Methods for suppressing isomerization of olefin metathesis products, methods of refining natural oils, and methods of producing fuel compositions.

(54) Title: METHODS TO SUPPRESS THE ISOMERIZATION OF OLEFIN METHESIS PRODUCTS, NATURAL OIL REFINEMENT METHODS, AND FUEL COMPOSITION PRODUCTION METHODS.

(54) Title: METHODS FOR SUPPRESSING ISOMERIZATION OF OLEFIN METATHESIS PRODUCTS, METHODS OF REFINING NATURAL OILS, AND METHODS OF PRODUCING FUEL COMPOSITIONS.

(57) Summary

One method of suppressing isomerization of an olefin metathesis product produced in a metathesis reaction includes adding an isomerization suppressing agent to a mixture that includes the olefin metathesis product and residual metathesis catalyst from the metathesis reaction under conditions which are sufficient to passivate at least a portion of the residual metathesis catalyst; the isomerization suppressing agent includes (i) a salt and / or an ester of an oxo acid of phosphorus, and / or (ii) a derivative of the oxo acid of phosphorus in which at least one PH bond has been replaced by a bond PC, and / or (II) a salt and / or an ester of the derivative; Methods for refining natural oils and methods for producing compositions for fuels are described.

(57) Abstract

A method for suppressing isomerization of an olefin metathesis product produced in a metathesis reaction ineludes adding an isomerization suppression agent to a mixture that ineludes the olefin metathesis product and residual metathesis catalyst from the metathesis reaction under conditions that are sufficient to passivate at least a portion of the residual metathesis catalyst. The isomerization suppression agent includes (i) a salt and / or an ester of a phosphorous oxo acid, and / or (¡i) a derivative of the phosphorous oxo acid in which at least one PH bond has been replaced by a PC bond, and / or (iii) a salt and / or an ester of the derivative. Methods of refining natural olls and methods of producing fuel compositions are described.

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Inventor (s)

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PATENT TITLE No. 348233

ELEVANCE RENEWABLE SCIENCES, INC.

2501 Davey Road, Woodridge, Illinois, 60517, USA

METHODS TO SUPPRESS THE ISOMERIZATION OF OLEFIN METATHESIS PRODUCTS, NATURAL OIL REFINEMENT METHODS, AND FUEL COMPOSITION PRODUCTION METHODS.

CIP:

CPC:

CSetl:

C07C6 / 04; C07C7 / 20; C07C11 / 02

C07C7 / 20; C10G45 / 00; C10G45 / 58; C10G50 / 00; C10L1 / 08; C11C3 / 00;

C11C3 / 003; C11C3 / 12; *

C07C7 / 20; C07G11 / 02

BRUCE E. FIRTH; SHARON E KIRK

Number:

MX / a / 2014/007747

SOMdTUD

International Presentation Date of December 2012

PRIORITY

Date:

December 2011 December 2011

Number:

13/335,601

13/335.517

Validity: Twenty years

Venue Date Expi nto Date: December 19, 2032&gt; n: May 30, 2017

The reference patent is granted on the basis of articles 4 °, 2 ° V, 6 ° useful fraction, and 59 of the · Industrial Property Law.

In accordance with article 23 of the Industrial Property Law, the topwfente Jétente has a validity of twenty years, counted from the date of submission of the application and will be subject to the gago of the law to keep the legal rights in force.

Whoever signs this title does so based on the provisions of articles 6 ° fraction III and 7 "Hs 2 of the Industrial Property Law (Official Gazette of the Federation (DOF.) 06/27/1991, amended" I 08/02/1994 .'- 10/25/1996, 26&gt; 12/1 »97, 05/17/1999, 01/26/2004, 06/16/2005, 01/25/2006, 05/06 / 2009, 06/01/2010, 06/18/2010, 06/28/2010, 01/07/2012 and 04/09/2012). Articles. 1. 3rd fraction V part a), 4^or and 12th sections I and III of the Regulations of the Mexican Institute of Property MuStriaf (0.0 F 1 * 02/1 »% raformsrfoel 07/01/2002, 07/15/2004, 07/28/2004 and 09/07/2007 ); items 1^or, 3’, 4^or, 5^or Section V subsection a), 16 sections I and III and 30 of the Statute ÓrgfoieO'déf Mexican Institute of Industrial Property (DOF 12/27/1999, amended on 10/10/2002, 07/29/2004, 08/04 2004 and 13709/2007): 1 «, 3^or and 5^or ineteoa) of the Agreement that delegates powers to the Deputy General Directors, Coordinator, Divisional Directors, Headlines &lt;»&lt;le-i» s Regional Offices, Divisional Deputy Directors, Departmental Coordinators and other subordinates of the Mexican Institute of Industrial Property (DOF 12/15 / 1999, amended on 02/04/2000, 07/29/2004, 08/04/2004 and 09/13/2007).

This document is signed with an advanced electronic signature (FIEL), based on articles 7 BIS 2 of the Industrial Property Law; 3 of its Regulations, and 1 section III, 2 section V, 26 BIS and 26 TER of the Agreement establishing the guidelines for the use of the Payment and Electronic Services Portal (PASE) of the Mexican Institute of Industrial Property, in the procedures indicated.

DIVISIONAL PATENT DIRECTOR NAHANNY CANAL REYES

Ξ

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B Original Chain:

·&gt; NAHANNY MARISOL CANAL REYES | 00001000000403252793 | Administration Service

Tax | 1695 || MX / 2017/43559 | MX / a / 2014/007747 | PCT patent title | 1027 | RGZ | Page (s) 2 | 09ewlroUIUdKfY3NaO6ESxFH6FE =

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V

I ίΝΓΤΤΠ ΓΓΟ MF ^ CaXO

OF INDUSTNAL PROPERTY

METHODS TO SUPPRESS ISOMERIZATION- ^ RRODUGT-QSD &amp; OLEFIN METHESIS, OIL REFINING METHODS

NATURAL, AND METHODS OF PRODUCTION OF FUEL COMPOSITIONS

CROSS REFERENCE TO RELATED REQUESTS

This is a continuation in part of application No. 13 / 335,517 (attorney's file No. 13687/285) filed on December 22, 2011, and a continuation in part of application No. 13 / 335,601 (No. of attorney-in-fact file 13687/298) filed on December 22, 2011, which in turn is a continuation in part of previous application No. 12 / 901,829, filed on October 11, 2010, which claims the benefit of the provisional application US No. 61 / 250,743, filed October 12, 2009. All content of all documents identified above are incorporated herein by reference, except that in the event of any inconsistent description or definition in this specification, the description or definition herein shall be deemed to prevails.

TECHNICAL FIELD

Current teachings generally refer to methods for suppressing isomerization of olefins - particularly olefins, ΪΜΡΙ @

INfTTTUTO MUttCAXO

OF THE industrial nOHETY produced in metathesis reactions. —------. .

BACKGROUND OF THE INVENTION

In recent years, there has been a growing demand for petroleum-based transportation fuels. There are concerns that world oil production may not be able to keep up with demand. Additionally, the growing demand for petroleum-based fuels has resulted in increased production of greenhouse gases. Due to the increasing demand for fuel and increased production of greenhouse gases, there is a need to explore alternative, environmentally friendly production methods of fuel sources. In particular, there is a need to explore environmentally friendly and chemical production methods of specialty fuel compositions from a natural raw material.

Researchers have been studying the feasibility of making biofuels, waxes, plastics, and the like, using natural oil raw materials, such as vegetable and seed-based oils. Metathesis reactions involving natural oil raw materials offer promising solutions for today and tomorrow.

The olefin metathesis reaction is a highly versatile and powerful technique for the synthetic preparation of alkenes. Transition metal carbene complexes - particularly those that incorporate, IMPI »

O fNSTFTVTü M £ X1GAN ('

Df LA P1ORBDAD

INDUSTRIAL 'ruthenium - are popular catalysts for metathesis ··· -However, the production of certain desired metathesis products can be significantly reduced by double bond isomerization. This is usually the result of residual metathesis catalyst and / or its by-products that are present in the reaction mixture. This problem becomes particularly acute if the metathesis mixture is heated and / or distilled in the presence of the residual catalyst.

Due to this problem, it is often necessary to remove residual metathesis catalyst from an olefin metathesis product (or otherwise passivate the residual catalyst) before subjecting the olefin metathesis product to further chemical reactions and / or processing. One method, as described in US Patent No. 6,215,019 B1, has been to add tris (hydroxymethyl) phosphine (THMP) to the reaction mixture as an isomerization inhibitor. Unfortunately, the commercial availability and pricing of THMP is not feasible on an industrial scale. Furthermore, although THMP can be prepared from precursor salts, such as tetrakis (hydroxymethyl) phosphonium sulfate (THPS) or tetrakis (hydroxymethyl) phosphonium chloride (TKC), the conversion involves the generation of formaldehyde - a human carcinogen. known - as a by-product. Also, if the pH is not strictly controlled during THMP formation (for example, if conditions become too basic), explosive hydrogen gas has been known to form.

An isomerization suppressing agent that efficiently

<img file="MX348233B_D0004.tif" />

IMPI ÍWSTnVT »MSUCAMC nor the passive INDUSTRIAL nonwAD the residual metathesis catalyst present olefinic metathesis product, and which is commercially available but does not produce carcinogenic by-products and / or involves the formation of explosive hydrogen gas is needed.

BRIEF DESCRIPTION OF THE INVENTION

The scope of the present invention is defined solely by the appended claims, and is not affected to any degree by the statements within this brief description.

By way of introduction, a first method of suppressing isomerization of an olefin metathesis product produced in a metathesis reaction includes adding an isomerization suppressing agent to a mixture that includes the olefin metathesis product and the catalyst of residual metathesis from the metathesis reaction under conditions that are sufficient to passivate at least a portion of the residual metathesis catalyst. The isomerization suppressing agent includes (i) a substantially water-insoluble salt and / or ester of an oxo phosphorous acid, and / or (ii) a derivative of oxo phosphorous acid in which at least one PH bond has been replaced by a PC bond, and / or (iii) a salt and / or an ester of the derivative.

A second method for suppressing the isomerization of an olefin metathesis product produced in a metathesis reaction

IMPI ^

INSTTR / ΓΟ MEXICANO h DI LA HtOBEDAD

INDUSTRY!

includes: (a) adding an isomerization suppressing agent to a mixture that includes the olefin metathesis product and the olefin metathesis catalyst from the metathesis reaction under conditions that are sufficient to passivate at least a portion of the olefin catalyst. residual metathesis; and (b) processing the mixture to provide a fraction comprising the olefin metathesis product and / or its derivative, wherein the isomerization suppressing agent is not removed from the mixture prior to processing. The isomerization suppressing agent includes (i) a salt or ester of an oxo phosphorous acid, and / or (ii) a derivative of oxo phosphorous acid in which at least one PH bond has been replaced by a PC bond, and / or (ii) a salt and / or ester of the derivative.

