Methods of refining and producing dibasic esters and acids from natural oil feedstocks.

METHODS TO REFINE AND PRODUCE DIBASIC ACIDS AND ESTERS FROM NATURAL OIL RAW MATERIALS

Field and Background of the Invention

[0003] Metathesis is a catalytic reaction that comprises the exchange of alkylidene units between compounds containing one or more double bonds (eg, olefinic compounds) through the formation and excision of carbon-carbon double bonds. Metathesis can occur between two similar molecules (frequently referred to as auto-metathesis) and / or it can occur between two different molecules (frequently referred to as cross-metathesis). Self-metathesis can be represented schematically as shown in equation I.

(I) R1-CH = CH-R₂ + R1-CH = CH-R2 W Ri-CH = CH-Ri + R₂-CH = CH-R₂ where R^{* 1 (II)} and R² they are organic groups.

[0004] Cross metathesis can be represented schematically as shown in equation II.

(II) 2 Ri-CH = CH-R₂ + 2 R₃-CH = CH-R4 θ Ri-CH = CH-R₃ + Ri-CH = CH-R4 + R₂-CH = CH-R₃ + R₂-CH = CH-R₄where R¹, R², R³, and R⁴ they are organic groups.

[0005] In recent years, there has been a growing demand for environmentally friendly techniques for making materials typically from petroleum sources. For example,

<img file="MX370894B_D0001.tif" />

Researchers have been studying the feasibility of producing biofuels, waxes, plastics, and the like, using raw materials from natural oils, such as vegetable and seed-based oils. In a non-limiting example, metathesis catalysts are used to produce candle wax, as described in WO 2006/076364, which is incorporated herein by reference in its entirety. Metathesis reactions comprising raw materials from natural oils offer promising solutions for today and tomorrow.

[0006] Natural oil feedstocks of interest include non-limiting examples, such as natural oils (eg, vegetable oils, fish oil, animal fats) and derivatives of natural oils, such as fatty acids and alkyd esters ( eg, methyl) of fatty acids. These raw materials can be converted into industrially useful chemicals (eg, waxes, plastics, cosmetics, biofuels, etc.) by any number of different metathesis reactions. Significant classes of reaction include, as non-limiting examples, auto-metathesis, olefin cross-metathesis, and ring-opening metathesis reactions. Representative, non-limiting examples of useful metathesis catalysts are provided below. Metathesis catalysts can be expensive and therefore desirable

<img file="MX370894B_D0002.tif" />

improve the efficiency of the metathesis catalyst.

[0007] In certain cases, the metathesis of natural oil raw materials can provide a useful way to make chemical intermediates that can be difficult to make by other means. Or, in some other cases, the metathesis of raw materials from natural oils can provide a useful way to produce green alternatives to existing compounds or materials. Therefore, there is a continuing need to develop processes and systems that employ natural oil metathesis to produce commercially and / or technically useful materials and compounds.

Brief Description of the Invention

[0008] In general, methods and systems for producing dibasic esters or dibasic acids by olefin metathesis are described. In some embodiments, one or more of the compounds used to make these dibasic esters or dibasic acids are derived from the refining of a natural oil feedstock, for example, through a metathesis reaction of the natural oil feedstock, or a derivative thereof, in the presence of a metathesis catalyst.

[0009] In a first aspect, the description provides methods for producing an unsaturated dibasic ester, comprising: providing a reagent composition that

<img file="MX370894B_D0003.tif" />

It comprises a terminal olefin ester and an internal olefin ester; and reacting the terminal olefin ester with the internal olefin ester in a reactor in the presence of a first metathesis catalyst to form an unsaturated dibasic ester and a first terminal olefin. In some embodiments, at least a portion of the first terminal olefin is removed from the reactor during the reaction. In some embodiments, at least a portion of one or both of the terminal olefin ester and the internal olefin ester are derived from a natural oil feedstock.

[00010] In some embodiments, the weight to weight ratio of the terminal olefin ester to the internal olefin ester in the reactor is between 5: 1 and 1: 5. In other embodiments, the weight to weight ratio of the terminal olefin ester to the internal olefin ester is 1: 1.

[00011] In some embodiments, the terminal olefin ester is selected from the group consisting of: 4-pentenoic acid ester, 5-hexenoic acid ester, 6-heptenoic acid ester, 7-octenoic acid ester, 8-nonenoic acid ester, 9-decenoic acid ester, 10-undecenoic acid ester, ester 11-dodecenoic acid, 12-tridecenoic acid ester, 13-tetradecenoic acid ester, 14-pentadecenoic acid ester, 15-hexadecenoic acid ester, 16-heptadecenoic acid ester, 17-octadecenoic acid ester, and mixtures of these . In some modalities, the

<img file="MX370894B_D0004.tif" />

Terminal olefin ester is a 9-decenoic acid ester, such as 9-decenoic acid methyl ester. In certain embodiments, the internal olefin ester is selected from the group consisting of: pentenoic acid esters, hexenoic acid esters, heptenoic esters, octenoic acid esters, nonenoic acid esters, decenoic acid esters, undecenoic acid esters, dodecenoic acid esters, tridecenoic acid esters, tetradecenoic acid esters, esters of pentadecenoic acids, hexadecenoic acid esters, heptadecenoic acid esters, octadecenoic acid esters, and mixtures of these. In some embodiments, the internal olefin ester is a 9-dodecenoic acid ester, such as 9-dodecenoic acid methyl ester.

[00012] In some embodiments, at least a portion of the internal olefin ester is formed by reacting a terminal olefin ester portion with a low molecular weight internal olefin or a medium weight internal olefin in the presence of a catalyst of metathesis. In certain embodiments, the low molecular weight internal olefin is selected from the group consisting of: 2-butene, 2-pentene, 2-hexene, 3-hexene, 2-heptene, 3-heptene, 2-octene, 3- octene, 4 -octene, 2-nonene, 3-nonene, 4-nonene, and any mixture thereof. In some embodiments, the low molecular weight internal olefin is 3-hexene.

<img file="MX370894B_D0005.tif" />

[00013] In some embodiments, at least a portion of the terminal olefin ester is formed by reacting a portion of the inner olefin ester with a low molecular weight terminal olefin or a medium weight terminal olefin in the presence of a medium weight terminal olefin. metathesis. In some embodiments, the low molecular weight terminal olefin or a medium weight terminal olefin is selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and any mixture thereof. In some embodiments, it is ethylene.

[00014] In some embodiments, the unsaturated dibasic ester formed is a dibasic 9octadecenedioic acid ester, such as 9octadecenedioic acid dimethyl ester.

[00015] In a second aspect, the description provides methods for producing a saturated dibasic ester, comprising: making an unsaturated dibasic ester according to any of the embodiments of the first aspect; and hydrogenate the unsaturated dibasic ester to form a saturated dibasic ester. In some embodiments, the saturated dibasic ester is a dibasic octadecanedioic acid ester, such as octadecanedioic acid dimethyl ester.

[00016] In a third aspect, the description provides methods for producing a dibasic acid, comprising: making a dibasic ester, wherein the making comprises

<img file="MX370894B_D0006.tif" />

making an unsaturated dibasic ester according to any method of the first aspect or making a saturated dibasic ester according to any method of the second aspect; and converting the dibasic ester to a dibasic acid. In embodiments where an unsaturated dibasic acid is formed, the unsaturated dibasic acid can be further hydrogenated to form a saturated dibasic acid. In some embodiments, the conversion comprises hydrolyzing the dibasic ester to a dibasic acid, for example, by reacting the dibasic ester with water in the presence of an acid catalyst. In some other embodiments, the conversion comprises saponifying the dibasic ester to form a dibasic acid salt (where acidic salt refers to a carboxylate anion, either in solution form or in solid state form), and optionally acidifying the salt. of dibasic acid to form dibasic acid. In some embodiments, the resulting dibasic acid is octadecanedioic acid. In some other embodiments, the resulting dibasic acid is 9octadecenedioic acid.

[00017] In a fourth aspect, the description provides methods for refining a natural oil, comprising: providing a raw material comprising a natural oil; reacting the raw material in the presence of a fourth metathesis catalyst to form a product

<img file="MX370894B_D0007.tif" />

metatized comprising one or more unsaturated glycerides and one or more olefins; separating the unsaturated glycerides in the metatized product from the olefins in the metatized product; transesterifying the separated unsaturated glycerides in the presence of an alcohol to form a transesterified product comprising a terminal olefin ester or an internal olefin ester; and using the terminal olefin ester or the internal olefin ester according to the method of any embodiment of the first aspect to form an unsaturated dibasic ester. In some embodiments, the alcohol is methanol. In some embodiments, the unsaturated dibasic ester is a 9octadecenedioic acid dibasic ester, such as 9octadecenedioic acid dimethyl ester. In some additional embodiments, the resulting unsaturated dibasic ester can be converted to a saturated dibasic ester and / or a saturated dibasic acid according to any of the embodiments of the second and / or third aspects.

[00018] In a fifth aspect, the description provides methods for refining a natural oil, which comprises providing a raw material comprising a natural oil; transesterifying the raw material in the presence of an alcohol to form a transesterified product comprising one or more unsaturated fatty acid esters; reacting the unsaturated fatty acid esters in the presence of a fifth metathesis catalyst to form a metatized product comprising one or more metatized unsaturated esters and one or more olefins; separating the metatized unsaturated esters in the metatized product from the olefins in the metatized product, wherein the separated metatized esters comprise a terminal olefin ester or an internal olefin ester; and using the terminal olefin ester or the internal olefin ester according to the method of any embodiment of the first aspect to form an unsaturated dibasic ester. In some modalities, alcohol is methano1. In some embodiments, the unsaturated dibasic ester is a 9-octadecenedioic acid dibasic ester, such as 9-octadecenedioic acid dimethyl ester. In some additional embodiments, the resulting unsaturated dibasic ester can be converted to a saturated dibasic ester and / or a saturated dibasic acid according to any of the embodiments of the second and / or third aspects.

[00019] New aspects and additional embodiments are provided in the following figures, detailed description and claims.

Brief Description of Figures

[00020] Figure 1 shows a schematic diagram of an embodiment of a process for producing a fuel composition and a transesterified product from a natural oil.

[00021] Figure 2 shows a flow chart illustrating certain modalities for making an unsaturated dibasic ester.

[00022] Figure 3 shows a flow chart illustrating certain modalities for making an unsaturated dibasic ester.

[00023] Figure 4 shows a flow chart illustrating certain modalities for making an unsaturated dibasic ester.

[00024] Figure 5 shows a flow chart illustrating certain modalities for making a saturated dibasic ester.

[00025] Figure 6 shows a flow chart illustrating certain modalities for making a dibasic acid.

[00026] Figure 7 shows a flow chart illustrating certain modalities for making an unsaturated dibasic ester from a raw material comprising a natural oil.

[00027] Figure 8 shows a flow chart illustrating certain modalities for making an unsaturated dibasic ester from a raw material comprising a natural oil.

[00028] Figure 9 shows a graph of 9-DAME and 9-DDAME (by weight) in the reactor versus reaction time (hr) for a process of an embodiment described herein.

<img file="MX370894B_D0008.tif" />

Detailed description of the invention

[00029] The following description cites various aspects and embodiments of the inventions described herein. It does not propose that particular modalities define the scope of the invention. Rather, the embodiments provide non-limiting examples of various compositions, and methods that are within the scope of the disclosed inventions. The description is to be read from the perspective of one of ordinary skill in the art. Therefore, information that is well known to the person skilled in the art is not unnecessarily included.

Definitions

[00030] The following terms and phrases have the meanings indicated below, unless otherwise provided herein. This description may employ other terms and phrases not expressly defined herein. These other terms and phrases should have the meanings that they would have within the context of this description to those skilled in the art. In some cases, a term or phrase can be defined in the singular or plural. In such cases, it is understood that any term in the singular may include its plural counterpart and vice versa, unless expressly stated otherwise.

[00031] As used herein, singular forms

<img file="MX370894B_D0009.tif" />

un, uno, el and la include plural referents unless the context clearly dictates otherwise. For example, reference to a substituent encompasses an individual substituent, as well as two or more substituents, and the like.

[00032] As used herein, the terms eg, exemplary, such as, or including are intended to introduce examples that further clarify more general subject matter. Unless otherwise specified, these examples are provided only as an aid to understanding the applications illustrated in the present description, and are not intended to be limiting in any way.

[00033] As used herein, the term "metathesis catalyst" includes any catalyst or catalyst system that catalyzes a metathesis reaction.

[00034] As used herein, the terms natural oils, natural raw materials, or natural oil raw materials can refer to oils derived from plant or animal sources. The term natural oil includes derivatives of natural oil, unless otherwise indicated. Examples of natural oils include, but are not limited to, vegetable oils, algae oils, fish oils, animal fats, wood pulp oils, derivatives of these oils, combinations of any of these oils, and the like. The examples

<img file="MX370894B_D0010.tif" />

Representative non-limiting vegetable oils include rapeseed oil, coconut oil, corn oil, cottonseed oil, olive oil, palm oil, peanut oil, safflower oil, sesame oil. , soybean oil, sunflower oil, linseed oil, palm kernel oil, tung oil, jatropha oil, mustard oil, carraspique oil, camelina oil, and castor oil. Representative non-limiting examples of animal fats include lard, tallow, poultry fat, yellow fat, and fish oil. Wood pulp oils are by-products of wood pulp processing.

[00035] As used herein, the term "natural oil derivatives" may refer to the compounds or mixture of compounds derived from natural oil using any one or a combination of methods known in the art. These methods include, but are not limited to, saponification, fat splitting, transesterification, esterification, hydrogenation (partial or complete), isomerization, oxidation, and reduction. Representative non-limiting examples of natural oil derivatives include gums, phospholipids, oil solubilizate, acidified oil solubilizate, distillate or distillate sludge, fatty acids, and fatty acid alkyl ester (for example, non-limiting examples such as 2-ethylhexyl14 ester), hydroxy substituted variations thereof from natural oil. For example, the natural oil derivative can be a fatty acid methyl ester (FAME) derived from the glyceride of natural oil. In some embodiments, a raw material includes canola or soybean oil, as a non-limiting example, soybean oil, refined, bleached, and deodorized (ie, RBD soybean oil). Soybean oil typically comprises about 95% by weight or more (eg, 99% by weight or more) of fatty acid triglycerides. Most of the fatty acids in soybean oil polyol esters include saturated fatty acids, as a non-limiting example, palmitic acid (hexadecanoic acid) and stearic acid (octadecanoic acid), and unsaturated fatty acids, as a non-limiting example. , oleic acid (9-octadecenoic acid), linoleic acid (9,12octadecadienoic acid) and linolenic acid (9,12,15octadecatrienoic acid).

[00036] As used herein, the terms olefin and olefins can refer to hydrocarbon compounds that have at least one unsaturated carbon-carbon double bond. In certain embodiments, the terms olefin or olefins can refer to a group of unsaturated carbon-carbon double bond compounds with different carbon lengths. A compound having a terminal carbon-carbon double bond can be referred to as a terminal olefin, while an olefin having a non-terminal carbon-carbon double bond can be referred to as an internal olefin.

[00037] As used herein, the term "low molecular weight olefin" can refer to any one or a combination of unsaturated straight, branched or cyclic hydrocarbons, in the range of C2 to C14. Low molecular weight olefins include alpha-olefins or terminal olefins, where the unsaturated carbon-carbon bond is present at one end of the compound. Low molecular weight olefins can also include dienes or tripnes. Low molecular weight olefins can also include internal olefins or low molecular weight internal olefins. In certain embodiments, the low molecular weight internal olefin is in the range of C4 to C14. Examples of low molecular weight olefins in the C2 to C6 range include, but are not limited to: ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene, 3-pentene, 2-methyl -1-butene, 2-methyl-2-butene, 3-methyl-l-butene, cyclopentene, 1,4-pentadiene, 1-hexene, 2-hexene, 3-hexene, 4-hexene, 2-methyl-1-pentene, 3 -methyl-l-pentene, 4-methyl-l-pentene, 2-methyl-2-pentene, 3-methyl-2-pentene, 4-methyl-2-pentene, 2-methyl-3-pentene, and cyclohexene. Non-limiting examples of low molecular weight olefins in the C7 to C9 range include 1,4-heptadiene, 116

<img file="MX370894B_D0011.tif" />

heptene, 3,6-nonadiene, 3-nonene, 1,4,7-octatriene. Other possible low molecular weight olefins include styrene and vinyl cyclohexane. In certain embodiments, it is preferred to use a mixture of olefins, the mixture comprising linear and branched olefins of low molecular weight in the C4-C10 range. In one embodiment, it may be preferable to use a mixture of linear and branched C4 olefins (ie, combinations of: 1-butene, 2-butene, and / or isobutene). In other embodiments, a larger range of CllC14 can be used.

[00038] As used herein, the term "medium weight olefin" can refer to any one or a combination of straight, branched, or cyclic, unsaturated hydrocarbons in the C15 to C24 range. Medium weight olefins include alpha-olefins or terminal olefins, where the unsaturated carbon-carbon bond is present at one end of the compound. Medium weight olefins can also include dienes or trines. Medium weight olefins also include internal olefins or medium weight internal olefins. In certain embodiments, it is preferred to use a mixture of olefins.

[00039] As used herein, the terms esters and esters can refer to compounds having the general formula: R^to-COO-R^b, where R^to and R^b denote any organic compound (such as alkyl, aryl, or silyl groups),

<img file="MX370894B_D0012.tif" />

including those having heteroatom-containing substituent groups. In certain modalities, R^to and R^bdenote alkyl or aryl groups. In certain embodiments, the term ester or esters can refer to a group of compounds with the general formula described above, where the compounds have different carbon lengths. In certain embodiments, the asters can be esters of glycerol, which is a trihydric alcohol. The term "glyceride" can refer to esters where one, two, or three of the -OH groups of glycerol have been esterified. Thus, the term unsaturated glyceride can refer to monoglycerides, diglycerides, or triglycerides, where one or more of the acidic portions of the ester contain unsaturation, eg, a carbon-carbon double bond.

[00040] It is pointed out that an olefin can also comprise an ester, and an ester can also comprise an olefin, and if the group R^to or R^b in the general formula R^to-COO-R^b it contains an unsaturated carbon-carbon double bond. For example, a terminal olefin ester can refer to an ester compound where R^to it has an olefin attached to the end of the chain. An internal olefin ester can refer to an ester compound where R has an olefin positioned at an internal location in the chain. Additionally, the term terminal olefin can refer to an ester or acid thereof, where R^b denotes hydrogen or any compound

<img file="MX370894B_D0013.tif" />

organic (such as an alkyl, aryl, or silyl group) and R^tohas an olefin placed at the end of the chain, and the term internal olefin can refer to an ester or an acid thereof, where R^b denotes hydrogen or any organic compound (such as an alkyl, aryl, or silyl group) and R^to it has an olefin placed in an internal location of the chain.

[00041] As used herein, the terms metathesis and metatization can refer to the reaction of a raw material in the presence of a metathesis catalyst to form a metatized product comprising a new olefinic compound. Metatization can refer to cross-metathesis (aka co-metathesis), auto-metathesis, ring-opening metathesis, ring-opening metathesis polymerizations (ROMP), ring-closure metathesis (RCM), and acyclic diene metathesis. (ADMET). As a non-limiting example, metatization can refer to the reaction of two triglycerides present in a natural raw material (auto-metathesis) in the presence of a metathesis catalyst, where each triglyceride has an unsaturated carbon-carbon double bond, forming thus a new mixture of definitions and esters that may include a triglyceride dimer. These triglyceride dimers can have more than one olefinic bond, thus higher oligomers can also be formed.

<img file="MX370894B_D0014.tif" />

Additionally, metatization can refer to the reaction of an olefin, such as ethylene, and a triglyceride in a natural raw material that has at least one unsaturated carbon-carbon double bond, thereby forming new olefin molecules as well as new ester molecules. (cross metathesis).

[00042] As used herein, the term "dibasic ester" can refer to compounds having the general formula R^to-OOC-Y-COO-R^b, where Y, R^to, and R^b denote any organic compound (such as alkyl, aryl, or silyl groups), including those that have heteroatom-containing substituent groups. In certain embodiments, Y is a saturated or unsaturated hydrocarbon, and R^toand R^b they are alkyl or aryl groups. In cases where Y is a saturated hydrocarbon, the dibasic ester can be referred to as a saturated dibasic ester. In cases where Y is an unsaturated hydrocarbon, the dibasic ester can be referred to as an unsaturated dibasic ester.

[00043] As used herein, the term "dibasic acid" can refer to compounds having the general formula R^to-OOC-Y-COO-R^b, where R^to and R^b are hydrogen, and Y denotes any organic compound (such as an alkyl, aryl, or silyl group), including those having heteroatom substituent groups. In certain embodiments, Y is a saturated or unsaturated hydrocarbon. In

<img file="MX370894B_D0015.tif" />

In cases where Y is a saturated hydrocarbon, the dibasic acid can be referred to as a saturated dibasic acid. In 1 cases where Y is an unsaturated hydrocarbon, the dibasic acid can be referred to as an unsaturated dibasic acid.

[00044] As used herein, hydrocarbon refers to an organic group composed of carbon and hydrogen, which can be saturated or unsaturated, and can include aromatic groups. The term "hydrocarbyl" refers to a monovalent or polyvalent hydrocarbon portion.

[00045] In some cases, the olefin may be an alkene, which refers to a straight or branched chain non-aromatic hydrocarbon having 2 to 30 carbon atoms and one or more carbon-carbon double bonds, which may optionally be substituted, as further described herein, with multiple degrees of substitution allowed. A monounsaturated alkene refers to an alkene that has one carbon-carbon double bond, while a polyunsaturated alkene refers to an alkene that has two or more carbon-carbon double bonds. A lower alkene, as used herein, refers to an alkene having 2 to 8 carbon atoms.

[00046] As used herein, alpha-olefin refers to an olefin (as defined above) having a terminal carbon-carbon double bond. In some

<img file="MX370894B_D0016.tif" />

In embodiments, the alpha-olefin is a terminal alkene, which is an alkene (as defined above) that has a terminal carbon-carbon double bond. Additional carbon-carbon double bonds may be present.

[00047] As used herein, "alcohol or alcohols" refer to compounds having the general formula: R^to-OH, where R^to denotes any organic moiety (such as alkyl, aryl, or silyl groups), including those that have heteroatom-containing substituent groups. In certain modalities, R^to denotes alkyl, aryl, or alcohol groups. In certain embodiments, the term alcohol or alcohols can refer to a group of compounds with the general formula described above, wherein the compounds have different carbon lengths. The term "hydroxyl" refers to an -OH moiety.

[00048] As used herein, "alkyl" refers to a saturated, straight or branched chain hydrocarbon having 1 to 3 0 carbon atoms, which may be optionally substituted, as further described herein, with multiples degrees of substitution that are allowed. Examples of alkyl, as used herein, include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, isobutyl, n-butyl, sec-butyl, tert-butyl, isopentyl, n-pentyl, neopentyl, n- hexyl, and 2-ethylhexyl. The number of carbon atoms in a group

<img file="MX370894B_D0017.tif" />

alkyl is represented by the phrase C_x._and alkyl, which refers to an alkyl group, as defined herein, that contains from x to y, including carbon atoms. In this way, Ci-₆ alkyl represents an alkyl chain having 1 to 6 carbon atoms and includes for example, but is not limited to, methyl, ethyl, n-propyl, isopropyl, isobutyl, n-butyl, sec-butyl, tert-butyl, isopentyl, npentyl, neopentyl, and n-hexyl. In some cases, the alkyl group may be divalent, in which case the group may alternatively be referred to as an alkylene group.

[00049] As used herein, "alkenyl" refers to a straight-chain or branched non-aromatic hydrocarbon having 2 to 30 carbon atoms and having one or more carbon-carbon double bonds, which may be optionally substituted, as further described herein, with multiple degrees of substitution allowed. Examples of alkenyl, as used herein, include, but are not limited to, ethenyl, 2-propenyl, 2-butenyl, and 3-butenyl. The number of carbon atoms in an alkenyl group is represented by the phrase C_x._and alkenyl, which refers to an alkenyl group, as defined herein, that contains from x to y, including carbon atoms. In this way, C₂-6 alkenyl represents an alkenyl chain having 2 to 6 carbon atoms, and includes for example, but is not limited to, ethenyl, 2-propenyl, 2-butenyl and 3-butenyl. In some cases, the alkenyl group may be divalent, in which case the group may alternatively be referred to as an alkenylene group.

[00050] As used herein, the terms paraffin and paraffin can refer to hydrocarbon compounds having only individual carbon-carbon bonds, having the general formula C_nH_2n+ 2 / where, in certain modalities, n is greater than approximately 20.

[00051] As used herein, the terms isomerization, isomerization, or isomerization can refer to the reaction and conversion of straight chain hydrocarbon compounds, such as normal paraffins, to branched hydrocarbon compounds, such as isoparaffins. In other embodiments, isomerization of an olefin or unsaturated ester indicates a change in the carbon-carbon double bond to another location in the molecule (e.g., conversion of 9-decenoic acid to 8-decenoic acid), or indicates a change in geometry. of the compound at the carbon-carbon double bond (eg, cis to trans). As a non-limiting example, n-pentane can be isomerized in a mixture of n-pentane, 2-methylbutane, and 2,2-dimethylpropane. Normal paraffin isomerization can be used to improve the overall properties of a fuel composition. Additionally, isomerization can refer to the conversion of branched paraffins into

<img file="MX370894B_D0018.tif" />

additional, more branched paraffins.

