Methods of producing monocarboxlyic and / or dicarboxylic acid species from unsaturated fatty acids

Abstract

A method of producing monocarboxylic and / or dicarboxylic acid species is provided. The method comprises reacting unsaturated fatty acids with a transition metal catalyst at a temperature from about 20℃ or more to about 160℃ or less and at a hydrogen pressure of from about 0 psi or more to about 1,500 psi or less so as to produce a reaction product comprising isomerized, or hydrogenated, fatty acids having the location of a double bond in a new location as compared to the starting unsaturated fatty acids. The method further comprises cleaving the fatty acids of the reaction product so as to produce monocarboxylic acid and / or dicarboxylic acid species.

Description

[0001] METHODS OF PRODUCING MONOCARBOXLYIC AND / OR DICARBOXYLIC ACID SPECIES FROM UNSATURATED FATTY ACIDS TECHNICAL FIELD

[0002] This disclosure relates to hydrogenation, isomerization, ozonolysis and / or oxidation reactions and, more particularly, to methods and processes for producing monocarboxylic acid and dicarboxylic acid species from non-traditional bio-based feedstocks.

[0003] BACKGROUND

[0004] Fatty acids, such as monocarboxylic and dicarboxylic acids, are widely used in, pharmaceutical, cosmetic, and biofuel industries. Fatty acids are used industrially in many applications including the production of soap, detergents, and surfactants; the manufacturing of lubricants; as emulsifiers; texturing agents; wetting agents; anti-foam agents; stabilizing agents; as emollients in cosmetics; in paints; in the production of fuel, such as biodiesel; in drug delivery systems; in medical formulations; and in the production of plastics. Fatty acids are found in oils and are important health components. Some shorter chain monocarboxylic and dicarboxylic acids are more prevalent and / or more easily producible than others. For example, the production of some shorter chain monocarboxylic and dicarboxylic acids requires the use of tropical oil feedstocks, such as palm and palm kernel oil, which are rich in Cl 6 fatty acids. However, the use of tropical oil feedstocks to produce these shorter chain monocarboxylic and dicarboxylic acids may be associated with a negative environmental impact. Thus, the development of additional pathways and processes for producing valuable and important chemical compounds, such as certain shorter chain monocarboxylic and dicarboxylic acids, from natural products is highly desirable.

[0005] SUMMARY

[0006] In an aspect, a method of producing monocarboxylic and / or dicarboxylic acid species is provided. The method comprises reacting unsaturated fatty acids with a transition metal catalyst at a temperature from about 20°C or more to about 160°C or less and at a hydrogen pressure of from about 0 psi or more to about 1,500 psi or less so as to produce a reaction product comprising isomerized, or hydrogenated, fatty acids 1

[0007] Classification: Confidentialhaving the location of a double bond in a new location as compared to the starting unsaturated fatty acids. The method further comprises cleaving the fatty acids of the reaction product so as to produce monocarboxylic acid and / or dicarboxylic acid species.

[0008] Further aspects and embodiments are provided in the drawings, detailed description, and claims.

[0009] BRIEF DESCRIPTION OF THE DRAWINGS

[0010] The following drawings are provided to illustrate certain embodiments described herein. The drawings are merely illustrative and are not intended to limit the scope of claimed inventions and are not intended to show every potential feature or embodiment of the claimed inventions. The drawings are not necessarily drawn to scale; in some instances, certain elements of the drawing may be enlarged with respect to other elements of the drawing for purposes of illustration.

[0011] Figure 1A is a graph depicting the fatty acid composition of soy and canola FAMEs reacted with selected catalysts.

[0012] Figure IB is a graph which depicts the C18:l content from the reaction of soy and canola FAMEs with selected catalysts.

[0013] Figures 2A and 2B are graphs which depict the resulting composition from the reaction of soy FAMEs with multiple palladium catalysts.

[0014] Figure 2C is a graph which depicts the content of C18:l isomers resulting from reacting soy FAMEs with multiple palladium catalysts.

[0015] Figures 3A and 3B are graphs which depict the resulting composition from the reaction of canola FAMEs with multiple palladium catalysts.

[0016] Figure 3C is a graph which depicts the concentration of C18:l isomers resulting from reacting canola FAMEs with multiple palladium catalysts.

[0017] Figures 4A and 4B are graphs which depict the resulting composition from the reaction of soy FAMEs with multiple platinum catalysts at low hydrogen pressure.

[0018] Figure 4C is a graph which depicts the concentration of C18: 1 isomers resulting from reacting soy FAMEs with multiple platinum catalysts at low hydrogen pressure.

[0019] Figure 5A is a graph which depicts the resulting composition from the reaction of soy FAMEs with multiple platinum catalysts at high hydrogen pressure.

[0020] 2

[0021] Classification: ConfidentialFigure 5B is a graph which depicts the concentration of C18:l isomers resulting from reacting soy FAMEs with multiple platinum catalysts at high hydrogen pressure.

[0022] Figures 6A and 6B are graphs which depict the resulting composition from the reaction of soy FAMEs with multiple nickel catalysts.

[0023] Figure 6C is a graph which depicts the concentration of C18:l isomers resulting from reacting soy FAMEs with multiple nickel catalysts.

[0024] Figure 7 is a graph showing the results of experiments to determine conditions for increased production of Cl 8:1 and C18:ln9 fatty acids.

[0025] Figures 8A and 8B are graphs showing the results of modifying the reaction time of canola FAMEs reacted with a palladium catalyst at 40°C and 100 psi hydrogen.

[0026] Figures 9A and 9B are graphs showing the results of modifying the reaction time of canola FAMEs reacted with a palladium catalyst at 60°C and 1,500 psi hydrogen.

[0027] Figure 10 is a graph showing the distribution of C18:l positional isomers produced from a representative reaction with methyl oleate and a variety of different isomerization catalysts.

[0028] Figure 11 is a graph showing the distribution of C18:l positional isomers produced from the representative reaction using a 5% Pd / AFO.i catalyst, canola oil FAMEs, and a variety of reaction times.

[0029] Figure 12 is a graph showing a representative acid product profile produced after subjecting the C18:l positional isomers, produced from the representative reaction using the 5% Pd / ATCE catalyst, to ozonolysis.

[0030] DETAILED DESCRIPTION

[0031] The following description recites various aspects and embodiments of the inventions disclosed herein. No particular embodiment is intended to define the scope of the invention. Rather, the embodiments provide non-limiting examples of various compositions and methods that are included within the scope of the claimed inventions. The description is to be read from the perspective of one of ordinary skill in the art. Therefore, information that is well known to the ordinarily skilled artisan is not necessarily included.

[0032] 3

[0033] Classification: ConfidentialDefinitions

[0034] The following terms and phrases have the meanings indicated below, unless otherwise provided herein. This disclosure may employ other terms and phrases not expressly defined herein. Such other terms and phrases shall have the meanings that they would possess within the context of this disclosure to those of ordinary skill in the art. In some instances, a term or phrase may be defined in the singular or plural. In such instances, it is understood that any term in the singular may include its plural counterpart and vice versa, unless expressly indicated to the contrary.

[0035] As used herein, the singular forms “a," “an,” and “the” include plural referents unless the context clearly dictates otherwise. For example, reference to “a substituent” encompasses a single substituent as well as two or more substituents, and the like.

[0036] As used herein, “for example,” “for instance,” “such as,” “include,” or “including” are meant to introduce examples that further clarify more general subject matter. Unless otherwise expressly indicated, such examples are provided only as an aid for understanding embodiments illustrated in the present disclosure and are not meant to be limiting in any fashion. Nor do these phrases indicate any kind of preference for the disclosed embodiment.