One method of refining natural oil includes: (a) providing a raw material that includes a natural oil; (b) reacting the raw material in the presence of a metathesis catalyst to form a metathesized product that includes olefins and esters; (c) passivating the residual metathesis catalyst with an agent selected from the group consisting of (i) a salt and / or ester of an oxo phosphorous acid, (ii) a derivative of oxo phosphorous acid in which at least one PH bond has been substituted by a ΡΩ bond, (iii) a salt and / or ester of the derivative and (iv) combinations thereof; (d) separating the olefins in the metathesized product from the esters in the metathesized product; and (e) transesterifying the esters in the presence of an alcohol to form a transesterified product and / or hydrogenation of the olefins to form a partially or fully saturated hydrogenated product.

<img file="MX348233B_D0005.tif" />

IMPI

INSTITUTO mcucano DI LA PROPERTY INDUSTRY!

A first method of producing a composition of oombuotiWe · includes: (a) providing a raw material comprising a natural oil; (b) reacting the raw material in the presence of a metathesis catalyst to form a metathesized product that includes olefins and esters; (c) passivating the residual metathesis catalyst with an agent selected from the group consisting of (i) a salt and / or ester of a phosphorous oxo acid, (ii) a derivative of phosphorous oxo acid in which at least one PH bond is has been replaced by a PC bond, (ii) a salt and / or ester of the derivative and (iv) their combinations; (d) separating the olefins in the metathesized product from the esters in the metathesized product; and (e) hydrogenate the olefins to form a fuel composition.

A second method of producing a fuel composition includes: (a) providing a raw material comprising a natural oil; (b) reacting the raw material in the presence of a metathesis catalyst under conditions sufficient to form a metathesized product including olefins and esters; (c) passivating the residual metathesis catalyst with an agent selected from the group consisting of (i) a salt and / or ester of a phosphorous oxo acid, (ii) a derivative of phosphorous oxo acid in which at least one PH bond has been replaced by a PC bond, (ii) a salt and / or ester of the derivative and (iv) combinations thereof; (d) hydrogenate the metatesized product to form a composition of fuel and at least partially saturated esters; and (e) separating the fuel composition from at least partially saturated esters.

<img file="MX348233B_D0006.tif" />

IMPI

INSTITUTE MMICANG Dtunwiiwu INDUSTRIAL

BRIEF DESCRIPTION OF THE DRAWINGS____

Figure 1 is a schematic diagram of a second embodiment of a process for producing a fuel composition and a transesterified product of a natural oil.

Figure 2 is a process flow chart depicting a representative scheme for isomerization suppression in an olefin metathesis product and shows optional extraction, separation, and transesterification.

Figure 3 is a process flow chart depicting a representative scheme for isomerization suppression in an olefin metathesis product and shows optional extraction, separation, and transesterification.

DETAILED DESCRIPTION OF THE INVENTION

An effective methodology to suppress the isomerization of olefin metathesis products - which is suitable for large-scale application, does not involve the generation of carcinogenic by-products, such as formaldehyde, and is not susceptible to the generation of explosive gas, such as hydrogen - has been discovered and is described here. In some embodiments, the inventive methodology uses (i) a salt and / or ester of an oxo phosphorous acid, and / or (ii) a derivative of oxo phosphorous acid in which at least

<img file="MX348233B_D0007.tif" />

IMPIí mrrTTUTO Mexican

FROM THE rNCMTTRLAL PROPERTY a PH link has been replaced by a PC link, 'y / u “(itirTma * SSty / O¹ester of the derivative. In some embodiments, the inventive methodology facilitates the preservation of the original location of a carbon-carbon double bond created during a metathesis reaction, thus facilitating subsequent processing of the metathesized product and preserving the integrity of the product.

In some embodiments of the inventive methodology, the mixture comprising the olefin metathesis product may be subjected to further processing - which, in some embodiments, optionally involves heating (e.g., distillation, transesterification, and / or the like) - to separate and / or deriving an olefin metathesis product. In some embodiments, surprisingly and unexpectedly, the mixture can be subjected to such processing directly and without the required first removal of the isomerization suppressing agent (eg, through water extraction and / or the like). In some embodiments, surprisingly and unexpectedly, processing without first removal of the isomerization suppressing agent - even when heating is involved - does not substantially compromise the integrity of the olefin metathesis product and / or its derivatives. In some embodiments, a metathesized oil treated with an isomerization suppressing agent in accordance with the present teachings can be separated (eg, via distillation) into a triacylglyceride fraction (which, in some embodiments, can optionally be transesterified) and an olefinic fraction without first

<img file="MX348233B_D0008.tif" />

IMPI

ΙΝΓΠΠΓΓ · MEXICAN

DELA NORIEDAL · INDUSTRIAL require removal of the added isomerization suppressing agent. _Ί

Definitions

Throughout this description and in the appended claims, 5 the following definitions are to be understood:

The term "olefin" refers to a hydrocarbon compound that contains at least one carbon-carbon double bond. As used herein, the term olefin encompasses hydrocarbons that have more than one carbon-carbon double bond (eg, di-olefins, tri-olefins, etc.). In some embodiments, the term olefin refers to a group of carbon-carbon double bond containing compounds with different chain lengths. In some embodiments, the term olefin refers to poly-olefins, straight, branched, and / or cyclic olefins.

The term "suppressing" as used in reference to the isomerization of an olefin refers to an inhibitory effect on the susceptibility of an olefin to isomerization under a given set of conditions. The term "suppress" is to be understood as encompassing but not necessarily implying 100% suppression (ie, 0% isomerization).

The term isomerization as used in reference to an olefin metathesis product refers to the migration of a carbon-carbon double bond in the product to another location within the molecule (e.g., from a terminal position to an internal position and / or from a

<img file="MX348233B_D0009.tif" />

IMPI

ΙΜίΤΓΠΛΌ MEXICAN CE UnORíDAi) 'NtXISTIUAI.

internal position to a terminal position and / or from an internal position · ρΤΐί'ΠύΙ¿I to a second internal position and / or from a first terminal position to a second terminal position, etc.

The phrase "olefin metathesis product" refers to any product produced in a metathesis reaction that contains at least one carbon-carbon double bond. In some embodiments, the olefin metathesis product is a non-functionalized hydrocarbon compound. In some embodiments, the phrase olefin metathesis product subsumes the term olefin. In some embodiments, the olefin metathesis product is functionalized and contains one or a plurality of additional functional groups in addition to its at least one carbon-carbon double bond.

The term "functionalized" and the phrase "functional group" refer to the presence in a molecule of one or more heteroatoms in a terminal and / or internal position, wherein the one or more heteroatoms is an atom other than carbon and hydrogen. In some embodiments, the heteroatom constitutes an atom of a polyatomic functional group with representative functional groups including but not limited to carboxylic acids, carboxylic esters, ketones, aldehydes, anhydrides, ether groups, cyano groups, nitro groups, sulfur-containing groups, groups phosphorus-containing, amides, imides, N-containing heterocycles, aromatic N-containing heterocycles, their salts and the like, and combinations thereof.

IMSirrUTO MEXICANO M LA nOHIBAD INDUSTRIAL

The phrase metathesis reaction refers to a reaction. chemistry involving a single type of olefin or a plurality of different types of olefin, which is carried out in the presence of a metathesis catalyst, and which results in the formation of at least one new olefin product. The phrase metathesis reaction encompasses self-metathesis, cross-metathesis (also known as co-metathesis; CM), ring-opening metathesis (ROM), ring-opening metathesis (ROMP) polymerizations, ring-closure metathesis ( RCM), acyclic diene metathesis (ADMET) and the like, and their combinations. In some embodiments, the phrase "metathesis reaction" refers to a chemical reaction that involves a natural oil feedstock.

The phrase "oxo phosphorous acid" refers to a molecule comprising a P-OH radical in which the hydrogen atom is ionizable.

The phrase "higher acid" as used in reference to an oxo phosphorous acid refers to an acid in which the phosphorus is in an oxidation state of +5.

The phrase "lower acid" as used in reference to an oxo phosphorous acid refers to an acid in which the phosphorus is in an oxidation state below +5 (for example, P¹¹¹).

The phrase "ester of a phosphorous oxo acid" refers to a molecule comprising a P-OR bond, where R denotes any substituted or unsubstituted alkyl or aryl group.

The phrase substantially insoluble in water as used in

<img file="MX348233B_D0010.tif" />

IMPI

ΙΜΓΠΤυΤΌ MUUCANO OF THE NUMBER IWSTXJAL refers to an ester of a phosphorous oxo acid se γρΑργρ. at one mlggiila it divides into an organic phase, preferably an aqueous phase. The phrase "substantially insoluble in water" is to be understood to encompass but does not necessarily imply 0% aqueous solubility.

The phrases natural oil, natural oil raw material and the like refer to oils derived from plant or animal sources. As used herein, these phrases include natural oil derivatives as well, unless otherwise indicated.

The term "derivative" as used in reference to a substrate (for example, a functionalized derivative of a carboxylic acid, such as 9-decenoic acid, etc.) refers to compounds and / or mixture of compounds derived from the substrate by any or any combination of methods known in the art, including but not limited to, saponification, transesterification, esterification, amidification, amination, imide preparation, hydrogenation (partial or complete), isomerization, oxidation, reduction and the like and their combinations.

The phrase "derivatives of natural oil" refers to the compounds and / or mixture of compounds derived from a natural oil using any or a combination of methods known in the art, including but not limited to saponification, transesterification, esterification, amidification, amination. , hydrogenation (partial or complete), isomerization, oxidation, reduction and the like and combinations thereof.

₁₃ IMPI ^ ικτττηπΌ mbbcano

OF THE PBOPftlMD C ^ «w3 INDUSTRIAL

The phrase "low molecular weight olefin" is. refers to any straight, branched, or cyclic olefin in the range of C₂ to C₃₀ and / or any combination of said olefins. The phrase "low molecular weight olefin" includes polyolefins including but not limited to dienes, trines, and the like. In some embodiments, the low molecular weight olefin is functionalized.

The term "ester" as used herein in reference to metathesis products and / or derivatives thereof refers to compounds having a general formula R-COO-R ', where R and R' denote any substituted alkyl or aryl group or not substituted. In some embodiments, the term "ester" refers to a group of compounds having a general formula as described above, wherein the compounds have different chain lengths.