[00052] As used herein, the term "yield" can refer to the total weight of fuel produced from the hydrogenation and metathesis reactions. It can also refer to the total weight of the fuel after a separation step and / or isomerization reaction. It can be defined in terms of a% yield, where the total weight of the fuel produced is divided by the total weight of the natural oil feedstock and, in some embodiments, the low molecular weight olefin and / or weight olefin. medium, combined.

[00053] As used herein, "admixture" or "mixing" or "blending" broadly refers to any combination of two or more compositions. The two or more compositions do not need to have the same physical state; in this way, solids can be mixed with liquids, for example, to form a slurry, suspension or solution. Furthermore, these terms do not require any degree of homogeneity or uniformity of the composition. In this way, these mixtures can be homogeneous or heterogeneous, or they can be uniform or non-uniform. Additionally, the terms do not require the use of any particular equipment to carry out the mixing, such as an industrial mixer.

[00054] As used herein, optionally

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it means that the events subsequently described may or may not occur. In some modalities, the optional event does not appear. In some other modalities, the optional event occurs one or more times.

[00055] As used herein, "comprising or comprising or" comprising or comprised "refers to groups that are open, meaning that the group may include additional members, in addition to those expressly cited. For example, the phrase "comprise A" means that A must be present, but other members may be present as well. The terms includes, has, and composed of and their grammatical variants have the same meaning. In contrast, consist of or consist of or consist of refer to groups that are closed. For example, the phrase consists of A means that A and only A is present.

[00056] As used herein, or is to be given its broadest reasonable interpretation, and is not limited to either / or construction. Thus, the term "comprising A or B" means that A may be present and not B, or that B is present and not A, or that A and B are both present. Additionally, if A, for example, defines a class that can have multiple members, for example Al and A2, then one or more members of the class can be present concurrently.

[00057] As used herein, "providing" is to be regarded as having its broadest reasonable scope. For example, providing a composition comprising a particular compound includes, but is not limited to, adding the compound to the composition, generating the compound in the composition by a chemical reaction, or receiving the composition, for example, as the product. from another process.

[00058] As used herein, the various functional groups depicted will be understood to have a point of attachment on the functional group having the dash (-) or asterisk (*). In other words, in the case of -CH2CH2CH3, the point of attachment will be understood to be the CH group₂ on the far left. If a group is cited without an asterisk or hyphen, then the point of attachment is indicated by the simple and ordinary meaning of the cited group.

[00059] As used herein, multi-atom bivalent species are to be read from left to right. For example, if the specification or claim cites ADE and D is defined as -OC (O) -, the resulting group with D replaced is: A-OC (O) -E and not AC (O) OE.

[00060] As used herein, the terms fuels and fuel compositions refer to materials that meet the required specifications or to the mixture of components that are useful in formulating fuel compositions but, by themselves, do not meet

<img file="MX370894B_D0020.tif" />

with all the specifications required for a fuel.

[00061] As used herein, the term "jet fuel" or "jet fuel" may refer to kerosene or naphtha-type fuel cuts, or military grade jet engine fuel compositions. Kerosene-type jet fuel (including Jet A and Jet Al) have a carbon number distribution between about 8 and about 16. Jet A and Jet Al typically have a flash point of at least about 38 ° C, an autoignition temperature of about 210 ° C, a freezing point of less than or equal to about -40 ° C for Jet A and -47 ° C for Jet Al, a density of about 0.8 g / cc at 15 ° C, and an energy density of about 42.8-43.2 MJ / kg. Wide-cut or naphtha-type jet fuel (including Jet B) has a carbon number distribution between about 5 and about 15. Typically Jet B comprises a flash point below about 0'C, a temperature of auto-ignition of approximately 250 ° C, a freezing point of approximately -51 ° C, a density of approximately 0.78 g / cc, and an energy density of approximately 42.8-43.5 MJ / kg. Military grade jet fuel refers to Jet Propulsion or

<img file="MX370894B_D0021.tif" />

JP numbering system (JP-1, JP-2, JP-3, JP-4, JP-5, JP6, JP-7, JP-8, etc.). Military grade jet engine fuels may comprise alternative or additional additives to have higher flash points than Jet A, Jet Al, or Jet B in order to cope with the heat and stress suffered during supersonic flight.

[00062] As used herein, the term diesel fuel can refer to a hydrocarbon composition that has the following property characteristics, including a carbon number distribution between about 8 and about 25. Diesel fuels typically also have a Specific gravity of approximately 0.82-1.08 at 15.6 ° C (60 ° F), based on water having a specific gravity of 1 to 60 ° F. Diesel fuels typically have a distillation range between about 180-340 ° C (356-644 ° F). Additionally, diesel fuels have a minimum cetane number of approximately 40.

[00063] As used herein, the term carbon number distribution can refer to the variety of compounds present in a composition, where each compound is defined by the number of carbon atoms present. As a non-limiting example, a naphtha-type jet fuel typically comprises a range of hydrocarbon compounds wherein the majority of these compounds have between 5 and 15 carbon atoms each. A kerosene type jet engine fuel typically comprises a range of hydrocarbon compounds wherein the majority of these compounds have between 8 and 16 carbon atoms each. A diesel fuel typically comprises a distribution of hydrocarbon compounds where most of these compounds have between 8 and 25 carbon atoms each.

[00064] As used herein, the term "energy density" may refer to the amount of energy stored in a given system per unit mass (MJ / kg) or per unit volume (MJ / L), where MJ refers to million joules. As a non-limiting example, the energy density of kerosene or naphtha type jet fuel is typically greater than about 40 MJ / kg.

Methods for making an unsaturated dibasic ester

[00065] The disclosure provides methods for making an unsaturated dibasic ester, comprising: providing a reagent composition comprising a terminal define ester and an internal olefin ester; and reacting the terminal olefin ester with the internal olefin ester in a reactor in the presence of a first metathesis catalyst to form an unsaturated dibasic ester and a first terminal olefin. In some embodiments, the unsaturated dibasic ester can be further converted to

<img file="MX370894B_D0022.tif" />

dibasic acids, for example, by methods including hydrolysis or saponification. In some of these embodiments, conversion may occur after hydrogenation.

[00066] In certain embodiments, dibasic acids and / or dibasic esters and olefin by-products can be formed by reacting terminal olefin esters having the following structure:

<img file="MX370894B_D0023.tif" />

O (where X is a saturated or unsaturated alkyl chain of C₃-Ci₈, and R is an alkyl group, which may be optionally unsaturated or contain ether, or hydrogen bonds) with internal olefins (eg, internal olefin esters) in the presence of a metathesis catalyst. In certain embodiments, the terminal olefin ester is derived from a natural oil feedstock (described in more detail below). In other embodiments, the terminal olefin is purchased or produced from an external source separate from those derived from the natural oil feedstock.

[00067] In some embodiments, X is - (CH2) 2-CH =, - (CH₂) 3CH =, - (CH₂) 4-CH =, - (CH₂) 5-CH =, - (CH₂) 6-CH =, - (CH₂) 7-CH =,

- (CHz) 8-CH =, - &lt;CH₂)₉-CH =, - (CHz) io-CH =, - (CH₂) 11-CH =, - (CH₂) i₂CH =, - (CH₂) 13-CH =, - (CH₂) 14-CH =, or - (CH2) 15-CH =. In some of these modalities, X is - (CH₂)₇-CH =. In some modalities, R

<img file="MX370894B_D0024.tif" />

is methyl, ethyl, isopropyl, propyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, neopentyl, hexyl, or 2-ethylhexyl. In some of these embodiments, R is methyl, ethyl, or isopropyl. In some of these embodiments, R is methyl.

[00068] In certain embodiments, the terminal olefin ester is selected from the group consisting of: an ester of 4-pentenoic acid, an ester of 5-hexenoic acid, an ester of 6-heptenoic acid, an ester of 7-octenoic acid, an ester of 8-nonenoic acid, an ester of 9-decenoic acid, an ester of 10-undecenoic acid, an ester of 11-dodecenoic acid, an ester of 12-tridecenoic acid, an ester of 13-tetradecenoic acid, an ester of 14-pentadecenoic acid, an ester of 15-hexadecenoic acid, an ester of 16-heptadecenoic acid, an ester of 17-octadecenoic acid, acids of these, and any mix of these. In some embodiments, the terminal olefin is a 9-decenoic acid ester, such as 9-decenoic acid methyl ester.

[00069] In certain embodiments, the weight to weight ratio of the terminal olefin ester to the inner olefin ester, eg, in the reagent composition, the cross-metathesis reaction is between 1:99 (inner terminal) and 99: 1 (terminal to internal). In some of the other embodiments, the weight ratio of the terminal and internal olefin is between

1: 5 and 5: 1. In some of the other modalities, the relationship in

<img file="MX370894B_D0025.tif" />

weight between terminal and internal olefin is between 1: 2 and 2: 1. In some embodiments, the weight ratio of terminal to internal olefin is about 1: 1.

[00070] In certain embodiments, dibasic acids and / or dibasic asters and olefin by-products can be formed by reacting internal olefin esters having the following structure:

<img file="MX370894B_D0026.tif" />

O (where X 'is a saturated or unsaturated alkyl chain of C₃-Ci8, R 'is an alkyl group, which may be optionally unsaturated or contain ether, or hydrogen linkages, and R is C1-8 alkyl, which is optionally unsaturated) with terminal olefins (eg terminal olefin esters) in the presence of a metathesis catalyst. In certain embodiments, the internal olefin ester is derived from a natural oil feedstock (described in more detail below). In other embodiments, the internal olefin ester is purchased or produced from an external source separate from that derived from the natural oil feedstock.

[00071] In some embodiments, X 'is - (CH2) 2-CH =, - (CH2) 3CH =, - (CH₂) 4-CH =, - (CH₂)₅-CH =, - (CH₂)₆-CH =, - (CH₂)₇-CH =,

- (CH2) b-CH =_z - (CH₂) 9-CH =, - (CH2) io-CH =, - (CH2) ii-CH =, - (CH₂) i2CH =, - (CH2) i3-CH =, - (CH2) u-CH =, or - (CH2) i5-CH =. In some of

<img file="MX370894B_D0027.tif" />

these modalities, X 'is - (CH₂) 7-CH =. In some embodiments, R 'is methyl, ethyl, isopropyl, propyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, neopentyl, hexyl, or 2-ethylhexyl. In some of these embodiments, R 'is methyl, ethyl, or isopropyl. In some of these embodiments, R 'is methyl. In some modalities, R is Ci-₆ I rent. In some of these embodiments, R is methyl, ethyl, propyl, or butyl. In some of these embodiments, R is methyl or ethyl. In some of these embodiments, R is ethyl, and where the first terminal olefin is 1-butene.

[00072] In certain embodiments, the internal olefin ester is selected from the group consisting of: esters of pentenoic acid, esters of hexenoic acid, esters of heptenoic acid, esters of octenoic acid, nonenoic esters, esters of decenoic acid, esters of undecenoic acid, esters of dodecenoic acid, esters of tridecenoic acids, esters of tetradecenoic acid, esters of pentadecenoic acid, hexadecenoic acid esters, heptadecenoic acid esters, octadecenoic acid esters, acids thereof, and mixtures thereof. In a particular embodiment, the internal olefin is 9-undecenoic acid ester. In another particular embodiment, the internal olefin is 9-dodecenoic acid ester.

[00073] In certain embodiments, the methods comprise providing a reagent composition comprising a

<img file="MX370894B_D0028.tif" />

terminal olefin ester (according to any of the previous modalities) and an internal olefin ester (according to any of the previous modalities). In some of these embodiments, the reagent composition may include an amount of a metathesis catalyst (described in more detail below) at suitable concentrations. The reagent composition can also include one or more olefins, such as terminal alkenes or internal alkenes. In some embodiments, the terminal olefin ester and the internal olefin ester collectively at least 50 percent by weight, or 60 percent by weight, or 70 percent by weight, or 80 percent by weight, of the weight. total of compounds in the reagent composition.

[00074] The metathesis reaction can be carried out under any suitable conditions to produce the desired metathesis product. For example, stoichiometry, atmosphere, solvent, temperature, and pressure can be selected by one of ordinary skill in the art to produce a desired product and minimize unwanted by-products. In some embodiments, the metathesis process can be carried out under an inert atmosphere. Similarly, in embodiments where a reagent is supplied as a gas, an inert gaseous diluent can be used in the gas stream. In these embodiments, the inert atmosphere or inert gaseous diluent is typically an inert gas, meaning that

<img file="MX370894B_D0029.tif" />

the gas does not interact with the metathesis catalyst to prevent catalysis to a substantial degree. For example, non-limiting examples of inert gases include helium, neon, argon, and nitrogen, used individually or in conjunction with other inert gases.

[00075] The reactor design for the metathesis reaction can vary depending on a variety of factors, including, but not limited to, the scale of the reaction, the reaction conditions (heat, pressure, etc.), the identity of the catalyst, the identity of the materials that are reacted in the reactor, and the nature of the raw material that is used. Suitable reactors can be designed by those of skill in the art, depending on relevant factors, and incorporated into processes, such as those described herein.

[00076] The metathesis reactions described herein generally occur in the presence of one or more metathesis catalysts. These methods can employ any suitable metathesis catalyst. The metathesis catalyst in this reaction can include any catalyst or catalyst system that catalyzes a metathesis reaction. Any known metathesis catalyst can be used, alone or in combination with one or more additional catalysts. Examples of metathesis catalysts and process conditions are described in US 2011/0160472,

<img file="MX370894B_D0030.tif" />

incorporated herein by reference in its entirety, except that in the event of any inconsistent description or definition in this specification, the description or definition herein shall be deemed to prevail. Several metathesis catalysts described in US 2011/0160472 are currently available from Materia, Inc. (Pasadena, Calif.).

[00077] In some embodiments, the metathesis catalyst includes a Grubbs-type defined metathesis catalyst and / or an entity derived therefrom. In some embodiments, the metathesis catalyst includes a first generation Grubbs-type olefin metathesis catalyst and / or an entity derived therefrom. In some embodiments, the metathesis catalyst includes a second generation Grubbs-type olefin metathesis catalyst and / or an entity derived therefrom. In some embodiments, the metathesis catalyst includes a first generation HovedaGrubbs type olefin metathesis catalyst and / or an entity derived therefrom. In some embodiments, the metathesis catalyst includes a second generation HovedaGrubbs type olefin metathesis catalyst and / or an entity derived therefrom. In some embodiments, the metathesis catalyst includes one or a plurality of the ruthenium-carbon metathesis catalysts sold by Materia, Inc., of Pasadena California and / or one or more entities derived from

<img file="MX370894B_D0031.tif" />

these catalysts. Representative metathesis catalysts from Materia, Inc. for use in accordance with the present teachings include, but are not limited to, those sold under the following product numbers, as well as combinations thereof: product no. C823 (CAS no.

172222-30-9), product no. C848 (CAS no. 246047-72-3), product no. C601 (CAS no. 203714-71-0), product no. C627 (CAS no. 301224-40-8), product no. C571 (CAS no. 927429-616), product no. C598 (CAS no. 802912-44-3), product no. C793 (CAS No. 927429-60-5), Product No. C801 (CAS no. 194659-03-9), product no. C827 (CAS no. 253688-91-4), product no. C884 (CAS no. 900169-53-1), product no. C833 (CAS no. 1020085-61-3), product no. C859 (CAS no. 832146-686), product no. C711 (CAS no. 635679-24-2), product no. C933 (CAS No. 373640-75-6).

[00078] In some embodiments, the metathesis catalyst includes a complex of molybdenum and / or tungsten carbon and / or an entity derived from this complex. In some embodiments, the metathesis catalyst includes a Schrock-type olefin metathesis catalyst and / or an entity derived therefrom. In some embodiments, the metathesis catalyst includes a high oxidation state alkylidene complex of molybdenum and / or an entity derived therefrom. In some embodiments, the metathesis catalyst includes a high state alkylidene complex

<img file="MX370894B_D0032.tif" />

oxidation of tungsten and / or an entity derived from it. In some embodiments, the metathesis catalyst includes molybdenum (VI). In some embodiments, the metathesis catalyst includes tungsten (VI). In some embodiments, the metathesis catalyst includes an alkylidene complex containing molybdenum and / or tungsten of a type described in one or more of (a) Angew. Chem. Int. Ed. Engl, 2003, 42, 45924633 .; (B) Chem. Rev., 2002, 102, 145-179; and / or (c) Chem. Rev. , 2009, 109, 3211-3226, each of which is incorporated herein by reference in its entirety, except that in the event of any inconsistent description or definition of this description, the description or definition in this description is deemed to prevail. the present.

[00079] In certain embodiments, the metathesis catalyst is dissolved in a solvent before conducting the metathesis reaction. In these certain embodiments, the chosen solvent can be selected to be substantially inert with respect to the metathesis catalyst. For example, substantially inert solvents include, without limitation: aromatic hydrocarbons, such as benzene, toluene, xylenes, and the like; halogenated aromatic hydrocarbons, such as chlorobenzene and dichlorobenzene; aliphatic solvents, including pentane, hexane, heptane, cyclohexane, and the like; and chlorinated alkanes, such as dichloromethane, chloroform, dichloroethane, and the like. In some embodiments, the solvent comprises toluene.

[00080] In other embodiments, the metathesis catalyst is not dissolved in a solvent prior to carrying out the metathesis reaction. The catalyst, instead, for example, can be slurried with the unsaturated ester, where the natural oil or unsaturated ester is in a liquid state. Under these conditions, it is possible to remove the solvent (eg toluene) from the process and eliminate the downstream olefin losses when the solvent is removed. In other embodiments, the metathesis catalyst can be added in a solid state (and not slurry) form to the unsaturated ester (eg, as a screw feed).

[00081] The temperature of the metathesis reaction may in some cases be a rate-controlling variable, where the temperature is selected to provide a desired product at an acceptable rate. In certain embodiments, the temperature of the metathesis reaction is greater than -40 ° C, or greater than -20 ° C, or greater than 0 ° C, or greater than 10 ° C. In certain embodiments, the metathesis reaction temperature is less than 200 ° C, or less than 150 ° C, or less than 120 ° C. In some embodiments, the metathesis reaction temperature is between 0 ° C and 150 ° C, or is between 10 ° C and 120 ° C.

[00082] The metathesis reaction can be run under any desired pressure. In some cases, it may be desirable to maintain a total pressure that is high enough to keep the cross-metathesis reagent in solution. Therefore, as the molecular weight of the cross-metathesis reagent increases, the lower pressure range typically decreases as the boiling point of the cross-metathesis reagent increases. The total pressure can be selected to be greater than 0.01 atm, or greater than 0.1 atm (10 kPa), or greater than 0.3 atm (30 kPa), or greater than 1 atm (100 kPa). In some embodiments, the reaction pressure is not more than about 70 atm (7000 kPa), or is not more than about 30 atm (3000 kPa). In some embodiments, the pressure for the metathesis reaction ranges from about 1 atm (100 kPa) to about 30 atm (3000 kPa).

[00083] This process of cross-metatization of a terminal olefin with an internal olefin may have certain advantages over an auto-metathesis reaction to create a diacid or diacid ester. Compared to the self-metathesis of a terminal olefin ester, the cross-metathesis reaction of a terminal olefin ester with an internal olefin ester results in the formation of an alkene by-product in addition to ethylene (e.g., a by-product C3 + alkene). For example, depending on the identity of the internal olefin esters used, the

<img file="MX370894B_D0033.tif" />

Alkene byproducts can include, in some embodiments, a C3-8 terminal alkene, such as propylene, 1-butene, 1-pentene, 1-hexene, and the like. In certain cases, the presence of substantial amounts of ethylene can function as a contaminant to the metathesis catalyst, thereby reducing the yield and increasing the costs of running the reaction, since increased concentrations of catalyst may be required. Additionally, in some cases, substantial amounts of ethylene can convert some metathesis catalysts to isomerization catalysts, which then requires the addition of isomerization inhibitors to avoid obtaining a fired array of products. And compared to the self-metathesis of an internal olefin ester, the cross-metathesis reaction of a terminal olefin ester with an internal olefin ester results in the formation of an alkene by-product that has fewer carbon atoms (and thus a lower boiling point). For example, auto-metathesis of 9-dodecenoic acid methyl ester produces 3-hexene as a by-product, whereas cross-metathesis of 9-dodecenoic acid methyl ester with 9-decenoic acid methyl ester produces 1-butene. as a by-product. The production of a lower-boiling alkene by-product may have certain advantages in some embodiments, such as making it easier to separate the

<img file="MX370894B_D0034.tif" />

byproduct of alkene from the reactor and improve the yield of the reaction. It also allows the use of lower temperatures and / or less severe pressure conditions. In both reactions self-metathesis of ester terminal olefin or ester internal olefin may occur even in the reactor, the availability of the route cross along metathesis with the option to manipulate the conditions to promote the metathesis reaction crossed, provides substantial advantages not so easily obtainable by auto-metathesis.

[00084] In certain embodiments, at least 70% by weight, 80% by weight, or 90% by weight of dibasic ester and / or dibasic acid is formed from the cross-metathesis reaction of a terminal olefin and an internal olefin in the presence of less than 150 ppm, 100 ppm, 50 ppm, 25 ppm or 10 ppm of catalyst. A comparable auto-metathesis reaction with terminal olefins (such as 9-decenoic acid ester) under similar reaction conditions may require more catalyst (eg, more than 150 ppm, or more than 500 ppm) to achieve similar ester yields. dibasic and / or dibasic acids (potentially due to the formation of the ethylene by-product).

[00085] In certain embodiments, the yield of dibasic ester and / or dibasic acid is enhanced by removing the olefin by-product (eg, a terminal olefin,

<img file="MX370894B_D0035.tif" />

such as propylene, 1-butene, 1-pentene, 1-hexene, etc.) formed in the cross-metathesis reaction of the metathesis product, while the reaction between the terminal olefin ester and internal olefin ester is running. For example, in some embodiments, at least a portion of the olefin by-product is removed from the reactor during the reaction of the terminal olefin ester and the internal olefin ester. In some modalities, at least 20%, or at least 30%, or at least 40%, or at least 50%, or at least 60%, or at least 70%, or at least 80%, or at least 90% , or at least 95%, or greater than 95%, of the terminal olefin formed by-product is removed from the reactor during the reaction. Removal of the olefin by-product can help to promote the cross-metathesis reaction at the expense of the auto-metathesis reactions, thereby improving the yield of the resulting dibasic acid or ester. Removal can be carried out by any suitable means. For example, in some embodiments, the reactor is equipped with a suitable gas outlet to release gases from the reactor. In some of these embodiments, the gas outlet may include a pressure regulator. Additionally, removal can be carried out during any suitable time or sequence. In some embodiments, the removal is continuous, or at least continuous after a certain stage of the reaction. In other modalities, however, removal occurs in certain

<img file="MX370894B_D0036.tif" />

discontinuous moments, such that the terminal olefin (as well as other gases) is removed from the reactor for a time, and then the removal is stopped for a time.

[00086] In other embodiments, the performance of the dibasic ether and / or dibasic acid is improved by sparging the metathesis products in the metathesis reactor with a chemically inert gas (eg, nitrogen, argon, or helium) to vent the gases. / Dissolved by-products (eg olefin by-products) in the metathesis product.

[00087] In certain embodiments, the cross-metathesis reaction of the terminal olefin ester and the internal olefin ester produces an unsaturated dibasic ester. In some embodiments, the resulting unsaturated dibasic ester is a compound of the following structure:

O /^R'RX' O

Or where R, R ', X, and X' are as defined in any of the above embodiments. In some embodiments, -X = X'es - (CH₂) 7-CH = CH-CH₂) 7-

[00088] In some embodiments, at least a portion of the internal olefin ester in the reagent composition is formed by reacting a portion of the ester terminal olefin with a low molecular weight internal olefin or a

<img file="MX370894B_D0037.tif" />

medium weight internal olefin in the presence of a metathesis catalyst. In certain embodiments, the low molecular weight internal olefin is selected from the group consisting of: 2-butene, 2-pentene, 2-hexene, 3-hexene, 2-heptene, 3-heptene, 2-octene, 3-octene, 4 -octene, 2-nonene, 3-nonene, 4-nonene, and mixtures of these. In some embodiments, the low molecular weight internal olefin is 2-butene. In some other embodiments, the internal low molecular weight olefin is 3-hexene. In some embodiments, this reaction to generate internal olefin ester is carried out in the same reactor as the cross-metathesis reaction of the internal olefin ester and the terminal olefin ester, for example, using the same metathesis catalyst. In some other embodiments, however, this reaction to generate internal olefin ester is carried out separately from the cross-metathesis of the internal olefin ester and the terminal olefin ester. For example, in some embodiments, it is carried out in a separate reactor and / or in the same reactor at an earlier time. In some of these embodiments, this metathesis reaction and the olefinic ester cross-metathesis reaction use the same metathesis catalyst. In some other embodiments, the separate metathesis reactions employ a different metathesis catalyst. This reaction can be used beneficially, for example, in cases where it can

<img file="MX370894B_D0038.tif" />

it is undesirable or inconvenient to obtain certain amounts of the internal olefin ester. Thus, in these embodiments, the internal olefin ester can be generated from the existing supply of the internal olefin ester.

