Multiple product routes from renewable oils to petroleum substitutes and lubricants containing same

Abstract

Methods for the production of renewable hydrocarbons, including alpha olefins, renewable diesel, synthetic gasoline, and acyl-glycerides from renewable oils are described herein. Also included are methods for production that include (a) blending a specific renewable oil mixture with appropriate free fatty acid characteristics, (b) acid hydrolysis of the free fatty acids and subsequent purification of unsaturated and saturated chains, (c) converting the saturated portion into renewable diesel, and (d) reacting the unsaturated free fatty acids via ethenolysis to form alpha olefins, and then converting the remaining free fatty acids to either synthetic gasoline or acyl-glycerols via glycerolysis.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of priority to U.S. Provisional Patent Application No. 63 / 224,245, filed July 21, 2021, and U.S. Provisional Patent Application No. 63 / 232,566, filed August 12, 2021, which are incorporated by reference in their entireties.

[0002] FIELD OF THEINVENTION Aspects of the present disclosure generally relate to a single method for the production of multiple unique renewable hydrocarbon products for a variety of industries, including processes for the formation of long and short chain alpha olefins, saturated hydrocarbons, and acyl-glycerides. [Background technology]

[0003] background It has been recognized that the increasing energy demands coupled with the depletion of non-renewable resources in the global economy require a major paradigm shift in the way energy and materials are made. Environmental concerns are forcing industries to look for alternative resources more than ever before. Thus, in the past few decades, the replacement of petroleum-based materials with organic materials derived from living organisms has become the focus of more and more research institutes and companies. Organic building blocks such as carbohydrates, glycerol, free fatty acids, lignocellulose, and amino acids are being investigated as alternative precursors to many fuel types and chemicals currently produced from petroleum sources. Currently, due to the complete lack of high-performance biolubricants and carbon-negative options, and therefore the absence of non-petroleum products capable of meeting manufacturers' performance specifications, industries are forced to utilize petroleum lubricants. Summary of the Invention

[0004] overview In an aspect, the present disclosure provides a method for preparing a base oil from a renewable oil comprising triglycerides, the method comprising: a) i) a free fatty acid mixture comprising saturated free fatty acids and unsaturated free fatty acids; ii) glycerin; and acidifying the renewable oil to produce a mixture comprising: b) isolating glycerin from the mixture of fatty acids; c) separating saturated free fatty acids from unsaturated free fatty acids; d) i) an alpha olefin; ii) short chain unsaturated fatty acids, optionally C6-C12 or C8-C12 short chain unsaturated fatty acids; subjecting the unsaturated free fatty acid to ethenolysis to prepare a mixture comprising: e) combining the glycerin from a) with at least a portion of the short chain unsaturated fatty acids of d) to produce a mixture, and subjecting the mixture to glycerolysis; The present invention provides a method comprising:

[0005] In some embodiments, the method further comprises decarboxylating at least a portion of the short chain unsaturated fatty acids of d) to produce saturated hydrocarbons, optionally the decarboxylation comprises catalytic or gas phase decarboxylation, optionally a Ni / C catalyst or an oxidative metal catalyst (e.g., silver(II)). In some embodiments, in a), the renewable oil is refined prior to acidification. In some embodiments, refining the renewable oil comprises clarification, degumming, bleaching, and / or filtering. In some embodiments, in a), the acidifying the renewable oil comprises contacting the renewable oil with an aqueous acid and an organic solvent to provide an organic fraction and an aqueous fraction, the organic fraction comprising a free fatty acid mixture and the aqueous fraction comprising glycerin. In some embodiments, in a), the acidifying the renewable oil comprises heating a mixture of renewable oil and water at a suitable pressure. In some embodiments, the range of renewable oil to water ratios at suitable pressures includes one or more of renewable oil to water ratios ranging from about 5:1 to about 1:5, about 4:1 to about 1:4, about 3:1 to about 1:3, or about 2:1 to about 1:2 based on the total weight of renewable oil and water, and the mixture is heated to a temperature ranging from about 100°C to about 350°C, about 200°C to about 300°C, or about 250°C to about 275°C, and the pressure ranges from about 500 psi to about 1000 psi, about 700 psi to about 900 psi, or about 800 psi to about 900 psi. In some embodiments, the acidifying step is repeated two or more times. In some embodiments, the acid comprises at least one of H2SO4, HCl, and H3PO4. In some embodiments, the organic fraction comprises 90% to about 100% free fatty acids by weight and about 0% to about 10% glycerin by weight. In some embodiments, the organic fraction comprises about 90% free fatty acids by weight and about 10% glycerin and / or glycerol by weight. In some embodiments, the organic fraction comprises at least about 50 to about 100%, about 60 to about 100%, about 70 to about 100%, about 80 to about 100%, about 90 to about 100%, about 60 to about 90%, or about 70 to about 80% free fatty acids by weight.In some embodiments, in c), the separation of saturated fatty acids from unsaturated fatty acids comprises a temperature dependent solvent extraction. In some embodiments, the saturated free fatty acids of a) are separated into short chain saturated free fatty acids, optionally C8-12 saturated free fatty acids, and long chain saturated free fatty acids, optionally C13-C22, C15-C19, or C16-C22 saturated free fatty acids. In some embodiments, the method further comprises decarboxylation of the long chain fatty acids. In some embodiments, the decarboxylation comprises a catalyst selected from Mo on Al2O3, MgO on Al2O3, and Ni on Al2O3, optionally comprising a single stage continuous process and / or subcritical water. In some embodiments, the ethenolysis optionally comprises a catalyst selected from tungsten, molybdenum, rhenium, and ruthenium. In some embodiments, the unsaturated free fatty acids comprise and / or consist of long chain unsaturated free fatty acids. In some embodiments, the method further comprises separating the alpha olefins from the short chain unsaturated fatty acids by oligomerization, optionally in the presence of a heterogeneous catalyst, to provide alpha olefin dimers, alpha olefin trimers, alpha olefin tetramers, and / or alpha olefin pentamers. In some embodiments, the heterogeneous catalyst is selected from metals, metal oxides, metal salts, or organic materials (e.g., organic hydroperoxides, ion exchangers, and enzymes). In some embodiments, the method further comprises isomerizing the alpha olefins, optionally in the presence of hydrogen or under inert conditions. In some embodiments, the isomerization is carried out inside a Parr reactor. In some embodiments, the temperature conditions of the isomerization reaction range from about 100°C to about 500°C, about 100°C to about 200°C, about 200°C to about 300°C, about 300°C to about 400°C, or about 400°C to about 500°C. In some embodiments, the pressure conditions for the isomerization reaction range from about 1,000 psi to about 3,000 psi, from about 1,000 psi to about 2,000 psi, from about 2,000 psi to about 3,000 psi, or from about 1,500 psi to about 2,500 psi. In some embodiments, the heterogeneous catalyst is selected from AlCl3 and BF3.In some embodiments, the glycerolysis produces short chain unsaturated acyl-glycerides. In some embodiments, the glycerolysis is base catalyzed, optionally where the catalyst is a methoxide selected from sodium methoxide, potassium methoxide, lithium methoxide, zinc methoxide, calcium methoxide, tributyltin methoxide, magnesium methoxide, tantalum(V) methoxide, titanium(IV) methoxide, antimony(III) methoxide, germanium methoxide, copper(II) methoxide, and combinations thereof.

[0006] In an aspect, the present disclosure provides a method for preparing a base oil from a renewable oil comprising triglycerides, the method comprising: a) i) a fatty acid ester mixture comprising saturated fatty acid esters and unsaturated fatty acid esters; ii) glycerin; and transesterifying a renewable oil to produce a mixture comprising: b) isolating glycerin from the fatty acid ester mixture; c) separating the saturated fatty acid esters from the unsaturated fatty acid esters; d) i) an alpha olefin; ii) short chain unsaturated fatty acid esters, optionally C6-C12 or C8-C12 short chain unsaturated fatty acid esters; subjecting the unsaturated fatty acid esters to ethenolysis to prepare a mixture comprising The present invention provides a method comprising:

[0007] In some embodiments, in a), the renewable oil is refined prior to acidification. In some embodiments, refining the renewable oil comprises clarification, degumming, bleaching, and / or filtration. In some embodiments, in a), the transesterification comprises reacting the renewable oil with an alcohol, optionally methanol, optionally in the presence of a catalyst. In some embodiments, in c), the separation of the saturated fatty acid esters from the unsaturated fatty acid esters comprises temperature-dependent solvent extraction. In some embodiments, the saturated fatty acid esters of a) are separated into short chain saturated fatty acid esters, optionally C8-12 saturated fatty acid esters, and long chain saturated fatty acid esters, optionally C13-C22, C15-C19, or C16-C22 saturated fatty acid esters. In some embodiments, the method includes d) converting at least a portion of the short chain unsaturated fatty acid esters to short chain unsaturated fatty acids, and e) decarboxylating the short chain unsaturated fatty acids to produce saturated hydrocarbons, optionally wherein the decarboxylating comprises catalytic or gas phase decarboxylating, optionally with Ni / C catalyst or oxidative metal catalyst (e.g., silver(II)). In some embodiments, the method further includes converting the long chain fatty acid esters to long chain fatty acids, and g) decarboxylating at least a portion of the long chain fatty acids to produce saturated hydrocarbons, optionally wherein the decarboxylating comprises catalytic or gas phase decarboxylating, optionally with Ni / C catalyst or oxidative metal catalyst (e.g., silver(II)). In some embodiments, the decarboxylating comprises a catalyst selected from Mo on Al2O3, MgO on Al2O3, and Ni on Al2O3, and optionally comprises a single-stage continuous process and / or subcritical water. In some embodiments, the ethenolysis optionally comprises a catalyst selected from tungsten, molybdenum, rhenium, and ruthenium. In some embodiments, the unsaturated fatty acid ester comprises and / or consists of long chain unsaturated fatty acid esters.In some embodiments, the method further comprises separating the alpha olefins from the short chain unsaturated fatty acid esters by oligomerization, optionally in the presence of a heterogeneous catalyst, to provide alpha olefin dimers, alpha olefin trimers, alpha olefin tetramers, and / or alpha olefin pentamers. In some embodiments, the heterogeneous catalyst is selected from metals, metal oxides, metal salts, or organic materials (e.g., organic hydroperoxides, ion exchangers, and enzymes). In some embodiments, the method further comprises isomerizing the alpha olefins, optionally in the presence of hydrogen or under inert conditions. In some embodiments, the isomerization is carried out inside a Parr reactor. In some embodiments, the temperature conditions of the isomerization reaction range from about 100°C to about 500°C, about 100°C to about 200°C, about 200°C to about 300°C, about 300°C to about 400°C, or about 400°C to about 500°C. In some embodiments, the pressure conditions of the isomerization reaction range from about 1,000 psi to about 3,000 psi, about 1,000 psi to about 2,000 psi, about 2,000 psi to about 3,000 psi, or about 1,500 psi to about 2,500 psi. In some embodiments, the heterogeneous catalyst is selected from AlCl3 and BF3. In some embodiments, the method further comprises combining the glycerin from a) with at least a portion of the short chain unsaturated fatty acids of e) to produce a mixture, and subjecting the mixture to glycerolysis. In some embodiments, the glycerolysis produces short chain unsaturated acyl-glycerides. In some embodiments, the glycerolysis is base catalyzed, and optionally the catalyst is a methoxide selected from sodium methoxide, potassium methoxide, lithium methoxide, zinc methoxide, calcium methoxide, tributyltin methoxide, magnesium methoxide, tantalum(V) methoxide, titanium(IV) methoxide, antimony(III) methoxide, germanium methoxide, copper(II) methoxide, and combinations thereof. In some embodiments, the renewable oil comprises or consists of one or more selected from seed oils, vegetable oils, and animal-derived oils.In some embodiments, the renewable oil is selected from rapeseed oil, soybean oil, castor oil, hi some embodiments, the renewable oil is derived from one or more of poultry, beef, and fish.

[0008] In an aspect, the present disclosure provides a lubricant comprising: a) a saturated hydrocarbon base oil in an amount ranging from about 50% by weight to about 70% by weight of the total weight of the lubricant, the saturated hydrocarbon base oil comprising oligomers of C14 to C18 olefin monomers, the dimers having an average carbon number ranging from 29 to 36; b) a viscosity modifier in an amount ranging from about 1% to about 30% by weight of the total weight of the lubricant, optionally in an amount of about 1.4%, about 1.80%, about 3.2%, about 4.13%, about 5.2%, about 16.25%, or about 26% by weight; c) a surfactant in an amount ranging from about 10% to about 15% by weight, optionally in an amount of about 12.3% by weight, of the total weight of the lubricant; d) a pour point depressant in an amount ranging from about 0.1 wt.% to about 1 wt.%, optionally in an amount of about 0.3 wt.%, of the total weight of the lubricant; and The present invention provides a lubricant comprising:

[0009] In some embodiments, the saturated hydrocarbon base oil has the following characteristics: a) a Noack volatility as measured by ASTM D5800 and / or CEC L-40-A-93 of less than about 14%, less than about 13%, less than about 12%, less than about 11%, less than about 10%, or less than about 9%, optionally less than about 7.4%; b) a Bromine Index, determined in accordance with D2710-09, of less than about 1000 mg Br2 / 100 g, less than about 500 mg Br2 / 100 g, or less than about 200 mg Br2 / 100 g; c) an average branching index (BI) as determined by H NMR in the range of about 22 to about 26; d) an average paraffin branching proximity (BP) as determined by C NMR in the range of about 18 to about 26; e) a viscosity index, determined in accordance with ASTM D2270, of about 125 or greater, about 130 or greater, about 135 or greater, or about 140 or greater; f) a pour point, as determined in accordance with ASTM D97, of less than about -20°C, less than about -27°C, less than about -30°C, less than about -33°C, less than about -36°C, less than about -39°C, or less than about -42°C; g) a cold crank simulated (CCS) dynamic viscosity as measured by ASTM D5293 at -35°C of less than about 1800 cP, less than about 1700 cP, less than about 1600 cP, less than about 1500 cP, less than about 1400 cP, less than about 1300 cP, less than about 1200 cP, or less than about 1100 cP; and h) a KV(100) as measured by ASTM D445-17a in the range of about 3.7 cSt to about 9.7 cSt, or about 3.7 cSt to about 4.8 cSt; Patients with one or more of the following symptoms may develop:

[0010] In some embodiments, the saturated hydrocarbon base oil comprises SynNova 4 in an amount ranging from about 50% to about 60% by weight of the total weight of the lubricant, and SynNova 9 in an amount ranging from about 3% to about 7% by weight of the total weight of the lubricant. In some embodiments, the viscosity modifier comprises one or more of Infineum SV603 and Infineum SV261L, the surfactant comprises Infineum P6003, and the pour point depressant comprises Infineum V385.

[0011] In some embodiments, the lubricant is a) a saturated hydrocarbon base oil comprising SynNova 4 in an amount ranging from about 56% to about 57% by weight of the total weight of the lubricant, and SynNova 9 in an amount ranging from about 4.5% to about 5.5% by weight of the total weight of the lubricant; b) a viscosity modifier comprising Infineum SV603 in an amount ranging from about 25.5% to about 26.5% by weight of the total weight of the lubricant; c) a surfactant, comprising Infineum P6003 in an amount ranging from about 12% by weight to about 13% by weight of the total weight of the lubricant; d) a pour point depressant comprising Infineum V385 in an amount ranging from about 0.2% to about 0.4% by weight of the total weight of the lubricant; Includes. [Brief description of the drawings]

[0012] The drawings illustrate generally, by way of example, but not by way of limitation, various embodiments discussed in the present document.