The phrase "residual metathesis catalyst" refers to a catalytic material left over from a metathesis reaction that is capable of participating in, catalyzing and / or otherwise promoting or facilitating the isomerization of a carbon-carbon double bond although it may or may not still be able to catalyze a metathesis reaction. As used herein, the phrase "residual metathesis catalyst" encompasses fully unreacted metathesis catalyst, partially reacted metathesis catalyst, and all kinds of chemical entities derived from a metathesis catalyst in the course of a metathesis reaction, including but it is not limited to all kinds of active or inactive intermediates (for example,

<img file="MX348233B_D0011.tif" />

carbenes, metallocycles, etc.), degradation products_y / íXjdescoj »pos4e + ©«&gt; (for example, metal hydrides, ligand fragments, etc.), metals, metal salts, metal complexes, and the like, and their combinations .

The term "passivate" as used in reference to residual metathesis catalyst refers to any reduction in the activity of the residual metathesis catalyst with respect to its ability and / or tendency to catalyze and / or otherwise participate in (e.g., to through a stoichiometric chemical reaction, sequestration or the like) the isomerization of a carbon-carbon double bond. The term "passivate" is to be understood to include but does not necessarily imply complete deactivation of the residual metathesis catalyst toward isomerization of a carbon-carbon double bond.

The phrase "conditions sufficient to passivate" as used in reference to the conditions under which an isomerization suppressing agent is added to a mixture comprising the olefin metathesis product and the residual metathesis catalyst refers to a variable combination of parameters. experiments, which together result in the passivation of at least a portion of residual metathesis catalyst. The selection of these Individual parameters is within the knowledge of the person of ordinary skill in view of the guided principles described herein and will vary according to the objective reduction in the degree of isomerization that is being sought for a particular application. As used here, the phrase sufficient conditions to passivate

<img file="MX348233B_D0012.tif" />

IMPI

MWCANO INSTITUTE

DE LA «INDUSTRIAL includes experimental parameters that include but are not limited to reagent concentrations, type of mixing and / or agitation provided (e.g., high cut-off, low intensity, etc.), reaction temperature, reaction time. residence, reaction pressure, reaction atmosphere (eg, exposure to atmosphere vs inert gas, etc.) and the like, and their combinations.

The phrase "degree of isomerization" as used in relation to an olefin metathesis product refers to an amount at which a carbon-carbon double bond in the olefin metathesis product undergoes migration from its original position to a posterior position (for example, the degree to which an initially formed olefin metathesis product is converted to one or more of its non-identical isomers). In some embodiments, the degree of isomerization refers to the degree to which a formed α-olefin metathesis product is converted to one or more of its internal isomers under a given set of conditions (for example, the amount of terminal migration to internal). In some embodiments, the degree of isomerization refers to the degree to which an olefin metathesis product containing an internal carbon-carbon double bond is converted to an α-olefin under a given set of conditions (e.g., the amount of internal migration to terminal). In some embodiments, the degree of isomerization refers to the degree to which an olefin metathesis product containing an internal carbon-carbon double bond is converted to one or more of its non-identical internal isomers under a given set of

<img file="MX348233B_D0013.tif" />

conditions (for example, the amount of internal migration) rTrT ~ ^ In some embodiments, "degree of isomerization refers to the degree to which an initially formed α-olefin metathesis product is converted to a different α-olefin under a given set of conditions (eg, the amount of terminal-to-terminal migration). In some embodiments, the degree of isomerization refers to any combination of the amount of terminal to internal migration, the amount of internal to terminal migration, the amount of internal to internal migration, and / or the amount of terminal to terminal migration.

The term "attached" as used in reference to a solid support and an isomerization suppressing agent is to be understood broadly and without limitation to include a range of associative-type forces, including but not limited to covalent bonds, ionic bonds, attractive forces. physical and / or electrostatic (eg hydrogen bonds, Van der Waals forces, etc.) and the like and their combinations.

The term paraffin refers to hydrocarbon compounds that have only single carbon-carbon bonds and that have a general formula C_nH2n + 2. In some modes, n is greater than 20.

The term "isomerization" as used in reference to a fuel composition refers to the reaction and conversion of straight chain hydrocarbon compounds, such as normal paraffins, to branched hydrocarbon compounds, such as iso-paraffins. As a representative and non-limiting example, n-pentane can be isomerized to

.. IMPIAS ή 7 IMSTRVro MEXICAN ¹ 'OF THE PROPERTY tVSQü

INDUSTRIAL a mixture of n-pentane, 2-methylbutane and 2,2-dimethylpropan. 'The' '- isomerization of normal paraffins can be used to improve the overall properties of a fuel composition. Additionally, isomerization can refer to the conversion of branched paraffins to additional more highly branched paraffins.

The term "yield" refers to the total weight of fuel produced from the metathesis and hydrogenation 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 is combined.

The term fuel and the phrase fuel composition refer to materials that meet certain specifications or a mixture of components that are useful in formulating fuel compositions but, by themselves, do not meet all the specifications required for a fuel. .

The phrases "turbine fuel" and "jet fuel" refer to gasoline and kerosene-type fuel cuts, and / or military-grade combustion turbine fuel compositions. Kerosene-type combustion turbine fuel (including Jet A and Jet A-1) has a carbon number distribution between about 8 and about 16. Jet A and Jet A-1 typically

<img file="MX348233B_D0014.tif" />

IMPI «βΤΠνΤΟ MEXICANO ΠΕ ΙΑ nOMHMD have a flash point of at least approximately · 38 ° · £ -γ · οοβ · auto-ignition temperature of approximately 210 ° C, a freezing point less than or equal to approximately -40 ° C for Jet A and -47 ° C for Jet A-1, a density of approximately 0.8 g / cc at 15 ° C and an energy density of approximately 42.8-43.2 MJ / kg. Wide-cut or naphtha-type combustion turbine fuel (including Jet B) has a carbon number distribution between about 5 and about 15. Jet B typically comprises a flash point below about 0 ° C, a temperature of self ignition of about 250 ° C, a freezing point of about 51 ° C, a density of about 0.78 g / cc, and an energy density of about 42.8-43.5 MJ / kg. Military grade combustion turbine fuel refers to a "JP" numbering system or combustion turbine propulsion (JP-1, JP-2, JP-3, JP-4, JP-5, JP-6, JP-7, JP-8, etc.). Military-grade combustion turbine fuels may comprise alternative or additional additives to have higher flash points than Jet A, Jet A-1, or Jet B in order to cope with the heat and stress experienced during supersonic flight.

The term diesel fuel refers to a hydrocarbon composition that has a carbon number distribution between about 20 and about 25. Diesel fuels typically have a specific gravity of about 0.82-1.08 at 15.6 ° C (60 ° F) based on water having a specific gravity of 1 to

<img file="MX348233B_D0015.tif" />

IMPI iRSTTTUTOMtJUCANf 'Dít ^ nompAD iNowsniAt

60 ° F. Diesel fuels typically comprise —fem4fttervafo- &lt;fe— distillation between approximately 180-340 ° C (356-644 ° F). Additionally, diesel fuels have a minimum cetane number of approximately 40.

As used herein, the term "carbon number distribution" refers to the range 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 combustion turbine fuel usually comprises a range of hydrocarbon compounds where the majority of these compounds have between 5 and 15 carbon atoms each. A fuel for kerosene-type combustion turbines usually comprises a distribution of hydrocarbon compounds where the majority of these compounds have between 8 and 16 carbon atoms. A diesel fuel comprises a distribution of hydrocarbon compounds where most of these compounds have between 8 and 25 carbon atoms each.

As used here, the term energy density refers 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 one million Joules. As a non-limiting example, the energy density of fuel for kerosene or naphtha type combustion turbines is usually greater than about 40 MJ / kg.

As a general background, as mentioned above, the

<img file="MX348233B_D0016.tif" />

presence of residual metathesis catalyst during heating, and / or. Distillation of an olefin metathesis product can result in the isomerization of a carbon-carbon double bond in the product, such that one or more isomers of the original olefin metathesis product are formed. Such isomerization is generally undesirable when end group functionalization within the product molecule is the goal. Furthermore, such isomerization is generally undesirable when leading to a mixture of products and the goal is a well-defined product in high yield and high purity. Labile olefins and / or olefins that are not as thermodynamically stable as other isomers readily accessible through isomerization are particularly - though not exclusively susceptible to isomerization (e.g., terminal olefins, vinyl olefins, vinylidene olefins, and the like. ).

By way of example, although methyl 9-decenoate is an expected product of the cross-metathesis between methyl oleate and the aolefin i-butene, some isomerization of the 9-substituted olefin to one or more internal olefins is found in practice (eg, migration of the double bond to the 7 and / or 8 positions) can occur when the cross-metathesis product is heated prior to removal and / or pacification of the residual metathesis catalyst. To assess the magnitude of isomerization, cross-metathesized material obtained from the cross-metathesis between methyl oleate and 1-butene is subjected to typical oil refining conditions, such as exposure to high temperatures, such as

<img file="MX348233B_D0017.tif" />

IMPI

INSTITUTO MgXICANC ·

Dt LA PROFIWAO INDUSTRIAL such as exposure to high temperatures (for example, about 250 ° C). In the absence of any isomerization suppressing agent, the degree of isomerization of methyl 9-decenoate to internal isomers under typical conditions is found to be about 25%. It is to be understood, however, that this degree of isomerization is only intended to be illustrative and that it may vary depending on the particular substrate and conditions.

However, by adding, for example, an ester of a phosphorous oxo acid as an isomerization suppressing agent particularly though not exclusively a phosphite ester (which, in some embodiments, has a sufficiently high molecular weight than the phosphite exhibits thermal stability), and particularly though not exclusively in excessive molar amounts relative to residual metathesis catalyst - the present inventors found that the degree of isomerization can be greatly reduced. On the other hand, many phosphorous oxo acid esters (for example, various high molecular weight phosphite esters that are used as secondary antioxidants during high temperature polymer processes, including but not limited to extrusion of polyolefins at temperatures higher than about 250 ° C) are available in commercial quantities and are not subject to the same carcinogenicity and explosion problems that are associated with THMP production.

It is to be understood that the elements and characteristics of the

<img file="MX348233B_D0018.tif" />

various representative modalities that are given into function --- can be combined in different ways to produce new modalities that also fall within the scope of the present teachings.

By way of general introduction, in some embodiments, a method according to the present teachings for suppressing the isomerization of an olefin metathesis product produced in a metathesis reaction comprises adding an isomerization suppressing agent to a mixture comprising the product. of olefin metathesis and the residual metathesis catalyst from the metathesis reaction. The isomerization suppressing agent is added under conditions sufficient to passivate at least a portion of the residual metathesis catalyst, and is selected from the group consisting of (i) a salt and / or an ester of a phosphorous oxo acid, (ii) a derivative of phosphorous oxo acid in which at least one PH bond has been replaced by a PC bond, (iii) a salt and / or an ester of the derivative, and (iv) combinations thereof. In some embodiments, the phosphorous oxo acid ester is substantially insoluble in water.