[00089] In some embodiments, at least a portion of the terminal olefin ester in the reagent composition is formed by reacting a portion of the inner olefin ester with a terminal olefin in the presence of a metathesis catalyst. In certain embodiments, the internal olefin is ethylene, propylene, 1-butene, or any mixture of these. In some embodiments, the terminal olefin is ethylene. In some embodiments, this reaction to generate terminal olefin ester is carried out in the same reactor as the cross-metathesis reaction of the internal olefin ester and the terminal olefin ester, for example, using the same metathesis catalyst. In some other embodiments, however, this reaction to generate the terminal olefin ester is carried out separately from the cross-metathesis of the internal olefin ester and the terminal olefin ester. For example, in some embodiments, it is carried out in a separate reactor and / or in the same reactor at an earlier time. In some of these embodiments, this metathesis reaction and the olefinic ester cross-metathesis reaction use the same metathesis catalyst. In some other embodiments, the separate reactions of

<img file="MX370894B_D0039.tif" />

metathesis employ a different metathesis catalyst. This reaction can be used beneficially, for example, in cases where it may be undesirable or inconvenient to obtain certain amounts of the terminal olefin ester. Thus, in these embodiments, the terminal olefin ester can be generated from the existing supply of the internal olefin ester.

[00090] Figure 2 shows a flow chart illustrating certain modalities for making an unsaturated dibasic ester. The illustrated method 200 comprises: providing a reagent composition 201, comprising a terminal olefin ester and an internal olefin ester; and reacting the terminal olefin ester with the internal olefin ester 202, for example, in a reactor in the presence of a metathesis catalyst, to form an unsaturated dibasic ester and a terminal olefin. The terminal olefin ester can be a terminal olefin ester according to any of the embodiments described above. The internal olefin ester can be an internal olefin ester according to any of the embodiments described above. The reaction can be carried out under any suitable condition using any suitable metathesis catalyst, as described above. In some embodiments, at least a portion of the terminal olefin formed can be removed from the reactor.

<img file="MX370894B_D0040.tif" />

<td>during</td><td>the</td><td>reaction.</td><td>In</td><td>some of these</td><td>modalities,</td><td>the</td>

<td>removal</td><td>it is</td><td>keep going.</td><td>In</td><td>other of these</td><td>modalities,</td><td>without</td>

<td>embargo,</td><td>the</td><td>removal</td><td>it is</td><td>discontinuous, by</td><td>example, what</td><td>I know</td>

<td>presents</td><td colspan="3">only in certain</td><td>points during</td><td>the reaction.</td><td>He</td>

The illustrated method can be incorporated into processes that include additional steps, either before or after those illustrated in Figure 2. In some embodiments, at least a portion of the terminal olefin ester and / or the internal olefin ester is derived from a natural oil raw material, for example, by a process that includes metathesis and transesterification (in any order) of a raw material comprising a natural oil.

[00091] Figure 3 shows a flow chart illustrating certain modalities for making an unsaturated dibasic ester. The illustrated method 300 300: reacting a terminal olefin ester with an internal olefin 301 to form an internal olefin ester (and a terminal olefin by-product), for example, in a reactor in the presence of a metathesis catalyst; and reacting the terminal olefin ester with the internal olefin ester 302, for example, in a reactor in the presence of a metathesis catalyst, to form an unsaturated dibasic ester and a terminal olefin. In some embodiments, the two reactions are carried out in the same reactor in approximately the same time. In some other modalities, however,

<img file="MX370894B_D0041.tif" />

Two reactions are carried out in different reactors and in some other embodiments, in different reactors and / or using different metathesis catalysts. The terminal olefin ester can be a terminal olefin ester according to any of the embodiments described above. The internal olefin ester can be an internal olefin ester according to any of the embodiments described above. The two reactions can be carried out under any suitable condition using any suitable metathesis catalyst, as described above. In some embodiments, at least a portion of the internal olefin formed by-product (from the first reaction) and / or at least a portion of the terminal olefin formed by-product (from the second reaction) can be removed from the reactor during the reaction. In some of these modalities, removal is continuous. In other of these embodiments, however, the removal is discontinuous, for example, occurring only at certain points during the reaction. The illustrated method can be incorporated into processes that include additional steps, either before or after those illustrated in Figure 3. In some embodiments, at least a portion of the terminal olefin ester and / or the internal olefin ester is derived from a natural oil feedstock, for example, by a process that includes metathesis and transesterification (in any order) of a material. raw comprising a natural oil.

[00092] Figure 4 shows a flow chart illustrating certain modalities for making an unsaturated dibasic ester. The illustrated method 400 comprises: reacting an internal olefin ester with a terminal olefin 401 to form a terminal olefin ester (and an internal olefin by-product), for example, in a reactor in the presence of a metathesis catalyst; and reacting the terminal olefin ester with the internal olefin ester 402, for example, in a reactor in the presence of a metathesis catalyst, to form an unsaturated dibasic ester and a terminal olefin. In some embodiments, the two reactions are carried out in the same reactor at approximately the same time. In some other embodiments, however, the two reactions are carried out in different, and in some embodiments, in different reactors and / or using different metathesis catalysts. The terminal olefin ester can be a terminal olefin ester according to any of the embodiments described above. The internal olefin ester can be an internal olefin ester according to any of the embodiments described above. The two reactions can be carried out under any suitable condition using any suitable metathesis catalyst, as described above. In some embodiments, at least a portion of the internal olefin formed by-product (from the first reaction) and / or at least a portion of the terminal olefin formed by-product (from the second reaction) can be removed from the reactor during the reaction. In some of these modalities, the removal is continuous. However, in other of these embodiments, the removal is discontinuous, for example, occurring only at certain points during the reaction. The illustrated method can be incorporated into processes that include additional steps, either before or after those illustrated in Figure 4. In some embodiments, at least a portion of the terminal olefin ester and / or the internal olefin ester is derived from a natural oil raw material, for example, by a process that includes metathesis and transesterification (in any order) of a raw material comprising a natural oil.

Unsaturated dibasic ester reactions

[00093] In certain different aspects, the unsaturated dibasic esters can be further reacted in various ways. These additional reactions include, but are not limited to, any combination of hydrogenation, isomerization, and reactions to convert the dibasic ester to a dibasic acid (eg, by methods including hydrolysis or saponification).

[00094] In certain aspects, the methods described in the

<img file="MX370894B_D0042.tif" />

present comprise: making a dibasic ester (eg, wherein the making comprises making an unsaturated dibasic ester according to any of the methods described above, which may optionally be hydrogenated); and converting the dibasic ester to a dibasic acid. In some embodiments, the conversion comprises hydrolyzing the dibasic ester to a dibasic acid, for example, by reacting the dibasic ester with water in the presence of an acid catalyst. Any suitable hydrolysis method can be used. In some other embodiments, the conversion comprises saponifying the dibasic ester to form a dibasic acid salt (where acid salt refers to a carboxylate anion, either in solution or in solid state form), and optionally acidifying the salt of dibasic acid to form dibasic acid. Any suitable saponification method can be used. In some embodiments, the resulting dibasic acid is octadecanedioic acid. In some other embodiments, the resulting dibasic acid is 9-octadecenedioic acid.

[00095] In other embodiments, the dibasic acid and / or dibasic ester is isomerized to form an isomerized dibasic acid and / or isomerized dibasic ester. The isomerization of the dibasic acid and / or dibasic ester can be carried out at an elevated temperature (ie, greater than 25 ° C). In certain embodiments, the heat treatment temperature

<img file="MX370894B_D0043.tif" />

for the isomerization reaction it is greater than 100 ° C, greater than 150 ° C, or greater than 200 ° C. In other modes, the temperature is between 100 ° C-300^andC, between 150-250 ° C, or about 200 ° C. In some embodiments, the heat treatment step is carried out in the presence of an isomerization catalyst. In a particular embodiment, the isomerization catalyst is (PCya) 2 (Cl) (H) Ru (CO), where Cy represents a cyclohexyl group.

[00096] In certain embodiments, the isomerized dibasic acid and / or isomerized dibasic ester comprises compounds selected from the group consisting of: isomerized dimethyl 9octadecenedioate or isomerized 9octadecenedioic acid.

[00097] In certain embodiments, the isomerized dibasic acid and / or isomerized dibasic ester is self-metatized or cross-metatized with a low molecular weight olefin or medium weight olefin. Typical metathesis reaction conditions and typical catalysts are discussed in more detail below. In one embodiment, the isomerized dibasic acid and / or isomerized dibasic ester self-metatizes in the presence of about 10 ppm, 20 ppm, 40 ppm, 50 ppm, 80 ppm, 100 ppm, 120 ppm, or more than 150 ppm of metathesis catalyst.

[00098] In certain embodiments, the dibasic acid, dibasic ester, isomerized dibasic acid, and / or isomerized dibasic ester are hydrogenated. Typical catalysts and conditions of the hydrogenation reaction are discussed in more detail below. In a particular example, the hydrogenation reaction is carried out in the presence of a nickel-based catalyst at approximately 150 ° C and 150 psi.² (10.54 kg / cm²) .

[00099] In certain embodiments, dibasic acids, dibasic esters, isomerized dibasic acids, and / or isomerized dibasic esters can be used in a variety of different commercial applications, including, but not limited to: lubricants, waxes, films, paints, paint thinners, coatings, plasticizers, resins, binders, solvents, polyols, soil stabilization, chemical plasters, oil field drilling fluids, crop protection products, surfactants, intermediates, and adhesives.

[000100] Figure 5 shows a flow chart illustrating certain modalities for making a saturated dibasic ester. The illustrated method 500 comprises: making an unsaturated dibasic ester 501, for example, according to any of the modalities discussed above; and hydrogenate the unsaturated dibasic ester. Any suitable hydrogenation condition can be used, as described above.

[000101] Figure 6 shows a flow chart illustrating certain modalities for making a dibasic acid. The illustrated method 600 comprises: making a dibasic ester 601, for example, according to any of the modalities described above; and converting the dibasic ester to a dibasic acid 602. In some embodiments, the dibasic ester is an unsaturated dibasic ester, which can be made, for example, according to any of the methods described above. In some other embodiments, the dibasic ester is a saturated dibasic ester, which, for example, can be made by making an unsaturated dibasic ester (according to any of the modalities described above) and then hydrogenating the unsaturated dibasic ester to form a saturated dibasic ester. Any suitable method u can be used to convert the ester groups to acidic groups. For example, in some embodiments, the conversion comprises hydrolyzing the dibasic ester, for example, by reacting with water, and in some embodiments, in the presence of an acid catalyst. In some other embodiments, the conversion comprises saponifying the dibasic ester, followed by acidification.

Unsaturated esters derived from natural oil raw materials

[000102] As mentioned above, the terminal olefin ester and / or the internal olefin ester can be derived from a natural oil feedstock, in addition to other

<img file="MX370894B_D0044.tif" />

valuable compositions. For example, various valuable compositions can be targeted through the auto-metathesis reaction of a natural oil feedstock, or the cross-metathesis reaction of the natural oil feedstock with a low molecular weight olefin or olefin. medium weight, in the presence of a metathesis catalyst. These valuable compositions can include fuel compositions, detergents, surfactants, and other specialty chemicals. Non-limiting examples of fuel compositions include jet engine fuel, kerosene, and diesel fuel. Additionally, transesterified products (ie, products formed from the transesterification of an ester in the presence of an alcohol) may also be targeted, non-limiting examples of which include: fatty acid methyl esters; biodiesel; 9-Decenoic acid (9DA) esters, 9-undecenoic acid (9UDA) esters, and / or 9-dodecenoic acid (9DDA) esters; 9DA, 9UDA, and / or 9DDA; alkali metal salts and alkaline earth metal salts of 9DA, 9UDA, and / or 9DDA; dimers of the transesterified products; and mixtures of these. Any suitable method can be used to derive the internal unsaturated ester and / or terminal unsaturated ester from a natural oil feedstock.

[000103] In certain embodiments, prior to a reaction of

<img file="MX370894B_D0045.tif" />

metathesis, a natural oil feedstock can be treated to render the natural oil more suitable for the subsequent metathesis reaction. In certain embodiments, the natural oil is preferably a vegetable oil or derived from vegetable oil, such as soybean oil, palm oil, or rapeseed (rapeseed) oil.

[000104] In one embodiment, the natural oil treatment comprises the removal of catalyst contaminants, such as peroxides, which can potentially decrease the activity of the metathesis catalyst. Non-limiting examples of natural oil feedstock treatment methods to decrease catalyst contaminants include those described in WO 2009/020665, WO 2009/020667, and US Patent Application Publication Nos. 2011/0160472 and 2011/0313180, incorporated herein by reference in their entirety. In certain embodiments, the natural oil feedstock is heat treated by heating the feedstock to a temperature greater than 100 ° C in the absence of oxygen and maintaining the temperature for a sufficient time to reduce catalyst contaminants in the feedstock. . In other embodiments, the temperature is between approximately 100 ° C and 300 ° C, between approximately 120 ° C and 250 ° C, between approximately 150 ° C and 210 ° C, or approximately 190 and

200 ° C. In one embodiment, the absence of oxygen is achieved by

<img file="MX370894B_D0046.tif" />

sparging the natural oil feedstock with nitrogen, where the nitrogen gas is pumped into the feedstock treatment vessel at a pressure of approximately 10 atm (150 psi²) .

[000105] In certain embodiments, the natural oil feedstock is chemically treated under conditions sufficient to decrease catalyst contaminants in the feedstock through a chemical reaction of the catalyst contaminants. In certain embodiments, the raw material is treated with a reducing agent or an inorganic-cationic base composition. Non-limiting examples of reducing agents include bisulfite, borohydride, phosphine, thiosulfate, individually or combinations of these.

[000106] In certain embodiments, the natural oil feedstock is treated with an adsorbent to remove catalyst contaminants. In one embodiment, the raw material is treated with a combination of thermal and adsorbent methods. In another embodiment, the raw material is treated with a combination of chemical and adsorbent methods. In another embodiment, the treatment comprises a partial hydrogenation treatment to modify the reactivity of the natural oil feedstock with the metathesis catalyst. Additional non-limiting examples of the feedstock treatment are also described below when discussing the various catalysts of

<img file="MX370894B_D0047.tif" />

metathesis.

[000107] Additionally, in certain embodiments, the low molecular weight olefin or medium weight olefin can also be treated prior to the metathesis reaction with the natural oil. Like natural oil treatment, low molecular weight olefin or medium weight olefin can be treated to remove contaminants that can impact or decrease catalyst activity.

[000108] In certain embodiments, the low molecular weight olefin or medium weight olefin can self-metatize to form a metatized low molecular weight olefin or metatized medium weight olefin in order to adjust the properties of the olefin and the products. potential after metathesis with natural oil. In some embodiments, the low molecular weight olefin or medium weight olefin self-metatizes in the presence of a rhenium oxide catalyst (eg, alumina supported rhenium oxide) or tungsten oxide catalyst (eg, silica supported tungsten oxide). This reaction can be carried out in a fixed bed reactor. In one embodiment, the low molecular weight olefin is 1-butene. The low molecular weight olefin can be self-metatized over rhenium oxide catalyst in a fixed bed reactor to produce mainly 3-hexene and ethylene. Ethylene can be separated from the reactor effluent to

<img file="MX370894B_D0048.tif" />

additional processing, such as being sent to an ethylene purification system or ethylene oxide system. The unreacted low molecular weight olefin (eg 1-butene) can be recycled to the fixed bed reactor and the metatized low weight olefin (eg 3-hexene) can be sent to the metathesis reactor for metathesis with natural oil.

[000109] In other embodiments, the low molecular weight olefin or medium weight olefin is isomerized before it metatizes with the natural oil. Adjusting the composition and properties of the low molecular weight olefin or medium weight olefin through isomerization may allow different products or different product ratios to be formed after metathesis of the low molecular weight olefin or weight olefin. medium with a natural oil. In some embodiments, the isomerized or branched low molecular weight olefin is in the range of C4 to CIO. In one embodiment, hexene is isomerized to form a low molecular weight branched olefin. Non-limiting examples of low molecular weight branched olefins include isobutene, 3-methyl-1-butene, 2-methyl-3-pentene, and 2,2-dimethyl-3-pentene.

[000110] By using low molecular weight branched olefins or medium weight branched olefins in the metathesis reaction, the metatized product will include branched olefins, which can be subsequently hydrogenated to iso-paraffins. In certain embodiments, low molecular weight branched olefins or medium weight branched olefins can help achieve the desired performance properties for a fuel composition, such as jet fuel, kerosene, or diesel fuel. In certain embodiments, C11-C14 olefins can be targeted after metathesis and separation steps through isomerization of the low molecular weight olefin. In other embodiments, low molecular weight branched olefins or medium weight branched olefins can help to target longer chain esters for use as detergents or cleaning compositions. In some embodiments, C10-C15 or C11-C14 methyl esters can be searched after metathesis, separation, and transesterification steps (discussed in detail below). Isomerization reactions are well known in the art, as described in US Patent Nos. 3,150,205; 4,210,771; 5,095,169; and 6,214,764, incorporated herein by reference in their entirety.

[000111] After any optional pre-treatment, the natural oil can be refined in any suitable manner to form an internal unsaturated ester and / or a terminal unsaturated ester. In some modalities, the description

<img file="MX370894B_D0049.tif" />

provides methods for refining a natural oil, comprising: providing a raw material comprising a natural oil; reacting the raw material in the presence of a fourth metathesis catalyst to form a metatized product comprising one or more unsaturated glycerides and one or more olefins; separating the unsaturated glycerides in the metatized product from the olefins in the metatized product; and transesterifying the separated unsaturated glycerides in the presence of an alcohol to form a transesterified product comprising a terminal olefin ester or an internal olefin ester. In some embodiments, the terminal olefin ester and / or the internal olefin ester can be used according to the method of any of the above embodiments, for example, to form an unsaturated dibasic ester. In some embodiments, the alcohol is methanol. In some embodiments, the unsaturated dibasic ester is a 9octadecenedioic acid dibasic ester, such as 9octadecenedioic acid dimethyl ester. In some additional embodiments, the resulting unsaturated dibasic ester can be converted to a saturated dibasic ester and / or a saturated dibasic acid according to any of the embodiments of the second and / or third aspects.

[000112] Figure 1 provides an illustration of one embodiment to carry out this refining process. How

<img file="MX370894B_D0050.tif" />

shown in figure 1, after this optional treatment of the raw material of natural oil, low molecular weight olefin, and / or medium weight olefin, the natural oil 12 is reacted with itself, or combined with a low molecular weight olefin 14 or medium weight olefin 15 in a metathesis reactor 20 in the presence of a metathesis catalyst. Metathesis catalysts and metathesis reaction conditions are discussed in more detail below. In certain embodiments, in the presence of a metathesis catalyst, natural oil 12 undergoes an auto-metathesis reaction with itself. In other embodiments, in the presence of the metathesis catalyst, natural oil 12 undergoes a cross-metathesis reaction with low molecular weight olefin 14 and medium weight olefin 15. In certain embodiments, natural oil 12 undergoes both self-metathesis and cross-metathesis reactions in parallel metathesis reactors. The self-metathesis and / or cross-metathesis reaction forms a metatized product 22 wherein the metatized product 22 comprises olefins 32 and esters 34.

[000113] In certain embodiments, the low molecular weight olefin is in the range of C2 to C6. As a non-limiting example, in one embodiment, the low molecular weight olefin 14 may comprise at least one of the following: ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene,

<img file="MX370894B_D0051.tif" />

2-pentene, 3-pentene, 2-methyl-l-butene, 2-methyl-2-butene, 3-methyl-l-butene, cyclopentene, 1,4-pentadiene, 1-hexene, 2-hexene, 3-hexene, 4- hexene, 2-methyl-l-pentene, 3-methyl-pentene, 4-methyl-l-pentene, 2-methyl-2-pentene, 3-methyl-2-pentene, 4-methyl-2-pentene, 2-methyl- 3-pentene, and cyclohexene. Non-limiting examples of low molecular weight olefins in the C7 to C9 range include 1,4-heptadiene, 1-heptene, 3,6-nonadiene, 3-nonene, 1,4,7-octatriene. In another embodiment, the low molecular weight olefin 14 comprises at least one of styrene® and vinyl cyclohexane. In another embodiment, the low molecular weight olefin 14 may comprise at least one of ethylene, propylene, 1-buten®, 2-buten®, and isobutene. In another embodiment, the low molecular weight olefin 14 comprises at least one alpha-olefin or terminal olefin in the range of C2 to CIO.

[000114] In another embodiment, the low molecular weight olefin 14 comprises at least one branched olefin of low molecular weight in the range of C4 to CIO. Non-limiting examples of low molecular weight branched olefins include isobutene, 3-methyl-1-butene, 2-methyl-3-pentene, and 2,2-dimethyl-3-pentene.

[000115] In certain embodiments, the medium weight olefin comprises straight, branched or cyclic unsaturated hydrocarbons in the range of C15 to C24. In some embodiments, the medium weight olefin is an alpha-olefin or terminal olefin.

[000116] As noted, it is possible to use a mixture of various low molecular weight branched linear definitions and medium weight linear or branched olefins in the reaction to achieve the desired distribution of metathesis products. In certain embodiments, the mixture comprises low molecular weight linear and / or branched olefins. In other embodiments, the blend comprises medium weight linear and / or branched olefins. In one embodiment, a mixture of butenes (1-butene, 2-butenes, and optionally, isobutene) can be employed as the low molecular weight olefin, offering a low cost, commercially available raw material in lieu of a purified source. of a particular butene. These inexpensive mixed butene raw materials are typically diluted with n-butane and / or isobutane.

[000117] In certain embodiments, recycle streams for separation units may be introduced downstream to metathesis reactor 20 in addition to natural oil 12 and in some embodiments, low molecular weight olefin 14 and / or medium weight olefin 15. For For example, in some embodiments, a recycled C2-C6 olefin stream or a C3-C4 bottoms stream from an overhead separation unit can be returned to the metathesis reactor. In one embodiment, as shown in FIG. 1, a light weight olefin stream 44 from a separation unit

<img file="MX370894B_D0052.tif" />

Olefin 40 may be returned to metathesis reactor 20. In another embodiment, the C3-C4 bottoms stream and light weight olefin stream 44 are combined together and returned to metathesis reactor 20. In another embodiment, A C15 + bottom stream 46 from olefin separation unit 40 is returned to metathesis reactor 20. In another embodiment, all of the above-mentioned recycle streams are returned to metathesis reactor 20.

[000118] In other embodiments, various ester streams may also be recycled or returned downstream of the transesterification unit (discussed below) to the metathesis reactor 20. In certain embodiments, a glycerolysis reaction may be carried out in the recycle ester stream to prevent or limit the amount of free glycerol entering the metathesis reactor 20. In some embodiments, the recycle ester stream will undergo a purification step to limit the amount of methanol that is recycled to the metathesis reactor 20. In some embodiments, the recycle ester stream is combined with the low molecular weight olefin 14 and / or or medium weight olefin 15 before carrying out the glycerolysis reaction and entering the metathesis reactor 20. The glycerolysis reaction can also limit or prevent the fatty acid methyl esters from entering the metathesis reaction and subsequently exiting the metathesis reactor as free fatty acid methyl esters which can boil close to various high value olefin products. In these cases, these methyl ester components can be separated with the olefins during the separation of the olefins and esters. These methyl ester components can be difficult to separate from olefins by distillation.

[000119] The metathesis reaction in metathesis reactor 20 produces a metatized product 22. In one embodiment, the metatized product 22 enters a vaporization vessel operated under conditions of temperature and pressure that have C2 or C2-C3 as compounds so that they evaporate and are stirred in a high way. The light ends of C2 or C2-C3 are comprised of most hydrocarbon compounds having a carbon number of 2 or 3. In certain embodiments, the light ends of C2 or C2-C3 are then sent to a high separation unit, where the C2 or C2-C3 compounds are further separated in a high way from the heavier compounds that were vaporized with the compounds. of C2-C3. These heavier compounds are typically C3-C5 compounds carried high with the C2 or C2-C3 compounds. After separation in the elevated separation unit, the elevated C2 or C2-C3 stream can then be used as a source.

<img file="MX370894B_D0053.tif" />

made out of fuel. These hydrocarbons have their own value outside the scope of a fuel composition, and can be used or separated at this stage for other valuable applications and compositions. In certain embodiments, the bottoms stream from the overhead separation unit containing primarily C3-C5 compounds is returned as a recycle stream to the metathesis reactor. In the evaporation vessel, the metatized product 22 that is not highly vaporized is sent downstream for separation in a separation unit 30, such as a distillation column.