[0037] As used herein, “fatty acid” refers to a carboxylic acid with an aliphatic chain, as well as triglycerides and fatty acid methyl esters (FAMEs). Fatty acids are classified in multiple different ways, such as length, saturation, carbon content, and linearity. Saturated fatty acids are fatty acids with no double bonds between any of the carbon atoms in the aliphatic tail; mono-unsaturated fatty acids have one double bond in the aliphatic tail; and poly-unsaturated fatty acids have multiple double bonds in the aliphatic tail. These designations can be written as lipid numbers, in the form C:D with the C referring to the number of carbon atoms and the D referring to the number of double bonds. For example, a mono-unsaturated fatty acid with 18 carbon atoms could be designated Cl 8:1, and a poly-unsaturated fatty acid with 18 carbon atoms could be designated C18:2 or C18:3. These are generic designations and refer to any monounsaturated or poly-unsaturated fatty acids with 18 carbons in the aliphatic chain. The designations can further specify the location of the double bond in the form C:DnX with X being the location of the double bond. For example, oleic acid would be designated C18:ln9.

[0038] 4

[0039] Classification: ConfidentialAs used herein, “fatty acid methyl ester” refers to fatty acids where the hydrogen from the carboxyl group has been replaced with a methyl group.

[0040] As used herein, “vegetable oil" refers to any oil extracted from various parts of plants. The parts of the plants from which the oil is extracted include seeds, nuts, fruit, and grains. Vegetable oils generally contain a mix of saturated, mono-unsaturated, and poly -unsaturated fatty acids. Different oils include different compositions of fatty acids.

[0041] An isomer is a molecule that has the same molecular formula as another molecule but a different structural arrangement of atoms. Isomerization is a chemical process in which a molecule undergoes a rearrangement of its chemical structure. This rearrangement of a molecule into isomers occurs without changing the molecular formula.

[0042] As used herein ozonolysis is a chemical reaction where ozone (O3) is used to cleave carbon -carbon double or triple bonds in unsaturated compounds. Ozonolysis involves the oxidative cleavage of carbon-carbon multiple bonds using ozone as the oxidizing agent. The reaction replaces carbon-carbon double or triple bonds with carbonyl groups (C=O), and under proper conditions, produces carboxylic acids.

[0043] The present disclosure relates generally to the hydrogenation of fatty acids. Vegetable oils contain multiple fatty acids, and among those fatty acids are polyunsaturated fatty acids. Mono-unsaturated fatty acids may be produced from polyunsaturated fatty acids by hydrogenation. Hydrogenation is a process which involves the addition of hydrogen atoms to unsaturated fatty acids, so as to replace one or more double bonds. Unsaturated fatty acids contain double bonds in the aliphatic chains. The addition of hydrogen “saturates” the chain, increasing the number of hydrogen atoms bonded to the carbon atoms in the aliphatic chain. In the production of fatty acid derived products, certain fatty acids are currently more desirable than others. While certain fatty acids are more desirable than others, hydrogenation has historically been an indiscriminate process that randomly produces species of saturated or unsaturated fatty acid.

[0044] Oleic acid (C18:ln9) is one of the most presently desirable fatty acids. Hydrogenation of vegetable oils increases the saturation of the fatty acids therein resulting in increased proportions of saturated fatty acids, mono-unsaturated fatty acids, and poly-unsaturated fatty acids with lower amounts of unsaturation. Many 5

[0045] Classification: Confidentialhydrogenation reactions result in a mixture of fatty acid species, such as a mixture of C18:l species. However, many known hydrogenation reactions are non-biased with respect to the positional isomers produced from the hydrogenation and contained in the Cl 8: 1 distribution. In addition, hydrogenation reactions are generally performed at high temperatures and pressures to achieve product profiles high in C18:l species.

[0046] Methods for producing target C18:l fatty acids, specifically C18:ln9 oleic (cis) and elaidic (trans) fatty acids, at fast and mild conditions and using cost-effective catalyst loadings have been developed. Representative methods for producing these target Cl 8:1 fatty acids will be further described. Vegetable oils contain multiple fatty acids, and among those fatty acids are poly-unsaturated fatty acids. Mono-unsaturated fatty acids may be produced from poly-unsaturated fatty acids by hydrogenation. The poly-unsaturated fatty acids are reacted with a catalyst at specific temperatures and hydrogen pressures.

[0047] Representative methods comprise reacting a feedstock comprising polyunsaturated fatty acids (examples of which include triglycerides and fatty acid methyl esters (FAMEs)) with a catalyst, under reaction conditions that are biased to the production of target mono-unsaturated fatty acids. In any of the embodiments described herein, the feedstock is a vegetable oil. The target mono-unsaturated fatty acids to which the production is biased may be C18:l species. More specifically, the reaction may be biased to the production of C18: ln9 species. The C18:ln9 produced may be in the cis or trans configuration. The biased production of C18:ln9 species may generate a product having an increased amount (i.e., increased concentration or increased percentage by GC-FID area) of the C18: ln9 fatty acid species. While the reaction is biased to the production of C18:ln9 species, other species may also be produced. Generally, the other species which may be produced keep the double bond within three positions of the n9 double bond. Effectively, the reaction product may include any of C18:ln6, C18:ln7, C18:ln8, C18:ln9, C18:lnl0, C18:lnll. or C18:lnl2. Additionally, reduced concentrations of C18:2 and C18:3 species may be present in the reaction product.

[0048] The feedstock may comprise poly-unsaturated fatty acids or poly-unsaturated fatty acid methyl esters (FAMEs). FAMEs may be produced from fatty acids through transesterification. Transesterification is a process by which triglycerides are reacted with methanol in the presence of a catalyst. The catalyst is typically a strong base such 6

[0049] Classification: Confidentialas sodium or potassium mentholate. It is generally desirable to use a poly-unsaturated fatty acid or a FAME feedstock that is liquid. Liquid feedstocks are flowable and more easily moved through a reaction than solid feedstocks.

[0050] The methods described herein do not require a specialty catalyst. That is, the hydrogenation catalysts described herein are affordable and readily available to enable their widespread industrial use in common industrial oil hydrogenation settings with little to no modification to the catalyst or reactor setup, thereby enabling the catalyst to serve as both the hydrogenation catalyst and the biased isomerization catalyst. In addition, the catalysts may be unexpectedly biased with respect to producing, in descending abundance, C18:ln9, C18:lnl0, C18:lnll, C18:lnl2, C18:ln8, and C18:ln6 positional isomers. That is, the catalysts may produce a tightly distributed set of isomers, with chain-walking of the double bond restricted to + / - 3 positions from the original C9 position. The combined concentration of isomers outside this range and unconverted poly-unsaturates has been found to be unexpectedly low, with these compounds sometimes accounting for less than 10-12% by GC-FID area of the final reaction product.

[0051] The methods described herein, depending on the catalyst, can be completed in short periods of time (e.g., ~6 minutes) under mild conditions (e.g., 40°C, 100 psi H2) and with low catalyst loadings (e.g., 0.001-0.003% Pd metal by weight) making it both safe and inexpensive when compared to current methods. The methods described herein have been found to achieve comparable, or higher C18:2 conversions in this reaction system when compared to current methods. The methods have also been found to work well across a variety of different fatty acid methyl ester feedstocks.

[0052] The present disclosure also relates generally to the production of monocarboxylic acid and dicarboxylic acid species. To produce monocarboxylic acid species such as nonanoic acid, or dicarboxylic acid species such as azelaic acid, a feedstock source rich in mono-unsaturated fatty acids may be used, such as a feedstock rich in C18:ln9 compounds, including oleic and elaidic acid. Such a feedstock may be a vegetable oil such as soy or canola oil, or a feedstock derived from these oils. Some monocarboxylic and dicarboxylic acids are more easily producible than others. For example, the production of shorter chain (e.g., C7 and C8) monocarboxylic and dicarboxylic acids generally requires the use of tropical oil feedstocks, such as palm and palm kernel oil, which are rich in C16 fatty acids. However, oils that contain oleic,

[0053] 7

[0054] Classification: Confidentiallinoleic, and linolenic acids such as soy and canola are generally more environmentally acceptable and cost effective relative to tropical oil feedstocks.