As described above, in some embodiments particularly though not exclusively embodiments in which the isomerization suppressing agent comprises a phosphite ester having a sufficiently high molecular weight and exhibiting a desired degree of thermal stability - the mixture comprising the metathesis product Olefins can be directly subjected to further processing in the presence of the isomerization suppressing agent. In other words, in

<img file="MX348233B_D0019.tif" />

In some embodiments, it may not be possible, necessary, and necessary to remove the isomerization suppressing agent by extraction with a polar solvent (eg, water) prior to further processing, including but not limited to processing involving heating. In some embodiments, such an isomerization suppressing agent comprises a substantially water-insoluble ester of a phosphorous oxo acid which, in some embodiments, cannot be divided to a significant degree in a polar solvent.

It should be understood that under a given set of biphasic conditions, a substantially water-insoluble ester of a phosphorous oxo acid can divide to some extent into the aqueous phase rather than the organic phase (although in an amount that is less than about 50% by weight, in some embodiments less than about 40% by weight, in some embodiments less than about 35% by weight, in some embodiments less than about 30% by weight, in some embodiments less than about 25% by weight, in some embodiments less than about 20% by weight, in some embodiments less than about 15% by weight, in some embodiments less than about 10% by weight, in some embodiments less than about 5% by weight, in some embodiments less than about 3% by weight, and in some embodiments less than about 1% by weight). The use of said substantially water-insoluble ester of a phosphorous oxo acid in accordance with

<img file="MX348233B_D0020.tif" />

IMPI

MUtCAN INSTITUTE OF INDUSTRIAL PROPERTY The present teachings are in stark contrast to conventional wisdom proposing removal of the metathesis catalyst with a water-soluble phosphine, such as THMP (e.g., International Patent Application Publication No. WO 01/36368 A2 ).

Therefore, as described above, after the isomerization suppressing agent has been added to the mixture comprising the olefin metathesis product and the residual metathesis catalyst, the isomerization suppressing agent, in some embodiments, It can be left in the mix and carried through, either in whole or in part, of a subsequent chemical reaction or processing step. In other embodiments, including but not limited to embodiments in which the isomerization suppressing agent comprises (i) at least one partially water soluble salt and / or ester of a phosphorous oxo acid, and / or (ii) at least one partially water soluble derivative of oxo phosphorous acid in which at least one PH bond has been replaced by a PC bond, and / or (iii) at least one partially water soluble salt and / or ester of the derivative, The isomerization suppressing agent can optionally be separated and removed from the mixture, either partially or completely, prior to any subsequent reaction or processing step.

For embodiments where it is desirable to separate and / or remove the isomerization suppressing agent after passivation of the residual metathesis catalyst, a method in accordance with the present teachings optionally may further comprise washing or extraction.

INSTITUTO MEXICANC. IX THE FNEHJSTWlAL PROPERTY of the reaction mixture of metathesis with a solvent (particularly though not exclusively, for modalities where the isomerization suppressing agent is at least partially soluble in the polar solvent). In some embodiments, the polar solvent is at least partially immiscible with the mixture, such that layer separation can occur. In some embodiments, at least a portion of the isomerization suppressing agent is split in 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 which include, but are not limited to polyethylene glycols and / or glymes, and the like and their combinations. In some embodiments, the mixture is extracted with water. In some embodiments, when the phosphorous oxo acid ester used as an isomerization suppressing agent is 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 thereof), washing the mixture with water can convert the phosphite ester to a corresponding acid. While not wishing to be bound by any particular theory or intended to limit in any way the scope of the appended claims or their equivalents, it is currently believed that such hydrolysis may occur more rapidly with lower weight esters.

LMP i

1NSTTTUTO MEXICANO DE LA PROPERTY INDUSTRIAL molecular. - - _............,

In addition or as an alternative to washing the mixture with a polar solvent to remove the isomerization suppressing agent, which, in some embodiments, may serve to remove at least a portion of the isomerization suppressing agent, a method in accordance with the present Teachings further comprise removing at least a portion of the isomerization suppressing agent by adsorbing it to an adsorbent, which can then optionally be physically separated from the mixture (eg, through filtration 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 trademark TRISYL by WR Grace &amp; Co., diatomaceous earths, and the like and their combinations.

In some embodiments, the olefin metathesis product comprises at least one terminal double bond, and in some embodiments, the isomerization comprises conversion of the terminal double bond to an internal double bond. In some embodiments, the olefin metathesis product comprises at least one internal double bond, and in some embodiments, the isomerization comprises converting the internal double bond to a different internal double bond (i.e., an internal double bond between two atoms of carbon at least one of which are not part of the internal double bond

<img file="MX348233B_D0021.tif" />

IMPI

INSTHVTO MLX1CAN &lt;FROM THE original INDUSTRIAL EKOHWAD). In some modalities, the product of¹ OleflhaS comprises at least one internal double bond and, in some embodiments, isomerization comprises converting the internal double bond to a terminal double bond. In some embodiments, isomerization suppression comprises an observed degree of isomerization that is less than about 5%, in some embodiments less than about 4%, in some embodiments less than about 3%, in some embodiments less than about 2%. in some modalities less than approximately 1%, in some modalities less than approximately 0.9%, in some modalities less than approximately 0.8%, in some modalities less than approximately 0.7%, in some modalities less than approximately 0.6%, in some modalities less than approximately 0.5%, in some modalities less than approximately 0.4%, in some modalities less than approximately 0.3%, in some modalities less than approximately approximately 0.2% and in some modalities less than approximately 0.1%.

In some embodiments, the olefin metathesis product is α, ω-di-functionalized. In some embodiments, the olefin metathesis product comprises a carboxylic acid radical. In some embodiments, the olefin metathesis product comprises a terminal olefin and a carboxylic acid radical. In some embodiments, the olefin metathesis product comprises an internal olefin and a carboxylic acid radical. In some embodiments, the olefin metathesis product

<img file="MX348233B_D0022.tif" />

IMPI

MRXiCAHO INSTITUTE OF LAPtOPIEDAD INDUSTRIA!

it comprises a carboxylic ester radical. In some embodiments, the olefin metathesis product comprises a terminal olefin and a carboxylic ester radical. In some embodiments, the olefin metathesis product comprises an internal olefin and a carboxylic ester radical. In some embodiments, the olefin metathesis product is selected from the group consisting of 9-decenoic acid, an ester of 9-decenoic acid, 9-undecenoic acid, an ester of 9-undecenoic acid, 9-dodecenoic acid, an ester of 9-dodecenoic acid, 1-decene, 2-dodecene, 3-dodecene and their combinations. In some embodiments, the esters of 9-decenoic acid, 9-undecenoic acid, and 9-dodecenoic acid are alkyl esters and, in some embodiments, methyl esters (for example, methyl 9-decenoate, methyl 9-undecenoate, methyl 9- dodecenoate, etc.).

In some embodiments, the olefin metathesis product is derived from a natural oil reagent. In some embodiments, the metathesis reaction that produces the olefin metathesis product comprises the auto-metathesis of natural oil and / or a derivative thereof. In some embodiments, the metathesis reaction that produces the olefin metathesis product comprises cross-metathesis between a natural oil and / or a derivative thereof and a low molecular weight olefin.

Representative examples of natural oils for use in accordance with the present teachings include but are not limited to vegetable oils, algal oils, animal fats, pasture oils (e.g., by-products of wood pulp manufacturing), derivatives

<img file="MX348233B_D0023.tif" />

IMPI

WSTITUTO MZXICANCJ

W THE FNDUSTIUAt FROMITY of these oils, and the similar and their combinations. Representative examples of vegetable oils for use in accordance with the present teachings include but are not limited to rapeseed oil, 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, hemp oil, castor oil and the like, and combinations thereof. Representative examples of fats of animal origin for use in accordance with the present teachings include but are not limited to lard, tallow, chicken fat, yellow fat, brown fat, fish oil, and the like and combinations thereof. In some embodiments, the natural oil can be refined, bleached, and / or deodorized.

Representative examples of natural oil derivatives for use in accordance with the present teachings include, but are not limited to, gums, phospholipids, oil solubilized, acidified oil solubilized, distillate, or distilled sediment, fatty acids, fatty acid alkyl esters (eg, non-limiting examples such as 2-ethylhexyl ester, etc.), their hydroxy-substituted variations, and the like, and combinations thereof. In some embodiments, the natural oil derivative is a fatty acid methyl ester (FAME) derived from the natural oil glyceride.

In some embodiments, the low molecular weight olefin is

<img file="MX348233B_D0024.tif" />

IMPI

IMSTTfUTD MEXICAN

OCLA &gt;&gt; If * lOA £&gt; rND &lt;J &lt;mUAL an α-olefin (also known as tprminai olefin) ρπ ia qhp ins unsaturated carbon-carbon bonds is present at one end of the enclosure. In some embodiments, the low molecular weight olefin is an internal olefin. In some embodiments, the low molecular weight olefin is functionalized. In some embodiments, the low molecular weight olefin is a C2-C30 olefin. In some embodiments, the low molecular weight olefin is a C2-C30 α-olefin. In some embodiments, the low molecular weight olefin is a C2-C25 olefin. In some embodiments, the low molecular weight olefin is a C2-C25 α-olefin. In some embodiments, the low molecular weight olefin is a C2-C20 olefin · In some embodiments, the low molecular weight olefin is a C2-C20 α-olefin · In some embodiments, the low molecular weight olefin is a C olefin₂-C₁₅. In some embodiments, the low molecular weight olefin is a C α-olefin₂-C₁₅. In some embodiments, the low molecular weight olefin is a C olefin.₂-C₁₀. In some embodiments, the low molecular weight olefin is a C α-olefin₂-Cio. In some embodiments, the low molecular weight olefin is a C₂-C₈. In some embodiments, the low molecular weight olefin is a C α-olefin₂-C₈. In some embodiments, the light weight olefin is a C olefin.₂-C₆. In some embodiments, the low molecular weight olefin is a C α-olefin₂-C₆. Representative low molecular weight definitions in the C range₂ to C₆ include but are not limited to ethylene, propylene, 1-butene, 2-butene, isobutene,

<img file="MX348233B_D0025.tif" />

IMPI iRrrnyro MapcAriRO

M la rromDAO

1-pentene, 2-pentene, 3-pentene, 2-methyl-1-butene, 2-methyl-2-butene, 3-methyl

1-butene, cyclopentene, 1-hexene, 2-hexene, 3-hexene, 4-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-methyl -2-pentene, 3-methyl-2-pentene, 4-methyl-2-pentene, 2-methyl-3-pentene, 1-hexene, 2-hexene, 3-hexene, cyclohexene and the like, and their combinations. In some embodiments, the low molecular weight olefin is an α-olefin selected from the group consisting of styrene, vinyl cyclohexane, and a combination thereof. In some embodiments, the low molecular weight olefin is a mixture of linear and / or branched olefins in the C range.₄-C₁₀. In some embodiments, the low molecular weight olefin is a mixture of olefins C₄linear and / or branched (eg, combinations of 1-butene, 2-butene, and / or iso-butene). In some embodiments, the low molecular weight olefin is a mixture of linear and / or branched olefins in the higher Cu-Cu range.