[000120] Prior to separation unit 30, in certain embodiments, metatized product 22 may be contacted with a reagent to deactivate or remove the catalyst. In certain embodiments, the metatized product 22 is introduced into an adsorbent or complexing agent to facilitate the separation of the metatized product 22 from the metathesis catalyst. In one embodiment, the adsorbing or complexing agent is a bed of clay. The clay bed will adsorb the metathesis catalyst, and after a filtration step, the metatized product 22 can be sent to separation unit 30 for further processing. In another embodiment, the adsorbing or complexing agent is a water soluble phosphine reagent such as tris-hydroxymethylphosphine (THMP).

<img file="MX370894B_D0054.tif" />

Catalyst can be separated with a water-soluble phosphine through known liquid-liquid extraction mechanisms by decanting the aqueous phase from the organic phase.

[000121] In some embodiments, the metatized product 22 can be sent to a catalyst kill drum where the reagent (eg, aqueous THMP solution) is added to deactivate the metathesis catalyst. THMP can be added at a ratio equivalent to at least a 1: 1, 5: 1, 10: 1, 25: 1, or 50: 1 molar ratio to the catalyst pumped into the catalyst annihilation drum.

[000122] In certain embodiments, the reagent (eg, THMP) can be left in the metatized product 22 and carried either in whole or in part to a subsequent chemical reaction or subsequent processing step. In other embodiments, the reagent can be separated and removed from the mixture, either partially or completely, prior to any subsequent reaction or subsequent processing step. In some embodiments, passivation and extraction can be coupled in one step (eg, by providing the reagent in the extraction material).

[000123] In one embodiment, catalyst removal occurs by sending the effluent from the catalyst kill drum to a catalyst settling drum. The decanting drum can function as a container

<img file="MX370894B_D0055.tif" />

horizontal with a vertical deflector and a boot to collect the aqueous phase containing the metathesis catalyst. In some embodiments, the decanting drum operates at a temperature between approximately 60-90 ° C and a pressure between 1-1.5 atm, or approximately 53 ° C (127 ° F) and 1.1 atm (16 lb / in.²) ) .

[000124] In other embodiments, catalyst removal comprises washing or extracting the mixture with a polar solvent (for example, particularly, but not exclusively, for embodiments in which the reagent is at least partially soluble in the solvent polar). In some embodiments, the polar solvent is delivered in a subsequent step after catalyst deactivation. In other embodiments, the polar solvent (eg, water) is added to the metatized product 22 in approximately the same motion as the deactivation reagent (eg, THMP). The almost simultaneous addition of the deactivation reagent and the polar solvent to the metatized product can eliminate the need for the additional reaction / separation vessel, which can simplify the process and now potentially capital.

[000125] In some embodiments, the polar solvent is at least partially immiscible with the mixture, such that layer separation may occur. In some embodiments, at least a portion of the reagent is split into the polar solvent layer, which can then be separated from the remaining immiscible layer and removed. Representative polar solvents for use in accordance with the present teachings include, but are not limited to, water, alcohols (eg, methanol, ethanol, etc.), ethylene glycol, glycerol, DMF, multifunctional polar compounds including, but not limited to, polyethylene glycols. and / or glymes, ionic liquids, and the like, and combinations thereof. In some embodiments, the mixture is extracted with water. In some embodiments, when a phosphite ester that is at least partially hydrolyzable (for example, in some embodiments, a phosphite ester that has a low molecular weight, including, but not limited to, trimethyl phosphite, triethyl phosphite, and a combination of these) is used as a reagent, washing the mixture with water to convert the phosphite ester to a corresponding acid. While it is neither intended to be bound by any particular theory, nor is it intended to limit in any way the scope of the appended claims or their equivalents, it is presently believed that this hydrolysis may occur more rapidly with lower molecular weight esters.

[000126] In some embodiments, when extraction with a polar solvent is desired, the extraction may comprise high shear mixing (eg, mixing of a type sufficient to disperse and / or transport at least

<img file="MX370894B_D0056.tif" />

a portion of a first phase and / or chemical species in a second phase with which the first phase and / or a chemical species will normally be at least partially immiscible), although this mixing, in some embodiments, may contribute to undesirable emulsion formation . In some embodiments, the extraction comprises low intensity mixing (eg, agitation that is not high cut). The present teachings are in no way restricted to any particular type or duration of mixing. However, for purposes of illustration, in some embodiments, the extraction comprises mixing the polar solvent and the mixture together for at least about 1 second, 10 seconds, 30 seconds, 1 minute, 2 minutes, 5 minutes, 10 minutes, 15 minutes. , 20 minutes, 25 minutes, 30 minutes, 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes, or 60 minutes. While it is not intended to be bound by any particular theory, nor is it intended to limit the scope of the appended claims or their equivalents in any way, it is presently believed that shorter mixing times can be achieved (e.g., in the order of a second or seconds) when inline cutting mixing is used for mixing.

[000127J When extraction with a polar solvent is desired, the present teachings are in no way restricted to any particular amount of polar solvent added to the mixture for extraction. However, for purposes of illustration, in some embodiments, the amount by weight of polar solvent (eg, water) added to the mixture for extraction is more than the weight of the mixture. In some embodiments, the amount by weight of polar solvent (eg, water) added to the mixture for extraction is less than the weight of the mixture. In some embodiments, the weight ratio of the mixture to the water added to the mixture is at least about 1: 1, 2: 1, 3: 1, 4: 1, 5: 1, 6: 1, 7: 1, 8 : 1, 9: 1, 10: 1, 20: 1, 40: 1, OR 100: 1. For higher oil to water ratios, extraction and separation using a centrifuge and / or coalescer may be desirable.

[000128] In some embodiments, when polar solvent extraction is desired, methods for suppressing dehydrogenation in accordance with the present teachings further comprise allowing a settling period after polar solvent washing to promote phase separation. The present teachings are not to be restricted in any way to any particular length of the settlement period. However, for illustration purposes, in some embodiments, the break-in period is at least about 1 minute, 2 minutes, 5 minutes, 10 minutes, 15 minutes, 30 minutes, 60 minutes, or 120 minutes.

[000129] In addition to or as an alternative to, washing the mixture with a polar solvent to remove the reagent (eg THMP): a method in accordance with the present teachings, may optionally further comprise removing at least a portion of the reagent by adsorbing onto an adsorbent, which can then optionally be physically separated from the mixture (eg, by filtration, centrifugation, crystallization, or the like). In some embodiments, the adsorbent is polar. Representative adsorbents for use in accordance with the present teachings include, but are not limited to, carbon, silica, silica-alumina, alumina, clay, magnesium silicates (eg, Magnesols), the synthetic silica adsorbent sold under the name Trisyl from WR Grace &amp; Co., diatomaceous earth, polystyrene, macroporous resins (MP), and the like, and combinations thereof.

[000130] Additionally, in certain embodiments, before the separation unit 30 (and after the catalyst separation, in some cases), the metathesis product 22 can be sent to a hydrogenation unit, where the carbon double bonds -Carbon in olefins and esters are partially to fully saturated with hydrogen gas. Hydrogenation can be carried out according to any method known in the art for hydrogenating compounds containing double bonds, such as the olefins and esters present in the metathesis product 22.

In certain embodiments, in the hydrogenation unit, hydrogen gas is reacted with the metathesis product 22 in the presence of a hydrogenation catalyst to produce a hydrogenated product comprising partially or fully hydrogenated paraffins / olefins and partially to fully hydrogenated esters. .

[000131] In some embodiments, the metathesis product 22 is hydrogenated in the presence of a hydrogenation catalyst comprising nickel, copper, palladium, platinum, molybdenum, iron, ruthenium, osmium, rhodium, or iridium, individually or combinations thereof. . The useful catalyst can be heterogeneous or homogeneous. In some embodiments, the catalysts are sponge nickel or supported nickel type catalysts.

[000132] In some embodiments, the hydrogenation catalyst comprises nickel that has been chemically reduced with hydrogen to an active state (ie, reduced nickel) provided on a support. The support may comprise porous silica (eg, kieselguhr, infusorial, diatomaceous earth or siliceous) or alumina. Catalysts are characterized by a high nickel surface area per gram of nickel.

[000133] Commercial examples of supported nickel hydrogenation catalysts include those available under the trade designations NYSOFACT,

<img file="MX370894B_D0057.tif" />

NYSOSEL, and NI 5248 D (from BASF Catalysts LLC, Iselin, NJ).

Supported nickel hydrogenation catalysts include those commercially available under the trade designations PRICAT 9910, PRICAT 9920, PRICAT 9908, PRICAT 9936 (ex Johnson Matthey Catalysts,

Ward Hill, MA).

[000134] Supported nickel catalysts can be of the type described in US Patent No. 3,351,566, US Patent No. 6,846,772, EP 10 0,168,091, and EP 0,167,201, incorporated herein by reference in their entirety. The hydrogenation can be carried out in a batch process or in a continuous process and can be partial hydrogenation or complete hydrogenation. In certain embodiments, the temperature ranges from about 50 ° C to about 350 ° C, from about 100 ° C to 300 ° C, from about 150 ° C to about 250 ° C, or from about 100 ° C to about 150 ' C. The desired temperature can vary, for example, with the pressure of hydrogen gas. Typically, a higher gas pressure will require a lower temperature. Hydrogen gas is pumped into the reaction vessel to achieve a desired H gas₂. In certain embodiments, the gas pressure H₂ ranges from approximately 15 lb / in² (1 atm) at approximately 3000 lb / in² (204.1 atm), approximately 15 25 lb / in² (1 atm) at approximately 90 psi² (6.1 atm), or

<img file="MX370894B_D0058.tif" />

approximately 100 lb / in² (6.8 atm) at approximately 500 psi² (34 atm). As gas pressure increases, more specialized high pressure processing equipment may be required. In certain embodiments, the reaction conditions are mild, where the temperature is between about about 50 ° C and about 100 ° C and the gas pressure H₂ is less than approximately 100 psi² (6.8 atm). In other embodiments, the temperature is between about 100 ° C and about 150 ° C, and the pressure is between about 100 psi (6.8 atm) and about 500 psi.² (34 atm). When the desired degree of hydrogenation is reached, the reaction mass is cooled to the desired filtration temperature.

[000135] The amount of hydrogenation catalyst is typically selected in view of various factors including, for example, the type of hydrogenation catalyst used, the amount of hydrogenation catalyst used, the degree of unsaturation in the material to be hydrogenated , the desired rate of hydrogenation, the desired degree of hydrogenation (for example, as measured by iodine number (IV)), the purity of the reagent, and the gas pressure H₂. In some embodiments, the hydrogenation catalyst is used in an amount of about 10% by weight or less, for example, about 5% by weight or less, or about 1% by weight or less.

<img file="MX370894B_D0059.tif" />

[000136] When the desired degree of hydrogenation is reached, the reaction mass is cooled to the desired filtration temperature. During hydrogenation, the carbon-carbon double bonds are partially to fully saturated by hydrogen gas. In one embodiment, those defined in metathesis product 22 are reacted with hydrogen to form a fuel composition comprising only or primarily paraffins. Additionally, the esters of the metathesis product are completely or almost completely saturated in the hydrogenation unit. In another embodiment, the resulting hydrogenated product includes only partially saturated olefins / paraffins and partially saturated esters.

[000137] In separation unit 30, in certain embodiments, metatized product 22 (from a hydrogenation unit, metathesis reactor 20, or catalyst separation unit) is separated into at least two product streams. In one embodiment, the metatized product 22 is sent to separation unit 30, or distillation column, to separate the olefins 32 from the asters of 34. In another embodiment, a by-product stream comprising C₇ and cyclohexadienes (eg, 1,4-cyclohexadienes) can be removed in a side stream from separation unit 30. In certain embodiments, the separated olefins 32 can comprise hydrocarbons with carbon numbers up to 24. In certain embodiments, the esters 34 may comprise metatized glycerides. In other words, the light terminal definas 32 are preferably highly separated or distilled for processing into definas compositions, whereas the esters of 34, comprised primarily of compounds having ester / carboxylic acid functionality, are extracted into the stream. Of funds. Based on the quality of the separation, it is possible that some ester compounds carried into the elevated olefin stream 32, and it is also possible that some heavier olefin hydrocarbons are carried or carried into the ester stream 34. Additionally Separated cyclohexadienes (eg, 1,4-cyclohexadiene) can be further processed in a dehydrogenation step to form benzene. Examples of catalytic dehydrogenation catalysts include platinum supported on alumina. Examples of oxidative dehydrogenation catalysts include mixed metal oxides consisting of molybdenum, vanadium, niobium, tellurium, magnesium, and / or aluminum. Other examples of dehydrogenation catalysts include cerium / zirconium, alkaline earth / nickel, calcium-nickel phosphate, chromium, chromium-iron oxide, bismuth / molybdenum, tin / antimony, silver, copper.

[000138] In one embodiment, the olefins 32 can be collected and sold for any of several known uses. In other embodiments, the olefins 32 are further processed in an olefin separation unit 40 and / or hydrogenation unit 50 (where the olefinic bonds are saturated with hydrogen gas 48, as described below). In other embodiments, esters 34 comprising heavier terminal glycerides and free fatty acids are separated or distilled as a bottom product for further processing into various products. In certain embodiments, further processing may be aimed at producing the following non-limiting examples: fatty acid methyl esters; biodiesel; 9DA esters, 9UDA esters, and / or 9DDA esters; 9DA, 9UDA, and / or 9DDA; alkali metal salts and alkaline earth metal salts of 9DA, 9UDA, and / or 9DDA; diacids, and / or diesters of the transesterified products; and mixtures of these. In certain embodiments, further processing may be aimed at the production of esters and / or fatty acids of Ci₅-Ci₈. In other embodiments, further processing may be aimed at the production of diacids and / or diesters. In still other embodiments, further processing may be aimed at producing compounds that have molecular weights greater than the molecular weights of stearic acid and / or linolenic acid.

[000139] As shown in Figure 1, with respect to the

<img file="MX370894B_D0060.tif" />

Elevated olefins 32 from the separation unit 30, the olefins 32 may be further separated or distilled from the olefin separation unit 40 to separate the various compositions. The olefin separation unit 40 may comprise several distillation towers. In some embodiments, the various streams of the composition are separated using at least four distillation towers. In other embodiments, three or fewer towers are used to separate the olefin compositions.

[000140] In one embodiment, the light terminal olefins 44 consisting primarily of C2-C9 compounds may be distilled in a high stream from olefin separation unit 40. In certain embodiments, the light terminal olefins 44 are comprised of a majority of C3-C8 hydrocarbon compounds. In other embodiments, heavier olefins having higher carbon numbers can be separated high in the light terminal olefin stream 44 to help target a specific fuel composition. Light terminal olefins 44 can be recycled to metathesis reactor 20, purged from the system for further processing and sold, or a combination of the two. In one embodiment, the light terminal olefins 44 can be partially purged from the system and partially recycled to the metathesis reactor 20. With respect to the other streams

<img file="MX370894B_D0061.tif" />

In olefin separation unit 40, a stream of heavier C16 +, C18 +, C20 +, C22 + or C24 + compounds can be separated as an olefin bottom stream 46. Olefin bottom stream 46 can be purged or recycled to the reactor metathesis 20 for further processing, or a combination of the two. In another embodiment, a center cut olefin stream 42 may be separated from the olefin distillation unit for further processing. Center cut olefins 42 can be designed to target a selected range of carbon numbers for a specific fuel composition. As a non-limiting example, a C5-C15 distribution may be targeted for further processing in a naphtha-type jet fuel. Alternatively, a C8-C16 distribution may be targeted for further processing in a kerosene-type jet fuel. In another embodiment, a distribution of C8-C25 may be targeted for further processing into a diesel fuel.

[000141] In some embodiments, processing steps can be carried out to maximize the purity of the alpha olefins. In other embodiments, processing steps can be carried out to maximize the purity of the CIO olefins. For example, C10 + olefins in separation unit 30, or a particular olefin stream, can be reacted with ethylene in the presence of a metathesis catalyst in a secondary metathesis reactor to improve the purity of the CIO olefins. In one embodiment, the metathesis catalyst is a rhenium oxide catalyst (eg, alumina supported rhenium oxide). In another embodiment, the metathesis is a tungsten oxide catalyst (eg, silica supported tungsten oxide). This metathesis reaction can be carried out in a fixed bed reactor. In some embodiments, the ethylene reagent can be recycled back to the secondary metathesis reactor. The lighter olefins (C4-C9) from the secondary metathesis reactor can be mixed with the olefins from the main metathesis reactor of the separation unit 30 for further processing.

[000142] In certain embodiments, olefins 32 can be oligomerized to form poly-alpha-olefins (PAO) or internal polyolefins (PIO), mineral oil substitutes, and / or biodiesel fuel. The oligomerization reaction can take place after distillation unit 30 or after high olefin separation unit 40. In certain embodiments, the by-products of the oligomerization reactions can be recycled back to the metathesis reactor 20 for further processing.

[000143] In other embodiments, olefins 32, light terminal olefins 44, or center cut olefins 42 are

<img file="MX370894B_D0062.tif" />

they can self-metathesis in the presence of a metathesis catalyst in a secondary metathesis reactor to produce heavier weight C14 +, C16 +, or C18 + olefin products. In one embodiment, the metathesis catalyst is a rhenium oxide catalyst (eg, alumina supported rhenium oxide). In another embodiment, the metathesis is a tungsten oxide catalyst (eg, silica supported tungsten oxide). This metathesis reaction can be carried out in a fixed bed reactor. The heavier weight C14 +, C16 +, C18 + olefins can be used as surfactants or petroleum lubricants. In some embodiments, the lighter olefin by-products of the auto-metathesis reaction can be recycled back to the secondary metathesis reactor or primary metathesis reactor 20 for further processing.

[000144] As mentioned, in one embodiment, olefins 32 from separation unit 30 can be sent directly to hydrogenation unit 50. In another embodiment, olefins center cut 42 from elevated olefin separation unit 40 are can send to hydrogenation unit 50. Hydrogenation can be carried out according to any method known in the art for hydrogenating compounds containing double bonds, such as olefins 32 or central cut olefins 42. In certain embodiments, in hydrogenation unit 50, hydrogen gas 4 8 is reacted with definitions 32 or center cutter definitions 42 in the presence of a hydrogenation catalyst to produce a hydrogenated product 52.

[000145] Typical hydrogenation catalysts and typical reaction conditions are discussed above. During hydrogenation, compounds containing carbon-carbon double bonds in olefins are partially to completely saturated by hydrogen gas 48. In one embodiment, the resulting hydrogenated product 52 includes hydrocarbons with a distribution centered between approximately CIO and C12 hydrocarbons and for gasoline-type and kerosene-type jet fuel compositions. In another embodiment, the distribution is centered between about C16 and C18 for a diesel fuel composition.

[000146] In certain embodiments, after hydrogenation, the hydrogenation catalyst can be removed from the hydrogenated product 52 using techniques known in the art, for example, by filtration. In some embodiments, the hydrogenation catalyst is removed using a plate and box filter, such as those commercially available from Sparkler Filters, Inc., Conroe

TX. In some embodiments, filtration is done with the aid of pressure or vacuum. In order to improve the performance of the

<img file="MX370894B_D0063.tif" />

filtration, a filter aid can be used. Filter aids can be added to the product directly or can be applied to the filter. Representative non-limiting examples of filter aids include diatomaceous earth, silica, alumina, and carbon. Typically, the filter aid is used in an amount of about 10% by weight or less, for example, about 5% by weight or less, or about 1% by weight or less. Other filtration techniques and filtration aids can also be employed to remove used hydrogenation catalyst. In other embodiments, the hydrogenation catalyst is removed using centrifugation followed by decantation of the product.

[000147] In certain embodiments, based on the quality of the hydrogenated product 52 produced in the hydrogenation unit 50, it may be preferable to isomerize the hydrogenated olefin product 52 to aid in targeting the desired fuel properties, such as flash point, freezing point, energy density, cetane number, or end point distillation temperature, among other parameters. Isomerization reactions are well known in the art, as described in US Patent Nos.

3,150,205; 4,210,771; 5,095,169; and 6,214,764, incorporated herein by reference in their entirety. In a

<img file="MX370894B_D0064.tif" />

In this embodiment, the isomerization reaction in this step can also fractionate some of the remaining C15 + compounds, which can further help produce a fuel composition that has compounds within the desired carbon number range, such as 5 to 16 for a jet engine fuel composition.

[000148] In certain embodiments, isomerization can occur concurrently with the hydrogenation step in hydrogenation unit 50, thereby targeting a desired fuel product. In other embodiments, the isomerization step may occur prior to the hydrogenation step (ie, olefins 32 or center cut olefins 42 may be isomerized prior to hydrogenation unit 50). In still other embodiments, it is possible that the isomerization step can be avoided or reduced in scope based on the selection of the low molecular weight olefins 14 and / or medium weight olefins 15 used in the metathesis reaction.

[000149] In certain embodiments, the hydrogenated product 52 comprises about 15-25% by weight of C7, about &lt;5% by weight of C8, about 20-40% by weight of C9, about 20-40% by weight of CIO , about &lt;5% by weight of Cll, about 15-25% by weight of C12, about &lt;5% by weight of C13, about &lt;5% by weight of C14, about &lt;5% in

<img file="MX370894B_D0065.tif" />

weight of C15, about &lt;1% by weight of C16, about &lt;1% by weight of C17, and about &lt;1% by weight of C18 +. In certain embodiments, the hydrogenated product 52 comprises a heat of combustion of at least about 40, 41, 42, 43, or 44 MJ / kg (as measured by ASTM D3338). In certain embodiments, the hydrogenated product 52 contains less than about 1 mg of sulfur per kg of hydrogenated product (as measured by ASTM D5453). In other embodiments, the hydrogenated product 52 comprises a density of about 0.70-0.75 (as measured by ASTM D4052). In other embodiments, the hydrogenated product has an end boiling point of approximately 220-240 ° C (as measured by ASTM D86).

[000150] Hydrogenated product 52 produced from hydrogenation unit 50 can be used as a fuel composition, non-limiting examples of which include jet engine fuel, kerosene, or diesel fuel. In certain embodiments, the hydrogenated product 52 may contain by-products of hydrogenation, isomerization, and / or metathesis reactions. As shown in Figure 1, the hydrogenated product 52 can be further processed in a fuel composition separation unit 60, removing any remaining by-products of the hydrogenated product 52, such as hydrogen gas, water, C2-C9 hydrocarbons or C15 + hydrocarbons, producing

<img file="MX370894B_D0066.tif" />

thus a sought-after combustible composition. The fuel composition separation unit 60 may comprise several distillation towers. In some embodiments, the various streams of the composition are separated using at least four distillation towers. In other embodiments, three or fewer towers are used to separate the compositions from the fuel.

[000151] In one embodiment, the hydrogenated product 52 can be separated into the desired fuel C9-C15 product 64, and a light end C2-C9 fraction 62 and / or a C15 + 66 heavy end fraction. you can use distillation to separate the fractions. Alternatively, in other embodiments, such as for a naphtha or kerosene type jet fuel composition, the heavy end fraction 66 can be separated from the desired fuel product 64 by cooling the hydrogenated product 52 to about -40 ° C. , -47 ° C, or

-65 ° C and then by removing the solid, heavy-ended fraction 66 by techniques known in the art such as filtration, decantation, or centrifugation.

[000152] With respect to the esters 34 from distillation unit 30, in certain embodiments, the esters 34 can be completely removed as an ester product stream 36 and further processed or sold for their own value, as shown in Figure 1. As a non-limiting example, the asters 34 can comprise various triglycerides that can be used as a lubricant. Based on the quality of the separation between the olefins and asters, the asters 34 may comprise some heavier olefin components carried or carried with the triglycerides. In other embodiments, the asters 34 can be further processed in a biorefinery or other chemical or fuel processing unit, known in the art, thereby producing various products, such as biodiesel or specialty chemicals that have higher value than that of triglycerides, by way of example. Alternatively, in certain embodiments, the asters 34 can be partially removed from the system and sold, with the remainder being further processed in the biorefinery or other fuel or chemical processing unit known in the art.

[000153] In certain embodiments, the ester stream 34 is sent to a transesterification unit 70. Within the transesterification unit 70, the asters 34 are reacted with at least one alcohol 3 8 in the presence of a transesterification catalyst. . In certain embodiments, the alcohol comprises methanol and / or ethanol. In another embodiment, alcohol 38 comprises glycerol (and the transesterification reaction is a glycerolysis reaction). In one embodiment, the transesterification reaction is carried out

<img file="MX370894B_D0067.tif" />

at about 60-70 ° C and about 1 atm. In certain embodiments, the transesterification catalyst is a homogeneous sodium methoxide catalyst. Various amounts of catalyst can be used in the reaction, and in certain embodiments, the transesterification catalyst is present in the amount of about 0.5-1.0% by weight of the esters 34.