[0055] To generate desired monocarboxylic and dicarboxylic acids, reaction products of the above-described hydrogenation and / or isomerization of poly-unsaturated fatty acids, or reaction products of hydrogen starved chain walking of fatty acids, may be cleaved at the location or modified location of the double bond of the fatty acid isomers. An ozonolysis reaction may be used to cleave the acid double bond and then convert the ozonates into their corresponding carboxylic acids. The ozonolysis reaction occurs as ozone attacks the double bond. The double bond is broken forming a carbonyl oxide and an aldehyde or two aldehydes. The carbonyl oxide and the aldehyde oxidized by known oxidation methods and the monocarboxylic and dicarboxylic acids are formed. The ozonolysis step produces both C9 monocarboxylic and dicarboxylic acids, as well as shorter chain monocarboxylic and dicarboxylic acids, from the C18 isomers, that were previously only obtainable through the ozonolysis of tropical oils.

[0056] In any of the embodiments described herein, a feedstock comprising polyunsaturated fatty acids may be reacted with a catalyst at a temperature of from about 20°C or more to about 160°C or less, and at a hydrogen pressure of from about 0 psi or more to about 1,500 psi or less, so as to produce a reaction product comprising monounsaturated fatty acids obtained from the poly-unsaturated fatty acids.

[0057] In any of the embodiments described herein, vegetable oil containing the polyunsaturated fatty acids is reacted to produce the non-unsaturated fatty acids. Example vegetable oils include, but are not limited to including, avocado, canola, coconut, corn, cottonseed, grapeseed, flaxseed, soy, safflower, olive, palm, peanut, sesame, sunflower, walnut, almond, argan, hempseed, and pumpkin seed oils. The vegetable oils may be selected from the group consisting of avocado, canola, coconut, corn, cottonseed, grapeseed, flaxseed, soy, safflower, olive, palm, peanut, sesame, sunflower, walnut, almond, argan, hempseed, pumpkin seed, and any mixtures thereof.

[0058] In any of the embodiments described herein, the catalyst is a heterogenous catalyst made from a porous support material and a catalyst material on the porous support material. Example porous support materials include, but are not limited to including, carbon, alumina, silica, and / or combinations thereof. The porous support materials may be selected from the group consisting of carbon, alumina, and silica. Example catalyst materials include, but are not limited to including, transition metals 8

[0059] Classification: Confidentialsuch as a Group IX, X, and / or XI transition metals. Specifically, example transition metals include, but are not limited to including, nickel (Ni), platinum (Pt), palladium (Pd), rhenium (Re), copper (Cu), and / or combinations thereof. The transition metals may be selected from the group consisting of nickel (Ni), platinum (Pt), palladium (Pd), rhenium (Re), copper (Cu), and combinations thereof. The catalyst material may be a single metallic material or be more than one metallic material, such as the aforementioned example transition metals.

[0060] The catalyst may be in any form including, but not limited to, a powdered form or a shaped form, such as spherical, prillic, and / or as an extrudate (e.g., elongated with various cross-sectional shapes). The transition metal may be deposited on the porous support material a uniform coating or an eggshell coating, for example.

[0061] In any of the embodiments described herein, the catalyst loading used in the reaction is from about 0.0005% or more to about 0.004% or less, or from about 0.001% or more to about 0.003% or less by weight, or is about 0.0005, 0.001, 0.0015, 0.002, 0.0025, 0.003, 0.0035, or 0.004% by weight.

[0062] In any of the embodiments described herein, the catalyst may be present in the reaction at a catalyst (mg) to feedstock (g) (e.g., vegetable oil or FAMES) ratio of from about 5:1 wt / wt% to 15:1 wt / wt%. In any of the embodiments described herein, the catalyst is added at about 10:1 wt / wt%. In any of the embodiments described herein, or in combination with any other embodiment, the catalyst is added at about 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11 :1, 12:1, 13:1, 14:1, or 15:1 wt / wt%.

[0063] In any of the embodiments described herein, the hydrogenation and / or isomerization reaction is performed at a temperature of from about 20°C or more to about 160°C or less, from about 30°C or more to about 100°C or less, or from about 40°C or more to about 60°C or less, or at about 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C. 140°C, 150°C, or 160°C.

[0064] In any of the embodiments described herein, the hydrogenation and / or isomerization reaction is performed at a hydrogen pressure of from about 50 psi or more to about 1,500 psi or less, from about 90 psi or more to about 750 psi or less, or from about 100 psi or more to about 500 psi or less, or about 80 psi, 90 psi, 100 psi, 200 psi, 300 psi, 400 psi, 500 psi, 750 psi, 900 psi, 1,200 psi, or 1,500 psi. The reactor pressure

[0065] 9

[0066] Classification: Confidentialmay be generated predominantly or substantially from hydrogen, such that these ranges of total pressure may also correspond to ranges of hydrogen partial pressure.

[0067] In any of the embodiments described herein, the hydrogenation and / or isomerization reaction is performed for less than about 120, 90, 60, 45, 30, 20, 15, 10, 6, or 5 minutes, from about 2 minutes or more to about 6 minutes or less, or for about 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 15, 20, 25, 30, 40, 50, 60, 90, or 120 minutes.

[0068] In any of the embodiments described herein, depending on the desired reaction products, hydrogen starved chain walking of fatty acids may be performed at a nominal hydrogen pressure of less than about 50 psi, less than about 40 psi, less than about 30 psi, less than about 20 psi, or less than about 10 psi, or at 50 psi, 40 psi, 30 psi, 20 psi, 10 psi, or 0 psi.

[0069] In any of the embodiments described herein, the hydrogen starved chain walking may be performed for greater than about 0, 30, 60, 120, 240, 1440, or 1860 minutes, or for about 0, 30, 60, 120, 240, 1440, or 1860 minutes.

[0070] In any of the embodiments described herein, the methods described herein and / or the catalyst may demonstrate bias for producing the at least partially hydrogenated reaction product comprising greater than about 60%, 70%, 80%, 90%, or 95% by GC-FID area C18: 1 mono-unsaturated fatty acid species.

[0071] In any of the embodiments described herein, the concentration by GC-FID area of C18:l species in the reaction product may increase by from about 30% or more to about 80% or less, from about 40% or more to about 60% or less, or by about 30, 40, 50, 60, 70, or 80% relative to the poly-unsaturated fatty acid-rich feedstock.

[0072] In any of the embodiments described herein, the methods described herein and / or the catalyst may demonstrate bias for producing C18:ln9 species by increasing the amount of C18:ln9 species in the reaction product by from about 10% or more to about 34% or less, or from about 20% or more to about 30% or less, or by about 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, 30%, 32%, or 34% relative to the poly-unsaturated fatty acid-rich feedstock.

[0073] In any of the embodiments described herein, the methods described herein and / or the catalyst may demonstrate bias for producing a C18: 1 fraction of the reaction product that is greater than about 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95% by

[0074] 10

[0075] Classification: ConfidentialGC-FID area C18:ln9 species. The C18:ln9 species produced may be in the form of cis and / or trans isomers.

[0076] In any of the embodiments described herein, the methods described herein and / or the catalyst may demonstrate bias for producing a C18: 1 fraction of the reaction 5 product that is greater than about 5%, 10%, 15%, or 20% by GC-FID area C18:lnl0 species. The C18: InlO species produced may be in the form of cis and / or trans isomers.

[0077] In any of the embodiments described herein, the methods described herein and / or the catalyst may demonstrate bias for producing a C18: 1 fraction of the reaction product that is less than about 12%, 10%, 8%, 6%, 4%, 2% by GC-FID area, or is 0% w by GC-FID area, C18: Ini 1 species. The C18: Ini 1 species produced may be in the form of cis and / or trans isomers.