In some embodiments, the olefin metathesis product comprises at least one internal double bond, which in some embodiments is cis and in some embodiments is trans. In some embodiments, the olefin metathesis product comprises at least one terminal double bond and at least one internal double bond. In some embodiments, the olefin metathesis product comprises at least one terminal double bond and / or at least one internal double bond, and at least one additional functional group. In some embodiments, at least one additional functional group is selected from the group consisting of carboxylic acids, esters

IMPI Mexican nwrmrio de la miohedad industrial carboxylics, mono-acylglycerides (MAG), di-acylglycerides £ S - 4i ^^J2 ^ - 'fc ^^ acylglycerides (TAG) and their combinations. In some embodiments, the olefin metathesis product is produced in an autometathesis reaction. In some embodiments, the olefin metathesis product is produced in a cross-metathesis reaction. In some embodiments, the olefin metathesis product is a downstream derivative of a self-metathesis or cross-metathesis product (including but not limited to, for example, transesterification products, hydrolysis products, and the like and combinations thereof). . In some embodiments, the olefin metathesis product is produced in a metathesis reaction involving one or more previously formed olefin metathesis products (e.g., the production of 9-ODDAME from the cross-metathesis of 9-DAME and 9- DDAME one or both of which is itself a product of a metathesis reaction).

In some embodiments, the metathesis reaction that produces the olefin metathesis product comprises the reaction of two triglycerides present in a natural raw material in the presence of a metathesis (auto-metathesis) catalyst, wherein each triglyceride comprises at least one carbon-carbon double bond, thus forming a new mixture of olefins and esters that in some embodiments comprises a triglyceride dimer. In some embodiments, the triglyceride dimer comprises more than one carbon-carbon double bond, such that higher oligomers can also form. In some modalities, the reaction of

<img file="MX348233B_D0026.tif" />

<img file="MX348233B_D0027.tif" />

IMPI

INSTITUTO MEXICANO DE LA PROPIEDA »INDUSTRIAL metathesis that produces the ollefin metathesis product comprises, reaction of an olefin (for example, a low molecular weight olefin) and a triglyceride in a natural raw material that comprises at least one carbon double bond- carbon, thus forming new olefinic molecules, as well as new ester molecules (cross-metathesis).

In some embodiments, the residual metathesis catalyst comprises a transition metal. In some embodiments, the residual metathesis catalyst comprises ruthenium. In some embodiments, the residual metathesis catalyst comprises rhenium. In some embodiments, the residual metathesis catalyst comprises tantalum. In some embodiments, the residual metathesis catalyst comprises nickel. In some embodiments, the residual metathesis catalyst comprises tungsten. In some embodiments, the residual metathesis catalyst comprises molybdenum.

In some embodiments, the residual metathesis catalyst comprises a ruthenium carbene complex and / or an entity derived from said complex. In some embodiments, the residual metathesis catalyst comprises a material selected from the group consisting of a ruthenium vinylidene complex, a ruthenium alkylidene complex, a ruthenium methylidene complex, a ruthenium benzylidene complex, and combinations thereof, and / or an entity derived from any complex or combination of such complexes. In some embodiments, the residual metathesis catalyst comprises a ruthenium carbene complex comprising at least iwyrnvro mwicaj *) nr. LA *: INF'limiAL minus a tricyclohexylphosphine ligand and / or an entity derived from said complex. In some embodiments, the residual metathesis catalyst comprises a ruthenium carbene complex comprising at least two tricyclohexylphosphine ligands [eg, (PCy₃)₂Cl2Ru = CH-CH = C (CH₃) 2, etc.) and / or an entity derived from said complex. In some embodiments, the residual metathesis catalyst comprises a ruthenium carbene complex comprising at least one imidazolidine ligand and / or an entity derived from said complex. In some embodiments, the residual metathesis catalyst comprises a ruthenium carbene complex comprising an isopropyloxy group attached to a benzene ring and / or entity derived from said complex.

In some embodiments, the residual metathesis catalyst comprises a Grubbs-type olefin metathesis catalyst and / or an entity derived therefrom. In some embodiments, the residual metathesis catalyst comprises a first generation Grubbs-type olefin metathesis catalyst and / or an entity derived therefrom. In some embodiments, the residual metathesis catalyst comprises a second generation Grubbs-type olefin metathesis catalyst and / or an entity derived therefrom. In some embodiments, the residual metathesis catalyst comprises a first generation Hoveda-Grubbs olefin metathesis catalyst and / or an entity derived therefrom. In some embodiments, the residual metathesis catalyst comprises a second generation olefin metathesis catalyst.

<img file="MX348233B_D0028.tif" />

IMPI

INSTITUTO MEXICANO DE LA HU&gt; n AGE INDUSTRIAL Hoveda-Grubbs type and / or an entity derived from the imsTnn ~ TETr'15 ^ modalities, the residual metathesis catalyst comprises one or a plurality of the ruthenium carbene metathesis catalysts sold by Materia, Inc., of Pasadena, California and / or one or more entities derived from such 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 their combinations: product no. G823 (CAS No. 17222230-9), 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. 927429-61-6), 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. 832146-68-6), product no. C711 (CAS no. 635679-24-2), product no. C933 (CAS No. 373640-75-6).

Representative oxo phosphorous acids for use in accordance with the present teachings include but are not limited to those described in FA Cotton and G. Wilkinson's Advanced Inorganic Chemistry, Fifth Edition, New York: John Wiley &amp; Sons, 1988, pages 382-443. By way of illustration, phosphorous oxo acids include but are not limited to phosphorous acid (H3PO3, also known as phosphonic acid), phosphinic acid (H3PO2, also known as hypophosphorous acid ”), acid

<img file="MX348233B_D0029.tif" />

Mexican IMPI twrrrrvTo DE LA NOEIXAD INDUSTRIAL PHOSPHORIC (H₃PO₄₁ also known as qrtofqsphoric acid "), ~ pyrophosphoric acid (H4P2O7), polyphosphoric acids, ultraphosphonic acid (Η2Ρ4Ο-11), d¡ and polyacids of phosphorus in lower formal oxidation states comprising PH and / or PP bonds, and the like and their salts and anions, and the like, and their combinations.

In some embodiments, the oxo phosphorous acid comprises a higher acid. In some embodiments, the higher acid comprises phosphoric acid. In some embodiments, the phosphoric acid ester is selected from the group consisting of mono-esters, di-esters, tri-esters, and combinations thereof. In some embodiments, the phosphoric acid ester comprises a mono-ester. In some embodiments, the phosphoric acid mono-ester is not a monophenyl phosphoester [P (O) (OPh) (OH) 2].

In some embodiments, the oxo phosphorous acid comprises a lower acid. In some embodiments, the lower acid is selected from the group consisting of phosphorous acid, phosphinic acid, and a combination thereof. In some embodiments, the oxo phosphorous acid comprises phosphorous acid. In some embodiments, as shown in Chemical Equation A, the phosphorous acid ester is selected from the group consisting of mono-esters, di-esters, tri-esters, and combinations thereof. In some embodiments, the phosphorous acid ester comprises a tri-ester. In some embodiments, the isomerization suppressing agent comprises a phosphite ester. In some embodiments, the phosphite ester comprises a P (OR¹R²R³)₃, where R¹, R² and R³ they are the same or different and they are

<img file="MX348233B_D0030.tif" />

IMPI

INSTm rro MEXICANO DE LA PROPERTY industrial each one R independently selected from the group consisting of alkyl ^ -...

of substituted or unsubstituted C1-C100, substituted or unsubstituted aryl and combinations thereof, and wherein covalent bonds may optionally exist between two or more of R¹, R² and R³, such that when two or more of R¹, R² Y

R³ are taken together, a bidentate or tridentate ligand to phosphorus is formed.

CHEMICAL EQUATION A

MONO-ESTERS DI-ESTERS

<img file="MX348233B_D0031.tif" />

PHOSPHORUS ACID

<img file="MX348233B_D0032.tif" />

PHOSPHONIC ACIDS

<img file="MX348233B_D0033.tif" />

<img file="MX348233B_D0034.tif" />

YOU GO OUT

DI-ESTERS

MONO-ESTERS

In some embodiments, the phosphite ester is selected from the group consisting of aryl organophosphites, alkyl organophosphites, mixed alkyl-alkyl organophosphites, and combinations thereof. In some embodiments, the phosphite ester comprises one or a plurality of high molecular weight phosphites commercially available from Dover Chemical Corporation of Dover, Ohio and / or Galata Chemicals of Southbury, Connecticut. Representative Dover Chemical Corporation phosphites for use in accordance with the present teachings include liquids and solids, and include but are not limited to those sold under the following product names as well as combinations thereof: trisnonylphenyl phosphite (DOVERPHOS® 4), trisnonylphenyl phosphite (+ 0.75% triisopropanolamine) (DOVERPHOS® 4-HR), trisnonylphenyl phosphite (+ 1.0% triisopropanolamine) (DOVERPHOS® 4-HR Plus), trisnonyl phenyl phosphite contains 0.1% maximum residual nonylphenol (DOVERPHOS ® HIPURE 4), trisnonylphenyl phosphite (+ 0.75% triisopropanolamine) containing 0.1% maximum residual nonylphenol (DOVERPHOS® HIPURE 4-HR), diphenyl phosphite (DOVERPHOS® 213) , triphenyl phosphite (DOVERPHOS® 10), diisodecyl phenyl phosphite (DOVERPHOS® 7), isodecyl diphenyl phosphite (DOVERPHOS® 8), isooctyl diphenyl phosphite (DOVERPHOS® 9), tetraphenyl dipropylene glycol diphosphite (DOVERPHOS® 11), phosphos® 11 poly (dipropylene glycol) phenyl (DOVERPHOS® 12), bidphenol A C12-C15 alkyl phosphite (DOVERPHOS® 613), bisphenol A C10 alkyl phosphite (DOVERPHOS® 675), triisodecyl phosphite (DOVERPHOS® 6), tris (tridecyl) phosphite (DOVERPHOS® 49), trilauryl phosphite (DOVERPHOS® 53), tris phosphite (dipropylene glycol) (DOVERPHOS® 72), dioleyl hydrogen phosphite (DOVERPHOS® 253), tris (2,4-di-tert-butylphenyl) phosphite (DOVERPHOS® S39 IMPIAS tNSTfTVTO MEXICAN

DELA MOCEDAD INDUSTRIA!