[0013] [Figure 1] FIG. 1 shows a flow chart depicting non-limiting pathways for the formation of renewable alpha olefins, renewable diesel, synthetic gasoline, and unsaturated acyl-glycerides from vegetable oils. [Diagram 2] 1 shows a gas chromatography (GC) spectrum of a base oil prepared by the method of the present disclosure. Carbon assignment is based on the oligomerization of C16 alpha olefins (AO). [Diagram 3] 1 shows images of the process of degumming soybean oil. [Figure 4] 1 shows an image of refined soybean oil. [Diagram 5] 1 shows images of the acid hydrolysis of oil during the process. [Figure 6] An image of the oil after hydrolysis is shown. [Figure 7] 1 shows an image of a fatty acid oxidative decarboxylation reactor. [Figure 8] 1 shows an image of the ethenolysis reactor. [Figure 9] 1 shows a gas chromatography (GC) spectrum of 1-decene yield. [Figure 10] 1 shows a gas chromatography (GC) spectrum for the ethenolysis of methyl oleate. [Figure 11]1 shows a gas chromatography (GC) spectrum for the ethenolysis of oleic acid. [Figure 12] FIG. 1 shows a flow chart illustrating non-limiting pathways for the formation of renewable alpha olefins, renewable diesel, synthetic gasoline, and unsaturated acyl-glycerides from vegetable oils involving the conversion of soybean to fatty acid esters using transesterification as a method to separate glycerin and provide pre-ethenolysis materials. [Figure 13] 4 shows a gas chromatogram of a soybean oil sample. [Figure 14] 1 shows a gas chromatogram of a product sample resulting from the transesterification of a soybean oil sample. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] definition Reference will now be made in detail to certain embodiments of the disclosed subject matter, examples of which are illustrated in part in the accompanying drawings. While the disclosed subject matter will be described in conjunction with the enumerated claims, it will be understood that the illustrated subject matter is not intended to limit the scope of the claims to the disclosed subject matter.

[0015] As used in the preceding paragraph and throughout the remainder of the specification, 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. All patents and publications referenced herein are incorporated by reference in their entirety.

[0016] Values ​​expressed in range format should be interpreted in a flexible manner to include not only the numerical values ​​explicitly recited as the limits of the range, but also all individual numerical values ​​or subranges subsumed within the range as if each numerical value and subrange were explicitly recited. For example, the range "about 0.1% to about 5%" or "about 0.1% to 5%" should be interpreted to include not only just about 0.1% to about 5%, but also the individual values ​​(e.g., 1%, 2%, 3%, and 4%) and subranges within the range recited (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%). The statement "about X to Y" has the same meaning as "about X to about Y" unless otherwise indicated. Similarly, the statement "about X, Y, or about Z" has the same meaning as "about X, about Y, or about Z" unless otherwise indicated.

[0017] As used herein, the terms "a," "an," or "the" are used to include one or more, unless the context clearly indicates otherwise. The term "or" is used to refer to an open-ended "or," unless otherwise indicated. The statement "at least one of A and B" has the same meaning as "A, B, or A and B." In addition, it is understood that terms or terminology used herein, unless otherwise defined, are for descriptive purposes only and not for limiting purposes. The use of section headings is intended to aid in the reading of this specification and should not be construed as limiting, and information associated with a section heading may occur within or outside that section. Commas may be used as left or right decimal separators or digit separators, e.g., "0.000,1" is equivalent to "0.0001." All publications, patents, and patent documents referenced herein are incorporated by reference in their entirety, as if each were individually incorporated by reference. In the event of inconsistent usage between this specification and those documents incorporated by reference, the usage in the incorporated references should be considered complementary to the usage in this specification, and in the event of any irreconcilable discrepancies, the usage in this specification will take precedence.

[0018] In the methods of manufacturing described herein, acts may be performed in any order unless a temporal or operational order is explicitly recited. Moreover, specified acts may be performed simultaneously unless explicit claim language recites that they are performed separately. For example, a claimed act of doing X and a claimed act of doing Y may be performed simultaneously in a single operation, and the resulting process would be within the literal scope of the claimed process.

[0019] The term "about" as used herein can allow for a degree of variation in a stated value or range, for example, within 10%, within 5%, or within 1% of a stated limit of a stated value or range.

[0020] As used herein, the term "substantially" refers to at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or a majority of at least about 99.999% or more.

[0021] The term "organic group" as used herein refers to any carbon-containing functional group, including, but not limited to, oxygen-containing groups such as alkoxy groups, aryloxy groups, aralkyloxy groups, oxo (carbonyl) groups, carboxyl groups including carboxylic acids, carboxylates, and esters, sulfur-containing groups such as alkyl and aryl sulfide groups, and other heteroatom-containing groups. Non-limiting examples of organic groups include OR, OOR, OC(O)N(R), CN, CF, OCF, R, C(O), methylenedioxy, ethylenedioxy, N(R), SR, SOR, SO, SO, N(R), SO, C(O)R, C(O)C(O)R, C(O)CHC(O)R, C(S)R, C(O)OR, OC(O)R, C(O)N(R), OC(O)N(R), C(S)N(R), (CH) 0-2 N(R)C(O)R, (CH2) 0-2Examples include N(R)N(R), N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)CON(R), N(R)SOR, N(R)SON(R), N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R), N(R)C(S)N(R), N(COR)COR, N(OR)R, C(=NH)N(R), C(O)N(OR)R, or C(=NOR)R, where R can be hydrogen (in examples containing other carbon atoms) or a carbon-based moiety, which can itself be further substituted.

[0022] As used herein, the term "composition" refers to a chemical, compound, or substance, or a mixture or combination of two or more such chemicals, compounds, or substances.

[0023] The term "solvent" as used herein refers to a liquid that can dissolve a solid, another liquid, or a gas. Non-limiting examples of solvents are silicones, organic compounds, water, alcohols, ionic liquids, and supercritical fluids.

[0024] As used herein, the term "room temperature" refers to a temperature between about 15°C and about 28°C.

[0025] As used herein, the term "standard temperature and pressure" refers to 20° C. and 101 kPa.

[0026] As used herein, the term "long chain free fatty acids" refers to unmodified free fatty acids that have either been hydrolyzed and separated from their glycerol backbone or are still in the acyl-glyceride form.

[0027] As used herein, the term "short chain free fatty acid" refers to unmodified free fatty acids in which the free fatty acids or free fatty acid moieties of acyl-glycerides have either been subjected to ethenolysis or are in the form of degraded molecules and separated from their glycerol backbone.

[0028] The term "olefin" as used herein refers to a hydrocarbon containing at least one carbon-carbon double bond. For example, according to aspects disclosed herein, the olefin may include a hydrocarbon chain length of C14 to C18 and may have the double bond at the end (primary position) or at an internal position (internal olefin) of the hydrocarbon chain (alpha-olefin). In one embodiment, the olefin is a mono-olefin, meaning that the olefin contains only a single double bond group.

[0029] The term "dimer" as used herein refers to a molecule formed by the combination of two monomers via a chemical process, where the monomers can be the same or different types of monomer units. Dimers can be formed by chemical reactions and / or other types of bonds between the monomers. In one embodiment, a dimer is the product of oligomerization between two olefin monomers.

[0030] The term "dimer total average carbon number" is used herein to refer to the total number of carbons in a dimer. Thus, a "C29-C36" dimer referred to herein is a dimer having a total average number of carbon atoms in the range of 29 to 36.

[0031] The term "trimer total average carbon number" is used herein to refer to the total number of carbons in a trimer. Thus, a "C45-C52" trimer referred to herein is a dimer having a total average number of carbon atoms in the range of 45-52.

[0032] The term "tetramer total average carbon number" is used herein to refer to the total number of carbons in a tetramer. Thus, a "C61-C68" tetramer as referred to herein is a dimer having a total average number of carbon atoms ranging from 61 to 68.

[0033] The term "pentamer total average carbon number" is used herein to refer to the total number of carbons in a pentamer. Thus, a "C77-C84" pentamer referred to herein is a dimer having a total average number of carbon atoms in the range of 77-84.

[0034] Detailed Description Method for preparing base oil In one aspect, the present disclosure provides a method for preparing base oils, including, but not limited to, hydrocarbon base oils such as long and short chain alpha olefins, saturated hydrocarbons, and acyl-glycerides, and lubricants containing the same.

[0035] In some embodiments, the process for preparing long chain alpha olefins includes oligomerization, isomerization, and hydrogenation of long chain alpha and internal olefins to provide a viable alternative to petroleum based lubricants. In some embodiments, when this product is combined with certain additive types, the resulting product may be capable of replacing synthetic petroleum based feedstocks when producing lubricant base stocks and / or base oils.

[0036] In some embodiments, the unsaturated and saturated free fatty acid by-products provide a synthetic gasoline replacement and renewable diesel via decarboxylation. In some embodiments, a secondary process for forming value-added acyl-glycerides from short chain free fatty acids that may be useful as a synthetic gasoline replacement is also described along with the overall process.

[0037] One relatively new approach to using renewable oils is to combine technologies for producing valuable lubricant base stocks with commercially available fuels such as renewable diesel and synthetic gasoline. Converting a percentage of the feedstock into value-added by-products such as alpha olefins for lubricant production, and then selectively separating a percentage for further conversion to biofuels such as renewable diesel and synthetic gasoline, can help diversify production. Renewable oils, which contain a combination of saturated and unsaturated free fatty acids, are ideal substrates for this process.

[0038] Using novel separation techniques, the saturated free fatty acids can be sequestered and processed separately into renewable or "green" diesel. Green diesel (also called renewable hydrocarbon diesel, hydrotreated vegetable oil or HVO) is essentially chemically the same as petroleum-derived diesel, but green diesel has recently been made from living biomass. Unlike biodiesel, which is an ester and has different chemical properties than petroleum diesel, green diesel is composed of long-chain hydrocarbons and may be blended with petroleum diesel in any proportion for use as a transportation fuel.

[0039] The unsaturated free fatty acids are then advanced to the production of both alpha and internal olefins as well as synthetic gasoline. Traditionally, olefins are produced from non-biological precursors, but one alternative to petroleum-based alpha olefins is the conversion of unsaturated fatty acids to linear alpha olefins. This can be accomplished through a process called "ethenolysis," which involves reacting the molecule ethylene with the double bonds on the carbon chain of the fatty acid molecule. The hydrocarbon chain is left with a terminal double bond on the last carbon in the chain, while the free fatty acids are converted to smaller chains of designated moieties. In the example of oleic acid (C18:1), the by-products are 1-decene (1-C10) and C10 fatty acids. The remaining fatty acids can be decarboxylated to form another alpha olefin, 1-nonene (1-C9), which can then be used in the synthesis of synthetic gasoline.

[0040] Aspects of the present disclosure also relate to lubricants that include non-fossil hydrocarbon base oils and have improved properties over petroleum-based lubricants.

[0041] Recent patents show various approaches to making petroleum substitutes for fuels and lubricants. Two patent publications, US 2020 / 0165538 A1 and US 10961167 B2, each of which is incorporated herein by reference in its entirety, detail the conversion of original alpha-olefins by oligomerization, hydrogenation, and isomerization to make lubricant base stocks. Both patents describe precursor alpha-olefins derived from petroleum sources. A third patent, US 9862906 B2, which is incorporated herein by reference in its entirety, discusses a similar process and product, but utilizes terpenes as feedstocks. In their current embodiments, these patents do not claim to use olefins derived from renewable sources.

[0042] Ethenolysis, a metathesis reaction applied to fatty acid esters, has been reported in many publications and scientific reviews and is well known in organic chemistry. It is carried out in the presence of a catalyst and consists of exchanging alkylidene groups between two olefins, in this case unsaturated free fatty acids and ethylene. Patent publication US 2006 / 0079704 A1, published in 2006 and incorporated herein by reference in its entirety, discusses the use of ethenolysis on triglycerides to produce alpha olefins. The process describes the catalytic mechanism of the reaction and various by-products, but does not discuss the use of the primary product alpha olefins or the by-product glycerol.

[0043] The use of glycerol-esterification or glycerolysis as a pretreatment for methyl ester (biodiesel) production has become popular over the past decade. Its ability to reduce free fatty acid levels to less than 0.2 wt% is attractive for methyl ester production, since the free fatty acids neutralize the catalyst in downstream reactions. However, utilizing glycerolysis as a means to treat approximately 100 wt% free fatty acid by-product streams using recycled glycerol is a new approach that requires the same chemical mechanisms, but significantly different reaction conditions and chemical charges.

[0044] The patents discussed above do not address the use of any of the by-products generated during processing to help reduce the carbon intensity (CI) of the overall process. By staging the sequence of operations according to the disclosed patents, the claims of the above-referenced patents can be synergistically improved to reduce the energy and logistical constraints of these independent technologies. In addition, by creating several oil substitutes in a single process, it becomes possible to claim government incentives such as Renewable Identification Numbers (RINs) and, in the case of California, the Low Carbon Fuel Standard. By utilizing the disclosed process, California can currently significantly reduce operating costs and address carbon intensity by collecting state and federal incentive funds.

[0045] Renewable oil refining In one aspect, the present disclosure provides a method for preparing base oils from renewable oils.Non-limiting examples of base oils that can be prepared by the method of the present disclosure include hydrocarbon base oils such as long-chain and short-chain alpha olefins, saturated hydrocarbons, and acyl-glycerides.

[0046] In some embodiments, the method for preparing the base oil and / or base stock includes clarification, degumming, purification, and / or refining of renewable oils. In some embodiments, the processes described herein can utilize a wide range of renewable oils, including but not limited to seed and vegetable oils (rapeseed, soybean, castor, etc.), as well as animal-derived oils (poultry, beef, fish, etc.). These oils will be known collectively as "renewable oils" for purposes of this disclosure. In some embodiments, the renewable oil comprises triglycerides. In some embodiments, the renewable oil comprises and / or consists of soybean oil. Soybean oil can include C16-C22 fatty acids, including triglycerides including C16-C22 fatty acids, and can include about 20% oleic acid (C18:1) and about 55% linoleic acid (C18:2).

[0047] In some embodiments, refining does not optimize the filter aid to oil ratio, but rather produces an oil precursor that remains of sufficiently high quality throughout the lubricant process. The final material is then free of debris and impossible to separate via laboratory centrifugation.

[0048] In some embodiments, the refining process of renewable oils includes, but is not limited to, clarification, degumming, bleaching, and filtration. In some embodiments, refining provides renewable oils that are free or substantially free of water, insoluble matter, and / or unsaponifiable matter (MIU).

[0049] In some embodiments, the purification and / or refining of renewable oils involves a degumming step. In a non-limiting example, the degumming step involves removing phospholipids and other gums using water and an acid. Non-limiting examples of acids include citric acid. In some embodiments, the acid (e.g., citric acid) is at a concentration of about 1% to about 10% by weight in water, or about 4% to about 6% by weight. In some embodiments, the acid (e.g., citric acid) is at a concentration of about 5% by weight in water. In some embodiments, the degumming step involves heating a mixture including renewable oil, water, and acid at a temperature ranging from about 50° C. to about 100° C., about 60° C. to about 70° C., or about 65° C. In some embodiments, the free fatty acids are typically neutralized using a base such as sodium hydroxide, which can produce a soapstock by-product stream.