[000154] In certain embodiments, the transesterification reaction can produce a transesterified product 72 comprising terminal olefin esters, such as terminal olefin esters having the following structure:

R ^ CH₂

Or where X is a saturated or unsaturated alkyl chain of C₃C₁₈, and R is an alkyl group, which may be optionally unsaturated or contain ether linkages. In some embodiments, R is an alkyl group. In some embodiments, R is methyl and X is - (CH₂)₇CH =. In certain embodiments, the transesterification reaction can produce a transesterified product 72 comprising internal olefin esters, such as internal olefin esters having the following structure:

<img file="MX370894B_D0068.tif" />

<img file="MX370894B_D0069.tif" />

Or where X 'is a saturated or unsaturated alkyl chain of C₃-C_ia, R 'is an alkyl group, which may be optionally unsaturated or contain ether linkages, or hydrogen, and R is Ci-₃alkyl, which is optionally unsaturated. In some embodiments, R 'is an alkyl group and R is Ci-₈ I rent. In some embodiments, R 'is methyl, R is ethyl, and X' is - (CH₂)₇CH =.

[000155] The transesterification reaction to produce transesterified products 72 including saturated and / or unsaturated fatty acid methyl esters (FAME), glycerin, methanol, and / or free fatty acids. In certain embodiments, the transesterified products 72, or a fraction thereof, may comprise a source of biodiesel. In certain embodiments, the transesterified products 72 comprise esters of C₁₀-Ci₅ or Cn-Ci₄. In certain embodiments, the transesterified products 72 comprise 9DA esters, 9UDA esters, and / or 9DDA esters. Non-limiting examples of 9DA esters, 9UDA esters, and 9DDA esters include methyl 9-decenoate (9-DAME), methyl 9-undecenoate (9-UDAME), and methyl 9-dodecenoate (9-DDAME), respectively. As a non-limiting example, in a transesterification reaction, a 9DA portion of a metatized glyceride is removed from the glycerol backbone to form a 9DA ester.

[000156] As discussed above, the types of transesterified products formed are based on the reagents entering the metathesis reactor 20. In a particular embodiment, C methyl esters are produced.₁₂ (9DDAME) downstream of the metathesis reaction between 3hexene and a natural oil.

[000157] In another embodiment, a glycerin alcohol can be used in reaction with a stream of glyceride. This reaction can produce monoglycerides and / or diglycerides.

[000158] In certain embodiments, the transesterified products 72 from the transesterification unit 70 can be sent to a liquid-liquid separation unit, where the transesterified products 72 (ie, FAME, free fatty acids, and / or alcohols) are separated from glycerin. Additionally, in certain embodiments, the glycerin by-product stream can be further processed in a secondary separation unit, where the glycerin is removed and any remaining alcohol is recycled back to transesterification unit 70 for further processing.

[000159] In one embodiment, the transesterified products 72 are further processed in a water wash unit. In this unit, the transesterified products undergo liquid-liquid extraction when washed with water. Excess alcohol, water and glycerin are removed from the transesterified products 72. In another embodiment, the water wash step is followed by a drying unit in which excess water is further removed from the desired mixture of esters (ie, specialty chemicals). These specialty chemicals include non-limiting examples such as 9DA, 9UDA, and / or 9DDA, alkali metal salts and alkaline earth metal salts of the foregoing, individually or in combinations thereof.

[000160] In one embodiment, the monomer specialty chemical (eg, 9DA) can be further processed in an oligomerization reaction to form a lactone, which can serve as a precursor to a surfactant.

[000161] In certain embodiments, the transesterified products 72 from the transesterification unit 70 or specialty chemicals from the water wash unit or drying unit are sent to an ester distillation column 80 for further separation of various individual compounds or groups of compounds, as shown in Figure 1. This separation may include, but is not limited to, the separation of 9DA esters, 9UDA esters, and / or 9DDA esters. In one embodiment, the 9DA 82 ester can be individually distilled or separated from the remaining mixture of transesterified products or specialty chemicals. Under certain process conditions, the 9DA ester 82 must be the lightest component in the specialty chemical or transesterified product stream, and exits at the top of the ester distillation column 80. In another embodiment, the remaining mixture 84, or heavier components, of the transesterified products or specialty chemicals can be separated from the bottom end of the column. In certain modalities, this stream of funds 84 can potentially be sold as biodiesel.

[000162] The 9DA esters, 9UDA esters, and / or 9DDA esters can be further processed after the distillation step in the ester distillation column. In one embodiment, under known operating conditions, the 9DA ester, 9UDA ester, and / or 9DDA ester can then undergo a hydrolysis reaction with water to form 9DA, 9UDA, and / or 9DDA, alkali metal salts and salts of alkaline earth metals from the foregoing, individually or in combinations of these.

[000163] In certain embodiments, the monomeric fatty acid esters of the transesterified products 72 can be reacted with each other to form other specialty chemicals such as dimers.

[000164] In other embodiments, the ester products

<img file="MX370894B_D0070.tif" />

Specific, such as 9DDA methyl ester, can be enriched through subsequent processing and reaction steps of the transesterified products. In one embodiment, a Ci methyl ester stream₀ can be separated from C methyl esters₁₂₊ heavier. The Ci methyl ester stream₀ It can then be reacted with 1-butene in the presence of a metathesis catalyst to form ethylene and Ci methyl esters.₂. The ethylene can be separated from the methyl esters and the CIO and C12 methyl esters can be removed or returned to an ester distillation column for further processing.

[000165] In certain embodiments, the monomer fatty acids and / or monomer fatty acid esters of the transesterified products 72 are isomerized to form isomerized monomer fatty acids and / or isomerized monomer fatty acid esters. The isomerization of the fatty acids and / or fatty acid esters of the transesterified products 72 can be carried out at an elevated temperature (ie, greater than 25 ° C). In certain embodiments, the heat treatment temperature for the isomerization reaction is greater than 100 ° C, greater than 150 ° C, or greater than 200 ° C. In other modes, the temperature is between 100 ° C-300 ° C, between 150-250 ° C, or about 200 ° C. In some embodiments, the heat treatment step is carried out in the presence of a catalyst of

<img file="MX370894B_D0071.tif" />

isomerization. In a particular embodiment, the isomerization catalyst is (PCy₃) ₂ (Cl) (H) Ru (CO), where Cy represents a cyclohexyl group.

[000166] In certain embodiments, the monomeric fatty acids and / or monomeric fatty acid esters that undergo the isomerization reaction are selected from the group consisting of: 9DA, 9DA esters, 9UDA esters, 9UDA esters, esters of 9DDA, and esters of 9DDA. Isomerization of fatty acids and / or fatty acid esters can produce isomerized monomer fatty acids and / or isomerized monomer fatty acid esters selected from the group consisting of isomerized 9DA, isomerized 9DA esters, isomerized 9UDA, 9UDA esters isomerized, isomerized 9DDA, and isomerized 9DDA esters.

[000167] Isomerization of monomeric fatty acids and / or monomeric fatty acid esters can improve various performance properties. For example, the isomerized product composition may have an observed broadening of the freezing and melting points, which may allow transport of the isomerized fatty acid / ester product composition to higher concentrations of the monomeric fatty acids and / or esters. of monomer fatty acids without incurring shipping problems.

[000168] The isomerized monomer fatty acids and / or

<img file="MX370894B_D0072.tif" />

Isomerized monomer fatty acid esters can be used in a variety of different commercial applications, including but not limited to: lubricants, waxes, films, paints, paint thinners, coatings, plasticizers, resins, binders, solvents, polyols , soil stabilization, chemical plasters, oil field drilling fluids, crop protection products, surfactants, intermediates, and adhesives.

[000169] In certain embodiments, the transesterification reaction can produce a transesterified product 72 comprising terminal olefin esters, such as terminal olefin esters having the following structure:

<img file="MX370894B_D0073.tif" />

where X is a saturated or unsaturated alkyl chain of C₃Cie, and R is an alkyl group, which may be optionally unsaturated or contain ether linkages. In some embodiments, R is alkyl. In some embodiments, R is methyl and X is - (CH₂) 7CH =. In certain embodiments, the transesterification reaction can produce a transesterified product 72 comprising internal olefin esters, such as internal olefin esters having the

<img file="MX370894B_D0074.tif" />

following structure:

<img file="MX370894B_D0075.tif" />

Or where X 'is a saturated or unsaturated Cj-Cib alkyl chain, R' is an alkyl group, which may be optionally unsaturated or contain ether linkages, or hydrogen, and R is C1-3 alkyl, which is optionally unsaturated. In some embodiments, R is Ci-s alkyl. In some embodiments, R 'is methyl, R is ethyl, and X' is - (CH₂) 7CH =.

[000170] In certain embodiments, the terminal olefin-internal olefin cross-metathesis reaction is carried out in a weight ratio between 1:99 (terminal to internal) and 99: 1 (terminal to internal). In other embodiments, the weight ratio of the internal and terminal olefin is between 1: 5 and 5: 1. In still other embodiments, the weight ratio between the terminal and internal olefin is between 1: 2 and 2: 1. In a particular embodiment, the weight ratio between the terminal and internal olefin is approximately 1: 1.

[000171] In certain embodiments, the terminal olefin is selected from the group consisting of: 4-pentenoic acid ester, 5-hexenoic acid ester, 6-heptenoic acid ester, 7-octenoic acid ester, 8-nonenoic acid ester, 9-decenoic acid ester, 10-undecenoic acid ester, 11-dodecenoic acid ester, acid ester

100

<img file="MX370894B_D0076.tif" />

12-tridecenoic acid, 13-tetradecenoic acid ester, 14-pentadecenoic acid ester, 15-hexadecenoic acid ester, 16-heptadecenoic acid ester, 17-octadecenoic acid ester, acids of these, and mixtures of these. In a particular embodiment, the terminal olefin is 9-decenoic acid ester.

[000172] In certain embodiments, the terminal olefin is cross-metatized with an internal olefin selected from the group consisting of: esters of pentenoic acid, esters of hexenoic acid, esters of heptenoic acid, esters of octenoic acid, esters of nonenoic acid, esters of decenoic acid, esters of undecenoic acid, esters of dodecenoic acid, esters of tridecenoic acid, esters of tetradecenoic acid, pentadecenoic acid esters, hexadecenoic acid esters, heptadecenoic acid esters, octadecenoic acid esters, acids thereof, and mixtures thereof. In a particular embodiment, the internal olefin is 9-undecenoic acid ester. In another particular embodiment, the internal olefin is 9-dodecenoic acid ester.

[000173] In some embodiments, the internal olefin is formed by reacting a portion of the terminal olefin ester derived from the transesterified product 72 with a low molecular weight internal olefin or medium weight internal olefin in the presence of a metathesis catalyst. In

101

<img file="MX370894B_D0077.tif" />

In certain embodiments, the low molecular weight internal olefin is selected from the group consisting of: 2-butene, 2-pentene, 2-hexene, 3-hexene, 2-heptene, 3-heptene, 2-octene, 3-octene, 4- octene, 2-nonene, 3-nonene, 4-nonene, and mixtures of these. In a particular embodiment, the low molecular weight internal olefin is 2-butene. In another particular embodiment, the low molecular weight internal olefin is 3-hexen.

[000174] In certain embodiments, at least 70% by weight, 80% by weight, or 90% by weight of dibasic ester and / or dibasic acid is formed from a cross-metathesis reaction of a terminal olefin and an internal olefin in the presence of less than 150 ppm, 100 ppm, 50 ppm, 25 ppm or 10 ppm of catalyst. A comparable auto-metathesis reaction with terminal olefins (such as 9-decenoic acid ester) under similar reaction conditions may require more catalyst (eg, more than 150 ppm, or more than 500 ppm) to achieve similar ester yields. dibasic and / or dibasic acids (potentially due to the formation of the ethylene by-product).

[000175] In certain embodiments, the yield of dibasic ester and / or dibasic acid is improved by separating the olefin by-product formed in the cross-metathesis reaction from the metatized product, whereas the reaction between the terminal olefin and the internal olefin is

102

<img file="MX370894B_D0078.tif" />

running. In other embodiments, the performance of the dibasic ester and / or dibasic acid is enhanced by sparging the metathesis products in the metathesis reactor with a chemically inert gas (e.g., nitrogen, argon, or helium) to vent dissolved gases / by-products ( eg olefin by-products) in the metathesis product.

[000176] In certain embodiments, the cross-metathesis reaction of the terminal olefin ester and internal olefin ester produces an unsaturated dibasic ester. In some embodiments, the resulting unsaturated dibasic ester is a compound of the following structure:

/ 0 / R 'rx' oo

where R, R ', X, and X' are as defined in any of the above embodiments. In some embodiments, -X = X'- is - (CH₂) ₇-ch = ch- (CH₂)₇-.

[000177] In some embodiments, the dibasic ester derived from the transesterified product 72 may further undergo a hydrolysis reaction with water to form a dibasic acid having the following structure:

OR

<img file="MX370894B_D0079.tif" />

OR

103 where X and X 'are as defined above. In some embodiments, -X = X'- is - (CH₂) ₇-CH = CH- (CH₂) ₇- · In some other embodiments, saponification can be used to obtain a dibasic acid salt (where acid salt refers to a carboxylate anion, either in solution or in solid state form), which can optionally be acidified to form dibasic acid.

[000178] After conversion to a dibasic acid, in some embodiments, the product stream can be sent to a steaming column or decanter to remove methanol and water, or other substances from the dibasic acid.

[000179] In other embodiments, the dibasic acid and / or dibasic ester is isomerized to form an isomerized dibasic acid and / or isomerized dibasic ester. The isomerization of the dibasic acid and / or dibasic ester can be carried out at an elevated temperature (ie, greater than 25 ° C). In certain embodiments, the heat treatment temperature for the isomerization reaction is greater than 100 ° C, greater than 150 ° C, or greater than 200 ° C. In other modes, the temperature is between 100 ° C-300 ° C, between 150-250 ° C, or about 200 ° C. In some embodiments, the heat treatment step is carried out in the presence of an isomerization catalyst. In a particular embodiment, the isomerization catalyst is (PCy₃) ₂ (Cl) (H) Ru (CO), where Cy represents a cyclohexyl group.

104

<img file="MX370894B_D0080.tif" />

[000180] In certain embodiments, the isomerized dibasic acid and / or isomerized dibasic ester comprises compounds selected from the group consisting of: isomerized dimethyl 9octadecenedioate or isomerized 9octadecenedioic acid.

[000181] In certain embodiments, the isomerized dibasic acid and / or isomerized dibasic ester is self-metatized or cross-metatized with a low molecular weight olefin or medium weight olefin. Typical metathesis and catalyst reaction conditions are discussed in more detail below. In one embodiment, the isomerized dibasic acid and / or isomerized dibasic ester self-metatizes in the presence of about 10 ppm, 20 ppm, 40 ppm, 50 ppm, 80 ppm, 100 ppm, 120 ppm, or more than 150 ppm of metathesis catalyst.

[000182] In certain embodiments, the isomerized fatty acid, isomerized fatty acid ester, dibasic acid, dibasic ester, isomerized dibasic ester, and / or isomerized dibasic ester are hydrogenated. Typical hydrogenation reaction conditions and typical catalysts are discussed above. In a particular example, the hydrogenation reaction is carried out in the presence of a nickel-based catalyst at approximately 150 ° C and 150 psi.² (10.2 atm).

[000183] As noted, the auto-metathesis of oil

105 natural, cross-metathesis between natural oil and low molecular weight olefin or medium weight olefin, or cross metathesis between a terminal olefin and an internal olefin can occur in the presence of a metathesis catalyst. As noted previously, the term "metathesis catalyst" includes any catalyst or catalyst system that catalyzes a metathesis reaction. Any known or future-developed metathesis catalyst can be done, individually or in combination with one or more additional catalysts. Exemplary non-limiting metathesis catalysts and process conditions are described in WO 2009/020667, incorporated herein by reference. Various metathesis catalysts as shown are made by Materia, Inc. (Pasadena, CA). [000184] The metathesis process can be carried out under any suitable conditions to produce the desired metathesis products. For example, stoichiometry, atmosphere, solvent, temperature, and pressure can be selected by one of ordinary skill in the art to produce a desired product and to minimize undesirable by-products. The metathesis process can be carried out under an inert atmosphere. Similarly, if a reagent is supplied as a gas, an inert gaseous diluent can be used. The inert atmosphere or inert gaseous diluent is typically an inert gas, meaning

106 that the gas does not interact with the metathesis catalyst to substantially prevent catalysis. For example, the particular inert gases are selected from the group consisting of helium, neon, argon, nitrogen, individually or in combinations of these.

[000185] In certain embodiments, the metathesis catalyst is dissolved in a solvent before conducting the metathesis reaction. In certain embodiments, the chosen solvent can be selected to be substantially inert with respect to the metathesis catalyst. For example, substantially inert solvents include, without limitation, aromatic hydrocarbons, such as benzene, toluene, xylenes, and the like; halogenated aromatic hydrocarbons, such as chlorobenzene and dichlorobenzene; aliphatic solvents, including pentane, hexane, heptane, cyclohexane, and the like; and chlorinated alkanes, such as dichloromethane, chloroform, dichloroethane, and the like. In a particular embodiment, the solvent comprises toluene.

[000186] In other embodiments, the metathesis catalyst is not dissolved in a solvent prior to conducting the metathesis reaction. The catalyst, on the other hand, can be formed in slurry with the natural oil 12, where the natural oil 12 is in a liquid state. Under these conditions, it is possible to remove the solvent (e.g. toluene) from the process and eliminate downstream losses

107

<img file="MX370894B_D0081.tif" />

of olefins when the solvent is removed. In other embodiments, the metathesis catalyst can be added as a solid state (and not slurry) to natural oil 12 (eg, as a screw feed).

[000187] The metathesis reaction temperature can be a rate-controlling variable, where the temperature is selected to provide a desired product at an acceptable rate. In certain embodiments, the temperature of the metathesis reaction is greater than about -40 ° C, greater than about -20 ° C, greater than about 0 ° C, or greater than about 10 ° C. In certain embodiments, the metathesis reaction temperature is less than about 150 ° C, or less than about 120 ° C. In one embodiment, the metathesis reaction temperature is between about 10 ° C and about 120 ° C.

[000188] The metathesis reaction can be run under any desired pressure. Typically, it will be desirable to maintain a total pressure that is high enough to keep the cross-metathesis reagent in solution. Therefore, as the molecular weight of the cross-metathesis agent increases, the lower pressure range typically decreases as the boiling point of the cross-metathesis reagents increases. The total pressure is

108

<img file="MX370894B_D0082.tif" />

You can select to be greater than approximately 0.1 atm (10 kPa), in some modes greater than approximately 0.3 atm (30 kPa), or greater than approximately 1 atm (100 kPa). Typically, the reaction pressure is no more than about 70 atm (7000 kPa), in some embodiments no more than about 30 atm (3000 kPa). An exemplary non-limiting pressure range for the metathesis reaction is from about 1 atm (100 kPa) to about 30 atm (3000 kPa).

[000189] The above description provides certain ways to make a dibasic ester and / or dibasic acid from a raw material comprising a natural oil. Other methods can be used as well. For example, in another aspect, the disclosure provides methods for refining a natural oil, comprising providing a raw material comprising a natural oil; transesterifying the raw material in the presence of an alcohol to form a transesterified product comprising one or more unsaturated fatty acid esters; reacting the unsaturated fatty acid esters in the presence of a metathesis catalyst to form a metatized product comprising one or more metatized unsaturated esters and one or more olefins; separating the metatized unsaturated esters in the metatized product from the olefins in the metatized product, wherein the separated metatized esters

109 they comprise a terminal olefin ester or an internal olefin ester. The resulting terminal olefin ester and / or internal olefin ester can be used to form an unsaturated dibasic ester, for example, according to any of the embodiments described above. In some embodiments, the alcohol is methanol. In some embodiments, the unsaturated dibasic ester is a 9-octadecenedioic acid dibasic ester, such as 9-octadecenedioic acid dimethyl ester. In some additional embodiments, the resulting unsaturated dibasic ester can be converted to a saturated dibasic ester and / or a saturated dibasic acid using any suitable combination of hydrogenation, hydrolysis, and / or saponification / acidification.

[000190] Figure 7 shows a flow chart illustrating certain modalities for making an unsaturated dibasic ester from a raw material comprising a natural oil. The illustrated method 700 comprises: providing a raw material comprising a natural oil 701; reacting the raw material in the presence of a metathesis catalyst 702 to form a metatized product comprising esters, eg, unsaturated glycerides and olefins; and separating (at least a portion of) the esters of the olefins 703 in the metatized product; transesterifying the separated esters 704, for example, in the presence of an alcohol (for example, methanol) to form an ester of

110 terminal olefin and / or internal olefin ester; and reacting the internal olefin ester and / or the terminal olefin ester (according to any of the aspects and embodiments described above) 705 to form an unsaturated dibasic ester. The unsaturated dibasic ester can be reacted, for example, further according to any of the above aspects and embodiments to form a saturated dibasic acid, such as octadecanedioic acid.

[000191] Figure 8 shows a flow chart illustrating certain modalities for making an unsaturated dibasic ester from a raw material comprising a natural oil. The illustrated method 800 comprises: providing a raw material comprising a natural oil 801; transesterifying the raw material 802, eg, in the presence of an alcohol (eg, methanol) to form a transesterified product comprising one or more unsaturated fatty acid esters; reacting unsaturated fatty acid esters 803, for example, in the presence of a metathesis catalyst to form a metatized product comprising one or more metatized unsaturated esters and one or more olefins; separating (at least a portion of) the metatized unsaturated esters of the 804 olefins, for example, into the metatized product, wherein the separated metatized product comprises an ester of

111 terminal olefin and / or an internal olefin ester; and reacting the internal olefin ester and / or the terminal olefin ester (according to any of the aspects and embodiments described above) 805 to form an unsaturated dibasic ester. The unsaturated dibasic ester can be further reacted, for example with any of the above aspects and embodiments to form a saturated dibasic acid, such as octadecanedioic acid.

[000192] While the invention as described may have alternative forms and modifications, various embodiments thereof have been described in detail. However, it should be understood that the description herein of these various embodiments is not intended to limit the invention, but rather, the invention will cover all modifications, equivalents and alternatives that fall within the spirit and scope of the invention. invention as defined by the claims. Furthermore, while the invention will also be described with reference to the following non-limiting examples, it will of course be understood that the invention is not limited thereto since modifications can be made by those skilled in the art, particularly in view of the previous teachings. Examples Example 1

[000193] A 5 gallon Parr reactor vessel (18.9

112

<img file="MX370894B_D0083.tif" />

liters) jacketed, stainless steel, dry, clean, equipped with dip tube, overhead stirrer, internal heated / cooled spirals, temperature probe, sampling valve, and gas release valve on top was purged with argon at 15 psig (1.05 atm). Soybean oil (SBO, 2.5 kg, 2.9 mol, Costco, MWn = 864.4 g / mol, 85 wt% unsaturation as determined by gas chromatographic analysis (per ge), 1 hour with sparged argon was added to the Parr reactor into the 5 gallon (18.92 liter) container). The Parr reactor was sealed and the SBO was purged with argon for 2 hours while cooling to 10 ° C. After 2 hours, the reactor was vented until the internal pressure reached 10 psi.² (0.68 atm). The dip tube valve in the reactor was connected to a 1-butene cylinder (Airgas, CP grade, 33 psi top pressure).² (2.25 atm),&gt; 99% by weight) and was re-pressurized to 15 lb / in² (1.02 atm) of 1-butene. The reactor was again vented at 10 psi (0.68 atm) to remove residual argon in the headspace. The SBO was stirred at 350 rpm and 9-15 ° C under 18-28 psi² (1.22-1.90 atm) of 1-butene until 3 mol of 1-butene was transferred per bound SBO olefin into the reactor (about 2.2 kg of 1-butene over about 4-5 hours). A toluene solution of [1,3-Bis- (2,4,6-trimethylphenyl) -2 imidazolidinylidene] dichlororutenium- (3-methyl-2113

<img file="MX370894B_D0084.tif" />

butenylidene) (tricyclohexylphosphine) (C827, Matter) in a Fischer-Porter pressure vessel by dissolving 130 mg of catalyst in 30 grams of toluene as a catalyst carrier (10 mol ppm per bound olefin of SBO) and added to the reactor via the reactor dip tube by pressurizing the headspace within the Fischer-Porter vessel to 50-60 psi² 3.40-4.08 atm) with argon. The Fischer-Porter container and dip tube were rinsed with an additional 30 g of toluene. The reaction mixture was stirred for 2.0 hours at 60 ° C. The reaction mixture was allowed to cool to room temperature while the gases in the headspace were vented. After the pressure was released, the reaction mixture was transferred to a 3-neck round bottom flask containing 58 g of bleaching clay (2% w / w SBO, Pure Flow B80 CG) and a magnetic stir bar . The reaction mixture was worked up by stirring at 85 ° C under argon. After 2 hours, during which time any remaining 1-butene was allowed to vent, the reaction mixture was allowed to cool to 40 ° C and filtered through a sintered glass filter. An aliquot of the product mixture was found by gas chromatographic analysis (after transesterification with 1% w / w NaOMe in methanol at 60 ° C) contains approximately 22% by weight of methyl 9-decenoate, approximately 16 % by weight of 9-dodecenoate

114

<img file="MX370894B_D0085.tif" />

methyl, about 3% by weight of dimethyl 9-octadecenoate, and about 3% by weight of methyl 9-octadecenoate (per ge). These results compare favorably with the calculated equilibrium requirements of 23.4% by weight of methyl 9-decenoate, 17.9% by weight of methyl 9-dodecenoate, 3.7% by weight of dimethyl 9-octadecenoate, and 1.8% in weight of methyl 9-octadecenoate.