480), distearyl pentaerythritol diphosphite (DOVERPHOS® S-680), distearyl pentaerythritol diphosphite (+ triisopropanolamine) (DOVERPHOS ® S-682), bis (2,4-dicumylphenyl) pentaerythritol diphosphite (DOVERPHOS® S-9228) the similar and its combinations. Representative Galata Chemical phosphites for use in accordance with the present teachings include liquids and solids, and include but are not limited to those sold under the following product names as well as their combinations: tris (nonylphenyl) phosphite, diphenyl phosphite, triphenyl phosphite, phenyl diisodecyl phosphite, diphenyl isodecyl phosphite, dodecyl nonylphenol phosphite mixture, triisodecyl phosphite, triisotridecyl phosphite, diphenyl 2-ethyl phosphite poly (dipropylene glycol) phenyl, tetraphenyl dipropylene glycol diphosphite, trilauryl phosphite, phenyl neopentylene glycol phosphite, heptakis (dipropylene glycol) triphosphite, trilauryl tritium phosphite, diphenyl tridecyl phosphite, tris (dipropylene glycol) phosphite, 4,4'-isopropylidenediphenol-C10-alcohol phosphite, 4,4'-isopropylidenediphenol-C12-15-alcohol phosphite, and the like and combinations thereof.

In some embodiments, the phosphorous acid derivative in which at least one PH bond has been replaced by a PC bond comprises a phosphonic acid. In some embodiments, the ester of the derivative is selected from the group consisting of mono-esters, di-esters, and a combination thereof. In some embodiments, the ester comprises a phosphonate. In some embodiments, the ester comprises one or a plurality of the phosphonates commercially available from Thermphos International BV.

MEXICAN INSTITUTE

['£ THE UNIT ^ SwñaSSLJe INDUSTRIAL (Vlissingen, The Netherlands) and sold under the trademark DFOUFST I The representative phosphonates of Thermphos for use in accordance with the present teachings include but are not limited to those sold under the following product names as well as their combinations: amino trimethylene phosphonic acid and its salts (DEQUEST® 2000, DEQUEST® 2000EG, DEQUEST® 2000LC, DEQUEST ® 2006), 1-hydroxyethylidene1,1-diphosphonic acid and its salts (DEQUEST 2010®, DEQUEST® 2010CS, DEQUEST® 201 OLA, DEQUEST® 201OLC, DEQUEST® 2014, DEQUEST ® 2016, DEQUEST ® 2016D, DEQUEST® 2016DG), DEQUEST ® 2046, DEQUEST ® 2047, DEQUEST® 2047G, diethylenetriamine penta (methylene phosphonic acid) and its salts (DEQUEST® 2060S, DEQUEST® 2066, DEQUEST® 2066A, DEQUEST® 2066C2), a registered polyamino phosphonic acid (DEQUEST ® 2086), bis (hexamethylene triamine penta (methylene phosphonic acid)) and its salts (DEQUEST ® 2090), diethylene triamine penta (methylene phosphonic acid) and its salts (DEQUEST® 4066), DEQUEST® 4266D, DEQUEST® 6004, and the like and their combinations.

In some embodiments, as shown in Chemical Equation B, phosphorous oxo acid consists of phosphinic acid. In some embodiments, the phosphinic acid ester is selected from the group consisting of mono-esters, di-esters, and a combination of these. In some embodiments, the phosphinic acid derivative in which at least one PH bond has been replaced by a PC bond comprises a phosphine acid. In some embodiments, the phosphine acid is selected from the group consisting of

<img file="MX348233B_D0035.tif" />

_Δ1 IMPI

4Ί INSTITUTO MEXICANO 'V LA Flor AGE

INDUSTRIAL

R¹HP (O) OH, R²R³P (O) OH, and a combination of the miomo &amp; .- cfrden R² and R³ are the same or different and each is independently selected from the group consisting of Ci-C alkyl_1Oor substituted or unsubstituted, substituted or unsubstituted aryl and combinations thereof, wherein a covalent bond may exist between R² and R³ , such that when R² and R³are taken together, a bidentate phosphorous ligand is formed. In some embodiments, the phosphine ester comprises a structure selected from the group consisting of R¹HP (O) O², R³R⁴P (O) OR⁵ and a combination of these, where R¹, R², R³, R⁴ and R⁵ are the same or different and each is independently selected from the group consisting of substituted or unsubstituted C1-C100 alkyl, substituted or unsubstituted aryl, and combinations thereof, wherein a covalent bond exists between R¹ and R², such that when R¹ and R² taken together, a bidentate to phosphorous ligand is formed, and where covalent bonds may optionally exist between two or more of R³, R⁴ and R⁵, such that when two or more of R³, R⁴ and R⁵ taken together, a phosphorous bidentate or tridentate ligand is formed.

<img file="MX348233B_D0036.tif" />

CHEMICAL EQUATION B

MONO-ESTERS

<img file="MX348233B_D0037.tif" />

<img file="MX348233B_D0038.tif" />

O and RZ ESTERES

In some embodiments, the isomerization suppressing agent is attached to a solid support (eg, silica gel) and comprises (i) a salt and / or an ester of a phosphorous oxo acid, and / or (ii) a derivative of phosphorous oxo acid in which at least one PH bond has been replaced by a PC bond, and / or (iii) a salt and / or an ester of the derivative. In some embodiments, the solid support comprises one or more polar functional groups. Representative solid supports for use in accordance with current teachings include but are not limited to carbon, silica, silica-alumina, alumina, clay, magnesium silicates (eg,

IMPI ΐΝπττυτο Mexican

OF THE INDUSTRIAL RO ^ HKDlAD

Magnesols), the synthetic silica adsorbent sold under-the-tide rogiotmdai TRISYL by WR Grace &amp; Co., diatomaceous earth and the like and combinations thereof.

In some embodiments, the isomerization suppressing agent is added to a mixture in accordance with the present teachings in molar excess relative to the residual metathesis catalyst. In some embodiments, the molar excess is at least about 2 to 1. In some embodiments, the molar excess is at least about 3 to 1. In some embodiments, the molar excess is at least about 4 to 1. In some embodiments, the molar excess is at least about 5 to 1. In some embodiments, the molar excess is at least about 10 to 1. In some embodiments, the molar excess is at least about 15 to 1. In some In some embodiments, the molar excess is at least about 20 to 1. In some embodiments, the molar excess is at least about 25 to 1. In some embodiments, the molar excess is at least about 30 to 1. In some embodiments, the molar excess is at least about 35 to 1. In some embodiments, the molar excess is at least about 40 to 1. In some embodiments, the molar excess is at least about 45 to 1. In some modalities, the molar excess is at least about 50 to 1. In some modalities, the molar excess is at least about 55 to 1. In some modalities, the molar excess is at least ⁴⁴ ΙΜΡΙ

INSmVTO M1X1CANC)

Dt THE FSOUtDAD 'CjwaJí'Wt?⁷INDUSTRIAL approximately 60 to 1. In some modalities, the molar excess is at least approximately 65 to 1. In some modalities, the molar excess is at least approximately 70 to 1. In some modalities, the molar excess is at least approximately 75 to 1. In some embodiments, the molar excess is at least about 80 to 1. In some embodiments, the molar excess is at least about 85 to 1. In some embodiments, the molar excess is at least about 90 to 1. In some embodiments, the molar excess is at least about 95 to 1. In some embodiments, the molar excess is at least about 100 to 1.

While it is not 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 as the organic solubility of an isomerization suppressing agent conforms to increases in the current teachings, can decrease the molar excess of isomerization suppressing agent to the residual metathesis catalyst without substantially decreasing the efficiency of isomerization suppression. Furthermore, while it is not wished 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 when high shear mixing is used, excess molar of the isomerization suppressing agent to residual metathesis catalyst without substantially decreasing the efficacy of

<img file="MX348233B_D0039.tif" />

isomerization suppression.

IMPL fWTTTVTO MEXICAN

OF AN ECUMM

In some embodiments, the conditions under which an isomerization suppressing agent in accordance with the present teachings is added to a mixture comprising an olefin metathesis product and residual metathesis catalyst comprise mixing. In some embodiments, the mixing comprises high shear mixing (e.g., mixing of a type sufficient to disperse and / or transport at least a portion of a first phase and / or chemical species in a second phase with which the first phase and / or a chemical species could normally be at least partially immiscible).

In some embodiments, the conditions under which an isomerization suppressing agent in accordance with the present teachings is added to a mixture comprising an olefin metathesis product and residual metathesis catalyst comprise heating. The present teachings are in no way limited to any particular heating temperature or temperature range. However, for purposes of illustration, in some embodiments, the conditions under which an isomerization suppressing agent in accordance with the present teachings is added to a mixture comprising an olefin metathesis product and residual metathesis catalyst comprises a temperature heating temperature of approximately 40 ° C or higher. In some embodiments, the heating comprises a temperature of about 50 ° C or higher. In

<img file="MX348233B_D0040.tif" />

In some embodiments, the heating comprises a temperature of about 60 ° C or higher. In some embodiments, the heating comprises a temperature of about 70 ° C or higher. In some embodiments, the heating comprises a temperature of about 80 ° C or higher. In some embodiments, the heating comprises a temperature of about 90 ° C or higher.

The present teachings are in no way restricted to any particular length of time of residence. However, for purposes of illustration, in some embodiments, the conditions under which an isomerization suppressing agent in accordance with the present teachings is added to a mixture comprising a definite metathesis product and the residual metathesis catalyst comprises a residence time of at least about 1 minute. In some embodiments, the conditions comprise a residence time of at least about 2 minutes. In some embodiments, the conditions comprise a residence time of at least about 3 minutes. In some embodiments, the conditions comprise a residence time of at least about 4 minutes. In some embodiments, the conditions comprise a residence time of at least about 5 minutes. In some embodiments, the conditions comprise a residence time of at least about 10 minutes. In some embodiments, the conditions comprise a residence time of at least about 15 minutes. In some

LMPI

TWSTHVro MEXICAN

OF INDUSTRIAL COMMUNITY

<img file="MX348233B_D0041.tif" />

In modalities, the conditions comprise a time of i ^ € teeGÍa-de-poxJQ ^ ._ minus approximately 20 minutes. In some embodiments, the conditions comprise a residence time of at least about 25 minutes. In some embodiments, the conditions comprise a residence time of at least about 30 minutes. In some embodiments, the conditions comprise a residence time of at least about 35 minutes. In some embodiments, the conditions comprise a residence time of at least about 40 minutes. In some embodiments, the conditions comprise a residence time of at least about 45 minutes. In some embodiments, the conditions comprise a residence time of at least about 50 minutes. In some embodiments, the conditions comprise a residence time of at least about 55 minutes. In some embodiments, the conditions comprise a residence time of at least about 60 minutes. In some modalities, the conditions include a residence time of one or more hours.