[0078] In any of the embodiments described herein, the methods described herein and / or the catalyst may demonstrate bias for producing a C18: 1 fraction of the reaction product that is less than about 10%, 5%, 4%, 3%, 2%, 1% by GC-FID area, or is 0% by % GC-FID area, C 18 : 1 n6 and / or C 18 : 1 n 12 species . The C 18 : 1 n6 and / or C 18 : 1 n 12 species produced may be in the form of cis and / or trans isomers.

[0079] In any of the embodiments described herein, the methods described herein and / or the catalyst may demonstrate bias for producing the reaction product comprising less than about 20%, 10%, or 5% by GC-FID area poly-unsaturated fatty acid species.

[0080] 20 The poly-unsaturated fatty acid species may be in the form of C18:2 and / or C18:3 fatty acids.

[0081] In any of the embodiments described herein, reaction products of the abovedescribed hydrogenation and / or isomerization of poly-unsaturated fatty acids, or reaction products of hydrogen starved chain walking of fatty acids, may be cleaved so as to produce monocarboxylic and dicarboxylic acid species, for example, by ozonolysis. The fatty acids may be ozonolyzed so as to cleave the fatty acids at the location of a double bond contained therein, thereby producing corresponding monocarboxylic acids and / or dicarboxylic acids. When following the hydrogenation and / or isomerization reaction, the reaction products may be filtered to remove the 0 hydrogenation and / or isomerization catalyst therefrom prior to performing the ozonolysis.

[0082] 11

[0083] Classification: ConfidentialIn any of the embodiments described herein, the ozonolysis is performed by reacting the reaction products with an organic acid solvent and ozone at ambient pressure under cooling, and then by reacting with hydrogen peroxide at from about 20°C or more to about 160°C or less for less than about 120 minutes.

[0084] An example organic acid solvent includes, but is not limited to including, an acetic acid mixture.

[0085] In any of the embodiments described herein, an initial ozonolysis mixture of the reaction products and the organic acid solvent are combined at a ratio of from about 1:20 or more to about 1:200 or less v / v%, or at 1:20, 1:30, 1:40, 1:50, 1:75, 1:100, 1:150, or 1:200 v / v%.

[0086] In any of the embodiments described herein, the organic acid solvent comprises acetic acid and methyl formate at a ratio of from about 10: 1 or more to about 1 : 1 or less by volume, or at 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, or 1:1 by volume.

[0087] In any of the embodiments described herein, ozone in the form of air or pure oxygen is flowed through the initial ozonolysis mixture at a rate of from about 1 gal / hour to about 15 gal / hour, from about 2 gal / hour to about 10 gal / hour, or from about 3 gal / hour to about 5 gal / hour, or at about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 gal / hour

[0088] In any of the embodiments described herein, a generally constant temperature may be maintained while performing the ozonolysis reaction by any suitable means, such as by at least partially submerging the reaction vessel containing the initial ozonolysis mixture in an ice bath while the reaction is running.

[0089] A sample of the initial ozonolysis reaction product may then be pulled and analyzed by nuclear magnetic resonance to verify the reaction is complete, as indicated by the disappearance of double bond proton peaks. Once complete, the initial ozonolysis reaction product may be reacted with hydrogen peroxide, thereby forming an intermediate ozonolysis mixture, at an elevated temperature.

[0090] In any of the embodiments described herein, the intermediate ozonolysis mixture comprises the initial ozonolysis reaction product and hydrogen peroxide at a ratio of from about 10:1 v / v% to 1:1 v / v%, or at 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, or 1:1 v / v%.

[0091] 12

[0092] Classification: ConfidentialIn any of the embodiments described herein, the hydrogen peroxide mixed with the initial ozonolysis reaction product may be in a solution comprising from about 20% or more to about 80% or less hydrogen peroxide by v / v%, or 20%, 30%, 40%, 50%, 60%, 70%, or 80% hydrogen peroxide by v / v%.

[0093] In any of the embodiments described herein, the hydrogen peroxide and initial ozonolysis reaction product are reacted at temperature of from about 20°C or more to about 160°C or less, from about 30°C or more to about 150°C or less, from about 50°C or more to about 130°C or less, or from about 75°C or more to about 125°C or less, or at about 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, I20°C, 130°C, 140°C, 150°C, or 160°C.

[0094] In any of the embodiments described herein, the hydrogen peroxide and initial ozonolysis reaction product are reacted for less than about 120, 90, 60, 45, 30, 20, 15, 10, 6, or 5 minutes, from about 30 minutes or more to about 90 minutes or less, or for about 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 15, 20, 25, 30, 40, 50, 60, 90, or 120 minutes.

[0095] The monocarboxylic and dicarboxylic acid species produced from the ozonolysis reaction may be C6, C7, C8, C9, CIO, Cl l, or C12 species. In any of the embodiments described herein, the monocarboxylic and / or dicarboxylic acid species comprise one or more of glycolic acid, succinic acid, pentanoic acid, glutaric acid, hexanoic acid, adipic acid, heptanoic acid, pimelic acid, 2-octanol, octanoic acid, suberic acid, nonanoic acid, azelaic acid, decanoic acid, sebacic acid, undecanoic acid, undecanedioic acid, dodecanoic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, palmitic acid, and / or stearic acid.

[0096] In any of the embodiments described herein, the monocarboxylic and / or dicarboxylic acids comprise from about 18% or more to about 40% or less, from about 21% or more to about 35% or less, or about 28% azelaic acid by GC-FID area.

[0097] In any of the embodiments described herein, the monocarboxylic and / or dicarboxylic acids comprise from about 10% or more to about 30% or less, from about 15% or more to about 25% or less, or about 20% nonanoic acid by GC-FID area.

[0098] In any of the embodiments described herein, the monocarboxylic and / or dicarboxylic acids comprise from about 3% or more to about 10% or less, or about 6% suberic acid by GC-FID area.

[0099] 13

[0100] Classification: ConfidentialIn any of the embodiments described herein, the monocarboxylic and / or dicarboxylic acids comprise from about 2% or more to about 6% or less, or about 4% adipic acid by GC-FID area.

[0101] In any of the embodiments described herein, the monocarboxylic and / or dicarboxylic acids comprise from about 3% or more to about 10% or less, or about 5% octanoic acid by GC-FID area.

[0102] The following examples are set forth as representative of the present invention. These examples are not to be constmed as limiting the scope of the invention as other equivalent embodiments will be apparent in view of the present disclosure and appended claims.

[0103] EXAMPLES

[0104] High-Throughput Screening

[0105] To identify catalysts demonstrating bias for Cl 8:1 species and particularly for C18:ln9 species, a series of high throughput screening tests were performed. Using a surface plasmon resonance (SPR) system, different catalyst screening plates were prepared and run under varying temperatures and hydrogen pressures. Reactions were run in duplicate, in SPR 24-well plates, with sample locations randomized to account for area effects. The SPR 24-well plates were loaded with 15 mg, 30 mg, or 60 mg of palladium, nickel, copper, or platinum catalyst, as shown in Figs. 1-6. The SPR 24-well plates were then loaded with 2.3mL canola oil FAMEs or soy FAMEs feedstock. The plates were loaded into the SPR reactor, and setpoints were chosen from the following reaction conditions: time: 1.5-2 hours; shake speed: 1000 rpm; temperature: 25-160°C; pressure: 50-1000psi hydrogen. Twelve total experiments per 24-well plate were performed at the various conditions. Heat-up times were approximately 22 minutes, followed by 1.5-2 hour holds at the various temperatures and pressures. After the reaction was completed, the SPR system was depressurized and allowed to cool. Samples were removed, filtered, and analyzed.