Example 2

[000194] By the general procedures described in Example 1, a reaction was carried out using 1.73 kg of SBO and 3 mol of 1-butene / SBO double bond. An aliquot of the product mixture was found by gas chromatographic analysis after transesterification with 1% w / w NaOMe in methanol at 60C containing approximately 24% by weight of methyl 9-decenoate, approximately 18% by weight of methyl 9-dodecenoate, about 2% by weight of dimethyl 9-octadecenoate, and about 2% by weight of methyl 9-octadecenoate (as determined by ge).

Example 3

[000195] By the general procedures described in example 1, a reaction was performed using 1.75 kg of SBO and 3 mol of 1-butene / SBO double bond. It was found by gas chromatographic analysis after transesterification with 1% w / w NaOMe in methanol at 60 ° C that an aliquot of the product mixture contains

115

<img file="MX370894B_D0086.tif" />

about 24% by weight of methyl 9-decenoate, about 17% by weight of methyl 9-dodecenoate, about 3% by weight of dimethyl 9-octadecenoate, and about 2% by weight of methyl 9-octadecenoate (as is determined by ge).

Example 4

[000196] By the general procedures described in Example 1, a reaction was carried out using 2.2 kg of SBO, 3 mol of 1-butene / SBO double bond, and 60 g of the toluene used to transfer the catalyst was replaced with SBO. By gas chromatographic analysis after transesterification with 1% w / w NaOMe in methanol at 60 ° C it was found that an aliquot of the product mixture contains approximately 25% by weight of methyl 9-decenoate, approximately 18% by weight of methyl 9-dodecenoate, about 3% by weight of dimethyl 9-octadecenoate, and about 1% by weight of methyl 9-octadecenoate (as determined by ge).

Example 5

[000197] A 12 liter, 3-necked, glass round bottom flask fitted with a magnetic stir bar, heating mantle, and temperature controller was charged with 8.42 kg of the combined reaction products of Examples 1 -4. A cooling condenser with a vacuum inlet was attached to the middle neck of the flask and to the

116

<img file="MX370894B_D0087.tif" />

condenser a receiving flask was connected. The hydrocarbon definitions were removed from the reaction product by vacuum distillation over the following range of conditions: 22-130 ° C kettle temperature, 19-70 ° C distillation head temperature, and a pressure of 2000-160 ptorr. The weight of the material remaining after the volatile hydrocarbons were removed was 5.34 kg. By gas chromatographic analysis after transesterification with 1% w / w NaOMe in methanol at 60 ° C it was found that an aliquot of the non-volatile product mixture contains approximately 32% by weight of methyl 9-decenoate, approximately 23% by weight of methyl 9-dodecenoate, about 4% by weight of dimethyl 9-octadecenoate, and about 5% by weight of methyl 9-octadecenoate (as determined by ge).

Example 6

[000198] A 12 liter 3 neck round bottom flask that was equipped with a magnetic stir bar, condenser, heating mantle, temperature probe, and gas adapter, was charged with 4 liters of 1 wt% NaOMe / w in MeOH and 5.34 kg of the non-volatile product mixture produced in Example 5. The resulting light yellow heterogeneous mixture was stirred at 60 ° C. After approximately one hour, the mixture took on a homogeneous orange color (pH detected = 11.) After a total time of

117

<img file="MX370894B_D0088.tif" />

2 hour reaction, the mixture was cooled to room temperature and two layers were observed. The organic phase was washed twice with 3 L of 50% (v / v) aqueous MeOH, separated, and neutralized by washing with glacial HOAc in MeOH (1 mole HOAc / mole NaOMe) at a detected pH of 6.5 , producing 5.03 kg.

Example 7

[000199] A 12 L glass 3 neck round bottom flask equipped with a magnetic stirrer, packed column, and temperature controller, was charged with the methyl ester mixture (5.03 kg) produced in Example 6 and placed on the warming mantle. The column attached to the flask was a 2-inch x 36-inch (5.08 cm x

MR

91.44 cm) containing 0.16 inch (0.41 cm) Pro-PAK stainless steel brackets. The distillation column was attached to a fractional distillation head to which a 1 L preweighed round bottom flask was fitted to collect the distillation fractions. Distillation was carried out under vacuum at 100-120 ptorr. A reflux ratio of 1: 3 was used to isolate both methyl 9-decenoate (9-DAME) and methyl 9-dodecenoate (9-DDAME). A reflux ratio of 1: 3 refers to 1 drop collected for every 3 drops sent back to the distillation column. Samples collected during distillation, vacuum distillation conditions, and the 9-DAME and 9-DDAME content of

118 The fractions, as determined by ge, are shown in Table 1. Combining fractions 2-7 produced 1.46 kg of 99.7% pure methyl 9-decenoate. After collection of fraction 16, 2.50 kg of material remained 5 in the distillation kettle: it was found per ge to contain about 14% by weight of 9 DDAME, about 42% by weight of methyl palmitate, and about 12% by weight of methyl stearate.

Table 1

<td> 10</td><td>Distillation fractions No.</td><td>Temp. head (° C)</td><td>Temp. of kettle (° C)</td><td>Void (jjtorr)</td><td>Weight (g)</td><td>9-DAME (% by weight)</td><td>9-DDAME (% by weight)</td>

<td></td><td> 1</td><td> 40-47</td><td> 104-106</td><td> 110</td><td> 6.8</td><td> 80</td><td> 0</td>

<td></td><td> 2</td><td> 45-46</td><td> 106</td><td> 110</td><td> 32.4</td><td> 99</td><td> 0</td>

<td></td><td> 3</td><td> 47-48</td><td> 105-110</td><td> 120</td><td> 223.6</td><td> 99</td><td> 0</td>

<td></td><td> 4</td><td> 49-50</td><td> 110-112</td><td> 120</td><td> 283</td><td> 99</td><td> 0</td>

<td> 15</td><td> 5</td><td> 50</td><td> 106</td><td> 110</td><td> 555</td><td> 99</td><td> 0</td>

<td></td><td> 6</td><td> 50</td><td> 108</td><td> 110</td><td> 264</td><td> 99</td><td> 0</td>

<td></td><td> 7</td><td> 50</td><td> 112</td><td> 110</td><td> 171</td><td> 99</td><td> 0</td>

<td></td><td> 8</td><td> 51</td><td> 114</td><td> 110</td><td> 76</td><td> 97</td><td> 1</td>

<td></td><td> 9</td><td> 65-70</td><td> 126-128</td><td> 110</td><td> 87</td><td> 47</td><td> 23</td>

<td rowspan="2"> 20</td><td> 10</td><td> 74</td><td> 130-131</td><td> 110</td><td> 64</td><td> 0</td><td> 75</td>

<td> 11</td><td> 75</td><td> 133</td><td> 110</td><td> 52.3</td><td> 0</td><td> 74</td>

<td></td><td> 12</td><td> 76</td><td> 135-136</td><td> 110</td><td> 38</td><td> 0</td><td> 79</td>

<td></td><td> 13</td><td> 76</td><td> 136-138</td><td> 100</td><td> 52.4</td><td> 0</td><td> 90</td>

<td></td><td> 14</td><td> 76</td><td> 138-139</td><td> 100</td><td> 25.5</td><td> 0</td><td> 85</td>

<td></td><td> 15</td><td> 76-77</td><td> 140</td><td> 110</td><td> 123</td><td> 0</td><td> 98</td>

<td></td><td> 16</td><td> 78</td><td> 140</td><td> 100</td><td> 426</td><td> 0</td><td> 100</td>

119

<img file="MX370894B_D0089.tif" />

Example 8

[000200] A reaction was carried out by the general procedures described in Example 1 with the following changes: 2.2 kg of SEO, 7 mol of propene / mol of SBO double bond, and 200 mg [1,3-bis- (2 , 4,6-trimethylphenyl) -2-imidazolidinylidene] dichlororuthenium (benzylidene) (tricyclohexylphosphine) [catalyst C848, Materia Inc., Pasadena, California, USA, 90 ppm (w / w) vs. SBO] at a reaction temperature of 40 ° C, were used. The catalyst removal step using bleaching clay was also replaced by the following: after the excess propene had been de-fused, the reaction mixture was transferred to a 3-neck round bottom flask to which 50 mol of tris- (hydroxymethyl) was added. ) phosphine (THMP) / mole of catalyst C848. THMP was formed as a 1.0 M solution in isopropanol, where phosphonium salt, inorganic salt, formaldehyde, THMPO, and THMP were mixed together. The resulting hazy yellow mixture was stirred for 20 hours at 60 ° C, transferred to a 6 L separatory funnel and extracted with 2x 2.5 L of H₂0 deionized. The organic layer was separated and dried over Na₂SW₄anhydrous for 4 hours, then filtered through a sintered glass filter containing a silica gel bed.

Example 9

[000201] A reaction was carried out by the procedures

120

<img file="MX370894B_D0090.tif" />

general described in Example 8, except that 3.6 kg of SBO and 320 mg of catalyst C848 were used. After removal of the catalyst, the reaction product from Example 9 was combined with that from Example 8, yielding 5.12 kg of material. An aliquot of the combined product mixture was found by gas chromatographic analysis after transesterification with 1% w / w NaOMe in methanol at 60 ° C, containing approximately 34% by weight of methyl 9-decenoate, approximately 13% by weight of methyl 9-undecenoate, &lt;1% by weight of dimethyl 9-octadecenedioate, and &lt;1% by weight of methyl 9-octadecenoate (as described by ge).

[000202] The hydrocarbon olefins were removed from the 5.12 kg of combined reaction product described above by vacuum distillation by the general procedure described in Example 5. The weight of the material remaining after the volatile olefins were removed was 4.0 kg. By gas chromatographic analysis after transesterification with 1% w / w NaOMe in methanol at 60 ° C it was found that an aliquot of the non-volatile product mixture contains approximately 46% by weight of methyl 9-decenoate, approximately 18% by weight of methyl 9-octadecenoate, about 2% by weight of dimethyl 9-octadecenoate, and about 1% by weight of methyl 9-octadecenoate (as determined by ge).

121

<img file="MX370894B_D0091.tif" />

Example 10

[000203] Two reactions were carried out by the general procedures described in Example 8, except that for each reaction, 3.1 kg of SBO and 280 mg of C848 catalyst were used. After removal of the catalyst, the reaction products of the two preparations were combined, yielding 5.28 kg of material. By gas chromatographic analysis after transesterification with 1% w / w NaOMe in methanol at 60 ° C it was found that an aliquot of the combined product mixture contains approximately 40% by weight of methyl 9-decenoate, approximately 13% by weight of methyl 9-undecenoate, about 2% by weight of dimethyl 9-octadecenedioate, and about 1% by weight of methyl 9-octadecenoate (as determined by ge).

[000204] The hydrocarbon olefins were removed from the 5.28 kg of the combined reaction product by vacuum distillation by the general procedure described in Example 5. The weight of the material remaining after the volatile olefins were removed was 4.02 kg. By gas chromatographic analysis after transesterification with 1% w / w NaOMe in methanol at 60 ° C it was found that an aliquot of the non-volatile product mixture contains approximately 49% by weight of methyl 9-decenoate, approximately 16% by weight of 9-undecenoate

<img file="MX370894B_D0092.tif" />

122 methyl, about 2% by weight of dimethyl 9-octadecenedioate, and about 3% by weight of methyl 9-octadecenoate (as determined by ge).

Example 11

[000205] By the general procedures described in Example 10, two metathesis reactions were performed using SBO, 7 mol cis-2-butene / mol SBO double bond, and 220 mg C848 catalyst / kg SBO. After removal of the catalyst, the reaction products of the two preparations were combined, yielding 12.2 kg of material. By gas chromatographic analysis after transesterification with 1% w / w NaOMe in methanol at 60 ° C it was found that an aliquot of the combined product mixture contains approximately 49% by weight of methyl 9undecenoate, approximately 2% by weight of dimethyl 9-octadecenoate, and about 1% by weight of methyl 9-octadecenoate (as determined by ge).

[000206] The hydrocarbon olefins were removed from the 12.2 kg of the combined reaction product by vacuum distillation by the general procedure described in Example 5. The weight of material remaining after the volatile olefins were removed was 7.0 kg. By gas chromatographic analysis after transesterification with 1% w / w NaOMe in methanol at 60 ° C it was found that an aliquot of the non-volatile product mixture

123 It contains about 57% by weight of methyl 9-undecenoate, about 4% by weight of dimethyl 9-octadecenedioate, and about 2% by weight of methyl 9-octadecenoate (as determined by ge).

Example 12

[000207] By the general procedures described in Example 1, approximately 7 kg of cross-metathesis product was produced by reacting SBO with 3 mol of 1butene / mol of SBO double bond using 43mg of C827 catalyst / kg of SBO, after removing the catalyst with THMP. An initial 2.09 kg portion of the metathesis product was hydrogenated at 136 ° C and 400 lb / in.²(27.22 atm) of H₂until hydrogen uptake ceased in a gallon (3.79 liter) batch autoclave using 105 g of Johnson-Matthey A-7000 Sponge Metal catalyst^MR. The resulting mixture was filtered hot (22-55 ° C), yielding 1.40 kg of filtrate and 350 g of a mixture consisting of the catalyst and the hydrogenated product. The entire mixture containing catalyst was returned to the one gallon (3.79 liter) reactor along with a second 2.18 kg portion of the metathesis product and a second hydrogenation reaction was carried out in a similar manner until uptake of hydrogen. The catalyst was allowed to settle and most of the organic product was decanted and filtered, yielding 1.99 kg of filtrate and 380 g of product mixture.

124 hydrogenated with catalyst. The remaining approximately 3 kg of metathesis product was hydrogenated in two additional batch reactions that were similarly carried out using the catalyst from the previous reaction, yielding 1.65 kg and 1.28 kg of hydrogenated product, respectively. The total weight of the hydrogenated product that was isolated after filtration was 6.32 kg. By gas chromatographic analysis it was found that the aliquots of the hydrogenated product contain approximately 30% by weight of C₆-Ci_to n-paraffins and about 70% by weight of triglycerides. The relative distribution of the C₈-Ci₈ nparaffins contained in the hydrogenated product compares well with the calculated distribution of olefins by the number of carbons: observed (calculated) 2.3 (0.6)% by weight of C₈, 35.6 (36.2)% by weight of C₉, 30.0 (27.6)% by weight of Cio, 0.6 (0.1)% by weight of Cu, 22.2 (23.6)% by weight of C₁₂, 3.4 (3.7)% by weight of Ci₃0.1 (0.0)% by weight of C₁₄, 4.4 (6.3)% by weight of C15, 0.4 (04)% by weight of Ci₆, 0.1% by weight of Ci₇ (0.0), and 1.0 (1.6)% by weight of C_i8. The paraffin components were removed by evaporation of cleaned film from a 4.84 kg aliquot of the triglyceride / hydrogenated paraffin product. Initial evaporation of the cleaned film was carried out at 75 ° C, 100 torr, 300 rpm, and condensation temperature of 15 ° C using a feed rate of 300 g / h and produced a condensate which was subjected to a second

125 evaporation of cleaned film at 125 ° C, 90 torr, 300 rpm, and 10 ° C condensing temperature to remove the lightest alkanes. The resulting residual liquid was found by gas chromatography to contain the following distribution of n-alkanes: 17.5% by weight of C₇, 1.7% by weight of C₈, 31.0% by weight of C₉, 28.3% by weight of C₁₀, 0.6% by weight of Cu, 17.4% by weight of C₁₂, 2.1% by weight of C₁₃, 0.1% by weight of Ci₄, 1.2% by weight of Ci₅, 0.1% by weight of Ci₆, 0.0% by weight of Ci₇, and 0.1% by weight of Ci₈. The material was found to have a heat of combustion of 43.86 MJ / kg (ASTM D3338), less than 1 mg / kg of sulfur (ASTM D5453), density of 0.7247 (ASTM D4052), and a final boiling point of 232.3 ° C (ASTM D86), indicating that most of this material would be suitable as a blending material in a fuel application such as diesel or jet fuel.

Example 13

[000208] An oligomerization reaction of l-olefin / 1,4diene (92% by weight of 1-decene, 4.5% by weight of 1,4-decadiene, 2% by weight of 1,4-undecadiene) that occurred from the 1-octene palm oil cross-metathesis was performed on a 550 g scale using 1.1 mol% ethyl aluminum dichloride (1 M solution in hexane) / ll mol% tert-butyl chloride for 3 hours at 10 ° C. The reaction mixture was quenched with water and 1M sodium hydroxide solution and stirred until it became colorless. I know

126

<img file="MX370894B_D0093.tif" />

Hexane (300 ml) was added and the mixture was transferred to a separatory funnel. The organic layer was washed with water and brine, and then concentrated on a rotary evaporator to remove the hexane. The oligomeric mixture was devolatilized by short path vacuum distillation (100 ° C and 5 Torr) and the product distribution was determined to be 97% mixed oligomers by GC / MS. The dynamic viscosity (Brookfield, spindle # 34, 100 rpm, 22 ° C) of the sample is 540 cps. The kinematic viscosity of the sample at 40 ° C is 232 cSt.

Example 14

[000209] An Aspen model was developed to simulate the process of maximizing the purity of an alpha-olefin (ie 1-decene), based on the metathesis process of using a soybean oil feed and 1 feed -butene at a molar ratio of 3: 1. A stream of C10-C18 + olefin (stream A) was created and separated downstream of the cross-metathesis reaction from the soybean oil feed and 1-butene feed. The C10-C18 + olefin stream was then cross metatized with ethylene in a fixed bed ethylene metathesis reactor to create an olefin product. The ethylene product was separated from the olefin product and recycled back to the ethylene metathesis reactor. The heavier olefin product stream (i.e., C16-C18 +) was also separated from the

127

<img file="MX370894B_D0094.tif" />

olefin product to form a final olefin product (stream B) and the heavier olefin product stream was recycled back to the ethylene metathesis reactor. The C10-C18 + olefin inlet stream (stream A) and the final olefin product stream (stream B) have the following olefin product distributions, shown in Table 2 below:

Table 2

<td></td><td>Current A</td><td>Current B</td>

<td>Olefin distribution</td><td>% in weigh</td><td>% in weigh</td>

<td>CIO: 1</td><td> 36.1</td><td> 86.8</td>

<td>CIO isomers</td><td> 52.7</td><td> 3.0</td>

<td>Cll</td><td> 0.0</td><td> 0.0</td>

<td>C12</td><td> 0.0</td><td> 1.8</td>

<td>C13</td><td> 0.0</td><td> 4.1</td>

<td>C14-18</td><td> 11.2</td><td> 4.3</td>

<td>Total</td><td> 100.0</td><td> 100</td>

Example 15

[000210] An Aspen model was developed to simulate the process of maximizing the heavier weight olefins (ie, C18 + olefins) based on the metathesis process using a soybean oil feed and an isomer feed of hexene at a molar ratio of 3: 1. A stream of C11-C18 + olefin (sequence A) was created and separated

128

<img file="MX370894B_D0095.tif" />

downstream of the cross-metathesis reaction of the soybean oil feed and hexene isomer feed. The C11-C18 + olefin stream was then automated in a fixed bed reactor to create an olefin product. A C11-C16 olefin stream was separated from the recycled olefin product back to the autometathesis reactor. The CIO olefin can also be separated as a product to form a final olefin product stream (B). The olefin inlet stream (stream A) and the end product stream (stream B) have the following olefin product distributions, shown in Table 3 below:

Table 3

<td></td><td>Current A</td><td>Current B</td>

<td>Olefin distribution</td><td>% in weigh</td><td>% in weigh</td>

<td>&lt;CIO</td><td> 0.0</td><td> 2.5</td>

<td>CIO</td><td> 0.0</td><td> 21.3</td>

<td>Cll</td><td> 24.7</td><td> 0.0</td>

<td>C12</td><td> 36.2</td><td> 0.0</td>

<td>C13</td><td> 16.8</td><td> 0.0</td>

<td>C14</td><td> 4.5</td><td> 0.0</td>

<td>C15</td><td> 12.1</td><td> 0.0</td>

<td>C16</td><td> 2.4</td><td> 0.0</td>

<td>C17</td><td> 0.4</td><td> 4.1</td>

<td>C18</td><td> 2.4</td><td> 46.7</td>

<td>C18 +</td><td> 0.5</td><td> 25.4</td>

<td>Total</td><td> 100.0</td><td> 100</td>

129

<img file="MX370894B_D0096.tif" />

Example 16

[000211] An Aspen model was developed to simulate the process of maximizing purity of C11-C15 methyl esters based on the metathesis process of using a soybean oil feed and a hexene isomer feed at a molar ratio of 3: 1. A stream of mixed triglycerides and esters is formed from the cross-metathesis reaction of the soybean oil and hexene isomer feeds. The mixed triglyceride and ester stream undergoes glycerolysis after metathesis, followed by olefin separation transesterification. A lighter CIO olefin stream was separated from the mixed triglyceride and ester stream and recycled back to the metathesis reactor. Also a stream of CIO methyl ester (ME) is recycled to the metathesis reactor. A C16 ME stream is purged. A fraction (eg 10%) of the C17-C20 ME stream is purged and the remaining fraction, mixed with the heavier esters, is recycled back to the metathesis reactor. The final ester product stream (comprising primarily C11-C15 ME) downstream of olefin separation, transesterification, and ester recycle streams has the following ester distribution, shown in Table 4:

130

<img file="MX370894B_D0097.tif" />

Table 4

<td></td><td>Ester product stream</td>

<td>Distribution FAME</td><td>% in weigh</td>

<td>&lt;CIOME</td><td> 0.0</td>

<td>CIOME</td><td> 0.0</td>

<td>C11ME</td><td> 17.3</td>

<td>C12ME</td><td> 21.7</td>

<td>C13ME</td><td> 17.7</td>

<td>C14ME</td><td> 4.6</td>

<td>C15ME</td><td> 16.8</td>

<td>C16ME</td><td> 15.6</td>

<td>C17ME</td><td> 0.1</td>

<td>C18ME</td><td> 6.2</td>

<td>C18 + ME</td><td> 0.0</td>

<td>Total</td><td> 100.0</td>

Example 17.- 9-DAME / 9-DDAME at a scale of 10 g

[000212] In this example, methyl 9-decenoate (distillation cut of butenolyzed palm oil, extracted, trans-esterified), and methyl 9-dodecenoate (distillation cut of palm oil) were prepared and cross-metatized. butenolized, extracted, trans-esterified). Their compositions are shown in Tables 5 and 6 below. No PV detected (AOCS method, AOCS method Peroxide index Cd

131

8b-90, acetic acid-isooctane method (revised 2003)).

[000213] Table 5. Feed composition of 9-DAME

<td>Component</td><td>% in weigh</td>

<td>1,4-tridecadiene</td><td> 0.18</td>

<td>Methyl 8-nonenoate</td><td> 0.08</td>

<td>Methyl Decanoate</td><td> 0.16</td>

<td>Methyl 9-decenoate</td><td> 98.51</td>

<td>Methyl 8-decenoate</td><td> 0.76</td>

<td>Others</td><td> 0.29</td>

<td>TOTAL</td><td> 100.00</td>

Table 6. Feed composition of 9-DDAME

<td>Component</td><td>% in weigh</td>

<td>6-pentadecene</td><td> 0.18</td>

<td>3,6-pentadecadiene</td><td> 0.21</td>

<td>7-hexadecene</td><td> 0.25</td>

<td>Methyl Decanoate</td><td> 0.01</td>

<td>Methyl 9-decenoate</td><td> 0.76</td>

<td>Methyl Decanoate</td><td> 3.01</td>

<td>Methyl 9-dodecenoate £</td><td> 95.46</td>

<td>Others</td><td> 0.12</td>

<td>TOTAL</td><td> 100.00</td>

♦ Contaminated with 11-isomer dodecenoic acid, methyl ester

132

<img file="MX370894B_D0098.tif" />

[000214] Clean, dry 20 CC echintillation flasks equipped with a magnetic stir bar and upper septum were loaded with 9-DAME or a mixture of 9-DAME / 9DDAME according to the experiment design of Table 7 below.

Table 7

<td>Example</td><td>9-DAME</td><td>9-DDAME</td><td>C-827 (ppm by weight)</td><td>Top clearance treatment</td>

<td>17a (comparative)</td><td>10.02 g</td><td>og</td><td> 80</td><td>Just vent</td>

<td>17b (comparative)</td><td>10.00 g</td><td>0 g</td><td> 80</td><td>Nitrogen purge</td>

<td>17c (comparative)</td><td>10.00 g</td><td>og</td><td> 500</td><td>Just vent</td>

<td>17d (comparative)</td><td>10.00 g</td><td>og</td><td> 500</td><td>Nitrogen purge</td>

<td>17e</td><td>4.42 g</td><td>5.60 g</td><td> 80</td><td>Just vent</td>

<td>17f</td><td>4.41 g</td><td>5.61g</td><td> 80</td><td>Nitrogen purge</td>

[000215] In Example 17e, approximately 50% by weight of the olefins formed (eg, 1-butene and 3-hexene) were removed during the reaction. In Example 17F, more than 95% by weight of the olefins formed (eg, 1-butene and 3-hexene) were removed during the reaction. In Examples 17a-17d, the olefin was not removed during the reaction.