[0050] In some embodiments, refining includes a bleaching step to remove color-bodies, polymeric compounds, free fatty acids, soaps, and / or trace metals. In some embodiments, the bleaching step may be used to deodorize the oil and / or remove potential oxidation products.

[0051] In some embodiments, refining comprises clarification. In some embodiments, clarification comprises separating solids from an oil from a renewable source to provide a clarified oil. In some embodiments, separating solids comprises filtering the oil to provide a particulate-free or substantially particulate-free liquid. In some embodiments, filtering removes insoluble components (e.g., debris such as plastics, biomass particulates, and / or other impurities) from the oil. Non-limiting examples of suitable filters include commercially available filter aids such as diatomaceous earth, filter paper (e.g., 50 microns), cellulose filter aids, and filter bags with a combination of filter pore sizes.

[0052] Transesterification of renewable oils to produce fatty acid esters and glycerol In one aspect, the method includes transesterification of a renewable oil. In some embodiments, the renewable oil includes triglycerides. In some embodiments, the method includes transesterifying the renewable oil to produce a mixture including 1) a fatty acid ester mixture including saturated and unsaturated fatty acid esters, and 2) glycerin and / or glycerol. In some embodiments, the renewable oil is refined (e.g., clarified and / or degummed) prior to transesterification.

[0053] As would be understood by one of ordinary skill in the art, any transesterification method is contemplated by the present disclosure. In a non-limiting example, renewable oil is dissolved in alcohol (e.g., methanol) and, optionally, transesterified under catalytic conditions to produce glycerin and / or glycerol and fatty acid esters (e.g., fatty acid methyl esters). Non-limiting examples of catalytic conditions useful for transesterification include acid catalysts (e.g., sulfonic acid, sulfuric acid, and trifluoroacetic acid), base catalysts (sulfonic acid and sulfuric acid), and enzyme catalysts (e.g., lipase). In some embodiments, the catalyst is a metal (e.g., potassium metal). In a non-limiting example, the metal can form metal alkoxides and / or alkoxylates (e.g., potassium methoxylate) with the alcohol. In some embodiments, the catalyst is added in an amount ranging from about 1% (w / vol) to about 5% (w / vol), or in an amount of about 1% (w / vol). In some embodiments, the transesterification is carried out in the absence of a catalyst. Non-limiting examples of alcohols include methanol, ethanol, and n-propanol, in some embodiments, the alcohol comprises and / or consists of methanol.

[0054] In some embodiments, transesterification involves reacting a renewable oil (e.g., a clarified and / or degummed renewable oil) with an alcohol (e.g., methanol), optionally in the presence of a catalyst. In some embodiments, the reaction further involves adding water and an organic solvent (e.g., dichloromethane, n-hexane, ethyl acetate) to provide an organic fraction comprising free fatty acid esters from the optionally refined (e.g., clarified and / or degummed) renewable oil, and an aqueous fraction comprising glycerin and / or glycerol (e.g., glycerin components).

[0055] In some embodiments, transesterification of renewable oil (e.g., clarified and / or degummed renewable oil) comprises reacting the renewable oil with an alcohol (e.g., methanol), optionally in the presence of a catalyst. In some embodiments, the reaction further comprises adding water and an organic solvent (e.g., dichloromethane, n-hexane, ethyl acetate) to provide an organic fraction and an aqueous fraction, the organic fraction comprising the free fatty acid ester mixture and the aqueous fraction comprising glycerin. In some embodiments, the transesterification is repeated two or more times to prepare the aqueous and organic fractions. In some embodiments, the organic fraction further comprises chemicals, compounds, and / or substances that are relatively insoluble in water.

[0056] In some embodiments, a portion of the organic solvent can be separated from the organic fraction after transesterification to provide oil-derived free fatty acid esters. In some embodiments, separating at least a portion of the organic solvent comprises heating the organic fraction to a temperature of at least about 50°C, about 55°C, about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, about 95°C, about 100°C, about 105°C, about 110°C, about 115°C, or about 120°C, exposing the organic fraction to a pressure of about 1 atmosphere or less, or both. In some embodiments, separation of the organic solvent from the organic fraction can be accomplished, for example, by rotary evaporation or a similar technique.

[0057] In some embodiments, the organic fraction comprises at least about 90% by weight fatty acid esters and about 10% by weight glycerin and / or glycerol. In some embodiments, the organic fraction comprises 90% to about 100% by weight fatty acid esters and about 0% to about 10% by weight glycerin and / or glycerol. In some embodiments, the organic fraction comprises at least about 50%, about 60%, about 70%, about 80%, or about 90% by weight fatty acid esters. In some embodiments, the organic fraction comprises about 50 to about 100%, about 60 to about 100%, about 70 to about 100%, about 80 to about 100%, about 90 to about 100%, about 60 to about 90%, or about 70 to about 80% by weight fatty acid esters.

[0058] In some embodiments, the renewable oil and alcohol are heated, optionally in the presence of a catalyst, to a temperature ranging from about 50° C. to about 150° C., from about 100° C. to about 125° C., or about 115° C.

[0059] In some embodiments, transesterification of the renewable oil comprises heating a mixture of renewable oil and alcohol at a suitable pressure. In some embodiments, the ratio of renewable oil to water ranges from about 5:1 to about 1:5, about 4:1 to about 1:4, about 3:1 to about 1:3, or about 2:1 to about 1:2, based on the total weight of the renewable oil and alcohol. In some embodiments, the ratio of renewable oil to alcohol is about 5:1, about 4:1, about 3:1, about 2:1, or about 1:1, based on the total weight of the renewable oil and alcohol.

[0060] In some embodiments, the renewable oil and alcohol are heated to a temperature ranging from about 100°C to about 350°C, from about 200°C to about 300°C, from about 250°C to about 275°C, or about 250°C, about 255°C, about 260°C, about 265°C, about 270°C, or about 275°C.

[0061] In some embodiments, transesterification of renewable oils is carried out at pressures ranging from about 500 psi to about 1000 psi, from about 700 psi to about 900 psi, or from about 800 psi to about 900 psi. In some embodiments, acidifying and / or acidulating renewable oils is carried out at pressures of about 800 psi, about 810 psi, about 820 psi, about 830 psi, about 840 psi, about 850 psi, about 860 psi, about 870 psi, about 880 psi, about 890 psi, or about 900 psi.

[0062] In some embodiments, the transesterification of the renewable oil is carried out in a reaction vessel, including but not limited to a high temperature and / or high pressure mixing reactor. In some embodiments, the reaction vessel is purged with an inert gas (e.g., nitrogen) after the renewable oil and water are added to the reaction vessel. In a non-limiting example, purging the reactor with an inert gas prevents undesirable oxidation during acidification and / or mild acidification.

[0063] In some embodiments, the method includes isolating glycerin and / or glycerol from the mixture of fatty acid esters. In some embodiments, the organic fraction is further separated into a denser organic phase and a lighter organic phase. In some embodiments, the glycerin and / or glycerol phase produced from the reaction is gravity separated to the bottom of the reactor vessel, optionally forming a portion of the denser organic phase. In some embodiments, the denser organic phase may be separated via methods such as, but not limited to, mechanical clarification or centrifugation. In some embodiments, the lighter organic phase is separated from the denser organic phase, which is composed primarily of fatty acid esters and includes glycerin and / or glycerol.

[0064] In some embodiments, transesterifying a renewable oil, optionally refined (e.g., clarified and / or degummed) renewable oil, further comprises separating at least a portion of the aqueous fraction from the organic fraction and then converting at least a portion of the fatty acid esters to glycerides (e.g., acylglycerides).

[0065] In some embodiments, the organic solvent is selected from at least one of hexane, diethyl ether, ethyl acetate, and dichloromethane. In some embodiments, the post-transesterification separation further comprises recycling a separated portion of the organic solvent for use in contacting the renewable oil (e.g., the clarified renewable oil).

[0066] In some embodiments, the glycerin and / or glycerol, as well as any alcohol (e.g., methanol), may be recycled to a downstream process known as glycerolysis.

[0067] In some embodiments, the transesterification includes heating the renewable oil (e.g., the clarified and / or degummed renewable oil) and further includes heating the renewable oil (e.g., the clarified and / or degummed renewable oil) and the alcohol. In some embodiments, the heating can be performed at a pressure of about 1 atmosphere to about 3 atmospheres, or about 1 atmosphere, 2 atmospheres, or 3 atmospheres.

[0068] In some embodiments, the glycerin and / or glycerol is dried at a temperature ranging from about 50° C. to about 200° C., or from about 100° C. to about 125° C., or about 115° C., and / or at a pressure ranging from about 40 mmHg to about 100 mmHg, or from about 50 mmHg to about 70 mmHg, or about 60 mmHg, and / or for a period ranging from about 5 minutes to about 2 hours, about 15 minutes to about 1 hour, or about 20 minutes.

[0069] In some embodiments, the fatty acid ester is dried at a temperature ranging from about 50° C. to about 200° C., or from about 100° C. to about 125° C., or about 115° C., and / or at a pressure ranging from about 40 mmHg to about 100 mmHg, or from about 50 mmHg to about 70 mmHg, or about 60 mmHg, and / or for a period ranging from about 5 minutes to about 2 hours, from about 15 minutes to about 1 hour, or about 20 minutes.

[0070] Acid hydrolysis of renewable oils to produce free fatty acids and glycerol. In some embodiments, the process includes acid hydrolysis (e.g., acidification and / or mild acidification) of a renewable oil. In some embodiments, the renewable oil includes triglycerides. In some embodiments, the method includes acidifying the renewable oil to produce a mixture including 1) a free fatty acid mixture including saturated fatty acids (e.g., free fatty acids) and unsaturated fatty acids (e.g., free fatty acids), and 2) glycerin and / or glycerol. In some embodiments, the renewable oil is refined (e.g., acidified and / or degummed) prior to acid hydrolysis (e.g., acidification and / or mild acidification).

[0071] In some embodiments, acidifying and / or mildly acidifying comprises contacting a renewable oil with an aqueous acid to provide an organic fraction comprising free fatty acids derived from the optionally refined (e.g., clarified and / or degummed) renewable oil, and an aqueous fraction containing the acid and a glycerol phase (glycerin component).

[0072] In some embodiments, acidifying and / or mildly acidifying a renewable oil (e.g., a clarified and / or degummed renewable oil) comprises contacting the renewable oil with an aqueous acid to form an organic fraction and an aqueous fraction, where the organic fraction comprises a free fatty acid mixture and the aqueous fraction comprises glycerin. In some embodiments, the acidification is repeated two or more times to prepare the aqueous and organic fractions. In some embodiments, the organic fraction further comprises chemicals, compounds, and / or substances that are relatively insoluble in water.

[0073] In some embodiments, the acid comprises at least one of H2SO4, HCl, H2PO4, and H3PO4. In some embodiments, the acid is added at about 1% to about 10% by weight, or about 3% to about 5% by weight. In some embodiments, the acid is added at about 4% by weight. In some embodiments, the acid is optionally H2PO4 at about 4% by weight. In some embodiments, the acid is optionally H2SO4 at about 4% by weight. In some embodiments, the organic fraction comprises at least about 90% by weight free fatty acids and about 10% by weight glycerin and / or glycerol. In some embodiments, the organic fraction comprises 90% to about 100% by weight free fatty acids and about 0% to about 10% by weight glycerin and / or glycerol. In some embodiments, the organic fraction comprises at least about 50%, about 60%, about 70%, about 80%, or about 90% by weight free fatty acids. In some embodiments, the organic fraction comprises about 50 to about 100% by weight, about 60 to about 100% by weight, about 70 to about 100% by weight, about 80 to about 100% by weight, about 90 to about 100% by weight, about 60 to about 90% by weight, or about 70 to about 80% by weight of free fatty acids.

[0074] In some embodiments, after the renewable oil is further contacted with the aqueous acid, the mixture is heated to a temperature ranging from about 50° C. to about 150° C., from about 100° C. to about 125° C., or about 115° C.

[0075] In some embodiments, acidifying and / or mildly acidifying the renewable oil comprises heating a mixture of renewable oil and water at a suitable pressure. In some embodiments, the ratio of renewable oil to water ranges from about 5:1 to about 1:5, about 4:1 to about 1:4, about 3:1 to about 1:3, or about 2:1 to about 1:2, based on the total weight of the renewable oil and water. In some embodiments, the ratio of renewable oil to water is about 5:1, about 4:1, about 3:1, about 2:1, or about 1:1, based on the total weight of the renewable oil and water.

[0076] In some embodiments, the mixture is heated to a temperature ranging from about 100°C to about 350°C, from about 200°C to about 300°C, from about 250°C to about 275°C, or about 250°C, about 255°C, about 260°C, about 265°C, about 270°C, or about 275°C.

[0077] In some embodiments, the acidification and / or mild acidification of the renewable oil is carried out at a pressure ranging from about 500 psi to about 1000 psi, from about 700 psi to about 900 psi, or from about 800 psi to about 900 psi. In some embodiments, the acidification and / or mild acidification of the renewable oil is carried out at a pressure of about 800 psi, about 810 psi, about 820 psi, about 830 psi, about 840 psi, about 850 psi, about 860 psi, about 870 psi, about 880 psi, about 890 psi, or about 900 psi.

[0078] In some embodiments, the acidification and / or mild acidification of renewable oil is carried out in a reaction vessel, including but not limited to a high temperature and / or high pressure mixing reactor. In some embodiments, the reaction vessel is purged with an inert gas (e.g., nitrogen) after the renewable oil and water are added to the reaction vessel. In a non-limiting example, purging the reactor with an inert gas prevents undesirable oxidation during acidification and / or mild acidification.

[0079] In some embodiments, the method includes isolating glycerin and / or glycerol from the mixture of fatty acids. In some embodiments, the organic fraction is further separated into a denser organic phase and a lighter organic phase. In some embodiments, the glycerin and / or glycerol phase produced from the reaction is gravity separated to the bottom of the reactor vessel, optionally forming a portion of the denser organic phase. In some embodiments, the denser organic phase may be separated via methods such as, but not limited to, mechanical clarification or centrifugation. In some embodiments, the lighter organic phase is composed primarily of free fatty acids and is separated from the denser organic phase, which is a mixture of acid, water, and glycerin.

[0080] In some embodiments, acidifying the renewable oil, optionally refined (e.g., clarified and / or degummed) renewable oil, further comprises separating at least a portion of the aqueous fraction from the organic fraction and then converting at least a portion of the free fatty acids to glycerides (e.g., acylglycerides).

[0081] In some embodiments, acidifying the renewable oil (e.g., clarified and / or degummed renewable oil) comprises contacting the material with an aqueous acid and an organic solvent to provide an organic fraction comprising a mixture of free fatty acids, and an aqueous fraction. In some embodiments, a portion of the organic solvent can be separated from the organic fraction after acidification separation to provide an acidified composition comprising free fatty acids derived from the oil. In some embodiments, separating at least a portion of the organic solvent comprises heating the organic fraction to a temperature of at least about 50° C., about 55° C., about 60° C., about 65° C., about 70° C., about 75° C., about 80° C., about 85° C., about 90° C., about 95° C., about 100° C., about 105° C., about 110° C., about 115° C., or about 120° C., exposing the organic fraction to a pressure of about 1 atmosphere or less, or both. In some embodiments, separation of the organic solvent from the organic fraction can be accomplished, for example, by rotary evaporation or a similar technique.