[0106] Figures 1A-1B illustrate the reaction product profiles of the catalysts that exhibited the most bias toward the production of C 18:1 species and C18:ln9 species. For example, Figure 1A illustrates the relative change in saturated fatty acid composition when compared to a soy blank sample. The catalysts shown in Figure 1A were chosen from the screens depicted in Figures 2A-C, 4A-C, 5A-B, and 6A-B. Figure 14

[0107] Classification: Confidential1A illustrates the relative change in Cl 8 isomer composition when compared to a canola blank sample. The catalysts shown in Figure 1A were chosen from screens depicted in Figures 3A-C. It was found that the representative catalysts increased the concentration of saturated species relative to the soy and canola blanks, particularly with respect to the concentration of shorter saturated fatty acids. Figure IB illustrates the amounts of C18:l isomer and C18:ln9 isomers produced when reacting soy or canola oils with catalysts chosen for their bias in producing C18:l and C18:ln9 isomers. These examples were chosen from the following examples as the catalysts that exhibited the most selectivity for C18:l and C18:ln9 species.

[0108] It was found that the palladium catalysts 5% Pd / AhCh and 5% Pd(S) / C increased the overall Cl 8:1 concentration and the C18:ln9 concentration in both soy and canola FAMEs. The 5% Pt / AhCh catalyst also showed increased concentrations of C18:l and C18:ln9 fatty acids in lesser quantities relative to the aforementioned palladium catalysts. The Pricat® 9910 catalyst is a catalyst containing 22 wt% nickel. The Pricat® catalyst was also found to increase the overall Cl 8:1 concentration while showing a lesser degree of increase in and C18:ln9 concentrations relative to the aforementioned palladium catalysts.

[0109] Figures 2A-2C illustrate the resulting composition after soy FAMEs were reacted with multiple palladium catalysts using the FreeSlate system. The soy FAMES were run through the high throughput experiments to determine which palladium catalysts exhibited bias for producing C18:l and C18:ln9 isomers. The reaction conditions were 50 psi hydrogen, 40°C, 1,000 rpm stir rate, and a time of 2 hours. The palladium catalysts were analyzed to determine which catalyst showed the most bias for Cl 8: 1 isomers and specifically Cl 8: 1 n9 isomers at the specified reaction conditions. Figures 2A and 2B show the overall composition of the product produced through the reaction of soy FAMEs with each catalyst. For example, it can be seen that the linoleic acid (C18:2n6 cis) and the linolenic acid (C18:3n3 cis) concentrations from reacting the soy FAMES with the catalysts were reduced relative to the soy blank. The linolenic acid was almost completely converted to other isomers. Figure 2C shows the C18:l isomers produced with the C18:ln9 cis and C18:ln9 trans each being identified, and the rest of the Cl 8:1 isomers grouped together. For example, it can be seen that the soy blanks began with a concentration of about 21% by GC-FID area C18:ln9 cis and a concentration of about 23% by GC-FID area for all C18:l species. The amount of 15

[0110] Classification: ConfidentialC18:ln9 cis increases to between 30 and 40% by GC-FID area for each of the catalysts with all Cl 8:1 species increasing from about 50% to about 72% by GC-FID area. The 5% Pd / AFOs uniform coated showed a relatively large increase in overall C18: 1 species and a relatively large increase in C18:ln9 species, whose increase (the addition of the C18:ln9 trans) indicated that the 5% Pd / AFOi uniform coated showed the largest relative increase in C18:ln9 species concentration. The 5% Pd(S) / C showed a similar increase in C18:ln9 species concentration with a lower increase in overall C18:l species concentration.

[0111] Figures 3A-3C illustrate the resulting composition after canola FAMEs were reacted with multiple palladium catalysts. The canola FAMES were run through the high throughput experiments to determine which palladium catalysts exhibited bias for producing C18:l and C18:ln9 isomers. The reaction conditions were 50 psi hydrogen, 2.3 mL feed, 40°C, 1,000 rpm stir rate, and a time of 2 hours. The palladium catalysts were analyzed to determine which catalyst showed bias for Cl 8:1 isomers and specifically C18:ln9 isomers at the specified reaction conditions. Figures 3 A and 3B show the overall composition of the product produced through the reaction of canola FAMEs with each catalyst. Figure 3C shows the C18:l isomers produced with the C 18: 1 n9 cis and Cl 8:1 n9 trans each being identified, and the rest of the Cl 8: 1 isomers grouped together. For example, it can be seen that the canola blanks begin with a concentration of about 62% by GC-FID area C18:ln9 cis and a concentration of about 66% by GC-FID area for all C18:l species. The amount of C18:ln9 cis remained about the same for each of the catalysts with all Cl 8:1 species increasing from about 68% to about 85% depending on the catalyst. The 5% Pd / AFOi uniform coated showed a relatively large increase in overall C18:l species and a relatively large increase in C18:ln9 species increase (the addition of the C18:ln9 trans) indicates that the 5% Pd / AhOa uniform coated shows the largest relative increase in C18:ln9 species concentration). The 5% Pd(S) / C showed a decrease in C18:ln9 cis and an increase in C18:ln9 trans species concentration with a greater increase in overall Cl 8:1 species concentration.

[0112] Figures 4A-4C illustrate the resulting composition after soy FAMEs were reacted with multiple platinum catalysts. The reaction conditions were 75 psi hydrogen, 50°C, 1,000 rpm stir rate, and a reaction time of 2 hours. The platinum catalysts were analyzed to determine which catalysts showed bias for C18:l isomers and specifically 16

[0113] Classification: ConfidentialC18:ln9 isomers at the specified reaction conditions. Figures 4A and 4B show the overall composition of the reaction product obtained from the reaction of soy FAMEs with each catalyst. For example, it can be seen that the linoleic acid (C18:2n6 cis) concentration decreased relative to the soy blank for some of the catalysts, and increased relative to the soy blank for other catalysts. Figure 4C shows the C18:l isomers produced with the C18:ln9 cis and C18:ln9 trans each being identified, and the rest of the C18: 1 isomers grouped together. For example, it can be seen that one of the soy blanks began with a concentration of about 27% by GC-FID area C18:ln9 cis and a concentration of about 39% by GC-FID area for all C18:l species. The amount of C18:ln9 cis increased to about 30% by GC-FID area for the 1% platinum catalysts. The concentration of all C18: 1 species increased from about 51% to about 56% by GC-FID area for the 1% platinum catalysts. The 5% Pt / AhOa catalyst increased the C18:ln9 species to about 34% by GC-FID area and the overall C18:l species to about 52% by GC-FID area. The 5% Pt / AFO; showed the greatest increase in in C18:ln9 isomers.

[0114] Figure 5A illustrates the resulting composition after soy FAMEs were reacted with multiple platinum catalysts. The reaction conditions were 1,000 psi hydrogen, 50°C, 1,000 rpm stir rate, and a reaction time of 2 hours. The platinum catalysts were analyzed to determine which catalyst showed bias for Cl 8:1 isomers and specifically C18:ln9 isomers at the specified reaction conditions. Figures 5A and 5B show the overall composition of the reaction product obtained from the reaction of soy FAMEs with each catalyst. For example, it can be seen that the linoleic acid (C18:2n6 cis) concentration decreased relative to the soy blank for some of the catalysts, and increased relative to the soy blank for other catalysts. Figure 5B shows the C18:l isomers produced with the C18:ln9 cis and C18:ln9 trans each being identified, and the rest of the C18: 1 isomers grouped together. For example, the soy blanks began with a concentration of about 21% by GC-FID area C18: ln9 cis and a concentration of about 23% by GC-FID area for all C18:l species. The amount of C18:ln9 cis increased to about 34% by GC-FID area for the 5% Pt / AEOj catalysts. The concentration of all C18:l species increased to about 53% by GC-FID area for the 5% Pt / AI2O3 catalysts. The 5% Pt / AbOi showed the greatest increase in in Cl 8: ln9 isomers.