In some embodiments, the conditions under which an isomerization suppressing agent in accordance with the present teachings is added to a mixture comprising an olefin metathesis product and residual metathesis catalyst comprise mixing, heating, and / or a time of mixing. residence of at least approximately 2 minutes.

IMPI

4" . nwmUWMEeCANO

INDUSTRIAL AGE

As presently contemplated, the addition of cteOTTagenfe ^ e ^ isomerization suppression to a mixture comprising an olefin metathesis product and residual metathesis catalyst in accordance with the present teachings may be practiced when desirable to prevent isomerization of an olefin product. olefin metathesis particularly but not exclusively potentially labile olefin products, such as terminal olefins - during any subsequent handling and / or processing including but not limited to heating, distillation, photolytic exposure, oxidant exposure, and the like and combinations thereof.

In some embodiments, methods for suppressing isomerization of an olefin metathesis product in accordance with the present teachings can be used in combination with metathesis-based methods to refine natural oil feedstocks. Methods based on metathesisRepresentative for refining natural oil feedstock include but are not limited to those described in parent application serial no. 12 / 901,829 (published as US Patent Application Publication No. 2011/0113679 A1), which is incorporated by reference in its entirety above. The metathesis-based methods for refining natural oil feedstocks described in parent application serial No. 12 / 901,829 are also described below with reference to Figures 1 and 2.

<img file="MX348233B_D0042.tif" />

A number of valuable compositions can be directed through ₄₉ IMPI

INSTITUTO MEXICANO Γ&gt; Ε THE INDUSTRIAL PROPERTY of the auto-metathesis reaction of oil raw material- naturalr-o-Jaireaction of cross-metathesis of the raw material of natural oil with a low molecular weight olefin, in the presence of a catalyst of metathesis. Such valuable compositions may include fuel compositions, non-limiting examples of which include turbine fuel, kerosene, or diesel fuel. Additionally, the transesterified products can 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 their mixtures.

In some embodiments, prior to a metathesis reaction, a natural oil feedstock can be treated to process the most suitable natural oil for the subsequent metathesis reaction. In some embodiments, the natural oil is preferably a vegetable oil or derived from vegetable oil, such as soybean oil.

In some embodiments, natural oil treatment involves the removal of catalyst poisons, 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 poisons include those described in WO 2009/020665 A1, WO 2009/020667 A1 and Application Publication of

<img file="MX348233B_D0043.tif" />

Mexican iwrrrnjTo DE LA PenriEDAC INDUSTRIAL US patent Nos. 2011/0160472 A1, and Application TnrpaitJl lie de □ .U-ASerie No. 12 / 672,652. In some modalities, the raw material of the natural oil is thermally treated by heating the raw material to a temperature higher than 100 ° C in the absence of oxygen and maintains the temperature for a sufficient time to reduce poisons of the catalyst in the raw material. . In other embodiments, the temperature is between about 100 ° C and 300 ° C, between about 120 ° C and 250 ° C, between about 150 ° C and 210 ° C, or between about 190 and 200 ° C. In some embodiments, the absence of oxygen is achieved by induction of 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 psig).

In some embodiments, the natural oil feedstock is chemically treated under conditions sufficient to decrease catalyst poisons in the feedstock through a chemical reaction of the catalyst poisons. In some embodiments, the raw material is treated with a reducing agent or cationic inorganic base composition. Non-limiting examples of reducing agents include bisulfate, borohydride, phosphine, thiosulfate, individually or combinations thereof.

In some embodiments, the natural oil feedstock is treated with an adsorbent to remove poisons from the catalyst. In some embodiments, the raw material is treated with a combination of thermal and adsorbent methods. In some modalities, the raw material is treated

IMPI

DE LA FFOMEL AD ^ ιι® * Γ INDMSTRiAL ^ ** - with a combination of chemical methods and adsorbents: ™ ^ modalities, the treatment involves a partial hydrogenation treatment to modify the reactivity of the natural oil raw material with the catalyst of metathesis. Additional non-limiting examples of raw material treatment are also described below when discussing the various metathesis catalysts.

Additionally, in some embodiments, the low molecular weight olefin can also be treated prior to the metathesis reaction. Like natural oil treatment, low molecular weight olefin can be treated to remove poisons that can affect or decrease the activity of the catalyst.

As shown in figure 1, after this optional treatment of the natural oil feedstock and / or low molecular weight olefins, the natural oil 12 is reacted with itself, or combined with a low molecular weight olefin. 14 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 some embodiments, in the presence of a metathesis catalyst, natural oil 12 undergoes a self-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. In some embodiments, natural oil 12 undergoes both auto- and cross-metathesis reactions. in the₅₂ ΐΝϊτπντο muucanc Di LA niOHIDAD INDUSTRIAL parallel metathesis reactors. The self-metathesis v / or cross-metathesis reaction forms a metathesized product 22, wherein the metathesized product 22 comprises olefins 32 and esters 34.

In some embodiments, the low molecular weight olefin 14 is in the range of C₂ to C₆. As a non-limiting example, in some embodiments, the low molecular weight olefin 14 may comprise at least one of the following: ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene, 3- pentene, 2-methyl-1-butene, 2-methyl-2-butene, 3-methyl-1-butene, cyclopentene, 1-hexene, 2-hexene, 3-hexene, 4-hexene, 2-methyl-1-pentene, 3- methyl-1-pentene, 4-methyl-1-pentene, 2-methyl-2-pentene, 3-methyl-2-pentene, 4-methyl-2-pentene, 2-methyl-3-pentene and cyclohexene. In some embodiments, the low molecular weight olefin 14 comprises at least one of styrene and vinyl cyclohexane. In some embodiments, the low molecular weight olefin 14 may comprise at least one of ethylene, propylene, 1-butene, 2-butene, and isobutene. In some embodiments, the low molecular weight olefin 14 comprises at least one alpha-olefin or terminal olefin in the range of C₂ to Cw.

In some embodiments, the low molecular weight olefin 14 comprises at least one low molecular weight olefin branched in the range of C₄ to C_1st. Non-limiting examples of branched low molecular weight olefins include isobutene, 3-methyl-1-butene, 2-methyl-3-pentene, and 2,2-dimethyl-3-pentene. Using these branched low molecular weight olefins in the metathesis reaction, the metatesized product will include

<img file="MX348233B_D0044.tif" />

branched olefins, which can be subsequently hydrogenated¹ to isu “paraffins. In some embodiments, the branched low molecular weight olefins can help achieve the desired performance properties for a fuel composition, such as turbine fuel, kerosene, or diesel fuel.

As noted, it is possible to use a mixture of various linear or branched low molecular weight olefins in the reaction to achieve the desired metathesis product distribution. In some embodiments, 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 rather than a purified source. of a particular butene. Such inexpensive mixed butene raw materials are usually diluted with n-butane and / or isobutane.

In some embodiments, recycled streams from downstream separation units may be introduced to metathesis reactor 20 in addition to natural oil 12 and, in some embodiments, low molecular weight olefin 14. For example, in some embodiments, an olefin stream Recycled C2-C6 or a C3-C4 background stream from an overhead separation unit can be returned to the metathesis reactor. In some embodiments, as shown in Figure 1, a light weight olefin stream 44 from an olefin separation unit 40 can be returned to the metathesis reactor 20. In some embodiments, the stream of r λ TNCTTTVTO MÜUCANC

Say LA HOMEtMD 'C. VewJKl

INW »ST» To the funds of C₃-C₄ and the light weight olefin stream 44 are combined together and returned to the metathesis reactor 20. In some embodiments, a bottom stream Ci₅₊ 46 from olefin separation unit 40 is returned to metathesis reactor 20. In some embodiments, all of the above-mentioned recycle streams are returned to metathesis reactor 20.

The metathesis reaction in metathesis reactor 20 produces a metathesized product 22. In some embodiments, the metathesized product 22 enters an evaporation vessel operated under the conditions of temperature and pressure that target C2 or C2-C3 compounds to evaporate and remove the head. The light ends of C₂ or C2-C3 are composed of a majority of hydrocarbon compounds that have a carbon number of 2 or 3. In some embodiments, the light ends C2 or C2-C3 are sent to a higher separation unit, where the C compounds₂ or C₂-C₃ They are also separated in the head of the heavier compounds that evaporate with the C2-C3 compounds. These heavier compounds are typically C3-C5 compounds brought to the head with the C compounds₂ or C2-C3. After separation of the head separation unit, the current of C₂ or C2-C3 header can be used as a fuel source. These hydrocarbons have their own value outside the scope of a fuel composition, and can be used or separated at this stage for other valued compositions and applications. In some modalities, the flow of funds from the

<img file="MX348233B_D0045.tif" />

IMPI

MEXICAN INSTITUTE

Dt THE “INDUSTRIAL OR1EDAD Head Separation Unit containing principally TOTnpOtíSlUS (JS · C3-C5 is returned as a recycled stream to the metathesis reactor. In the evaporation vessel, the metathesized product 22 that does not evaporate from the head is sent downstream to separation in a separation unit 30, such as a distillation column.

Prior to separation unit 30, in some embodiments, metathesized product 22 may be introduced to an adsorbent bed to facilitate separation of metathesized product 22 from metathesis catalyst. In some embodiments, the adsorbent is a bed of clay. The clay bed adsorbs the metathesis catalyst and after a filtration step, the metatesized product 22 can be sent to the separation unit 30 for further processing. In some embodiments, the adsorbent is a water soluble phosphine reagent (eg, THMP). The catalyst can be separated with a water soluble phosphine through known liquid-liquid extraction mechanisms by decanting the aqueous phase from the organic phase. In other embodiments, the metatesized product 22 may be contacted with a reagent to deactivate or to extract the catalyst, with a representative reagent that is an isomerization suppressing agent in accordance with the present teachings.