[0082] In some embodiments, the organic solvent is selected from at least one of hexane, diethyl ether, ethyl acetate, and dichloromethane. The organic solvent can be obtained from the acidification separation described above. In some embodiments, the acidification separation further comprises recycling a separated portion of the organic solvent for use in contacting with the renewable oil (e.g., the clarified renewable oil). In some embodiments, the aqueous acid comprises at least one of H2SO4, HCl, and H3PO4.

[0083] In some embodiments, acidifying the renewable oil (e.g., clarified and / or degummed renewable oil) comprises contacting the renewable oil with an aqueous acid, methanol, and glycerol. In some embodiments, the methanol and glycerol may be recycled to a downstream process known as glycerolysis.

[0084] In some embodiments, acidifying the clarified renewable oil further comprises heating the renewable oil (e.g., the clarified and / or degummed renewable oil) and the aqueous acid. In some embodiments, heating the material can be performed at a pressure of about 1 atmosphere to about 3 atmospheres, or at about 1 atmosphere, 2 atmospheres, or 3 atmospheres.

[0085] In some embodiments, the glycerin and / or glycerol is dried at a temperature ranging from about 50° C. to about 200° C., or from about 100° C. to about 125° C., or about 115° C., and / or at a pressure ranging from about 40 mmHg to about 100 mmHg, or from about 50 mmHg to about 70 mmHg, or about 60 mmHg, and / or for a period ranging from about 5 minutes to about 2 hours, about 15 minutes to about 1 hour, or about 20 minutes.

[0086] In some embodiments, the fatty acids (e.g., free fatty acids) are dried at a temperature ranging from about 50° C. to about 200° C., or from about 100° C. to about 125° C., or about 115° C., and / or at a pressure ranging from about 40 mmHg to about 100 mmHg, or from about 50 mmHg to about 70 mmHg, or about 60 mmHg, and / or for a period ranging from about 5 minutes to about 2 hours, about 15 minutes to about 1 hour, or about 20 minutes.

[0087] Solvent extraction and separation of saturated and unsaturated fatty acids and / or saturated and unsaturated fatty acid esters In one aspect, the process includes purifying and / or separating the fatty acids (e.g., free fatty acids) produced during acid hydrolysis into a fraction containing saturated free fatty acids and a fraction containing unsaturated free fatty acids.

[0088] In another aspect, the process includes purifying and / or separating the fatty acid esters produced during transesterification into a fraction containing saturated fatty acid esters and a fraction containing unsaturated fatty acid esters.

[0089] In some embodiments, an organic solvent, such as but not limited to acetone, is used to solubilize the unsaturated free fatty acids and / or unsaturated fatty acid esters while precipitating the saturated portion at low temperature. In some embodiments, the degree of purification depends on the time, temperature, and / or stoichiometric equivalent of organic solvent (e.g., acetone) to the saturated free fatty acids and / or saturated fatty acid esters. In some embodiments, separation of saturated fatty acids from unsaturated fatty acids and / or separation of saturated fatty acid esters from unsaturated fatty acid esters comprises a temperature-dependent solvent extraction.

[0090] In some embodiments, the reaction was carried out at a temperature of about 55°C, about 60°C, or about 65°C.

[0091] In some embodiments, the temperature was varied from -5 to +5 degrees Celsius during the precipitation reaction.

[0092] In some embodiments, the reactor mixture is stirred slowly. In some embodiments, the mixture is static and not mixed. In some embodiments, the reactor mixture is stirred for about 15 minutes, about 20 minutes, or about 25 minutes. In some embodiments, the time during cooling and precipitation is varied to maximize the solubility and ultimate purification of the saturates from the unsaturated free fatty acid stream and / or the saturates from the unsaturated fatty acid ester stream. In some embodiments, the amount of solvent is varied from a 1:1 stoichiometric equivalent ratio of organic solvent (e.g., acetone) to saturated free fatty acid up to a maximum of 100:1 stoichiometric equivalent ratio of organic solvent (e.g., acetone) to saturated free fatty acid, and / or from a 1:1 stoichiometric equivalent ratio of organic solvent (e.g., acetone) to saturated fatty acid ester up to a maximum of 100:1 stoichiometric equivalent ratio of organic solvent (e.g., acetone) to saturated fatty acid ester.

[0093] In some embodiments, once the reaction is complete, the reactor contents are cooled in a beaker to about -5°C, about -4°C, about -3°C, about -2°C, about -1°C, about 0°C, about 1°C, about 2°C, about 3°C, about 4°C, or about 5°C. In some embodiments, the reactor contents are cooled in an ethylene glycol and water bath. In some embodiments, the reactor contents are cooled for about 24 hours.

[0094] In some embodiments, the result is two phases, including a solid precipitate containing highly concentrated levels of saturated free fatty acids and / or saturated fatty acid esters, and a liquid phase containing a mixture of unsaturated free fatty acids and / or unsaturated fatty acid esters and acetone. In some embodiments, the solid phase produced from the reaction is separated from the liquid phase through methods including, but not limited to, filtration and / or centrifugation. In some embodiments, the organic solvent (e.g., acetone) is removed using a rotary evaporator, optionally under vacuum.

[0095] In some embodiments, the saturated free fatty acids are further separated into long chain saturated fatty acids (e.g., long chain saturated free fatty acids) and short chain saturated fatty acids (e.g., short chain saturated free fatty acids). In non-limiting embodiments, the long chain saturated fatty acids comprise and / or consist of C13-C22, C15-C19, or C16-C22 fatty acids. In non-limiting embodiments, the short chain saturated fatty acids comprise and / or consist of C6-C12 or C8-C12 fatty acids.

[0096] In some embodiments, the saturated fatty acid esters are further separated into long chain saturated fatty acid esters and short chain saturated fatty acid esters. In non-limiting embodiments, the long chain saturated fatty acid esters comprise and / or consist of C13-C22, C15-C19, or C16-C22 fatty acid esters. In non-limiting embodiments, the short chain saturated fatty acid esters comprise and / or consist of C6-C12 or C8-C12 fatty acid esters.

[0097] Decarboxylation of saturated fatty acids In one aspect, the method includes decarboxylation of saturated fatty acids (e.g., long chain saturated free fatty acids). In non-limiting embodiments, the long chain saturated fatty acids include and / or consist of C13-C22, C15-C19, or C16-C22 fatty acids. In some embodiments, decarboxylation of long chain saturated fatty acids (e.g., long chain saturated free fatty acids) provides saturated hydrocarbons. In some embodiments, the decarboxylated long chain saturated fatty acids (e.g., saturated hydrocarbons) are useful as renewable diesel precursors. In some embodiments, the process includes preparing a renewable diesel. In some embodiments, following separation of the saturates of the long chain saturated free fatty acids, the process includes removal of the terminal carboxyl functionality (e.g., decarboxylation). In some embodiments, the long chain saturated fatty acids (e.g., long chain saturated free fatty acids) are decarboxylated to produce renewable diesel fuel.

[0098] In some embodiments, the saturated fatty acid esters can be converted (e.g., by saponification) to saturated fatty acids and then decarboxylated. Non-limiting examples of methods for converting saturated fatty acid esters to saturated fatty acids include treatment with aqueous alkali (e.g., NaOH).

[0099] Non-limiting examples of catalysts useful for decarbonation include Mo on Al2O3, MgO on Al2O3, and Ni on Al2O3. Non-limiting examples have used catalysts including, but not limited to, Mo on Al2O3, MgO on Al2O3, and Ni on Al2O3 in the decarbonation in a single-stage continuous process, and / or using subcritical water. In some embodiments, linear hydrocarbons are obtained via decarbonation and hydrogenation reactions where no hydrogen is added. The Mo / Al2O3 catalyst was found to exhibit a higher degree of decarbonation and liquid yield compared to the other two tested catalysts (MgO / Al2O3, Ni / Al2O3) under the conditions of maximizing 375°C, 4 hours space-time, and 5:1 water to oleic acid volume ratio. The resulting liquid product was kerosene (0.78-0.82 kg / m 3 and 46.2 MJ / kg), jet fuel (0.78-0.84 kg / m 3 and 43.5 MJ / kg), and diesel fuel (0.80–0.96 kg / m 3 and 44.8 MJ / kg) with similar density to commercial fuels (0.85 kg / m at 15.6 °C). 3 ) and high heating value (44.7 MJ / kg). Reaction conditions including temperature, water-to-feed volume ratio, and space-time were maximized over the Mo / Al2O3 catalyst. Characterization of the spent catalyst showed that a significant amount of amorphous carbon deposited on the catalyst could be removed by simple carbon combustion in air, recycling and reusing the catalyst.

[0100] In some embodiments, residual solvent is removed by flash distillation under vacuum pressure prior to decarbonation and loss of CO2.

[0101] In some embodiments, the carbon chain length composition of the long chain saturated free fatty acids ranges from C13 to C22, C15 to C19, or C16 to C22, depending on the characteristics of the input oil. The mass percent of saturated free fatty acids recovered also depends on the characteristics of the input oil.

[0102] In some embodiments, saturated free fatty acids are decarboxylated to remove the terminal carboxylic acid functionality from the saturated carbon chain. In some embodiments, the reaction is carried out in the presence of a non-noble metal catalyst such as Ni / C, Pt / C, etc., followed by hydrogenation.

[0103] In some embodiments, the gas-phase decarboxylation of hydrolyzed free fatty acids (FFAs) was investigated in two fixed-bed reactors by varying reaction parameters such as temperature, FFA feed rate, and H2 to FFA molar ratio. 18 , as well as a little C 16 , C 20 , C 22 , and C 24 The FFA containing FFA was fed to the boiling zone, evaporated, carried by hydrogen flow at a rate of 0.5-20 ml / min, and reacted with 5% Pd / C catalyst in the reactor.

[0104] Ethenolysis In one aspect, the method includes subjecting an unsaturated fatty acid (e.g., unsaturated free fatty acid) and / or an unsaturated fatty acid ester to ethenolysis. In some embodiments, ethenolysis of an unsaturated fatty acid (e.g., unsaturated free fatty acid) provides a mixture comprising i) an alpha olefin and ii) a short chain unsaturated fatty acid. In some embodiments, ethenolysis of an unsaturated fatty acid ester provides a mixture comprising i) an alpha olefin and ii) a short chain unsaturated fatty acid ester. In some embodiments, the short chain unsaturated fatty acid comprises and / or consists of a C8-C12 short chain unsaturated fatty acid. In some embodiments, the short chain unsaturated fatty acid ester comprises and / or consists of a C8-C12 short chain unsaturated fatty acid ester. In some embodiments, the unsaturated fatty acid (e.g., unsaturated free fatty acid) is separated from the saturated free fatty acid in the free fatty acid mixture prepared during acidification. In some embodiments, the unsaturated fatty acid ester is separated from the saturated fatty acid ester in the fatty acid ester mixture prepared during transesterification. In some embodiments, the unsaturated free fatty acids comprise and / or consist of long-chain unsaturated free fatty acids. In some embodiments, the unsaturated fatty acid esters comprise and / or consist of long-chain unsaturated fatty acid esters. In a non-limiting example, following separation of the saturated and unsaturated long-chain fatty acids (e.g., saturated and unsaturated long-chain free fatty acids) and / or saturated and unsaturated long-chain fatty acid esters, a portion of the long-chain unsaturated free fatty acids and / or unsaturated long-chain fatty acid esters contained within the liquid phase after solvent extraction is sequestered for further processing into terminal alpha olefins and unsaturated short-chain free fatty acids and / or unsaturated short-chain fatty acid esters.

[0105] In one aspect, the olefin metathesis reaction, commonly known as ethenolysis, is an equilibrium reaction. In some embodiments, the olefin metathesis reaction can occur in either homogeneous and / or heterogeneous phases in the presence of a wide variety of catalysts, typically based on transition metals from Groups IVA-VIII, including, but not limited to, tungsten, molybdenum, rhenium, and ruthenium.

[0106] Various types of catalysts have been described to carry out this transformation. In some embodiments, the first systems based on tungsten and tetraalkyltins, e.g., WCl / SnMea, were homogeneous. In some embodiments, this was followed by heterogeneous systems based on rhenium activated by tetraalkyltins. In some embodiments, ruthenium-based complexes themselves rapidly proved to be of great interest due to their tolerance of a wide range of functional groups. In some embodiments, their properties, often combined with high activity, explain their great development in the field of polymer synthesis and organic synthesis. In some embodiments, their use to catalyze the metathesis of vegetable oils has been widely studied. The following references can be provided: International Patent Application No. WO-A-96 / 04289 (R. Grubbs et al.) describes the ethenolysis of methyl oleate. In the presence of excess ethylene (100 psi), the reaction produces a mixture of decene (43%) and methyl decanoate. Additional non-limiting examples of catalysts include Grubbs' catalysts (ruthenium carbene complexes) and Schrock's alkylidene catalysts (molybdenum(VI) and tungsten(VI) based catalysts). In some embodiments, the catalyst is Grubbs' (I) catalyst (benzylidene-bis(tricyclohexylphosphine)-dichlororuthenium) and Grubbs' (II) catalyst (benzylidene[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(tricyclohexylphosphine)ruthenium).

[0107] In some embodiments, the amount of catalyst used ranges from about 1% to about 10%, from about 2% to about 5%, based on the total weight of the saturated fatty acids.

[0108] In some embodiments, ethenolysis is carried out in a non-ionic solvent. Non-limiting examples of non-ionic solvents include dichloromethane, n-hexane, and isooctane. In some embodiments, ethenolysis is carried out in an ionic solvent. Non-limiting examples of ionic solvents include 1,1,3,3-tetramethylguanidinium lactate [TMG][L], monoethanolammonium lactate [MEA][L], i-butyl-3-methylimidazolium tetrafluoroborate [BMIm][BF4], i-butyl-3-methylimidazolium methylsulfate [BMIm][MeSO4], i-hexyl-3-methylimidazolium methylsulfate [HMIm][MeSO4], i-ethyl-3-methylimidazolium methylsulfate [EMIm][MeSO4], and i-butyl-3-methylimidazolium hexafluorophosphate [BMIm][PF6].

[0109] In some embodiments, the purified unsaturated fatty acids (e.g., unsaturated free fatty acids) and / or unsaturated fatty acid esters are combined with a non-ionic solvent (e.g., dichloro-methane or n-hexane), a heterogeneous catalyst, and / or gaseous ethylene. In some embodiments, the reaction temperature is about 30° C., about 35° C., about 40° C., about 45° C., or about 50° C. In some embodiments, the reaction pressure is about 5 bar, about 6 bar, about 7 bar, about 8 bar, about 9 bar, about 10 bar, about 11 bar, about 12 bar, about 13 bar, about 14 bar, or about 15 bar.