[0115] Figures 6A and 6B illustrate the resulting composition after soy FAMEs were reacted with multiple nickel catalysts. The reaction conditions were 150 psi hydrogen, 160°C, 1,000 rpm stir rate, and a reaction time of 1.5 hours. The nickel catalysts were 17

[0116] Classification: Confidentialanalyzed to determine which catalyst showed bias for Cl 8:1 isomers and specifically C18:ln9 isomers at the specified reaction conditions. Figures 6A and 6B show the overall composition of the product obtained from the reaction of soy FAMEs with each catalyst. For example, it can be seen that the linoleic acid (Cl 8:2n6 cis) and the linolenic acid (C18:3n3 cis) concentrations decreased relative to the soy blank. The linolenic acid decrease demonstrated conversion to other isomers. Figure 6C shows the Cl 8: 1 isomers produced with the C18: ln9 cis and C18: ln9 trans each being identified, and the rest of the C18:l isomers grouped together. For example, it can be seen that the soy blanks began with a concentration of about 21% by GC-FID area C18:ln9 cis and a concentration of about 23% by GC-FID area for all C18:l species. The amount of C18: ln9 cis increased to between about 25% and 29% by GC-FID area for each of the catalysts with all Cl 8:1 species increasing from about 24% to about 60% by GC-FID area. The Pricat® 9910 catalyst showed a relatively large increase in overall C18:l species and a modest increase in C18:ln9 species, whose increase (the addition of the C18:ln9 trans) indicated that the Pricat® 9910 catalyst showed the largest relative increase in C18:ln9 species concentration. The Pricat® 9910 catalyst showed the greatest increase in C18: 1 isomers of any of the tested catalysts. The C18:ln9 isomers were increased to a lesser degree.

[0117] Batch Reactor Screening:

[0118] Figure 7 shows the resulting composition of reacting canola methyl esters with a palladium catalyst for 6-10 minutes at differing temperature and hydrogen pressure conditions. The low temperature / low pressure condition is 40°C and 100 psi hydrogen. The high temperature / low pressure condition is 60°C and 100 psi. The low temperature / high pressure condition is 40°C and 1,500 psi. The high temperature / high pressure condition is 60°C and 1,500 psi. The low temperature / low pressure conditions produced the highest amount of C18:ln9 species. The high temperature / high pressure condition produced higher levels of complete saturation resulting in C18:0 species. The low temperature / low pres sure condition produced largest amount ofC18:l andC18:ln9 species. This indicated these conditions provided bias for the conversion of polyunsaturated fatty acids to certain fatty acid species.

[0119] Palladium-catalyzed Selective Hydrogenation - IL Reactor Screening:

[0120] Reaction #1

[0121] 18

[0122] Classification: Confidential400 g liquid canola FAMEs were placed in a 1 L reactor. 240 mg palladium catalyst JM A302099-5 (5% Pd) was added to the reactor. The reactor was heated to 40°C under nitrogen, stirring at 1450 RPM or slightly below the otherwise specified maximum temperature. Both the gas lines and manifold were purged to ensure that no hydrogen was present during the time the reactor was heating up to the reaction temperature. The temperature of the reactor was verified to be stable at approximately 40°C. Once the reactor had reached a stable temperature, the vessel was purged and filled with hydrogen at 100 psi. The reaction was run for 0, 2, 6, 10, 18, and 30 minutes. At the conclusion of the reaction time, the hydrogen was vented, and the reactor was cooled. After the specified time had elapsed, the heating mantle was lowered to quickcool the system with water. A beaker of water was placed on a jack-stand and raised up to the level of the reactor body. The reactions were stopped at the specified time. The start times were staggered by a few minutes in order to make it easier to ensure hydrogen was vented and cooling was applied properly. The samples were run on the User Analytical GCMS. A Shimadzu GC was used to analyze the samples. The GC operating parameters were as follows: Column: SP-2560 100m x 0.25mm x 0.2um; Oven: 175°C Isothermal; Carrier Gas: Helium at 20cm / sec; Detector: FID @ 250°C; Injector: 200°C. Initially, a sample of Cis-Trans FAME Isomer Standard (Mixture Matreya Chemical 1131 / Cayman Chemical 29363) was injected to calibrate for the respective C18:l isomers.

[0123] Preparation of the reaction products for GCMS analysis is now described in detail. For liquid FAME products, the product was filtered to remove the catalyst. A Buchner filter with filter paper and a vacuum flask was used. For solid FAMEs or products with solid and liquid products. The solid material was scraped out of the reactor, and the liquid material was poured out. The product was heated, and hot filtered. To remove the ester from the carboxylic acid of the FAME, 4 mE of hexane were added into a 13 x 100 mm glass tube. A sample of 2 drops of liquid product or about 30 mg of the solid product were added to the glass tube. Solid samples were heated for about 5-10 minutes at 65°C until dissolved. The sample was vortexed for 5 minutes. The sample was mixed well and centrifuged at 3500 rpm for 5 minutes.

[0124] Figure 8 A shows the distribution of C18:l species and Figure 8B shows the distribution of fatty acid species. At 40°C and 100 psi hydrogen, at times of 2 minutes and 6 minutes, the amount of C18:ln9 species was about 66% by GC-FID area and the 19

[0125] Classification: Confidentialamount of Cl 8:1 species was about 83% by GC-FID area. The low temperature / low pressure condition run for from about 2 minutes or more to about 6 minutes or less resulted in the largest amount of Cl 8:1 and C18:ln9 species. Running the reaction for a longer period of time at the low temperature / low pressure condition resulted in a larger conversion of C18:2 species up to about 95% by GC-FID area or more, as seen in the conversion of unsaturates indicators on Figure 8B, however the amount of C18:l and C18:ln9 species decreased. Therefore, to react vegetable oils to specifically produce C18:l and C18:ln9 fatty acids, it was found reaction times of from about 2 minutes or more to about 6 minutes or less may be used.

[0126] Reaction #2

[0127] 400 g liquid canola FAMEs were placed in a 1 L reactor. 120 mg palladium catalyst JM A302099-5 was added to the reactor. The reactor was heated to 60°C under nitrogen, stirring at 1450 RPM or slightly below the otherwise specified maximum temperature. Both the gas lines and manifold were purged to ensure that no hydrogen was present during the time the reactor was heating up to the reaction temperature. The temperature of the reactor was verified to be stable at approximately 60°C. Once the reactor had reached a stable temperature, the vessel was purged and filled with hydrogen at 1,500 psi. The reaction was run for 0, 2, 6, 10, 18, or 30 minutes. At the conclusion of the reaction time, the hydrogen was vented, and the reactor was cooled. After the specified time had elapsed, the heating mantle was lowered to quick-cool the system with water. A beaker of water was placed on a jack-stand and raised up to the level of the reactor body. The reactions were stopped at the specified time. The start times were staggered by a few minutes in order to make it easier to ensure hydrogen was vented and cooling applied properly. The samples were run on the User Analytical GCMS. A Shimadzu GC was used to analyze the samples. The GC operating parameters were as follows: Column: SP-2560 100m x 0.25mm x 0.2um; Oven: 175°C Isothermal: Carrier Gas: Helium at 20cm / sec; Detector: FID @ 250°C; Injector: 200°C. Initially, a sample of Cis-Trans FAME Isomer Standard (Mixture Matreya Chemical 1131 / Cayman Chemical 29363) was injected to calibrate for the respective C18:l isomers.

[0128] Preparation of the reaction products for GCMS analysis is now described in detail. For liquid FAME products, the product was filtered to remove the catalyst. A Buchner filter with filter paper and a vacuum flask was used. For solid FAMEs or 20

[0129] Classification: Confidentialproducts with solid and liquid products, the solid material was scraped out of the reactor, and the liquid material was poured out. The product was heated, and hot filtered. To remove the ester from the carboxylic acid of the FAME, 4 mL of hexane were added into a 13 x 100 mm glass tube. A sample of 2 drops of liquid product or about 30 mg of the solid product were added to the glass tube. Solid samples were heated for about 5-10 minutes at 65°C until dissolved. The sample was vortexed for 5 minutes. The sample was mixed well and centrifuged at 3500 rpm for 5 minutes.