[000216] The flasks were placed in an eight cell aluminum block on top of a heater / shaker. The aluminum block was heated to 60 ° C. While

133

<img file="MX370894B_D0099.tif" />

that the aluminum block is heating up (~ 15 min). The headspace of the flask was degassed by providing a nitrogen inlet (~ 65 mL / min) and an exhaust needle. Meanwhile, a metathesis catalyst solution (0.01 mg / 1) was prepared by first placing C-827 (21.10 mg) in a 2 ml volumetric flask, second by covering the bottle with a rubber septum, third by purging with nitrogen, and adding toluene to the 2.00 ml mark. A metathesis catalyst solution was added to each reaction mixture (time = 0). According to the experimental design, the nitrogen inlet (65 mL / min) was left in place to sweep the by-product olefins away from the reaction or was removed. In both cases, the vent needle was left in place to avoid over-pressurization of the echintillation flask. In the latter case, the oxygen-free headspace was provided by the olefin formed by the metathesis. After 2 hours, the composition (normalized weight% exclusive of light olefins) was determined by GC FID2, table 8.

134

Table 8

<td></td><td>17th</td><td>17b</td><td>17α</td><td>17d</td><td>17e</td><td>17f</td>

<td>Methyl 8-nonenoate</td><td> 1.39</td><td> 1.67</td><td> 3.58</td><td> 3.65</td><td> 0.00</td><td> 0.00</td>

<td>Methyl 9-decenoate</td><td> 80.51</td><td> 77.53</td><td> 41.12</td><td> 28.66</td><td> 28.41</td><td> 17.48</td>

<td>Methyl 8-decenoate</td><td> 0.00</td><td> 0.00</td><td> 4.41</td><td> 4.86</td><td> 0.00</td><td> 0.00</td>

<td>Methyl undecenoate</td><td> 0.00</td><td> 0.00</td><td> 3.87</td><td> 3.41</td><td> 0.00</td><td> 0.00</td>

<td>Methyl 9-dodecenoate</td><td> 0.00</td><td> 0.00</td><td> 0.00</td><td> 0.00</td><td> 29.44</td><td> 12.59</td>

<td>Methyl 9-octadecenoate</td><td> 0.09</td><td> 0.10</td><td> 0.18</td><td> 0.19</td><td> 0.35</td><td> 0.58</td>

<td>Hexadecenedioate dimethyl</td><td> 0.12</td><td> 0.17</td><td> 0.41</td><td> 0.96</td><td> 0.00</td><td> 0.00</td>

<td>heptadecenedioate dimethyl</td><td> 0.45</td><td> 0.65</td><td> 5.14</td><td> 8.63</td><td> 0.62</td><td> 1.04</td>

<td>9-octadecenedioate dimethyl</td><td> 16.25</td><td> 18.80</td><td> 39.08</td><td> 46.37</td><td> 36.28</td><td> 62.68</td>

<td>Nonadecenedioate dimethyl</td><td> 0.00</td><td> 0.00</td><td> 0.50</td><td> 1.09</td><td> 0.00</td><td> 0.00</td>

<td>dimethyl eicosenodioate</td><td> 0.00</td><td> 0.00</td><td> 0.00</td><td> 0.00</td><td> 0.89</td><td> 1.54</td>

<td>Others</td><td> 1.20</td><td> 1.08</td><td> 1.73</td><td> 2.19</td><td> 4.00</td><td> 4.11</td>

<td>Total</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td>

Example 18- 9-DAME / 9-DDAME on a 330 g scale

[000217] A dibasic ester composition was produced by carrying out a cross-metathesis reaction between methyl 9decenoate (9-decenoic acid methyl ester, 9DAME) and methyl 9-dodecenoate (9-dodecenoic acid methyl ester, 9-DDAME ). A mixture at a molar ratio at

1.0: 1.0 mol of 9-DAME and 9-DDAME (332 g) was charged to a flask

135 round bottom of 1 L and heated to 60 ° C. The pressure was adjusted to 100 mg Hg with a ChemGlass model CG-4812-30 / diaphragm vacuum pump and JKem Scientific model 200 digital vacuum regulator, and stirring was started with a magnetic stir bar. The feed composition (butenolyzed, extracted, trans-esterified palm oil distillation cut) is shown below in Table 9.

Table 9

<td>Component</td><td>% in weight</td>

<td>Methyl Decanoate</td><td> 0.04</td>

<td>Methyl 9-decenoate</td><td> 44.81</td>

<td>Methyl 8-decenoate</td><td> 0.07</td>

<td>Methyl undecenoate</td><td> 0.19</td>

<td>Methyl Decanoate</td><td> 0.76</td>

<td>Methyl 9-dodecenoate *</td><td> 52.87</td>

<td>Methyl 9,12-tridecadienoate</td><td> 0.86</td>

<td>Methyl tetradecenoate</td><td> 0.20</td>

<td>Methyl 9-pentadecenoate</td><td> 0.03</td>

<td>Methyl 9,12-pentadienoate</td><td> 0.02</td>

<td>Methyl hexadecanoate</td><td> 0.15</td>

<td>Total</td><td> 100</td>

* Contaminated with methyl 11-dodecenoate

136

<img file="MX370894B_D0100.tif" />

[000218] After the system stabilized at the desired conditions, 80 ppm of C-827 (as solution in toluene) was added (t = 0 min). At about 15-20 min, the reaction began to bubble vigorously and the pressure increased to about 500 mm Hg. The pressure re-stabilized at 100 mm Hg after about 5-10 more minutes. Samples were taken at 30, 60, 90, 120, 150, 180, 240, and 300 minutes. At 180 min, an additional 40 ppm of C-827 (as a solution in toluene) was added. The graph in Figure 9 shows 9-DAME and 9-DDAME (wt%) versus reaction time (h).

[000219] The composition of crude products ((normalized weight%, exclusive of light olefins)) at five hours is shown in table 10 below:

Table 10

<td>FAME</td><td>% in weigh</td>

<td>Methyl Decanoate</td><td> 0.05</td>

<td>Methyl 9-decenoate</td><td> 6.79</td>

<td>Methyl 8-decenoate</td><td> 0.56</td>

<td>Methyl undecenoate</td><td> 0.37</td>

<td>Methyl dodecanoate</td><td> 0.84</td>

<td>Methyl 9-dodecenoate *</td><td> 6.53</td>

<td>Methyl 9,12-tridecadienoate</td><td> 0.05</td>

<td>Methyl tetradecenoate</td><td> 0.20</td>

<td>Methyl hexadecanoate</td><td> 0.14</td>

137

<td>FAME</td><td>% in weigh</td>

<td>dimethyl hexadecenedioate</td><td> 0.07</td>

<td>dimethyl heptadecenedioate</td><td> 1.11</td>

<td>Dimethyl 9-octadecenedioate</td><td> 78.92</td>

<td>dimethyl nonadecenedioate</td><td> 0.45</td>

<td>dimethyl eicosenodioate</td><td> 2.85</td>

<td>Dimethyl 9,12-heneicosadiene dioate</td><td> 0.53</td>

<td></td><td> 99.46</td>

♦ Contaminated with methyl 11-dodecenoate

[000220] Subsequently, the catalyst was deactivated with 25 equivalents of THMP at C-827 at 80 ° C for 120 tnin, the THMP which was prepared by the general procedure of Example 8. The catalyst was then removed by extraction with water (oil to water 5: 1). The composition was dried with MgSO₄. Then, light FAME extraction was carried out at 1 mm Hg and about 100 ° C. The weight% concentration of the various products included a large 18: 1 dibasic ester fraction, see table 11.

Table 11

<td>Component</td><td>Contained in weight)</td>

<td>Methyl hexadecenoate</td><td> 0.17</td>

<td>Dimethyl 8-hexadecenedioate</td><td> 0.06</td>

<td>Dimethyl 8-heptadecenedioate</td><td> 1.34</td>

138

<img file="MX370894B_D0101.tif" />

<td>Dimethyl 9-octadecenedioate</td><td> 92.95</td>

<td>dimethyl nonadecenedioate</td><td> 0.58</td>

<td>dimethyl eicosenodioate</td><td> 3.41</td>

<td>Dimethyl 12-heneicosadiene dioate</td><td> 0.92</td>

<td>Heavier</td><td> 0.57</td>

Example 19, - 9-DAME / 9-DDAME on a 3 kg scale

[000221] A 12 L glass round bottom flask equipped with 1) a reflux condenser (5 C) to which a vacuum calibrator and a ChemGlass model CG-4812-30 diaphragm vacuum pump were attached, 2) a rubber septum through which nitrogen and catalyst were introduced, magnetic stir bar and thermocouple and alternate vent (in the event that the vacuum pump will fail to maintain a sub-atmospheric pressure). No vacuum regulator was used for this example. Heating was provided by the heating mantle.

[000222] To the nitrogen purged 12 L reaction flask, low PV 9-DAME (1.34 kg) and 9-DDAME (1.68 kg) were added. The condenser was cooled to 5 ° C with glycol. Under the continuous flow of nitrogen, the mixture was heated to ~ 70 ° C and then placed under full vacuum. The addition of the first catalyst solution (C-827 in toluene) marked the beginning of the reaction (t = 0 min). Temperature and pressure were recorded, see table 12.

139

Table 12

<img file="MX370894B_D0102.tif" />

<td>Weather (min)</td><td>Temperature (degrees C)</td><td>Pressure (mm from Hg)</td>

<td> 0</td><td> 73.4</td><td> 35.0</td>

<td> 5</td><td> 74.2</td><td> 30.5</td>

<td> 10</td><td> 74.0</td><td> 30.7</td>

<td> 15</td><td> 72.8</td><td> 28.7</td>

<td> 20</td><td> 71.5</td><td> 28.3</td>

<td> 25</td><td> 70.3</td><td> 28.4</td>

<td> 30</td><td> 69.9</td><td> 28.3</td>

<td> 35</td><td> 72.2</td><td> 28.4</td>

<td> 40</td><td> 72.3</td><td> 30.9</td>

<td> 45</td><td> 71.4</td><td> 65.9</td>

<td> 50</td><td> 71.1</td><td> 233.0</td>

<td> 55</td><td> 70.0</td><td> 237.5</td>

<td> 60</td><td> 69.0</td><td> 196.0</td>

<td> 65</td><td> 68.4</td><td> 218.6</td>

<td> 70</td><td> 69.1</td><td> 215.8</td>

<td> 75</td><td> 68.5</td><td> 188.5</td>

<td> 80</td><td> 68.2</td><td> 194.2</td>

<td> 85</td><td> 70.1</td><td> 207.9</td>

<td> 90</td><td> 70.0</td><td> 185.9</td>

<td> 95</td><td> 68.8</td><td> 175.6</td>

<td> 100</td><td> 68.6</td><td> 172.8</td>

<td> 105</td><td> 70.2</td><td> 172.1</td>

<td> 110</td><td> 72.2</td><td> 169.5</td>

<td> 115</td><td> 71.6</td><td> 170.1</td>

<td> 120</td><td> 71.1</td><td> 147.0</td>

<td> 125</td><td> 69.3</td><td> 140.5</td>

140

<img file="MX370894B_D0103.tif" />

<td>Weather (min)</td><td>Temperature (degrees C)</td><td>Pressure (mm from Hg)</td>

<td> 140</td><td> 70.4</td><td> 92.1</td>

<td> 150</td><td> 69.8</td><td> 74.1</td>

<td> 155</td><td> 71.0</td><td> 68.6</td>

<td> 160</td><td> 71.1</td><td> 64.9</td>

<td> 165</td><td> 70.8</td><td> 57.5</td>

<td> 175</td><td> 69.6</td><td> 57.5</td>

<td> 185</td><td> 70.9</td><td> 56.6</td>

<td> 195</td><td> 67.3</td><td> 54.7</td>

<td> 210</td><td> 63.6</td><td> 56.4</td>

<td> 239</td><td> 56.0</td><td> 64.5</td>

[000223] In Example 19, more than 95% by weight of the olefins formed (eg, 1-butene and 3-hexene) were removed during the reaction.

[000224] Catalyst solution was added in 30 mg increments at 0, 10, 22, 32, 40, 60, 76, 97, 110, 120, and 121 minutes. The total catalyst added was 0.33 g (110 ppm). The reaction started approximately 5 minutes after the fifth catalyst increment. With each addition of catalyst except the last two, an increasing rate of bubbling was observed. After 239 minutes, the heat was turned off and the reaction was cooled to room temperature. The vacuum was turned off and the system was filled with nitrogen. A total of 2.66 kg of product were collected

141 liquid. Its composition, analyzed by analysis of liquid samples (% in normalized weight) is shown in table 13.

Table 13

<td></td><td>Initial (% in weigh)</td><td>Final (% by weight)</td>

<td>Butenos</td><td> 0.00</td><td> 0.12</td>

<td>3-hexene</td><td> 0.00</td><td> 0.32</td>

<td>1,4-tridecadiene</td><td> 0.03</td><td> 0.00</td>

<td>Pentadecene</td><td> 0.09</td><td> 0.00</td>

<td>Pentadecadiene</td><td> 0.15</td><td> 0.00</td>

<td>Methyl 8-nonenoate</td><td> 0.00</td><td> 0.13</td>

<td>Methyl 9-decenoate</td><td> 43.59</td><td> 8.65</td>

<td>Methyl 8-decenoate</td><td> 0.10</td><td> 0.00</td>

<td>methyl undecenoate</td><td> 0.07</td><td> 0.74</td>

<td>Methyl 9-dodecenoate *</td><td> 55.78</td><td> 11.50</td>

<td>Methyl 9,12-tridecadienoate</td><td> 0.06</td><td> 0.00</td>

<td>methyl tetradecenoate</td><td> 0.00</td><td> 0.19</td>

<td>Methyl 9-pentadecenoate</td><td> 0.00</td><td> 0.19</td>

<td>Methyl 9,12-pentadienoate</td><td> 0.00</td><td> 0.08</td>

<td>Methyl 9-octadecen.oatp</td><td> 0.00</td><td> 0.28</td>

<td>dimethyl hexadecenedioate</td><td> 0.00</td><td> 0.16</td>

<td>Dimethyl heptadecenechloroate</td><td> 0.00</td><td> 2.19</td>

<td>Dimethyl 9-octadecenedioate</td><td> 0.13</td><td> 72.41</td>

<td>dimethyl nonadecenedioate</td><td> 0.00</td><td> 0.23</td>

<td>Dimethyl eicosenodioate</td><td> 0.00</td><td> 2.74</td>

<td>others</td><td> 0.00</td><td> 0.09</td>

<td>TOTAL</td><td> 100.00</td><td> 100.00</td>

* Contaminated with methyl 11-dodecenoate

142

<img file="MX370894B_D0104.tif" />

[000225] Pump exhaust samples were collected at 54 minutes (highest proportion of residual gas) and 239 minutes (end of experiment) and then analyzed on the GASPRO column (see table 14 below). Ethylene formation is evidenced by 9-DAME auto-metathesis. The formation of propylene and 2-butene is evidenced by isomerization (eg, 9-DAME to 8-DAME).

Table 14

Gas sample analysis (area%, known components)

<td></td><td>54 minutes</td><td>In 239 minutes</td>

<td>Ethylene</td><td> 1.67</td><td> 0.57</td>

<td>Propylene</td><td> 1.07</td><td> 1.84</td>

<td>1-buten ©</td><td> 92.17</td><td> 46.46</td>

<td>trans-2-butene</td><td> 0.08</td><td> 0.09</td>

<td>cis-2-butene</td><td> 0.03</td><td> 0.03</td>

<td>trans-3-hexene</td><td> 2.95</td><td> 14.99</td>

<td>cis-3-hexene</td><td> 1.02</td><td> 2.69</td>

<td>Toluene</td><td> 0.62</td><td> 30.15</td>

Example 20.- 9-DAME / 9-DDAME on a 10 kg scale

[000226] A clean, dry, stainless steel 20-liter jacketed Parr reactor vessel equipped with a dip tube, overhead stirrer, internal cooling / heating coils, temperature probe, sampling valve, and pressure release valve. free space gas

143 top, purged with nitrogen. Premixed 9-DAME / 9-DDAME raw material (10.08 kg, PV = ~ 13) was charged to the reactor; see table 15 for composition. The reaction was purged with nitrogen through the dip tube at 14.2 L / min (0.5 scfm) for 30 minutes while the mixture was gently stirred. The reactor was heated to 200 ° C and held for 30 minutes while maintaining a nitrogen purge of 14.2 L / min (0.5 scfm) through the dip tube and a gentle stirring speed. The mixture was cooled to 60 ° C and the nitrogen flow was reduced to 5.7 L / min (0.2 scfm) with continuous stirring. The shaker was turned off and a sample was removed through the sample port. The PV was measured and no peroxide was detected. The analysis by ge is shown in table 15. While maintaining gentle stirring and a reactor temperature of 60 ° C, the reactor pressure was reduced to 100 mm Hg. Catalyst solution (0.33 g of C827 in 40 g of toluene) was added through the sample hole (T = 0) (09:26). The pressure was maintained at 100 mm Hg with gentle agitation. The first sample (first metathesis sample) was collected at 1 hr. At 1.5 hr another charge of catalyst solution was added (0.33 g of C827 in 40 g of toluene). A second sample (second metathesis sample) was collected at 2.25 h.

144

Table 15

<img file="MX370894B_D0105.tif" />

<td></td><td>Food tation</td><td>Treaty thermal -mind</td><td>Sample of 1 hr</td><td>2.25 hr sample</td><td>Produc- to final</td>

<td>Methyl 9-decenoate</td><td> 43.68</td><td> 42.78</td><td> 10.92</td><td> 8.00</td><td> 6.32</td>

<td>Methyl 9-dodecenoate *</td><td> 55.50</td><td> 56.10</td><td> 10.95</td><td> 8.56</td><td> 7.93</td>

<td>9,12-tridecadienoate methyl</td><td> 0.00</td><td> 0.00</td><td> 0.00</td><td> 0.01</td><td> 0.01</td>

<td>hexadecenedioate dimethyl</td><td> 0.00</td><td> 0.00</td><td> 0.05</td><td> 0.08</td><td> 0.11</td>

<td>heptadecenedioate dimethyl</td><td> 0.00</td><td> 0.00</td><td> 0.54</td><td> 1.17</td><td> 1.79</td>

<td>9-octadecenedioate dimethyl</td><td> 0.00</td><td> 0.00</td><td> 69.64</td><td> 73.43</td><td> 74.76</td>

<td>nonadecenedioate dimethyl</td><td> 0.00</td><td> 0.00</td><td> 0.11</td><td> 0.25</td><td> 0.38</td>

<td>dimethyl eicosenodioate</td><td> 0.00</td><td> 0.00</td><td> 4.95</td><td> 5.33</td><td> 5.33</td>

<td>9,12-heneicosadiene dioate dimethyl</td><td> 0.00</td><td> 0.00</td><td> 0.34</td><td> 0.24</td><td> 0.25</td>

<td>Others</td><td> 0.82</td><td> 1.12</td><td> 2.26</td><td> 2.93</td><td> 3.12</td>

<td>Total</td><td> 100.00</td><td> 100.00</td><td> 100.00</td><td> 100.00</td><td> 100.00</td>

♦ Contaminated with methyl 11-dodecenoate

[000227] The reaction was stopped. A total of 2.9 kg of olefins was collected in cold traps. The liquid contents of the 20 liter Parr reactor were transferred at 60 ° C to a 20 liter nitrogen purged glass reactor and then heated to 80 ° C. With 567 L / min (20 scfm) of

145 nitrogen flowing through the headspace, 1 M THMP solution (433 g) was added and vigorous stirring was provided. After 2 h, the mixture was cooled to 35 ° C and the stirrer was turned off. The reactor was allowed to settle overnight. The next day, the mixture was reheated and the temperature was kept between 50 ° C and 55 ° C. Deionized water (1.8 kg) was added and the two-phase system was vigorously stirred for 30 minutes. The stirrer was turned off to allow the phases to separate. The bottom aqueous phase was removed. Another portion of deionized water (1.8 kg) was added to the reactor. The mixture was stirred well mixed. The stirrer was then turned off to allow the phases to separate. The bottom aqueous phase was removed. The final product (6.29 kg) was removed from the reactor and analyzed by GC.

Example 21.- 9-DAME / 3-hexene at 10 g scale

[000228] Table 5 gives the composition of 9-DAME (distillation cut of butenolyzed palm oil, extracted, transesterified). Clean, dry 20 cc echintillation flasks, fitted with a magnetic stir bar and septum top, were charged with 9-DAME (PV &lt;1) and 3-hexen (olefin distillation cutoff of butenolyzed palm oil) according to the design of the experiment, table 16. Each flask was placed in an eight cell aluminum block on top of a heater / shaker. The aluminum block was heated to 60 ° C. While the

146

<img file="MX370894B_D0106.tif" />

aluminum block being heated (~ 15 min), the headspace of each flask was degassed by providing a nitrogen inlet (-65 ml / min) and an escape needle. Meanwhile, a 0.01 mg / pL metathesis catalyst solution was prepared by first placing C827 (21.10 mg) in a 2 mL volumetric flask, second by covering the flask with a rubber septum, third by purging with nitrogen, and fourth by adding toluene at the 2.00 mL mark ·. The metathesis catalyst was added to the reaction mixture (time = 0). According to the experimental design, the nitrogen inlet (65 mL / min) was left in place to scavenge the by-product olefins of the reaction or was removed. In both cases, the vent needle was left in place. In the latter case, the olefin formed by the metathesis provided the oxygen-free environment needed by the catalyst. After 2 hours, an aliquot was analyzed by GC. The composition ((normalized weight%, exclusive of light olefins) is shown in table 17.

Table 16

<td>Example</td><td>9-DAME</td><td>3-Hexene</td><td>C-827 (pprn weight)</td><td>Top clearance treatment</td>

<td>21a</td><td>6.42 g</td><td>3.61 g</td><td> 80</td><td>Just vent</td>

<td>21b</td><td>6.43 g</td><td>3.66 g</td><td> 80</td><td>Nitrogen purge</td>

<td>21c</td><td>6.42 g</td><td>3.60 g</td><td> 120</td><td>Just vent</td>

<td>2 Id</td><td>6.44 g</td><td>3.58 g</td><td> 120</td><td>Nitrogen purge</td>

147

Table 17

<img file="MX370894B_D0107.tif" />

<td>Example</td><td>21a</td><td>21b</td><td>21c</td><td>21d</td>

<td>Methyl 8-nonenoate</td><td> 0.00</td><td> 0.00</td><td> 0.00</td><td> 0.00</td>

<td>Methyl 9-decenoate</td><td> 72.85</td><td> 0.44</td><td> 10.91</td><td> 0.46</td>

<td>Methyl 8-decenoate</td><td> 0.90</td><td> 0.00</td><td> 0.00</td><td> 0.00</td>

<td>Methyl undecenoate</td><td> 0.00</td><td> 0.00</td><td> 2.17</td><td> 0.00</td>

<td>Methyl 9-dodecenoate</td><td> 23.24</td><td> 19.45</td><td> 58.87</td><td> 19.34</td>

<td>Methyl tridecenoate</td><td> 0.00</td><td> 0.00</td><td> 0.00</td><td> 0.00</td>

<td>Methyl tetradecenoate</td><td> 0.00</td><td> 0.00</td><td> 0.00</td><td> 0.00</td>

<td>Methyl 9-octadecenoate</td><td> 0.00</td><td> 0.00</td><td> 0.14</td><td> 0.40</td>

<td>dimethyl hexadecenedioate</td><td> 0.00</td><td> 0.00</td><td> 0.00</td><td> 0.00</td>

<td>dimethyl heptadecenedioate</td><td> 0.10</td><td> 1.75</td><td> 0.79</td><td> 1.95</td>

<td>Dimethyl 9-octadecenedioate</td><td> 1.68</td><td> 74.27</td><td> 24.48</td><td> 73.96</td>

<td>Others</td><td> 1.23</td><td> 4.09</td><td> 2.64</td><td> 3.88</td>

<td>Total</td><td> 100.00</td><td> 100.00</td><td> 100.00</td><td> 100.00</td>

Example 22.- 9-DAME / trans-2-butene on a 40 g scale

[000229] 9-DAME (40.16 g) was charged to a 100 mL 3-neck round bottom flask equipped with a spiral-type reflux condenser (vented to an oil bubbler), a magnetic stir bar, and caps. September. The reaction system was purged for 30 minutes, with nitrogen through a needle inserted into one of the septum caps and the bubbler was allowed to escape. The reaction flask was immersed in an oil bath that was heated to 55 ° C. The condenser was cooled by means of glycol fluid to 15 ° C. The nitrogen purge was replaced by a flow of

148

<img file="MX370894B_D0108.tif" />

trans-2-butene through the liquid. After a consistent reflux of trans-2-butene was observed, 80 ppm of catalyst (T = 0) was added. The trans2-butene flow was continued for the duration of the reaction except as follows. The reaction was monitored by stopping the flow of trans-2-butene and observing the rate of bubbles in the bubbler. In addition to the initial 80 ppm catalyst charge, three additional 20 ppm catalyst increments were added at T = 30, 81, 125 minutes. The final weight of the product was 31.25 g. The conversion to diesters was 85% and the selectivity to 9ODDAME was 81%.