[0110] In one aspect, if the metathesis of unsaturated fatty acids (e.g., long-chain unsaturated free fatty acids) resulting from ethenolysis is applied to a mixture of fatty acid chains, but not to a single chain of fatty acid, such as oleic acid or linoleic acid, as above, a mixture of products will be obtained, as in the case of products of plant or animal origin. In one aspect, if the metathesis of unsaturated fatty acid esters (e.g., long-chain unsaturated fatty acid esters) resulting from ethenolysis is applied to a mixture of fatty acid esters, but not to a single chain of fatty acid ester, such as methyl oleate or methyl linoleate, a mixture of products will be obtained. In some embodiments, the nature of the products obtained, and their amount, will therefore depend on the fatty acid and / or fatty acid ester composition of the fatty starting material used. In some embodiments, obtaining a product rich in 1-decene suggests using a starting material rich in oleic acid esters and / or oleic acid. In some embodiments, these oils are characterized at least by their fatty acid composition, the nature and proportion of their unsaturated fatty acids. In some embodiments, at least about 80% of the fatty acid chains and / or fatty acid ester chains comprise oleic acid chains, the amount of linoleic acid fatty chains does not exceed 12%, and the amount of linoleic acid fatty chains does not exceed about 0.3%. In some embodiments, the amount of saturated chains, e.g., palmitic acid or stearic acid, ranges from about 5% to about 15%, while other olefinic chains are present in the oil in amounts greater than about 0.3%.

[0111] In some embodiments, the resulting unsaturated fatty acids (e.g., long chain unsaturated free fatty acids) are reacted with ethylene in a metathesis reaction in the presence of at least one non-aqueous ionic liquid to produce both an olefin fraction and a composition of mono-alcohols and short chain free fatty acids. In some embodiments, the resulting unsaturated fatty acid esters (e.g., long chain unsaturated free fatty acid esters) are reacted with ethylene in a metathesis reaction in the presence of at least one non-aqueous ionic liquid to produce both an olefin fraction and a composition of mono-alcohols and short chain free fatty acids.

[0112] In some embodiments, the metathesis of renewable oils with an excess of ethylene can be carried out in a closed (batch), semi-open, or continuous system with one or more reaction steps. It is also possible to carry out the reaction using reactive distillation. Vigorous stirring ensures good contact between the reagents (gas and liquid) and the catalyst mixture.

[0113] In some embodiments, the reaction temperature may be in the range of about 0° C. to about 150° C., or in the range of about 20° C. to about 120° C., or in the range of about 25° C. to about 50° C., or in the range of about 25° C. to about 40° C. The operation may be carried out above or below the melting temperature of the medium, and the dispersed solid state is not a limitation for the reaction. The pressure may be, for example, in the range of atmospheric pressure (about 0.1 MPa) to 50 MPa. In some embodiments, ethylene may be used pure or as a mixture or diluted with paraffin (inert).

[0114] In some embodiments, the reaction products can be separated by decanting. In some embodiments, if the ionic liquid is non-volatile and thermally stable, it is also possible to separate the products by distillation.

[0115] Hydroisomerization of Alpha Olefins In one aspect, the method includes isomerizing (e.g., hydroisomerizing) the alpha olefins of the present disclosure. In some embodiments, isomerizing the alpha olefins provides compounds useful as lubricant base stocks and / or base oils. Isomerization is defined as the conversion of a molecule into different isomers.

[0116] In some embodiments, alpha olefins are separated from short chain free fatty acids (FFAs) to arrive at the desired structure for use in lubricants. In some embodiments, co-solvent extraction and / or fractional distillation are used for the separation. In some embodiments, the differences in polarity and specific gravity between the two major components (alpha olefins and short chain FFAs) can result in an inherent phase separation, avoiding the need for additional chemical processing.

[0117] In some embodiments, after separation of the alpha olefin portion, the material is oligomerized in the presence of a heterogeneous catalyst comprising one or more catalysts selected from metals, metal oxides, metal salts, or organic materials such as organic hydroperoxides, ion exchangers, and enzymes. In some embodiments, the heterogeneous catalyst is one or more of AlCl3 or BF3. In some embodiments, post-oligomerization analysis is used to confirm the extent of the reaction. In some embodiments, the alpha olefins are separated from the short chain unsaturated fatty acids by oligomerization. In some embodiments, the oligomerization provides alpha olefin dimers, alpha olefin trimers, alpha olefin tetramers, alpha olefin pentamers, and mixtures thereof. In some embodiments, once oligomerization (e.g., dimerization, trimerization, tetramerization, pentamers) has reached the published levels, the material is ready to be isomerized. Non-limiting methods useful for isomerization include in the presence of hydrogen and a catalyst (e.g., Pd / C), or under inert conditions. In some embodiments, the purpose of the isomerization is to increase the terminal branching character to dimerized alpha olefins, while hydrogen is used to saturate any residual double bond character. In some embodiments, the isomerization and hydrogenation can be carried out inside a reactor, optionally with the degree of isomerization controlled by the type of heterogeneous catalyst, temperature, pressure, and residence time. In some embodiments, the isomerization is carried out inside a Parr reactor.

[0118] In some embodiments, the temperature conditions of the isomerization reaction can range from about 100° C. to about 500° C., from about 100° C. to about 200° C., from about 200° C. to about 300° C., from about 300° C. to about 400° C., or from about 400° C. to about 500° C., optionally in the presence of a catalyst, e.g., a heterogeneous catalyst.

[0119] In some embodiments, pressure conditions for the isomerization reaction, optionally in the presence of a heterogeneous catalyst, can range from about 1,000 psi to about 3,000 psi, about 1,000 psi to about 2,000 psi, about 2,000 psi to about 3,000 psi, or about 1,500 psi to about 2,500 psi. In some embodiments, catalyst loading, temperature, and / or pressure parameters are published and can be developed for laboratory use.

[0120] Decarboxylation of unsaturated fatty acids In one aspect, the method includes decarboxylating unsaturated fatty acids (e.g., short-chain unsaturated fatty acids prepared from ethenolysis of unsaturated free fatty acids, including long-chain unsaturated free fatty acids). In some embodiments, decarboxylating the unsaturated fatty acids produces saturated hydrocarbons. In some embodiments, the primary product after ethenolysis of the long-chain unsaturated free fatty acids is an alpha olefin (e.g., linear alpha olefin), and the second by-product is a short-chain unsaturated free fatty acid. In some embodiments, the short-chain unsaturated free fatty acids resulting from ethenolysis of the unsaturated long-chain fatty acids are separated from the alpha olefin position via binary distillation. In some embodiments, the concentrated short-chain unsaturated free fatty acids are now decarboxylated to remove terminal carboxylic acid functionality from the saturated carbon chain. In some embodiments, the carbon chain length composition of the unsaturated free fatty acids ranges from C6 to C12 or C8 to C12, depending on the characteristics of the input oil. In some embodiments, the mass percent of the saturated free fatty acids recovered also depends on the characteristics of the input oil.

[0121] In some embodiments, the unsaturated fatty acid esters can be converted (e.g., by saponification) to unsaturated fatty acids and then decarboxylated. Non-limiting examples of methods for converting unsaturated fatty acid esters to unsaturated fatty acids include treatment with aqueous alkali (e.g., NaOH).

[0122] In some embodiments, the decarboxylation of fatty acids over non-precious metal catalysts without added hydrogen was studied. Non-limiting examples of catalysts useful for decarboxylation include Mo on Al2O3, MgO on Al2O3, Ni on Al2O3, and metal oxides (e.g., silver(II) which can be prepared in situ from silver nitrate and sodium persulfate). For a non-limiting example of the decarboxylation of unsaturated fatty acids using oxidative decarboxylation catalyzed by silver(II), see van der Kils et al., Eur. J. Lipid Sci. Tech. 113:562-571 (2011), which is incorporated by reference in its entirety. In some embodiments, Ni / C catalysts were prepared and exhibited excellent activity and retention for decarboxylation. In some subsequent embodiments, the effects of nickel loading, catalyst loading, temperature, and carbon number on the decarboxylation of fatty acids were investigated. In some embodiments, the results show that with high nickel loading or catalyst loading, the catalytic cracking of products increased. In some embodiments, the temperature significantly affected the conversion of stearic acid but not the selectivity. In some embodiments, fatty acids with high carbon numbers tend to be catalytically cracked in this reaction system. In some embodiments, stearic acid can be completely converted at 370° C. for 5 hours, with a selectivity to heptadecane of about 80%.

[0123] In some embodiments, the decarboxylation may be carried out in an organic solvent, including but not limited to, acetonitrile.

[0124] In some embodiments, the gas-phase decarboxylation of hydrolyzed unsaturated fatty acids (e.g., short-chain unsaturated free fatty acids) was investigated in two fixed-bed reactors by varying reaction parameters such as temperature, FFA feed rate, and H2 to FFA molar ratio. Most C8, as well as small amounts of C6, C 10 , and C 12 The FFA containing FFA was fed to the boiling zone, evaporated, carried by hydrogen flow at a rate of 0.5-20 ml / min, and reacted with 5% Pd / C catalyst in the reactor.

[0125] In some embodiments, the single-stage continuous decarboxylation of linear liquid hydrocarbons from free fatty acids is carried out using one or more catalysts selected from the group of Mo on Al2O3, MgO on Al2O3, and Ni on Al2O3 and / or subcritical water. In some embodiments, the linear hydrocarbons are obtained via decarboxylation and hydrogenation reactions where no hydrogen is added.

[0126] Glycerolysis (glycerol esterification) In one aspect, the method includes combining glycerin and / or glycerol (e.g., glycerin and / or glycerol produced from acidification of renewable oils) with unsaturated fatty acids (e.g., a portion of short chain unsaturated fatty acids prepared from ethenolysis of unsaturated fatty acids (e.g., unsaturated free fatty acids)) to produce a mixture and subjecting the mixture to glycerolysis to produce short chain unsaturated acyl-glycerides.

[0127] In some embodiments, fatty acid esters (e.g., unsaturated and saturated fatty acid esters) can be converted (e.g., by saponification) to fatty acids and then decarboxylated. Non-limiting examples of methods for converting unsaturated fatty acid esters to unsaturated fatty acids and saturated fatty acid esters to saturated fatty acids include treatment with aqueous alkali (e.g., NaOH).

[0128] Glycerol esterification or "glycerolysis" has been used to reduce FFAs in low-grade oils without the use of acid, methanol, or vacuum stripping. In some embodiments, when the glycerin produced during "acid-hydrolysis" and / or acidification is combined with short-chain unsaturated free fatty acids at a temperature of approximately 238°C, the free fatty acids will react with the glycerin to form acylglycerols or glycerides and water. In some embodiments, the resulting glycerides formed during glycerolysis can then be directly converted to biodiesel via base-catalyzed transesterification. In some embodiments, since glycerolysis is carried out at such high temperatures, any water formed is immediately vented via a nitrogen purge. In some embodiments, the continuous removal of water throughout the process via a nitrogen purge is important for several reasons. In some embodiments, drying the renewable oil to a moisture level below 0.5% avoids the formation of excess soaps during base-catalyzed transesterification and possible decanting problems. In some embodiments, purging water from the system also shifts the reaction equilibrium towards the product side, lowering the free fatty acid concentration to less than 0.2%. This is a result of Le Chatelier's principle, or "law of equilibrium," which states that when an equilibrium system is subjected to a change (i.e., removal of low concentrations of water), the system will readjust itself to counter the effect of the change and establish a new equilibrium. In some embodiments, volatile organic compounds and / or light carboxylic acids are removed along with the water during purging. In some embodiments, these compounds are the result of organic oxidation and can be very malodorous. In some embodiments, the system is blanketed with nitrogen to avoid any further oxidation of the oil components at high temperatures.

[0129] In some embodiments, converting at least a portion of the free fatty acids in the acidified composition to acyl-glycerides comprises esterification of the free fatty acids. As used herein, the term glycerlysis refers to the formation of acyl-glycerides by combining free fatty acids with glycerol in an inert environment.

[0130] In some embodiments, converting at least a portion of the free fatty acids in the acidified composition to glycerides comprises contacting the free fatty acids in the acidified composition with glycerol.

[0131] In some embodiments, contacting the free fatty acids in the acidified composition with glycerol is carried out at a temperature of about 175°C to 260°C, 200°C to 255°C, 220°C to 250°C, 230°C to 245°C, or about 235°C to 240°C, or about 175°C, 200°C, 225°C, 230°C, 235°C, 238°C, 245°C, 250°C, or about 260°C.

[0132] In some embodiments, the converting of at least a portion of the free fatty acids in the acidified composition to glycerides is acid-catalyzed.

[0133] In some embodiments, the converting of at least a portion of the free fatty acids in the acidified composition to glycerides is base catalyzed.

[0134] In some embodiments, the base-catalyzed esterification, transesterification, and combinations thereof include treating the free fatty acid with a methoxide, wherein the methoxide is selected from sodium methoxide, potassium methoxide, lithium methoxide, zinc methoxide, calcium methoxide, tributyltin methoxide, magnesium methoxide, tantalum(V) methoxide, titanium(IV) methoxide, antimony(III) methoxide, germanium methoxide, copper(II) methoxide, and combinations thereof.

[0135] Sustainable Lubricants In one aspect, the present disclosure provides a novel non-fossil, high-performance sustainable lubricant comprising a non-fossil hydrocarbon molecular structure derived from sustainable plant biomass. In some embodiments, the lubricant comprises one or more base oils (e.g., hydrocarbon base oils). Non-limiting examples of base oils useful in the present disclosure include long-chain and short-chain alpha-olefins, saturated hydrocarbons, and acyl-glycerides. In some embodiments, the lubricant of the present disclosure outperforms traditional high-performance synthetic petroleum products, is cost-competitive with synthetic oils, has direct drop-in compatibility with current systems, meets or exceeds 19 applicable American Petroleum Institute (API) certifications, and / or is a viable alternative to inferior petroleum-based lubricants.

[0136] In some embodiments, the lubricants of this disclosure comprise a base oil (e.g., a hydrocarbon base oil) prepared using the methods of this disclosure.

[0137] In some embodiments, the base oil comprises dimers, trimers, tetramers, and / or pentamers of C14-C18 olefin monomers (e.g., C14-C18 alpha olefin monomers). In some embodiments, the olefin monomer is a C16 olefin monomer (e.g., C16 alpha olefin monomer). In some embodiments, the base oil comprises C28-C36 dimers of C14-C18 olefin monomers (e.g., C14-C18 alpha olefin monomers), C42-C54 trimers of C14-C18 olefin monomers (e.g., C14-C18 alpha olefin monomers), C56-C72 tetramers of C14-C18 olefin monomers (e.g., C14-C18 alpha olefin monomers), and / or C70-C90 pentamers of C14-C18 olefin monomers (e.g., C14-C18 alpha olefin monomers). In some embodiments, the base oil comprises a C32 dimer, a C48 trimer, a C64 tetramer, and / or a C80 pentamer of a C16 olefin monomer (e.g., a C16 alpha olefin monomer).

