e.g., acetonitrile.

[0085] In any aspect or embodiment disclosed herein, the nitrile, e.g., acetonitrile, is no greater than about 0.1% of the treated fatty acids.

[0086] In any aspect or embodiment disclosed herein, evaporating is performed for at least about 30 minutes.

[0087] In any aspect or embodiment disclosed herein, evaporating is performed for about

30 minutes to about 3 hours.

[0088] In any aspect or embodiment disclosed herein, evaporating is performed for about

1 hour.

[0089] In any aspect or embodiment disclosed herein, the yield of the treated fatty acids in the treated fatty acid filtrate is at least about 65%.

[0090] In any aspect or embodiment disclosed herein, the yield of the treated fatty acids in the treated fatty acid filtrate is at least 75%.

[0091] In any aspect or embodiment disclosed herein, the yield of the treated fatty acids in the treated fatty acid filtrate is about 80%. [0092] In any aspect or embodiment disclosed herein, the co-solvent is selected from the group consisting of an alcohol, methanol, acetone, ethyl acetate, dichloromethane, hexane, or a combination thereof.

[0093] In any aspect or embodiment disclosed herein, the treated fatty acids in the fatty acid filtrate have at least one of the following: a reduced titer point, a reduced cloud point, or a combination thereof.

[0094] In any aspect or embodiment disclosed herein, the treated fatty acid filtrate of the filtered cooled mixture has at least one of: an increased percent of unsaturated fatty acids relative to the untreated fatty acids mixture, a reduced percent of saturated fatty acids relative to the untreated fatty acids mixture, or a combination thereof

[0095] In any aspect or embodiment disclosed herein, the fatty acids mixture is selected from the group consisting of TOFA (e.g., TOFA from the Kraft process), vegetable oil, mineral oil, rapeseed oil, coconut oil, palm oil, corn oil, sunflower seed oil, soya oil, linseed oil, or a combination thereof.

[0096] In any aspect or embodiment disclosed herein, the tall oil fatty acids is selected from the group consisting of Altapyne™ L-5, Altapyne™ M-28B, Altapyne™ 1483, Altapyne™ L-l, Altapyne™M-15, Altapyne™ M-38, and Altapyne™ M-50B.

[0097] According to a further aspect, a method of reducing precipitation of a fatty acid mixture in a petroleum product. The method comprises: adding a fatty acid composition comprising treated fatty acids from the fatty acid filtrate according to any of the methods described herein to the petroleum product, wherein the resultant mixture has reduced fatty acid precipitation in the petroleum product relative to untreated fatty acids.

[0098] In any aspect or embodiment disclosed herein, the petroleum product is selected from the group consisting of diesel fuel, diesel oil, kerosene, gasoline, jet fuel or a combination thereof. In any aspect or embodiment disclosed herein, the treated fatty acids from the treated fatty acid filtrate are present in an amount in a range of about 5% to about 15% of the petroleum mixture.

[0099] According to yet another aspect, the disclosure provides a petroleum product produced according to the method of reducing precipitation of a fatty acid mixture in a petroleum product of the present disclosure. [0100] While preferred embodiments of the present disclosure have been shown and described herein, it will be understood that such embodiments are provided by way of example only. Numerous variations, changes and substitutions will occur to those skilled in the art without departing from the spirit of the present disclosure. Accordingly, it is intended that the appended claims cover all such variations as fall within the spirit and scope of the invention. Furthermore, the system may comprise at least one device for charging and/or discharging the system or a plurality of devices for charging and/or discharging the system.

[0101] The contents of all references, patents, pending patent applications and published patents, cited throughout this application are hereby expressly incorporated by reference.

[0102] Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the present disclosure described herein. Such equivalents are intended to be encompassed by the following claims. It is understood that the detailed examples and embodiments described herein are given by way of example for illustrative purposes only, and are in no way considered to be limiting to the invention. Various modifications or changes in light thereof will be suggested to persons skilled in the art and are included within the spirit and purview of this application and are considered within the scope of the appended claims. For example, the relative quantities of the ingredients may be varied to optimize the desired effects, additional ingredients may be added, and/or similar ingredients may be substituted for one or more of the ingredients described. Additional advantageous features and functionalities associated with the systems, methods, and processes of the present disclosure will be apparent from the appended claims. Moreover, those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the present disclosure. Such equivalents are intended to be encompassed by the following claims.

REFERENCES

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