Example 23.- 9-DAME / trans-2-butene in a Fisher-Porter tube [000230] Using a Fisher-Porter tube of 3 ounces (88 mm) equipped with an addition orifice for the catalyst and trans-2-butene . In a glove compartment, 40.0 mg of C827 was dissolved in 1 mL of toluene. Sixty microliters of catalyst solution was charged to the catalyst addition manifold using a 250 uL syringe, removed from the glove box, and attached to the pressure vessel manifold. Twenty grams of 9-DAME charged to the pressure tube which was subsequently degassed for 30 minutes with nitrogen. Meanwhile, the trans-2-butene was condensed / transferred to a second Fisher-Porter 3 ounce (88 mm) tube. The pressure vessel containing trans-2-butene is. . . . . ·; &lt;· Χ. • .νΧ ^ .ά: .......

'''''^:W ^^:·-·’·^'''' · - --^:

149 pressurized with nitrogen at 4 psi² (0.72 atm). The pressure vessel containing the ester was heated to 60 ° C in a Silicon oil bath. The catalyst solution was transferred to the ester under nitrogen. Immediately, approximately 7.6 mL (4.57 g) of trans-2butene (target for 0.75: 1 ratio) was transferred to the pressure vessel containing the 9-DAME, which washed away any residual catalyst solution in the reaction vessel.

[000231] The volume was measured using the mm graduation marks on the container and the measured cross-sectional area of ​​the tube. The target volume was based on the conversion of the target mass to a target volume assuming a trans-2-butene density of 0.6 g / mL. The pressure tube containing the reaction mixture was then pressurized to 36 psi.² (2.45 atm) with nitrogen. Samples were taken at 10 minutes and 60 minutes using a sampling tube apparatus. The vessel was slowly depressurized to atmospheric pressure and sparged with nitrogen. After 60 minutes of spraying, the container was disassembled, and the sample was collected. Pressure, bath temperature, and liquid level were monitored as a function of time and are summarized in Table 18. The GC analysis (normalized weight%, exclusive of light olefins) is summarized in table 19.

150

Table 18

<img file="MX370894B_D0109.tif" />

<td>Weather (min)</td><td>Pressure (lb / in²)</td><td>Temperament (° C)</td><td>Liquid level (mm)</td><td>Comments</td>

<td> 0</td><td> 36</td><td> 58.9</td><td> 60.5</td><td>System closed</td>

<td> 5</td><td> 76</td><td> 59.2</td><td> 55.0</td><td>System closed</td>

<td> 10</td><td> 83</td><td> 59.3</td><td> 55.0</td><td>System closed, Sample 1</td>

<td> 10</td><td> 84</td><td> 59.2</td><td> 53.5</td><td>System closed</td>

<td> 15</td><td> 84</td><td> 59.1</td><td> 53.5</td><td>System closed</td>

<td> 20</td><td> 88</td><td> 59.1</td><td> 54.0</td><td>System closed</td>

<td> 30</td><td> 91</td><td> 58.9</td><td> 53.5</td><td>System closed</td>

<td> 40</td><td> 92</td><td> 58.9</td><td> 53.5</td><td>System closed</td>

<td> 50</td><td> 92</td><td> 58.9</td><td> 53.5</td><td>System closed</td>

<td> 60</td><td> 92</td><td> 58.9</td><td> 53.5</td><td>System closed, Sample # 2</td>

<td> 60</td><td> 96</td><td> 58.9</td><td> 43.5</td><td>Nitrogen spray</td>

<td> 120</td><td> 0</td><td></td><td></td><td>End of reaction. Sample # 3</td>

151

Table 19

<td></td><td>Sample 1 (10 minutes)</td><td>Sample 2 (60 min)</td><td>Sample 3 (120 min)</td>

<td>Methyl 9-decenoate</td><td> 36.2</td><td> 36.9</td><td> 35.3</td>

<td>Methyl undecenoate</td><td> 31.9</td><td> 39.0</td><td> 39.1</td>

<td>Methyl 8-decenoate</td><td> 2.5</td><td> 4.3</td><td> 5.6</td>

<td>Methyl 8-nonenoate</td><td> 1.3</td><td> 1.4</td><td> 1.3</td>

<td>dimethyl hexadecenedioate</td><td> 0.2</td><td> 0.1</td><td> 0.2</td>

<td>dimethyl heptadecenedioate</td><td> 2.4</td><td> 1.8</td><td> 1.9</td>

<td>Dimethyl 9-octadecenedioate</td><td> 25.4</td><td> 16.4</td><td> 16.6</td>

<td>Dimethyl nonadecenedioate</td><td> 0.1</td><td> 0.1</td><td> 0.1</td>

Example 24.- 9-DAME / trans-2-butene in 8 kg scale

[000232] A two-step cross-metathesis strategy was employed using 9-DAME and purchased trans-2-butene. In the first stage, 9-DAME was partially converted on-site to 9UDAME. In the second stage, the mixture of 9-DAME and 9-UDAME was converted to 9-ODDAME. The raw material 9-DAME (from octenolized palm oil) for this example was contaminated with significant concentrations of 8-DAME and 7-tetradecene, table 20. Table 20

<td></td><td>Lot A (% by weight)</td><td>Lot B (% by weight)</td>

<td>Methyl 9-decenoate</td><td> 81.4</td><td> 88.6</td>

<td>Methyl 8-decenoate</td><td> 8.9</td><td> 5.7</td>

<td>7-tetradecene</td><td> 8.0</td><td> 4.6</td>

152

<img file="MX370894B_D0110.tif" />

[000233] The two-step synthesis was performed eight times and found to be scalable without difficulty. The first batch was made using an initial load of 4 kg of an 81% pure 9-DAME and 1.2 mol of trans-2-butene / mol of 9-DAME, producing a crude product containing 57% by weight of 9ODDAME. The second preparation used a 6 kg load of the 81% pure 9DAME and only 0.75 mol of trans-2-butene / mol of 9DAME, producing a crude product containing 53% by weight of 9-ODDAME. The remaining preparations used initial batches of 8 kg of 89% pure 9-DAME and 0.75 mol of trans-2butene / mol of 9-DAME, producing crude products containing 60-69% by weight of 9-ODDAME. Table 21 summarizes the key reaction measurements for the eight batches. The composition is in normalized% by weight, exclusive of light olefins.

153

Table 21

<td>Cumshot #</td><td>24th</td><td>24b</td><td>24C</td><td>24d</td><td>24e</td><td>24f</td><td>24g</td><td>24h</td>

<td>Lot of 9-DAME</td><td>TO</td><td>TO</td><td>B</td><td>B</td><td>B</td><td>B</td><td>B</td><td>B</td>

<td>Run size (kg of 9-DAME)</td><td> 4</td><td> 6</td><td> 8</td><td> 8</td><td> 8</td><td> 8</td><td> 8</td><td> 8</td>

<td>(kg of trans-2-butene)</td><td> 1.4</td><td> 1.4</td><td> 1.9</td><td> 1.9</td><td> 1.9</td><td> 1.9</td><td> 1.9</td><td> 1.9</td>

<td colspan="9"></td>

<td>Molar ratio (2butene: 9-DAME)</td><td> 1.2</td><td> 0.75</td><td> 0.75</td><td> 0.75</td><td> 0.75</td><td> 0.75</td><td> 0.75</td><td> 0.75</td>

<td>C-827 loading (ppm weight) stage 1</td><td> 93</td><td> 68</td><td> 68</td><td> 68</td><td> 68</td><td> 68</td><td> 68</td><td> 68</td>

<td>stage 2</td><td> 93</td><td> 68</td><td> 68</td><td> 68</td><td> 68</td><td> 68</td><td> 68</td><td> 68</td>

<td colspan="9"></td>

<td>9-UDAME Stage 1 Weight Ratio: 9DAME</td><td> 4.93</td><td> 2.43</td><td> 2.21</td><td> 2.37</td><td> 1.88</td><td> 1.92</td><td> 1.98</td><td>NA</td>

<td colspan="9"></td>

<td>Stage 2 composition (¾ by weight)</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>1-octene</td><td> 0.00</td><td> 0.00</td><td> 0.31</td><td> 0.18</td><td> 0.31</td><td> 0.00</td><td> 0.00</td><td> 0.00</td>

<td>2-nonene</td><td> 0.00</td><td> 2.62</td><td> 1.09</td><td> 0.48</td><td> 0.68</td><td> 1.17</td><td> 0.58</td><td> 0.46</td>

<td>7-tetradecene</td><td> 0.75</td><td> 0.75</td><td> 0.20</td><td> 0.18</td><td> 0.25</td><td> 0.27</td><td> 0.11</td><td> 0.22</td>

<td>Methyl Decanoate</td><td> 0.35</td><td> 0.43</td><td> 0.42</td><td> 0.41</td><td> 0.55</td><td> 0.65</td><td> 0.69</td><td> 0.00</td>

<td>Methyl 9-decenoate</td><td> 0.23</td><td> 1.02</td><td> 2.08</td><td> 1.90</td><td> 2.84</td><td> 2.20</td><td> 1.69</td><td> 1.70</td>

<td>Methyl 8-decenoate</td><td> 0.38</td><td> 1.71</td><td> 0.86</td><td> 0.65</td><td> 0.91</td><td> 1.14</td><td> 0.89</td><td> 1.04</td>

<td>Methyl undecenoate</td><td> 2.13</td><td> 13.64</td><td> 10.38</td><td> 8.47</td><td> 11.57</td><td> 14.00</td><td> 11.66</td><td> 11.43</td>

<td>methyl pentadecenoate</td><td> 1.39</td><td> 0.08</td><td> 0.50</td><td> 0.58</td><td> 0.68</td><td> 0.77</td><td> 0.65</td><td> 0.66</td>

<td>methyl hexadecenoate</td><td> 10.30</td><td> 9.64</td><td> 5.14</td><td> 5.83</td><td> 6.46</td><td> 6.96</td><td> 6.46</td><td> 6.68</td>

<td>Methyl heptadecenoate</td><td> 2.08</td><td> 0.28</td><td> 0.00</td><td> 0.00</td><td> 0.19</td><td> 0.22</td><td> 0.19</td><td> 0.20</td>

<td>Dimethyl hexadecenedioate</td><td> 1.19</td><td> 1.18</td><td> 0.96</td><td> 1.11</td><td> 1.11</td><td> 1.15</td><td> 1.12</td><td> 1.08</td>

<td>Dimethyl heptadecenedioate</td><td> 13.02</td><td> 12.24</td><td> 9.26</td><td> 9.91</td><td> 9.54</td><td> 9.42</td><td> 9.64</td><td> 9.40</td>

<td>Dimethyl 9-octadecenedioate</td><td> 57.05</td><td> 53.15</td><td> 66.79</td><td> 68.68</td><td> 64.20</td><td> 60.34</td><td> 65.06</td><td> 65.24</td>

<td>Total</td><td> 97.06</td><td> 96.74</td><td> 97.99</td><td> 98.39</td><td> 99.28</td><td> 98.29</td><td> 98.74</td><td> 98.10</td>

154

[000234] Purification was achieved in batches of about 2 kg by crystallizing trans-ODDAME from the crude product using four volumes of cold methanol, vacuum filtration, including an additional cold methanol wash, and then vacuum drying. The typical yield was approximately 50% and the typical purity is shown in Table 22.

Table 22

<td></td><td>Of batch feed A</td><td>Batch feed B</td>

<td>Dimethyl 9-octadecenedioate</td><td> 96.9</td><td> 97.6</td>

Example 30

[000235] The time of treatment with trishydroxymethylphosphine (THMP) and treatment with water, as well as the type of water, were varied to study the effects on the removal of ruthenium from a natural oil / metathesis catalyst solution.

[000236] In the described experiments, THMP was supplied from a concentrated solution by the following method: 10.20 g of tetraquishydroxymethylphosphonium sulfate 75% by weight in water (Bricorr 75, Rhodia) 3 7.69 of deionized water (type II ) under an inert atmosphere with

155 nitrogen, then 4.02 g 50% wt sodium hydroxide (Aldrich) was added to the dilute solution, followed by the addition of 4.08 g of 75% wt tetraquishydroxymethylphosphonium sulfate to the mixture, to adjust the pH to 8. The pH of the solution was measured using a pH probe. The solution was transferred to a plastic container and stored until use. The molar concentration of THMP in the solution was based on the total amount of the limiting reagent sodium hydroxide (1 mole of trishydroxymethylphosphine = 1 mole of sodium hydroxide in excess of tetraquishydroxymethylphosphonium sulfate). In a 500 mL kettle flask (4 in. (10.16 cm) inner diameter), equipped with an overhead stirrer (4 part blades, 45 °, 2 in. (5.08 cm) diameter), overhead condenser (set to 5 ° C), and baffles, a stream of water containing extracted ruthenium and trishydroxymethylphosphine (derived from tetraquishydroxymethylphosphonium sulfate) was generated by the following procedure.

[000237] In a 500 mL kettle flask (4 inch (10.16 cm) inner diameter), equipped with an overhead stirrer (4.45 ° spaced blades, 2 inches (5.8 cm) inner diameter), raised condenser (set at 5 ° C), and baffles, a stream of water containing extracted ruthenium and trishydroxymethylphosphine (derived from tetraquishydroxymethyl phosphonium sulfate) was generated by the following

156 process: 1-octene (Aldrich, 98%) was reacted with palm oil (Wilmar, refined, bleached, deodorized, pretreated at 200 ° C for 2 hours per batch under nitrogen sparge) at a 1.5: 1 molar double bond ratio 1-octene: palm oil in the presence of 800 ppmw catalyst (C827, Matter, based on oil mass), batch contact time of 60 minutes, reaction temperature of 60 ° C, atmospheric pressure, and under a nitrogen blanket headroom. After generating the metatized mixture, the mixture was heated to 90 ° C and a 19: 1 molar equivalent of trishydroxymethyl phosphine to catalyst (target) was added to the metatized mixture. The metatized mixture containing trishydroxymethylphosphine was stirred for 60 minutes per batch. Then, deionized water (type II) was added to the metatized mixture in 1 pg of water to 5 g of metatized oil and stirred for 1 hour, batch at 72 to 90 ° C. After 1 hour of mixing with water, the mixture was allowed to gravity set for 1 hour while heating to 90 ° C. The undercoat was removed from the mix and stored. This bottom layer was assumed to simulate a 20: 1 recycle ratio of water in a continuous extraction process (based on a typical catalyst concentration of 40 ppmw, based on the mass of the oil), and refers to as a recycled water stream simulated herein.

157

<img file="MX370894B_D0111.tif" />

[000238] Additional metatized oil mixtures were generated by reacting 1-octene with palm oil (1.5: 1 molar double bond ratio of 1-octene: palm oil) in the presence of 40 ppmw of catalyst (based on to oil mass), batch contact time of 60 minutes, reaction temperature of 60 ° C, atmospheric pressure, and under a headspace with nitrogen blanket. A sample was removed after 60 minutes to analyze the ruthenium concentration. Samples generated from the described method are referred to herein as prior to THMP treatment.

[000239] After generating the additional metatized mixture, the mixture was heated to 90 ° C, and to the metatized mixture 19: 1 molar equivalent of trishydroxymethylphosphine was added to (target) catalyst. The metatized mixture containing trishydroxymethylphosphine was stirred for 60 minutes per batch. Samples generated from the described method are referred to herein as after THMP treatment.

[000240] Then, the simulated recycled water was added to the metatized mixture in 1 pg of water to 5 g of metatized oil and stirred for several times (15 minutes, 30 minutes, 60 minutes) per batch at 72 to 90 ° C. . After mixing with water, the mixture was allowed to settle by gravity for 1 hour at 90 ° C. The top layer and the bottom layers

158

<img file="MX370894B_D0112.tif" />

they were sampled for the ruthenium concentration and the top layer was sampled for the isomerization test. Samples generated from the described method are referred to herein as after water extraction.

[000241] Ruthenium analysis was performed using ICP-MS at STAT Analysis Corporation, Chicago, Illinois. Ruthenium efficiency (%), assuming mass is conserved, is defined by the following equation:

Excaecün Absis Fire Extraction

Ruthenium removal efficiency (%) = 103 ------------------------------------^cSu Aaíes by EjaraceLóo

[000242] Isomerization tests were performed on the samples to determine the effectiveness of the reaction of trishydroxymethyl phosphine with the ruthenium-containing catalyst. The isomerization test included heating the sample to 250 ° C for 1 hour under an open system nitrogen headspace, maintained at 1 lb / in.² (0.07 atm).

[000243] Normal sample analysis was performed on the isomerized samples. Approximately 6 drops (-100-200 mg) of the sample were transferred to a 20 mL borosilicate ecythelation bottle. 1 mL of 1% mass sodium methoxide in methanol (Aldrich) was added to the flask using autopipet. The flask was sealed and heated to 60 ° C, while

159 which is stirred at 240 rpm for at least 40 minutes until a liquid phase is visually observed. Using an autopipet, 5 mL of saturated brine solution was added to the flask. Then, 5 mL of ethyl acetate were added to the flask using an autopipet. The mixture was further stirred and allowed to settle into two different phases. Approximately 1.5-2 mL of the upper layer (ethyl acetate) was transferred to a 2 mL gas chromatography flask.

[000244] The flask was analyzed for 9-decenoic acid ester isomerization using an Agilent 7890 gas chromatograph, equipped with a split / no split orifice, an RTX-65TG column (Restek 17008, length 30 mx inside diameter of 0.25mm x 0.1mm film thickness), mass spectrometer quadrupole detector. Helium was used as the carrier gas.

[000245] The 9-decenoic acid ester and isomers were quantified using ion extraction of the ester fragments with the MS Chem software; the integrated areas were assumed to be proportional to the relative mass concentration of the esters.

[000246] The percentage of isomerization was defined by the following equation:

160

Isomerization (%) = 100 ^ Isomer Z isomer 3

A ^ Sraers l ^^ IsimgroS * 'Ai_s¿¡_31rB j + A ^ tsrá «arid 9-d» c «noic« where Armero 1 is the integrated area of ​​the 1-isomer of the 9-decenoic acid ester, A_Isomer 2 is the integrated area of ​​the 9-decenoic acid ester isomer 2, Ai_SOmer 3 is the integrated area of ​​the 9-decenoic acid ester isomer 3, 9-decenoic acid Agster is the integrated area of ​​the 9decenoic acid ester. Isomer 1 and isomer 2 are the methyl esters of cis and trans 8-decenoic acids. Isomer 3 is a 7-decenoic acid methyl ester. Other isomers can be formed, but were not chromatographically resolved from the observed peaks.

[000247] The test was performed within a 24 hour period of sampling the reactor vessel. For most cases, the test was in a one hour sampling period. The sample analysis was run in duplicate, and an average of two runs was reported. For reference, the result of the isomerization test on a sample not treated with THMP was typically 20-40% isomerization (average of two samples) at the catalyst loads studied. The results are shown in table 23.

161

<img file="MX370894B_D0113.tif" />

Table 23

<td>Type of water</td><td>Process</td><td>Terms</td><td>Isom%</td><td>Water content</td><td>Ru (ppmw)</td><td>Ru removal efficiency (%)</td>

<td rowspan="3">DI type II</td><td rowspan="3">60 min THMP treatment, 60 min extraction with water, and 60 min settlement</td><td>Before treatment with THMP</td><td> 44.41</td><td> 93</td><td> 3.8</td><td rowspan="3"> 80</td>

<td>After treatment with THMPt</td><td> 0.08</td><td> 88</td><td> --</td>

<td>After extraction with water</td><td> 0.18</td><td> 1524</td><td> 0.75</td>

<td rowspan="3">Simulated recycled, 20 recycled, ~ 360 ppmw Ru</td><td rowspan="3">.. 60 min : ... treatment „|| **** imfc extraction with water, and. settlement</td><td>.Before .treatment with THMP</td><td> 31.10</td><td> ., 51</td><td></td><td rowspan="3"> 47 /</td>

<td>After treatment with SSSliBK * ThOÍÍÍ: üB</td><td> 0.60</td><td>Ι | 1Ι: Β |</td><td></td>

<td>After extraction with :: a®S :: SÍB »Í! íííÍB ::</td><td> 0.69</td><td> 11.62</td><td> 1.8</td>

<td rowspan="3">Simulated recycled, 20 recycled, -360 ppmw Ru</td><td rowspan="3">60 min THMP treatment, 30 min extraction with water, and 60 min settlement</td><td>Before treatment with THMP</td><td> 34.70</td><td> 50</td><td> 5</td><td rowspan="3"> 48</td>

<td>After treatment with. THMP</td><td> 0.06</td><td> 57</td><td> --</td>

<td>After extraction with water</td><td> 0.28</td><td> 1657</td><td> 2.6</td>

<td rowspan="3">Recycled simulated: /: ... lili *: .......... recycled, ~ 360 ppmw Ru</td><td rowspan="3">60 min jKB'traÉñMento ........ ΒκβΙΙΙΜ .. ........ Sismin * O'ggjj extraction with water, and , 60 min settlement</td><td>Before :_;treatment with: ' ** B®JiMP '</td><td> 43.25</td><td> 28</td><td> 9.3</td><td rowspan="3"> ~ 63</td>

<td>After THMP treatment</td><td> 1-06</td><td> ; 37</td><td>.Β-&gt; ΒΒ / ·:</td>

<td>After extraction with lltiiís ^ iBlilSíagua LSlff^í:·</td><td> 0.21</td><td>: j_S:, | 33aBJ</td><td>/Β3..4 :,</td>

<td rowspan="3">Simulated recycled, 20 recycled, -360 ppmw Ru</td><td rowspan="3">0 min THMP treatment, 60 min extraction with water, and 60 min settlement</td><td>Before treatment with THMP</td><td> 31.65</td><td> 43</td><td> 6.2</td><td rowspan="3"> 42</td>

<td> —</td><td> --</td><td> --</td><td> --</td>

<td>After extraction with water</td><td> 0.57</td><td> 1750</td><td> 3.6</td>

<td rowspan="3">Simulated recycled, 20 recycled, -320 ppmw Ru</td><td rowspan="3">THMP treatment, 15- min extraction with water, and 60 min settlement</td><td>Β; Βϊ 'Before THMP treatment</td><td> 33.5</td><td> 125.1</td><td> 3.5</td><td rowspan="3"> 46</td>

<td>After 'treatment with ^:</td><td> 0.50</td><td> 1854</td><td> — .</td>

<td>After extraction with water</td><td> 0.31</td><td> 974</td><td> 1.9</td>

162

<img file="MX370894B_D0114.tif" />

[000248] Unless described otherwise, the above-mentioned examples used the following analytical methods described below:

[000249] Volatile products were analyzed by gas chromatography and flame ionization detector (FID). Alkene analyzes were performed using an Agilent 6890 instrument and the following conditions:

Column: Restek Rtx-5.30mx 0.25 mm (ID) x 0.25 pm film thickness

Injector temperature: 250 ° C

Detector temperature: 280 ° C

Oven temperature: 35 ° C start temperature, 4 minute hold time, 12 ° C / min ramp rise to 260 ° C, 8 minute hold time Carrier gas: Helium

Average gas velocity: 31.3 + 3.5% cm / sec (calculated)

Division ratio: ~ 50: l

[000250] Products were characterized by comparing the peaks to known standards, in conjunction with supporting data from mass spectral analysis (GCMS-Agilent 5973N). GCMS analysis was achieved with a second Rtx-5 GC column, 30m x 0.25mm, 0.25pm ​​x film thickness (ID), using the same method as before.

[000251] Alkene analyzes were performed using a

163

<img file="MX370894B_D0115.tif" />

Agilent 6850 instrument and the following conditions:

Column: Restek Rtx-65, 3 0m x 0.32mm (ID) x 0. Ιμτη film thickness

Injector temperature: 250 ° C

Detector temperature: 350 ° c

Oven temperature: 55 ° C start temperature, 5 minute hold time, 20 ° C / min ramp rise to 350 ° C, 10 minute hold time Carrier gas: Hydrogen

Flow rate: 1.0 mL / min

Division ratio: 40: 1

[000252] The products were characterized by comparing the peaks with known standards. Fatty acid methyl esters (FAME) analyzes were performed using an Agilent 6850 instrument and the following conditions:

Column: J&amp;W Scientific, DB-Wax, 30m x 0.32mm (ID)

0.5pm x film thickness

Injector temperature: 250 ° C

Detector temperature: 300 ° C

Oven temperature: start temperature at 70 ° C, hold time 1 minute, ramp-type rise from 20 ° C / min to 180 ° C, ramp-type rise from 3 ° C / min to 220 ° C, hold time of 10 minutes

Carrier gas: Hydrogen

Flow rate: 1.0 mL / min

164

[000253] The above examples collectively demonstrate the major steps outlined in the process schemes, showing the production of olefins, paraffins, metatized triglycerides, unsaturated fatty acid acids and esters, and diacid compounds of natural oils that are useful as chemicals , solvents and fuel mixing materials.