[0138] In one aspect, the present disclosure provides a lubricant comprising: a) a saturated hydrocarbon base oil in an amount ranging from about 50% by weight to about 70% by weight of the total weight of the lubricant, the saturated hydrocarbon base oil comprising oligomers of C14 to C18 olefin monomers, the dimers having an average carbon number ranging from 29 to 36; b) a viscosity modifier in an amount ranging from about 1% to about 30% by weight, or from about 20% to about 30% by weight (e.g., about 1.4% by weight, about 1.80% by weight, about 3.2% by weight, about 4.13% by weight, about 5.2% by weight, or about 16.25% by weight, about 26% by weight) of the total weight of the lubricant; c) a surfactant in an amount ranging from about 10% by weight to about 15% by weight (e.g., about 12.3% by weight) of the total weight of the lubricant; d) a pour point depressant in an amount ranging from about 0.1 wt. % to about 1 wt. % (e.g., about 0.3 wt. %) of the total weight of the lubricant; and The present invention provides a lubricant comprising:

[0139] In one aspect, the lubricant comprises a saturated hydrocarbon base oil. In some embodiments, the saturated hydrocarbon base oil comprises oligomers (e.g., dimers, trimers, tetramers, and / or pentamers) of C14-C18 olefin monomers. In some embodiments, the dimers have an average carbon number in the range of 29 to 36. In some embodiments, the dimer moiety has a weight average molecular weight in the range of about 422 to about 510. In some embodiments, the trimers have an average carbon number in the range of 42 to 55. In some embodiments, the tetramers have an average carbon number in the range of 56 to 72. In some embodiments, the pentamers have an average carbon number in the range of 70 to 90. Non-limiting examples of suitable saturated hydrocarbon base oils include SynNova 4 and SynNova 9. See also U.S. Patent No. 2020 / 0165538 and U.S. Patent No. 2020 / 0216772, each of which is incorporated herein by reference in its entirety.

[0140] In some embodiments, the lubricants of the present disclosure comprise and / or exhibit a viscosity index in the range of about 1% to about 30%, about 1% to about 6%, about 1% to about 17%, or about 205 to about 30% (e.g., about 1.4%, about 1.80%, about 3.2%, about 4.13%, about 5.2%, or about 16.25%, about 26%). In non-limiting examples, the lubricants are Euro 0W40 and comprise and / or exhibit a viscosity index in the range of about 20% to about 30%, or about 25% to about 27%, or about 26%. In non-limiting examples, the lubricants are 5W30 and comprise and / or exhibit a viscosity index in the range of about 1% to about 6%, or about 3% to about 4%, or about 3.2%. In non-limiting examples, the lubricant is 5W20 and includes and / or exhibits a viscosity index in the range of about 1% to about 6%, or about 1% to about 2%, or about 1.4%. In non-limiting examples, the lubricant is 5W40 and includes and / or exhibits a viscosity index in the range of about 1% to about 6%, or about 4% to about 5%, or about 5.2%. In non-limiting examples, the lubricant is ISO32 and includes and / or exhibits a viscosity index in the range of about 1% to about 17%, or about 1% to about 2%, or about 1.80%. In non-limiting examples, the lubricant is ISO46 and includes and / or exhibits a viscosity index in the range of about 1% to about 17%, or about 4% to about 5%, or about 4.13%. In non-limiting examples, the lubricant is ISO 68 and includes and / or exhibits a viscosity index in the range of about 1% to about 17%, or about 16% to about 17%, or about 16.25%.

[0141] In some embodiments, the lubricant comprises a saturated hydrocarbon base oil in an amount ranging from about 50% to about 70%, about 55% to about 65%, about 58% to about 60%, or about 59% to about 60% by weight of the total weight of the lubricant. In some embodiments, the lubricant comprises a saturated hydrocarbon base oil in an amount ranging from about 59%, about 59.1%, about 59.2%, about 59.3%, about 59.4%, about 59.5%, about 59.6%, about 59.7%, about 59.8%, about 59.9%, or about 60% by weight of the total weight of the lubricant.

[0142] In some embodiments, the saturated hydrocarbon base oil is a mixture or blend comprising two or more different saturated hydrocarbon base oils. In some embodiments, the saturated hydrocarbon base oil comprises two different saturated hydrocarbon base oils. In a non-limiting example, the saturated hydrocarbon base oil comprises SynNova 4 and SynNova 9. In some embodiments, the saturated hydrocarbon base oil comprises SynNova 4 in an amount ranging from about 50% to about 60%, about 52% to about 58%, about 55% to about 57%, or about 56% to about 57% by weight of the total weight of the lubricant, and SynNova 9 in an amount ranging from about 3% to about 7%, about 4% to about 6%, or about 4.5% to about 5.5% by weight of the total weight of the lubricant. In some embodiments, the saturated hydrocarbon base oil comprises SynNova 4 in an amount of about 56 wt%, about 56.1 wt%, about 56.2 wt%, about 56.3 wt%, about 56.4 wt%, about 56.5 wt%, about 56.6 wt%, about 56.7 wt%, about 56.8 wt%, about 56.9 wt%, or about 57 wt% of the total weight of the lubricant, and SynNova 9 in an amount of about 4.5 wt%, about 4.6 wt%, about 4.7 wt%, about 4.8 wt%, about 4.9 wt%, about 5 wt%, about 5.1 wt%, about 5.2 wt%, about 5.3 wt%, about 5.4 wt%, or about 5.5 wt% of the total weight of the lubricant.

[0143] In one embodiment, the saturated hydrocarbon base oil comprises dimers as a major weight percent of the base oil composition, hi some embodiments, the saturated hydrocarbon base oil comprises dimers in an amount of about 50% or more, about 80% or more, about 90% or more, about 95% or more, about 98% or more, or about 99% or more by weight of the total weight of the lubricant.

[0144] In some embodiments, the saturated hydrocarbon base oil containing dimer is substantially free of any 1-decene.For example, the base oil embodiment may contain less than 5 wt.%, for example, less than 3 wt.%, or even less than 1 wt.% of 1-decene in any form, whether monomeric, dimeric, or trimeric, or even higher oligomeric form.In some embodiments, the saturated hydrocarbon base oil contains less than about 10%, less than about 5%, or less than about 1% of dimer containing single branched isomer according to simulated distillation test ASTM D2887.

[0145] In some embodiments, the saturated hydrocarbon base oil, or each saturated hydrocarbon base oil when the saturated hydrocarbon base oil comprises two or more different saturated hydrocarbon base oils, has the following characteristics: a) a Noack volatility as measured by ASTM D5800 and / or CEC L-40-A-93 of less than about 14%, less than about 13%, less than about 12%, less than about 11%, less than about 10%, or less than about 9% (e.g., about 7.4%); b) A bromine index determined in accordance with D2710-09 of approximately 1000 mg Br 2 / 100g or less or about 500mg Br 2 / 100g or less or about 200mg Br 2 / Below 100g, c) 1 an average branching index (BI) in the range of about 22 to about 26 as determined by H NMR; d) 13 the average paraffin branching proximity (BP) as determined by C NMR is in the range of about 18 to about 26; e) a viscosity index, determined in accordance with ASTM D2270, of about 125 or greater, about 130 or greater, about 135 or greater, or about 140 or greater; f) a pour point, as determined in accordance with ASTM D97, of less than about -20°C, less than about -27°C, less than about -30°C, less than about -33°C, less than about -36°C, less than about -39°C, or less than about -42°C; g) a cold crank simulated (CCS) dynamic viscosity as measured by ASTM D5293 at -35°C of less than about 1800 cP, less than about 1700 cP, less than about 1600 cP, less than about 1500 cP, less than about 1400 cP, less than about 1300 cP, less than about 1200 cP, or less than about 1100 cP; and / or h) a KV(100) as measured by ASTM D445-17a in the range of about 3.7 cSt to about 9.7 cSt, or about 3.7 cSt to about 4.8 cSt; Patients with one or more of the following symptoms may develop:

[0146] The average paraffin branching proximity (BP) is a measure of the content of repeating methylene groups in the dimer moiety according to the following formula: Paraffin branching proximity (BP) = (number of ε carbon groups / total number of carbon groups) * 100 where the ε carbon group is defined as an α carbon group separated from any terminal carbon atom group, or a carbon group branched by at least four carbon groups.

[0147] The branching index is a measure of the degree of branching and can be determined according to the following formula: Branching index (BI) = (total methyl group hydrogen content / total hydrogen content) * 100.

[0148] In one aspect, the lubricant includes a viscosity modifier. In some embodiments, the viscosity modifier is used to minimize the lubricant viscosity at low temperatures, meet industrial performance standards, have good shear stability at low processing speeds, retain low temperature performance, and provide viscosity control at high temperatures. As would be understood by one of ordinary skill in the art, any viscosity modifier is contemplated by the present disclosure. Non-limiting examples of viscosity modifiers include Infineum SV603 and Infineum SV261L.

[0149] In some embodiments, the lubricant comprises a viscosity modifier in an amount ranging from about 20% to about 30%, from about 21% to about 29%, from about 22% to about 28%, from about 23% to about 27%, from about 25% to about 27%, or from about 25.5% to about 26.5% by weight of the total weight of the lubricant. In some embodiments, the lubricant comprises a viscosity modifier in an amount of about 25 wt%, about 25.1 wt%, about 25.2 wt%, about 25.3 wt%, about 25.4 wt%, about 25.5 wt%, about 25.6 wt%, about 25.7 wt%, about 25.8 wt%, about 25.9 wt%, about 26 wt%, about 26.1 wt%, about 26.2 wt%, about 26.3 wt%, about 26.4 wt%, about 26.5 wt%, about 26.6 wt%, about 26.7 wt%, about 26.8 wt%, about 26.9 wt%, or about 27 wt% of the total weight of the lubricant.

[0150] In one aspect, the lubricant includes a surfactant. In some embodiments, the surfactant is used to neutralize acidic blow-by gases, control rust, reduce lacquer, and prevent deposits on engine components such as pistons. As would be understood by one of ordinary skill in the art, any surfactant is contemplated by the present disclosure. Non-limiting examples of surfactants include Infineum P6003.

[0151] In some embodiments, the lubricant comprises a surfactant in an amount ranging from about 10% to about 15%, about 11% to about 14%, or about 12% to about 13% by weight of the total weight of the lubricant. In some embodiments, the lubricant comprises a surfactant in an amount ranging from about 12%, about 12.1%, about 12.2%, about 12.3%, about 12.4%, about 12.5%, about 12.6%, about 12.7%, about 12.8%, about 12.9%, or about 13% by weight of the total weight of the lubricant.

[0152] In one aspect, the lubricant includes a pour point depressant. In some embodiments, the pour point depressant is used to prevent wax crystals in the lubricant from agglomerating or fusing at reduced ambient temperatures. In some embodiments, the pour point depressant is also useful as a flow improver. As would be understood by one of ordinary skill in the art, any pour point depressant is contemplated by the present disclosure. A non-limiting example of a pour point depressant includes Infineum V385.

[0153] In some embodiments, the lubricant comprises a pour point depressant in an amount ranging from about 0.1 wt.% to about 1 wt.%, 0.1 wt.% to about 0.5 wt.%, or 0.2 wt.% to about 0.4 wt.% of the total weight of the lubricant. In some embodiments, the lubricant comprises a pour point depressant in an amount ranging from about 0.1 wt.%, about 0.2 wt.%, about 0.3 wt.%, about 0.4 wt.%, about 0.5 wt.%, about 0.6 wt.%, about 0.7 wt.%, about 0.8 wt.%, about 0.9 wt.%, or about 1 wt.% of the total weight of the lubricant.

[0154] In some embodiments, the lubricant further comprises one or more additives. Non-limiting examples of additives include anti-wear additives. In some embodiments, the anti-wear additive comprises zinc dialkyldithiophosphate (ZDDP). Non-limiting examples of additives that include ZDDP include Infineum D3337, Infineum P5920, and Infineum P6003.

[0155] In one embodiment, the lubricant is a) a saturated hydrocarbon base oil comprising SynNova 4 in an amount ranging from about 56% to about 57% by weight of the total weight of the lubricant, and SynNova 9 in an amount ranging from about 4.5% to about 5.5% by weight of the total weight of the lubricant; b) a viscosity modifier comprising Infineum SV603 in an amount ranging from about 25.5% to about 26.5% by weight of the total weight of the lubricant; c) a surfactant, comprising Infineum P6003 in an amount ranging from about 12% by weight to about 13% by weight of the total weight of the lubricant; d) a pour point depressant comprising Infineum V385 in an amount ranging from about 0.2% to about 0.4% by weight of the total weight of the lubricant; Includes.

[0156] In one embodiment, the lubricant is a) SynNova4 in an amount of about 56.4% by weight of the total weight of the lubricant; b) SynNova 9 in an amount of about 5% by weight of the total weight of the lubricant; c) Infineum SV603 in an amount of about 26% by weight of the total weight of the lubricant; d) Infineum P6003 in an amount of about 12.3% by weight of the total weight of the lubricant; e) Infineum V385 in an amount of about 0.3% by weight of the total weight of the lubricant; Includes.

[0157] While preferred embodiments of the present disclosure have been shown and described herein, such embodiments are provided by way of example only and are not intended to limit the scope of the present disclosure, and various alternatives to the described embodiments of the present disclosure may in fact be employed. EXAMPLES

[0158] The embodiments encompassed herein will now be described with reference to the following examples, which are provided for illustrative purposes only, and the disclosure encompassed herein should in no way be construed as being limited to these examples, but rather as encompassing any and all variations that become evident as a result of the teachings provided herein.

[0159] Example 1: Exemplary preparation of renewable oil-based feedstocks Non-limiting examples of methods for preparing base oils / base stocks from renewable oils are shown in FIG. 1 and FIG.

[0160] Oil pretreatment The first step is to pretreat approximately 7.8 L (2 gallons) of the selected renewable oil precursor, in this case soybean oil. The initial size of the oil to be pretreated depends on multiple factors, including but not limited to unanticipated sample losses, multiple reaction scenarios requiring assay test development, and laboratory-scale equipment limitations covering all unit operations.

[0161] An oil filtration method can be established using commercially available filter aids (diatomaceous earth, cellulose filter aids, filter bags with a combination of filter pore sizes). The objective of this stage is not to optimize the filter aid to oil ratio, but to produce an oil precursor that will remain of sufficiently high quality throughout the lubricant process. The final material should be free of debris and impossible to separate via laboratory centrifugation.

[0162] TIFF2024530075000002.tif108165

[0163] Acid hydrolysis of renewable oils The filtered oil from the pretreatment stage is collected and two single-stage acid-hydrolysis reactions are carried out on approximately 7.5L of oil. In a non-limiting embodiment, the reaction is carried out between fats or oils at a suitable temperature (about 100°C at reflux, or 120°C under pressure) with provisions for mixing, either by steam or mechanical agitation. In addition, a small amount of mineral acid (1% sulfuric acid by weight relative to the oil) or organic sulfonic acid sulfuric acid, known as "saponifier", "emulsifier", "disintegrator", etc., is added. The use of two acid types, sulfonic acid (97% by weight) and methylsulfonic acid (MSA), allows for some degree of performance optimization. The results of the test comparison have a significant impact on the overall operating costs of the developed equipment.

[0164] In the process, the oil is heated and stirred in the presence of a stoichiometric excess of water (4x) to the desired temperature. Once at temperature, the selected acid is charged to either a reflux vessel at atmospheric pressure and / or an autoclave reactor under positive pressure and elevated temperature (120°C). The reaction mixture is stirred vigorously for 1 hour, after which the reaction is stopped and transferred to a separatory funnel. After phase separation, the top free fatty acid layer is tested to establish the reaction rate. Depending on the analytical results, the free fatty acid phase layer may be rehydrolyzed or transferred to the next stage. All weights, data, and reaction parameters are recorded for later analysis.