[0130] Figure 9 A shows the distribution of C18:l species and Figure 9B shows the distribution of fatty acid species. At 40°C and 1,500 psi hydrogen, at times of 2 minutes and 6 minutes, the amount of C18:ln9 species was about 55% by GC-FID area and the amount of C18:l species was about 79% by GC-FID area. The high temperature / high pressure condition ran for from about 2 minutes or more to about 6 minutes or less resulted in the largest amount of Cl 8:1 and C18:ln9 species. Running the reaction for a longer period of time at the high temperature / high pressure condition resulted in a larger conversion of Cl 8:2 species up to about 95% by GC-FID area, as seen in the conversion of unsaturates indicators on Figure 9B, however the amount of C18:l and C18:ln9 decreased. Therefore, to react vegetable oils to bias towards Cl 8:1 and C18:ln9 fatty acids, it was found times of from about 2 minutes or more to about 6 minutes or less may be used. The high temperature / high pressure condition results in lower amounts of C18:l and C18:ln9 and is therefore less biased for those fatty acids.

[0131] Isomerization Profiling Study:

[0132] Isomerization experiments were performed according to the following general procedure. Catalyst was loaded into 20 mL scintillation vials at a rate of 15mg catalyst per gram of FAMEs added. A stir bar was next placed into the vial, followed by approximately 9mL of either nitrogen-sparged methyl oleate, or canola FAMEs. The vials were capped with septa lids and purged with nitrogen. Stirring was turned on, and the vials were next purged with hydrogen gas from an attached balloon. The stir plate heating was turned on, and the FAMEs reacted with hydrogen in the presence of the catalyst at a temperature of 60°C and nominal hydrogen pressure resulting from use of the attached balloon. The reaction was allowed to progress for 0, 30, 60, 120, 240, 1440, or 1860 minutes.

[0133] A first isomerization experiment was performed that included reacting nitrogen-sparged methyl oleate with a variety of different catalysts under the same reaction 21

[0134] Classification: Confidentialtemperature, hydrogen pressure, and time (60 minutes) in accordance with the aforementioned general procedure. Figure 10 shows the distribution of C 18 : 1 positional isomers produced therefrom. It was found that the representative reaction performed with the 5% Pd / AhCF catalyst produced the largest amount of C18:lnll, C18:lnl2, and C18:ln6,8 isomers in comparison to the other catalysts tested. In other words, the 5% Pd / AhCh catalyst demonstrated the highest degree of positional shifting, where the bond was shifted to a new location that was more than one position from its original location.

[0135] Based on these results, a second isomerization experiment was performed that included reacting canola FAMEs with the 5 % Pd / AFCF catalyst under the same reaction temperature, same hydrogen pressure, and a variety of different reaction times (0, 30, 60, 120, 240, 1440, or 1860 minutes) in accordance with the aforementioned general procedure.

[0136] Figure 11 shows the distribution of C18:l positional isomers produced therefrom. Generally, it was found that the longer the reaction progresses the more trans-Cl 8: 1 n 10 and / ra / z.s-CI 8: 1 n 11 isomers were produced. For example, as shown in Figure 11, approximately 80% to 75% of the Cl 8:1 material by GC-FID area was unconverted or only underwent cis / trans isomerization at the C-9 position at 0, 30, 60, 120, and 240 minutes of reaction time, whereas approximately 70% of the C18:l material by GC-FID area was unconverted or only underwent cis / trans isomerization at the C9 position at 1440 and 1860 minutes of reaction time. In addition, approximately 5% of the material by GC-FID area shifted to the CIO or Cl 1 position at 0, 30, 60, 120, and 240 minutes of reaction time, whereas approximately 8% of the material by GC-FID area shifted to the CIO or Cl 1 position at 1440 and 1860 minutes of reaction time. Approximately 1% of the material by GC-FID area shifted three places to the Cl 2 or C6 position regardless of reaction time. No additional Cl 8: 1 isomerization of note was observed, providing some insight into the generally defined “unquantified C18:l isomers.”

[0137] A Shimadzu GC was used to analyze the samples obtained from the isomerization profiling study. The GC operating parameters were as follows: Column: SP-2560 100m x 0.25mm x 0.2um; Oven: 175°C Isothermal; Carrier Gas: Helium at 20cm / sec; Detector: FID @ 250°C; Injector: 200°C. Initially, a sample of Cis-Trans

[0138] 22

[0139] Classification: ConfidentialFAME Isomer Standard (Mixture Matreya Chemical 1131 / Cayman Chemical 29363) was injected to calibrate for the respective C18: 1 isomers.

[0140] Ozonolysis procedure:

[0141] Ozonolysis of C18:l positional isomers, obtained by reacting canola FAMEs 5 with the 5% Pd / A12O3 catalyst at a temperature of 60°C, nominal hydrogen pressure, and a reaction time of 60 minutes, was performed according to the following procedure.

[0142] 0.5 mL of the isomerization product was added to a 2-necked lOOmL round bottom flask with a stir bar. Next was added 15mL glacial acetic acid, and 5mL methyl formate. The vial was purged with ozone while stirring for 15 minutes. A vigreux column was w attached to the flask, and through the second neck was added 5mL 50% hydrogen peroxide. The glass stopper previously sealing this arm was replaced, and the mixture was stirred and refluxed at 100°C overnight. The next morning, the mixture was tested with a peroxide strip; if peroxides were present, the mixture was allowed to continue refluxing, and if they were not, the mixture was subsequently analyzed, by gas 15 chromatography.

[0143] Figure 12 shows the ozonolysis product distribution produced from the aforementioned procedure. The ozonolysis procedure produced monocarboxylic and dicarboxylic acid species comprising C6, C7, C8, C9, CIO, Cll, or C12 species. The monocarboxylic and dicarboxylic acid product comprised between about 20% or more 20 and about 30% or less azelaic acid by GC-FID area, between about 15% or more and about 25% or less nonanoic acid by GC-FID area, between about 6% or more and about 10% or less suberic acid by GC-FID area, between about 2% or more and about 6% or less adipic acid by GC-FID area, between about 3% or more and about 10% or less octanoic acid by GC-FID area, between about 3% or more and about 10% or less glutaric acid by GC-FID area, between about 2% or more and about 8% or less hexanoic acid by GC-FID area, between about 2% or more and about 6% or less pimelic acid by GC-FID area, between about 2% or more and about 6% or less sebacic acid by GC-FID area, between about 2% or more and about 6% or less heptanoic acid by GC-FID area, between about 1% or more and about 5% or less undecanedioic acid by GC-FID area, 0 between about 0% or more and about 4% or less dodecanedioic acid by GC-FID area, between about 0% or more and about 4% or less pentanoic acid by GC-FID area, between about 0% or more and about 4% or less palmitic acid by GC-FID area, between about 0% or more and about 4% or less decanoic acid by GC-FID area, between about 23

[0144] Classification: Confidential0% or more and about 3% or less glycolytic, stearic, tridecanedioic, undecanoic, tetradecanedioic, 2-octanol, dodecanoic, and pentadecanedioic acid by GC-FID area.

[0145] The percentages of each of the monocarboxylic and dicarboxcylic acid species corresponds to the isomers produced in the isomerization reaction. Azealic acid is a C9 dicarboxylic acid and nonanoic acid is a C9 monocarboxylic acid, the concentration of these acids shows that the ozonolysis breaks the double bond of the C18:ln9 oleic acid. The percentages of the other monocarboxylic and dicarboxylic acids following ozonolysis further indicates that the concentration of monocarboxylic and dicarboxylic acid species decreases for each monocarboxylic acid or dicarboxylic acid containing more or less than 9 carbons in the acid chain. The majority of the monocarboxylic acid or di carboxy lie acid species have between 6 and 12 carbons in the acid chain. The 5% Pd / AFOs catalyst shows specificity for moving the double bond in the acid chain of a carboxylic acid.