[0165] TIFF2024530075000003.tif133165

[0166] Chemical separation of free fatty acids After separation of the free fatty acids from the glycerol, the upper phase is transferred to a 5 L round-bottom reactor with stirring. Two hydrolysis trials are subjected to the acetone extraction reaction in a volume of 2 L. The mixture is stirred for 20 minutes at 60° C. using a 1:1 oil to solvent ratio under cooling reflux using ethylene glycerol and water (50 wt%) as the condenser medium. Once the reaction is complete, the reactor contents are transferred to four individual 1.0 L beakers with closed lids in ethylene glycol and water baths and cooled to 0° C. To ensure complete saturation, the beakers are cooled for 24 hours before separating the solid saturated free fatty acids from the liquid unsaturated free fatty acids. In a non-limiting embodiment, only the liquid portion is of interest for producing lubricant base stocks. The saturated portion of the free fatty acids is analyzed to determine its characteristics (i.e., iodine value, % inerts content, FFA profile, etc.) with the aim of providing a substrate useful for renewable diesel production. The liquid unsaturated portion is transferred to a rotor evaporator and the majority of the acetone solvent is evaporated at low temperature. After most of the solvent has been removed, the beaker containing the extracted unsaturated FFAs is placed in a vacuum chamber to remove traces of solvent before proceeding to the next unit operation.

[0167] TIFF2024530075000004.tif145165

[0168] Ethenolysis of unsaturated free fatty acids Using the unsaturated free fatty acids purified during the final stage, approximately 0.5 L of material is charged to a 1 L Parr reactor (series 4843 with temperature control and mixing). Non-ionic solvent (dichloro-methane or n-hexane), heterogeneous catalyst (several types cited below), and gaseous ethylene are combined in the reactor with the oil at previously published charges based on previous work. Reaction conditions are maintained at approximately 40° C. and 10 bar pressure for 10 hours or more. In a non-limiting example, the results replicate published results for obtaining lubricant base stocks with the desired specifications.

[0169] The reaction is considered complete when the product components are quantitatively determined and meet the published yields. Once this is established, the oil phase is separated from the gaseous and solvent components via rotor evaporation. Due to the scale of the study, no solvent gas recovery system is implemented at this stage. After removing most of the solvent via natural evaporation, the beaker containing the extracted alpha olefins and newly formed short chain free fatty acids is placed in a vacuum chamber to remove traces of solvent before proceeding to the next unit operation.

[0170] TIFF2024530075000005.tif139165

[0171] Hydroisomerization of Alpha Olefins to Lubricant Base Stocks To convert the alpha olefin portion of the resulting mixture into the desired form, it was first necessary to separate it from the short chain FFAs. This can be accomplished using several different extraction techniques, including but not limited to co-solvent extraction to fractional distillation. Depending on the characteristics of the resulting laboratory mixture, the separation approach is determined based on the need. Without wishing to be limited by theory, the difference in polarity and specific gravity between the two major components (alpha olefins and short chain FFAs) may result in an inherent phase separation, avoiding the need for additional chemical processing.

[0172] After isolating the alpha olefin portion, it is oligomerized in the presence of heterogeneous catalysts (AlCl3 and BF3). The reaction is carried out in a Parr reactor (series 4843 with continuous mixing). Post-oligomerization analysis is required to confirm the extent of the reaction. Once oligomerization (e.g., dimerization) has reached the published levels, the material is ready to be isomerized either in the presence of hydrogen or under inert conditions. The purpose of isomerization is to increase the terminal branching character to the oligomerized (e.g., dimerized) alpha olefins, while hydrogen is used to saturate any residual double bond character. Isomerization and hydrogenation can be carried out inside a Parr reactor, and the extent of isomerization is controlled by the type of heterogeneous catalyst, temperature, pressure, and residence time. Reaction conditions for the isomerization reaction can range from above 200°C and above 2,000 psi in the presence of heterogeneous catalysts such as AlCl3 and BF3. Catalyst loading, temperature, and pressure parameters are published and can be developed for laboratory use.

[0173] TIFF2024530075000006.tif115165

[0174] Example 2: Lubricant 0W-40 A lubricant 0W-40 was prepared containing the following components as shown in Table 1.

[0175] [Table 1]

[0176] The analyses were performed according to ASTM test procedures and were used without deviation or correction. The precision of these test results should be consistent with that stated in the referenced test procedures. The test results are shown in Tables 2 and 3 below.

[0177] [Table 2]

[0178] [Table 3]

[0179] Example 3: Oil Refining - Filtration and Degumming material Equipment: 2 L of soybean oil (purchased oleic acid (Carolina Chemical) TAN (D974)), a 5 L round bottom flask, a separatory funnel, citric acid, drinking water, a filter apparatus with filter media (diatomaceous earth), filter paper (50 micron), and applicable glassware.

[0180] method As shown in Figure 3, refined soybean oil was purchased and degummed to ensure triglyceride purity. 2000 grams of soybean oil was mixed with 400g (20% by weight) water and citric acid solution (5% by weight citric acid in water) at 150°F for 30 minutes. After reaction, the mixture was allowed to settle in a separatory funnel for 1 hour and then decanted. The upper oil phase was filtered through a filter media (diatomaceous earth) and filter paper (50 micron) at 120°F. After filtration, 1995g of soybean oil was recovered. A 20g sample was sent for third party analytical analysis for free fatty acid profile analysis.

[0181] Acid hydrolysis of feed oils (Twitchell digestion). Attempt #1 - Atmospheric reflux material 2 L of degummed soybean oil, 5 L round bottom flask, 5 L flask glass stirrer, 5 L flask heating mantle with top glass insulation, reflux condenser with chilled glycol circulating bath, sulfuric acid (97% by weight), separatory funnel.

[0182] Method #2 As shown in Figure 4, refined soybean oil (1653g) was heated to 150°F in a 5L round bottom flask. The calculated stoichiometric equivalent of water for hydrolysis was equal to 34.5g water, but the actual charge was 10 times the stoichiometric amount (345g). Sulfuric acid (98%) was added to the mixture at 4% by weight relative to the soybean oil (66g sulfuric acid). The mixture was refluxed at 235°F for 12 hours in a 5L round bottom flask. The condenser temperature was maintained at 15°F to ensure that all water vapor was returned to the reactor. The acid hydrolysis in process is shown in Figure 5. After the reaction was complete, the mixture was allowed to cool to room temperature and then charged to a separatory funnel. After settling for 60 minutes, the lower water / glycerin phase (460g) was removed. The upper oil phase (1630g) was removed, weighed, and sampled for analytical testing. These layers of oil and water / glycerin are shown in Figure 6. Subsequent testing showed that only 20% conversion of triglycerides to free fatty acids was obtained at lower temperatures.

[0183] Attempt #2 - High Pressure / High Temperature Reactor material 2L degummed soybean oil, 1L high temperature and high pressure stainless steel mixing reactor, nitrogen gas, separatory funnel.

[0184] Method #2 In response to Trial #1, the reaction conditions for acid hydrolysis were modified to achieve a higher reaction temperature. Refined soybean oil (500 g) is mixed with water (250 g) and then charged into a high-temperature, high-pressure mixing reactor. The reactor vapor space is purged with nitrogen gas to avoid undesired oxidation. The reactor is heated to 500° F. while the internal pressure is increased to 870 psi. The reaction conditions are maintained for 3 hours with stirring. Upon completion, the reactor is cooled to room temperature and the excess pressure is released. The reactor contents are allowed to settle in a separatory funnel for 2 hours, and the dense glycerin and excess aqueous phase are collected and removed via the separatory funnel. The glycerin is vacuum dried at 240° F. and 60 mmHg while maintaining the conditions for 20 minutes. The less dense free fatty acid component is dried under the same conditions as the glycerin, and is expected to yield approximately 89% free fatty acids by weight.

[0185] Chemical separation of unsaturated and saturated free fatty acids material free fatty acid (FFA) phase, a double jacketed glass lined reactor, a 5 L flask with glass stirrer, a chilled ethylene glycol bath, a separatory funnel, ACS grade acetone, a filter apparatus with applicable glassware, a solvent vacuum pump, and a rotary evaporator for solvent recovery.

[0186] method The free fatty acids (1630 g) produced during acid-hydrolysis (Test #1) were combined with ACS grade acetone (1:1.5, oil to solvent). The two components were mixed and then cooled to 0° F. using a chilled circulating bath for 24 hours. The mixture was subcooled and then the contents were filtered immediately upon removal from the chilled system. The material was filtered through a chilled porous cloth capable of retaining the solid phase crystallized free fatty acids. The liquid filtrate was weighed and then the residual acetone was evaporated using a rotary evaporator under vacuum (100 mmHg). The resulting oil (8.2 wt%) was sampled and tested to confirm the degree of unsaturation and free fatty acid profile. The test results of acid-hydrolysis (Test #1) indicated that the lack of free fatty acid conversion was the cause of the low extraction yield. It is expected that the yield during extraction will be improved by repeating the acid-hydrolysis process using the method of Trial #2.

[0187] Example 4: Decarboxylation and ethenolysis Fatty acids are decarboxylated using silver(+2) as a catalyst, which is generated from silver(+1) by the action of sodium persulfate. The reaction is carried out in an acetonitrile + water solvent system at reflux temperature (about 78°C) for a reaction time of 20 minutes.

[0188] Oxidative decarboxylation of oleic acid Reactants: ●1.9874 grams of Oleic Acid (Carolina Biological Supply Co.-Laboratory Grade Catalog #87-8340) 1.31 grams of silver nitrate (MCB-reagent grade catalog #SX205) diluted in 50 ml of deionized water ●90ml of acetonitrile (EMD-HPLC grade >99.99% Catalog #AX0142-1) 3.70 grams of sodium persulfate (Sigma-Aldrich->98% Catalog #216232) diluted in 40 ml of deionized water

[0189] Device: 250cc 3-neck boiling flask with water-cooled condenser, SS type K TC, 1 / 8 inch Teflon liquid addition tube and magnetic stir bar. A heating mantle and power control are used to regulate the reaction mixture temperature. The boiling flask and heating mantle are placed on a magnetic stirrer and stirred constantly during the experiment. A constant speed syringe pump is used to deliver the sodium persulfate solution from a 50 cc syringe to the reaction mixture. An example of this experimental setup is shown in Figure 7.

[0190] procedure: Place oleic acid, silver nitrate solution, and acetonitrile into the boiling flask. Start the cooling water for the condenser and power the heating mantle. After the reaction mixture reaches approximately 78°C, some boiling action and / or reflux at the base of the condenser should be visible. At this point, begin the slow addition (4ml / min) of sodium persulfate. After all the persulfate solution has been added (10 minutes), allow the reaction to continue for an additional 10 minutes. At the end of the reaction period, quickly cool the reaction mixture to room temperature by removing the heating mantle and replacing it with an ice bath.

[0191] Product Recovery: After cooling, add 0.877 grams of nC16 to the reaction mixture and mix well. Transfer the reaction mixture to a 250 cc separatory funnel and wash three times with ethyl ether. Rinse the 250 cc reaction flask with each ethyl ether wash and add to the reaction mixture. Combine the three ethyl ether extracts and wash twice with saturated sodium bicarbonate solution.

[0192] analysis: 2 ml of the final ethyl ether extract (0.45 um) is filtered into a 2 ml vial and analyzed by GC.

[0193] GC Settings: ●Column-100M×0.25mm×1um RT×-5 ●Temp Prog-100℃-2min-6℃ / min-300℃ final-20min ●Injection - 100:1 decomposition of 1ul at 300℃ Carrier gas - Hydrogen, 46psig ●Detector - FID, 300℃

[0194] result: As shown in FIG. 9, C17 mono-olefin (ID by MS) yield=about 32 wt.%.

[0195] Ethenolysis of fatty acids, esters, or internal olefins Olefin metathesis with ethylene and unsaturated fatty esters or internal olefins produces a mixture of short chain alpha-olefins and methyl esters. In a non-limiting example, ionic liquids can be used as reaction solvents, allowing the expensive Grubbs catalyst to be reused multiple times. This example demonstrates the use of lower cost solvents than ionic liquids in the ethenolysis of initial fatty esters and fatty acids as feedstocks.

[0196] Experiment #1 – Ethenolysis of methyl oleate (FAME) Reactants: 0.0425 grams of HG2 (Grubbs(II)) catalyst 1.0544 grams of methyl oleate ●Dried with 20ml of dry isooctane-5A MS ●Ethylene gas > 100psig -> 99% purity

[0197] Device: A 160cc Parr SS autoclave was fitted with a glass liner to reduce the reaction volume to approximately 50cc. The reactor is fitted with a SS Type K TC, mag drive internal stirrer, multiple ports for N2 purge, ethylene addition, pressure sensing, and syringe injection of dry solvent under N2 purge. The lower reactor section can be heated with a removable external heater. An example of this experimental setup is shown in Figure 8.

[0198] procedure: Prior to the experiment, perform a hot (225-250°F) N2 purge of the lining and autoclave overnight and allow to cool completely. Quickly open the autoclave, remove the glass lining and place in an N2 purged desiccator. Partially reassemble the autoclave and maintain the dry N2 purge until ready to insert the loaded lining. Set the N2 purge on the analytical balance fume hood for approximately 30 minutes, then weigh out the reactants. Working quickly, weigh out the required HG2 catalyst and liquid feeds, using the liquid feed to cover the HG2 catalyst powder to prevent oxidation. Transfer the loaded lining back to the autoclave in the N2 purged desiccator. Again, working quickly, briefly open the autoclave, reinstall the loaded lining, close the autoclave, and re-establish the dry N2 purge while tightening the autoclave closure to a tight seal. Check the autoclave for leaks with dry N2 to 100 psig. Dry N2 purging of the HG2 catalyst is continued and fed for 1 hour, after which dry isooctane is introduced into the reactor during the N2 purging. N2 purging is continued slowly for 10 minutes, after which the gas flow is switched to ethylene and 3-4 pressure-depressurization cycles are quickly performed at 20-30 psig, then the system is finally pressurized to 100 psig with ethylene. Ethylene pressure and reaction temperature are continued to be monitored until the ethylene pressure in the reactor is stable. The reaction time is 8 hours and the temperature is varied from 29-36°C.

[0199] Product Recovery: The reactor is depressurized slowly and the ethylene is replaced with dry nitrogen to inert the reactor, then opened. The contents of the reactor are pipetted into a small bottle that has been flushed three times with a small amount of dry isooctane. A few drops of water are added to the bottle and shaken well to deactivate the catalyst. 0.4954 grams of nC14(IS) are added and mixed well.

[0200] analysis: 2 ml of the reaction product (0.45 um) is filtered into a 2 ml vial and analyzed by GC.

[0201] GC Settings: ●Column-100M×0.25mm×1um RT×-5 ●Temp Prog-100℃-2min-6℃ / min-300℃ final-20min ●Injection - 100:1 decomposition of 1ul at 300℃ Carrier gas - Hydrogen, 46psig ●Detector - FID, 300℃

[0202] result: 1-Decene yield (based on methyl oleate weight) about 41 wt%. Methyl oleate conversion about 99 wt%. Figure 10 shows a chromatogram illustrating these results.

[0203] Experiment #2 – Ethenolysis of Oleic Acid Reactants: 0.0450 grams of HG2 catalyst 0.9986 grams of oleic acid ●Dried with 20ml of dry isooctane-5A MS ●Ethylene gas > 100psig -> 99% purity

[0204] Device: A 160cc Parr SS autoclave was fitted with a glass liner to reduce the reaction volume to approximately 50cc. The reactor is fitted with a SS Type K TC, mag drive internal stirrer, multiple ports for N2 purge, ethylene addition, pressure sensing, and syringe injection of dry solvent under N2 purge. The lower reactor section can be heated with a removable external heater. An example of this experimental setup is shown in Figure 8.

[0205] procedure: Prior to the experiment, perform a hot (225-250°F) N2 purge of the lining and autoclave overnight and allow to cool completely. Quickly open the autoclave, remove the glass lining and place in an N2 purged desiccator. Partially reassemble the autoclave and maintain the dry N2 purge until ready to insert the loaded lining. Set the N2 purge on the analytical balance fume hood for approximately 30 minutes, then weigh out the reactants. Working quickly, weigh out the required HG2 catalyst and liquid feeds, using the liquid feed to cover the HG2 catalyst powder to prevent oxidation. Transfer the loaded lining back to the autoclave in the N2 purged desiccator. Again, working quickly, briefly open the autoclave, reinstall the loaded lining, close the autoclave, and re-establish the dry N2 purge while tightening the autoclave closure to a tight seal. Check the autoclave for leaks with dry N2 to 100 psig. Dry N2 purging of the HG2 catalyst is continued and fed for 1 hour, after which dry isooctane is introduced into the reactor during the N2 purging. N2 purging is continued slowly for 10 minutes, after which the gas flow is switched to ethylene and 3-4 pressure-depressurization cycles are quickly performed at 20-30 psig, then the system is finally pressurized to 100 psig with ethylene. Ethylene pressure and reaction temperature are continued to be monitored until the ethylene pressure in the reactor is stable. The reaction time is 8 hours and the temperature is varied from 29-36°C.

[0206] Product Recovery: The reactor is depressurized slowly and the ethylene is replaced with dry nitrogen to inert the reactor, then opened. The contents of the reactor are pipetted into a small bottle that has been flushed three times with a small amount of dry isooctane. A few drops of water are added to the bottle and shaken well to deactivate the catalyst. 0.4954 grams of nC14(IS) are added and mixed well.

[0207] analysis: 2 ml of the reaction product (0.45 um) is filtered into a 2 ml vial and analyzed by GC.

[0208] GC Settings: ●Column-100M×0.25mm×1um RT×-5 ●Temp Prog-100℃-2min-6℃ / min-300℃ final-20min ●Injection - 100:1 decomposition of 1ul at 300℃ Carrier gas - Hydrogen, 46psig ●Detector - FID, 300℃

[0209] result: 1-Decene yield about 22%, other compounds not observed in experiment #1 around 10% or much higher levels. It was not possible to calculate the conversion rate since it was not possible to measure the residual oleic acid. See Figure 11 which shows these results.

[0210] Example 5: Analysis of base oil The base oil samples were analyzed by gas chromatography. The base oil was found to contain C32 (dimer), C48 (trimer), C64 (tetramer), and C80 (pentamer). Figure 2 shows the gas chromatography trace. The carbon assignment is based on the oligomerization of C16 alpha olefin (AO). The boiling point distribution is shown in Table A below.

[0211] [Table A] TIFF2024530075000011.tif241165TIFF2024530075000012.tif164165

[0212] Example 6: Oleic Acid Process Feed Samples of soy-based oleic acid were analyzed by gas chromatography (maximum oven temperature 380° C.) and also by GC / MS (maximum oven temperature 355° C.).

[0213] Analysis by gas chromatography showed that only a small fraction of the material (0.08%) was in the form of triglycerides, with a diglyceride content of 1.14%. The remaining material (98.79%) was essentially all fatty acids, as detailed in the GC / MS shown in Figure 13 and Table B. The majority of the fatty acids were C18, with C18:1 (oleic acid) making up approximately 79.19% of the total sample by peak area. No other compounds were immediately detected. Several peaks appeared to be fatty acids but were not conclusively identified by the instrument (reported as "other" in Table B). A separate breakdown of the individual free fatty acids, expressed as a percentage of the total free fatty acid components, is shown in Table C. All components are expressed as a percentage of the total sample and are determined by peak area. Results should be considered approximate.

[0214] [Table B]

[0215] [Table C]

[0216] Example 7: Soybean Oil Interesterification Soybean oil samples were converted to methyl esters by transesterification and the results were analyzed by gas chromatography (maximum oven temperature 380° C.) and GC / MS (maximum oven temperature 355° C.).

[0217] Transesterification was carried out using a 6:1 molar ratio of potassium methoxylate to soybean oil with 1% (w / vol) potassium as catalyst. The reaction was left overnight for glycerin separation, followed by centrifugation of the ester layer to further clarify the sample. Analysis by gas chromatography showed that the transesterification was successful with less than 3% di- and triglycerides remaining. The GC / MS diagram shown in Figure 14 details the methyl esters and other compounds detected, and the methyl ester composition is detailed in Table D. Individual methyl esters are expressed as a percentage of the total methyl ester content. Results should be considered approximate.

[0218] [Table D]

[0219] References TIFF2024530075000016.tif70158TIFF2024530075000017.tif212159TIFF2024530075000018.tif103156

Claims

1. A method for preparing a base oil from a renewable oil containing triglycerides, comprising: a） i) a free fatty acid mixture containing saturated free fatty acids and unsaturated free fatty acids, and ii) glycerin, acidifying the renewable oil to produce a mixture containing the above; b) isolating the glycerin from the mixture of fatty acids; c) separating the saturated free fatty acids from the unsaturated free fatty acids; d） i) an alpha olefin, and ii) short-chain unsaturated fatty acids, optionally C6-C12 or C8-C12 short-chain unsaturated fatty acids, subjecting the unsaturated free fatty acids to ethenolysis to prepare a mixture containing the above, and e) combining the glycerin from a) with at least a portion of the short-chain unsaturated fatty acids of d) to produce a mixture, and subjecting the mixture to glycerolysis; including the renewable oil contains or consists of one or more selected from seed oils, vegetable oils, and animal-derived oils, the method.

2. The method further includes decarboxylating at least a portion of the short-chain unsaturated fatty acids of d) to produce saturated hydrocarbons, optionally, the decarboxylation includes a catalyst or gas-phase decarboxylation, optionally including a Ni / C catalyst or an oxidative metal catalyst such as silver (II); and / or in a), the renewable oil is purified before acidification, and optionally, purifying the renewable oil includes clarification, degumming, bleaching, and / or filtration. The method according to claim 1.

3. In a), the step of acidifying the renewable oil includes contacting the renewable oil with an aqueous acid and an organic solvent to provide an organic fraction and an aqueous fraction, the organic fraction contains the free fatty acid mixture, and the aqueous fraction contains the glycerin; or In a), the step of acidifying the renewable oil includes heating a mixture of the renewable oil and water at a suitable pressure, optionally including the following: i) the ratio of renewable oil to water is in the range of about 5:1 to about 1:5, about 4:1 to about 1:4, about 3:1 to about 1:3, or about 2:1 to about 1:2 based on the total weight of the renewable oil and water, ii) the mixture is heated to a temperature in the range of about 100°C to about 350°C, about 200°C to about 300°C, or about 250°C to about 275°C, and iii) the pressure is in the range of from about 500 psi to about 1000 psi (from about 3,400 kPa to about 6,900 kPa), from about 700 psi to about 900 psi (from about 4,800 kPa to about 6,200 kPa), or from about 800 psi to about 900 psi (from about 5,500 kPa to about 6,200 kPa); The method according to claim 1, comprising one or more of the above.

4. the step of acidifying is repeated two or more times; and / or, The method according to claim 3, wherein the acid comprises at least one of H2SO4, HCl, and H3PO4.

5. the organic fraction comprises from 90 wt% to about 100 wt% free fatty acid and from about 0 wt% to about 10 wt% glycerin, and optionally, the organic fraction comprises about 90 wt% free fatty acid and about 10 wt% glycerin and / or glycerol; The method according to claim 3 or 4.

6. the organic fraction comprises at least about 50 to about 100 wt%, about 60 to about 100 wt%, about 70 to about 100 wt%, about 80 to about 100 wt%, about 90 to about 100 wt%, about 60 to about 90 wt%, or about 70 to about 80 wt% free fatty acid, and optionally, in c), the separation of the saturated fatty acid from the unsaturated fatty acid comprises temperature-dependent solvent extraction; The method according to claim 3 or 4.

7. the saturated free fatty acid of a) is separated into short-chain saturated free fatty acids, optionally C8-12 saturated free fatty acids, and long-chain saturated free fatty acids, optionally C13-C22, C15-C19, or C16-C22 saturated free fatty acids; The method according to claim 1.

8. further comprising decarboxylation of the long-chain fatty acid, and optionally, the decarboxylation comprises a catalyst selected from Mo on Al2O3, MgO on Al2O3, and Ni on Al2O3, and optionally, a single-stage continuous process and / or subcritical water; The method according to claim 7.

9. the ethenolysis is optionally selected from tungsten, molybdenum, rhenium, and ruthenium, and optionally, the unsaturated free fatty acid comprises or consists of long-chain unsaturated free fatty acids; The method according to claim 1.

10. Optionally, in the presence of a heterogeneous catalyst, optionally, by oligomerization to provide an alpha olefin dimer, alpha olefin trimer, alpha olefin tetramer, and / or alpha olefin pentamer, further comprising the step of separating the alpha olefin from the short-chain unsaturated fatty acid, optionally, the heterogeneous catalyst being selected from metals, metal oxides, metal salts, or organic materials such as organic hydroperoxides, ion exchangers, and enzymes, the method according to claim 1.

11. Optionally further comprising the step of isomerizing the alpha olefin in the presence of hydrogen or under inert conditions, optionally, the isomerization being carried out inside a Parr reactor; and / or the temperature conditions of the isomerization reaction being in the range of about 100°C to about 500°C, about 100°C to about 200°C, about 200°C to about 300°C, about 300°C to about 400°C, or about 400°C to about 500°C, the method according to claim 1.

12. The pressure conditions of the isomerization reaction are in the range of about 1,000 psi to about 3,000 psi (about 6,900 kPa to about 20,700 kPa), about 1,000 psi to about 2,000 psi (about 6,900 kPa to about 13,800 kPa), about 2,000 psi to about 3,000 psi (about 13,800 kPa to about 20,700 kPa), or about 1,500 psi to about 2,500 psi (about 10,300 kPa to about 17,200 kPa), the method according to claim 11.

13. The heterogeneous catalyst is AlCl ３ and / or BF ３ The method of claim 10, wherein the

14. The glycerolysis produces short-chain unsaturated acyl-glycerides, optionally, the glycerolysis is base-catalyzed, optionally, the catalyst is a methoxide selected from sodium methoxide, potassium methoxide, lithium methoxide, zinc methoxide, calcium methoxide, tributyltin methoxide, magnesium methoxide, tantalum(V) methoxide, titanium(IV) methoxide, antimony(III) methoxide, germanium methoxide, copper(II) methoxide, and combinations thereof, the method according to claim 1.

15. The renewable oil is selected from rapeseed oil, soybean oil, castor oil; or, The renewable oil is derived from one or more of poultry, beef, and fish, the method according to claim 1.

16. A lubricant, comprising the following: a) A saturated hydrocarbon base oil in an amount in the range of about 50 wt% to about 70 wt% of the total weight of the lubricant, wherein the saturated hydrocarbon base oil contains oligomers of C14 - C18 olefin monomers, and the oligomers have an average carbon number in the range of 29 - 36, the saturated hydrocarbon base oil, and b) An amount in the range of about 1 wt% to about 30 wt% of the total weight of the lubricant, optionally in an amount of about 1.4 wt%, about 1.80 wt%, about 3.2 wt%, about 4.13 wt%, about 5.2 wt%, about 16.25 wt%, or about 26 wt% of a viscosity modifier, and c) An amount in the range of about 10 wt% to about 15 wt% of the total weight of the lubricant, optionally in an amount of about 12.3 wt% of a surfactant, and d) An amount in the range of about 0.1 wt% to about 1 wt% of the total weight of the lubricant, optionally in an amount of about 0.3 wt% of a pour point depressant, and comprising the lubricant.

17. The lubricant according to claim 16, wherein the oligomers comprise, optionally include, and / or consist of dimers, trimers, tetramers, and / or pentamers, optionally dimers.

18. The saturated hydrocarbon base oil has the following properties: a) The Noack volatility measured by ASTM D5800 and / or CEC L - 40 - A - 93 is less than about 14%, less than about 13%, less than about 12%, less than about 11%, less than about 10%, or less than about 9%, optionally about 7.4%, b) the bromine index determined in accordance with D2710 is less than about 1000 mg of Br ２ / 100 g, less than about 500 mg of Br ２ / 100 g, or less than about 200 mg of Br ２ / 100 g, c) １ The average branching index (BI) determined by 1H NMR is in the range of about 22 to about 26, d) １３ The average paraffin branch proximity (BP) determined by 13C NMR is in the range of about 18 to about 26, e) The viscosity index determined according to ASTM D2270 is about 125 or more, about 130 or more, about 135 or more, or about 140 or more, f) The pour point determined according to ASTM D97 is less than about - 20°C, less than about - 27°C, less than about - 30°C, less than about - 33°C, less than about - 36°C, less than about - 39°C, or less than about - 42°C, g) The cold crank simulation (CCS) dynamic viscosity measured at - 35°C by ASTM D5293 is less than about 1800 cP, less than about 1700 cP, less than about 1600 cP, less than about 1500 cP, less than about 1400 cP, less than about 1300 cP, less than about 1200 cP, or less than about 1100 cP, and h) The KV(100) measured by ASTM D445 - 17a is in the range of about 3.7 cSt to about 9.7 cSt, or about 3.7 cSt to about 4.8 cSt, and the lubricant according to claim 16 exhibits one or more of the above.

19. The lubricant according to claim 16, wherein the saturated hydrocarbon base oil comprises SynNova4 in an amount in the range of about 50 wt% to about 60 wt% of the total weight of the lubricant, and SynNova9 in an amount in the range of about 3 wt% to about 7 wt% of the total weight of the lubricant.

20. The lubricant according to claim 16, wherein the viscosity modifier comprises one or more of Infineum SV603 and Infineum SV261L, the surfactant comprises Infineum P6003, and the pour point depressant comprises Infineum V385.

21. a) a saturated hydrocarbon base oil comprising SynNova4 in an amount in the range of about 56 wt% to about 57 wt% of the total weight of the lubricant, and SynNova9 in an amount in the range of about 4.5 wt% to about 5.5 wt% of the total weight of the lubricant; b) a viscosity modifier comprising Infineum SV603 in an amount in the range of about 25.5 wt% to about 26.5 wt% of the total weight of the lubricant; c) a surfactant comprising Infineum P6003 in an amount in the range of about 12 wt% to about 13 wt% of the total weight of the lubricant; d) a pour point depressant comprising Infineum V385 in an amount in the range of about 0.2 wt% to about 0.4 wt% of the total weight of the lubricant; The lubricant according to claim 16, comprising:

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