[0146] The invention has been described with reference to various specific embodiments and techniques. Nevertheless, it is understood that many variations and modifications may be made while remaining within the spirit and scope of the invention.

[0147] 24

[0148] Classification: Confidential

Claims

WHAT IS CLAIMED IS:

1. A method of producing monocarboxylic and / or dicarboxylic acid species comprising:reacting unsaturated fatty acids with a transition metal catalyst at a temperature from about 20°C or more to about 160°C or less and at a hydrogen pressure of from about 0 psi or more to about 1,500 psi or less so as to produce a reaction product comprising isomerized, or hydrogenated, fatty acids having the location of a double bond in a new location as compared to the starting unsaturated fatty acids; andcleaving the fatty acids of the reaction product so as to produce monocarboxylic acid and / or dicarboxylic acid species.

2. The method of claim 1, wherein the reacting comprises reacting a vegetable oil comprising the poly-unsaturated fatty acids.

3. The method of claim 2, wherein the vegetable oil comprises soy oil or canola oil.

4. The method of claim 2, wherein the vegetable oil is selected from the group consisting of soy oil or canola oil.

5. The method of claim 2, wherein the vegetable oil is selected from the group consisting essentially of soy oil or canola oil.

6. The method of any of the preceding claims, wherein the reacting unsaturated fatty acids comprises reacting the unsaturated fatty acids in the form of fatty acid methyl esters and / or triglycerides.

7. The method of any of the preceding claims, wherein the transition metal catalyst comprises a catalyst material on a porous support material.

8. The method of claim 7, wherein the catalyst material comprises a Group IX, X, or XI metal.

9. The method of claim 8, wherein the catalyst material comprises one or more of nickel, platinum, palladium, rhenium, and copper.

10. The method of claim 8, wherein the catalyst material consists of nickel, platinum, palladium, rhenium, or copper.25Classification: Confidential11. The method of claim 8, wherein the catalyst material consists essentially of nickel, platinum, palladium, rhenium, or copper.

12. The method of claim 7, wherein the porous support material comprises one or more of carbon, alumina, and silica.

13. The method of claim 12, wherein the porous support material consists of carbon, alumina, or silica.

14. The method of claim 12, wherein the porous support material consists essentially of carbon, alumina, or silica.

15. The method of any of the preceding claims, wherein the transition metal catalyst is present at catalyst (mg) to feedstock (g) ratio of from about 5:1 wt / wt% or more to 15:1 wt / wt% or less, or about 10:1 wt / wt%.

16. The method of any of the preceding claims, wherein loading of the transition metal catalyst is from about 0.0005% or more to about 0.004% or less, or from about 0.001% or more to about 0.003% or less by weight.

17. The method of any of the preceding claims, wherein the temperature is from about 30°C or more to about 100°C or less, or from about 40°C or more to about 60°C or less.

18. The method of any of the preceding claims, wherein the hydrogen pressure is from about 50 psi or more to about 1,100 psi or less, from about 90 psi or more to about 750 psi or less, or from about 100 psi or more to about 500 psi or less.

19. The method of any of the preceding claims, wherein the hydrogen pressure is less than about 50 psi, less than about 40 psi, less than about 30 psi, less than about 20 psi, or less than about 10 psi.

20. The method of any of the preceding claims, wherein the reaction is performed for less than about 120, 90, 60, 45, 30, 20, 15, 10, 6, or 5 minutes.

21. The method of any of the preceding claims, wherein the reaction is performed for greater than about 0, 30, 60, 120, 240, 1440, or 1860 minutes.

22. The method of any of the preceding claims, wherein the reaction product comprises less than about 20%, 10%, or 5% by GC-FID area poly-unsaturated fatty acid species.26Classification: Confidential23. The method of any of the preceding claims, wherein the reaction product comprises greater than about 60%, 70%, 80%, 90%, or 95% by GC-FID area C18:l mono-unsaturated fatty acid species.

24. The method of any of the preceding claims, wherein the Cl 8: 1 fraction of the reaction product is greater than about 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95% by GC-FID area C18:ln9 species.

25. The method of any of the preceding claims, wherein the Cl 8: 1 fraction of the reaction product is greater than about 5%, 10%, 15%, or 20% by GC-FID area C18:lnl0 species.

26. The method of any of the preceding claims, wherein the Cl 8:1 fraction of the reaction product is less than about 12%, 10%, 8%, 6%, 4%, 2% by GC-FID area, oris 0% by GC-FID area, C18:lnll species.

27. The method of any of the preceding claims, wherein the Cl 8: 1 fraction of the reaction product is less than about 10%, 5%, 4%, 3%, 2%, 1% by GC-FID area, oris 0% by GC-FID area, C18:ln6 and / or C18:lnl2 species.

28. The method of any of the preceding claims, wherein the reaction product comprises less than about 20%, 10%, or 5% by GC-FID area poly-unsaturated fatty acid species.

29. The method of any of the preceding claims, wherein cleaving the fatty acids is performed by ozonolysis the fatty acids contained in the reaction product.

30. The method of any of the preceding claims, wherein the ozonolysis is performed by reacting the reaction products with an organic acid solvent and ozone at ambient pressure, and then by reacting an initial ozonolysis reaction product with hydrogen peroxide at from about 20°C or more to about 160°C or less for less than about 120 minutes.

31. The method of Claim 30, wherein the organic acid solvent comprises acetic acid and methyl formate.

32. The method of Claim 30, wherein the organic acid solvent consists of acetic acid and methyl formate.27Classification: Confidential33. The method of any of Claims 30-32, wherein an initial ozonolysis mixture of the reaction products and the organic acid solvent are combined at a ratio of from about 1 :20 or more to about 1 :200 or less v / v%.

34. The method of any of Claims 30-33, wherein the ozone is flowed through the initial ozonolysis mixture at a rate of from about 1 gal / hour to about 15 gal / hour, from about 2 gal / hour to about 10 gal / hour, or from about 3 gal / hour to about 5 gal / hour.

35. The method of any of Claims 30-34, wherein the ozonolysis is performed under cooling.

36. The method of any of Claims 30-35, wherein the ozonolysis reaction product with hydrogen peroxide form an intermediate oxidation mixture comprising ozonolysis reaction product and hydrogen peroxide at a ratio of from about 10: 1 v / v% to 1:1 v / v%.

37. The method of any of Claims 30-36, wherein the ozonolysis is performed at temperature of from about 30°C or more to about 150°C or less, from about 50°C or more to about 130°C or less, or from about 75°C or more to about 125°C or less.

38. The method of any of Claims 30-37, wherein the ozonolysis is performed for less than about 120, 90, 60, 45, 30, 20, 15, 10, 6, or 5 minutes.

39. The method of any of Claims 30-38, wherein the ozonolysis is performed at temperature of from about 75°C or more to about 125°C or less for less than about 60 minutes.

40. The method of any of the preceding claims, wherein the monocarboxylic and / or dicarboxylic acid species comprise one or more of glycolic acid, succinic acid, pentanoic acid, glutaric acid, hexanoic acid, adipic acid, heptanoic acid, pimelic acid, 2-octanol, octanoic acid, suberic acid, nonanoic acid, azelaic acid, decanoic acid, sebacic acid, undecanoic acid, undecanedioic acid, dodecanoic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, palmitic acid, and stearic acid.

41. The method of any of the preceding claims, wherein the unsaturated fatty acids are reacted in the presence of the transition metal catalyst at a temperature of from about 40°C or more to about 60°C or less, at a hydrogen pressure of less than 28Classification: Confidentialabout 50 psi, for a reaction time of greater than about 240 minutes, so as to produce a reaction product comprising about 70% by GC-FID area unconverted or C9 cis / trans isomerized unsaturated fatty acids, about 8% by GC-FID CIO or Cl l shifted unsaturated fatty acids, and about 1% by GC-FID area C6 or Cl 2 shifted unsaturated fatty acids.29Classification: Confidential

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