In separation unit 30, in some embodiments, metathesis product 22 is separated into at least two product streams. In some embodiments, the metathesis product 22 is sent to separation unit 30, or distillation column, to separate the

<img file="MX348233B_D0046.tif" />

olefins 32 from asters 34. In some forms ~ 'LTné "CT) Trténte''de -" = ~' "'~ by-product composed of C₇s and cyclohexadiene can be removed in a side stream from separation unit 30. In some embodiments, the separated olefins 32 can be composed of hydrocarbons with carbon numbers up to 24. In some embodiments, the esters 34 can be composed of metathesis glycerides. In other words, the lighter-ended olefins 32 are preferably separated or overhead distilled for processing into olefin compositions, while the esters 34, composed primarily of carboxylic acid / ester functional compounds, are extracted in a stream. Of funds. Based on the quality of the separation, it is possible that some ester compounds are carried in the olefin stream of header 32, and it is also possible that some heavier hydrocarbons of the olefin are carried in the ester stream 34.

In some embodiments, the olefins 32 can be collected and sold for any number of 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 end glycerides and free fatty acids separated or distilled as a bottom product for further processing into various products. In some embodiments, post-processing may

IMPI

INSTITUTO MEXICANO DF LA MONEDAD INW5T1UA1 directing the production of the following non-limiting examples- e ^ terpc m ^ tíiLcoc of fatty acids; 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 their mixtures. In some embodiments, further processing can direct the production of fatty acids Ci₅-C₁₈and / or esters. In other embodiments, further processing can direct the production of diacids and / or diesters. In still other embodiments, post-processing can direct the production of compounds with molecular weights greater than the molecular weight of stearic acid and / or linolenic acid.

As shown in Figure 1, with respect to the olefins in the header 32 from the separation unit 30, the olefins 32 can be further separated or distilled in the olefin separation unit 40 to separate the various components of the stream. In some embodiments, the light-ended olefins 44 consist primarily of C compounds₂-C₉ may be distilled into a stream from the olefin separation unit 40. In some embodiments, the light-ended olefins 44 are composed of a majority of C hydrocarbon compounds.₃-C₈. In other embodiments, the heavier olefins with a higher carbon number may be separated at the head in the light-ended olefin stream 44 to aid in targeting a specific fuel composition. Light End Olefins

<img file="MX348233B_D0047.tif" />

IMPI iNrrmrro Mexican I heard the nomAD ΙΝΠΙ / STHAI.

they can be recycled to metathesis reactor 20, purged from the system for further processing and commercialization, or a combination of the two. In some embodiments, the light-end definitions 44 may be partially purged from the system and partially recycled to the metathesis reactor 20. With respect to the other streams in olefin separation unit 40, a heavier compound stream C₁₅₊, C₁₈+, C₂o +, C₂₂₊ or C₂₄+ can be separated as an olefin bottoms stream 46. This olefin bottoms stream 46 can be purged or recycled to metathesis reactor 20 for further processing, or a combination of the two. In some embodiments, a center cut olefin stream 42 may be separated from the olefin distillation unit for further processing. The center cutter definitions 42 may be designed to address a range of carbon numbers selected for a specific fuel composition. As a non-limiting example, a distribution of C₅-C₁₅ it can be directed for further processing into a naphtha-type combustion turbine fuel. Alternatively, a distribution of C₈-Ci₆ it can be directed for further processing into a kerosene-type combustion turbine fuel. In some embodiments, a distribution of C₈-C25 can be directed for further processing into a diesel fuel.

In some embodiments, olefins 32 can be oligomerized to form poly-alpha-olefins (PAO) or poly-internal olefins (PIO), mineral oil substitutes and / or biodiesel fuel. Reaction of

<img file="MX348233B_D0048.tif" />

IMPI

INSTITUTO MHUCANS pt la monioAo

INDUSTRIAL Oligomerization can take place after the dujlilauiúi r 3ϋ "σ unit after the head 40 define separation unit. In some embodiments, the by-products of the oligomerization reactions can be recycled to the metathesis reactor 20 for later prosecution.

As mentioned, in some embodiments, the olefins 32 from the separation unit 30 can be sent directly to the hydrogenation unit 50. In some embodiments, the cut olefins at the center 42 of the header olefin separation unit 40 can be sent to hydrogenation unit 50. Hydrogenation can be carried out according to any method known in the art of hydrogenation of double bond compounds such as olefins 32 or center cut olefins 42. In some embodiments, in hydrogenation unit 50, hydrogen gas 48 reacted with the olefins 32 or center cut olefins 42 in the presence of a hydrogenation catalyst to produce a hydrogenated product 52.

In some embodiments, olefins are hydrogenated in the presence of a hydrogenation catalyst comprised of nickel, copper, palladium, platinum, molybdenum, iron, ruthenium, osmium, rhodium, or iridium, individually or in combinations thereof. The useful catalyst can be homogeneous or heterogeneous. In some embodiments, the catalysts are nickel or sponge nickel type supported catalysts.

In some embodiments, the hydrogenation catalyst consists of

IMPI

INSTTrUTO MM1CAMO Df LA ΜΙΟΙΊΟΑΓ INDUSTRIAL Nickel that has been chemically reduced with hydrogen to an active state (i.e. reduced nickel) provided on a support. The support can encompass porous silica (eg, kieselguhr, infusoria, diatoms, or siliceous earth) or alumina. Catalysts are characterized by a high nickel surface area per gram of nickel.

Commercial examples of supported nickel hydrogenation catalysts include those available under the trade names NYSOFACT, NYSOSEL and NI 5248 D (from BASF Catalysts LLC, Iselin, NJ). Additional supported nickel hydrogenation catalysts include those commercially available under the trade names PRICAT 9910, PRICAT 9920, PRICAT 9908, PRICAT 9936 (ex Johnson Matthey Catalysts, Ward Hill, MA).

Nickel supported catalysts can be of the type described in US Patent No. 3,351,566, US Patent No. 6,846,772, EP 0166091 and EP 0167201. Hydrogenation can be carried out in a batch or continuous process and can be partial hydrogenation or complete hydrogenation. In some embodiments, the temperature ranges from about 50 ° C to about 350 ° C, about 100 ° C to about 300 ° C, about 150 ° C to about 250 ° C, or about 100 ° C to about 150 ° C. . The desired temperature can vary, for example, with hydrogen gas pressure. Generally, a higher gas pressure will require a lower temperature. Hydrogen gas is pumped into the container of the

<img file="MX348233B_D0049.tif" />

IMPIO * INSTITUTO MEXICANO b 1 DE LA ΤΚΟΠΕΟΑΓ reaction to reach a desired pressure of gas H₂. In some embodiments, the gas pressure H₂ ranges from about 15 psig (1 atm) to about 3000 psig (204.1 atm), about 15 psig (1 atm) to about 90 psig (6.1 atm), or about 100 psig (6.8 atm) to about 500 psig (34 atm). As gas pressure increases, more specialized high pressure processing equipment may be required. In some embodiments, the reaction conditions are medium, where the temperature is approximately between approximately 50 ° C and approximately 100 ° C and the pressure of the gas H₂ it is less than approximately 100 psig (6.8 atm). In other modes, the temperature ranges from about 100 ° C to about 150 ° C and the pressure is between about 100 psig (6.8 atm) and about 500 psig (34 atm). When the desired degree of hydrogenation is reached, the reaction mass is cooled to the desired filtration temperature.

The amount of hydrogenation catalyst is typically selected taking into account a number of 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 rate desired degree of hydrogenation, the desired degree of hydrogenation (for example, as measured by the iodine (IV) value), the purity of the reagent, and the pressure of the H gas₂. 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="MX348233B_D0050.tif" />

During hydrogenation, the compounds containing the carbon-carbon double bond in olefins are partially to fully saturated by hydrogen gas 48. In some embodiments, the resulting hydrogenated product 52 includes hydrocarbons with a distribution centered between about C hydrocarbons.₁₀ and C₁₂ for gasoline and kerosene type combustion turbine fuel compositions. In some modalities, the distribution is centered between approximately C₁₆ and C₁₈ for a diesel fuel composition.

In some 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 frame plate and filter such as those commercially available from Sparkler Filters, Inc., Conroe TX. In some embodiments, filtration is done with the help of pressure or vacuum. In order to improve filtering performance, a filter aid can be used. A filter aid can be added directly to the product or it 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 filter techniques and filter aids can also be employed to remove the used hydrogenation catalyst. In other modalities the

<img file="MX348233B_D0051.tif" />

IMPI

IRSTITUTE MtXiCANC

FROM THE INTEGRATED POWDER hydrogenation catalyst is extracted by solid centrifugation by decanting the product.

In some 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 properties of the desired fuel such as evaporation point, freezing, 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 No. 3,150,205; 4,210,771; 5,095,169; and 6,214,764. In some embodiments, the isomerization reaction at this stage can also break down some of the C compounds₁₅₊remaining, which can further help to make a fuel composition having compounds within the desired carbon number range, such as 5 to 16 for a combustion turbine fuel composition.

In some embodiments, the isomerization can occur simultaneously with the hydrogenation step in the hydrogenation unit 50, thereby directing 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.

<img file="MX348233B_D0052.tif" />

in scope based on the selection of low molecular weight olefin (s) 14 which is (are) used in the metathesis reaction.

In some embodiments, the hydrogenated product 52 comprises about 15-25% by weight of C7, about &lt;5% by weight of Cs, about 20-40% by weight of C₉, about 20-40% by weight of C₁₀, about &lt;5% by weight Cu, about 1525% by weight C₁₂, about &lt;5% by weight of C₁₃, about &lt;5% by weight of Ci₄, about &lt;5% by 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 some 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 some 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 a final boiling point of approximately 220-240 ° C (as measured by ASTM D86).

Hydrogenated product 52 produced from hydrogenation unit 50 can be used as a fuel composition, non-limiting examples of which include turbine fuel, kerosene, or diesel. In some modalities, the product

<img file="MX348233B_D0053.tif" />

The hydrogenated IMPI rwrmvro méxicano OF LA MOVIEDA O ÍNW'STTIIAL 52 may contain by-products of -4a-h-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, C hydrocarbons.₂-C₉ or Ci hydrocarbons₅₊, thereby producing a targeted fuel composition. In some embodiments, the hydrogenated product 52 can be divided into the desired fuel product C₉-Ci₅ 64 and a fraction C2-C₉ 62 light ends and / or a C15 + 66 heavy ended fraction. Distillation can be used to separate the fractions. Alternatively, in other embodiments, such as for a naphtha or kerosene type combustion turbine 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 the solid, heavy end fraction 66 was removed by techniques known in the art such as filtration, decantation or centrifugation.

With respect to the esters 34 from the distillation unit 30, in some embodiments, the esters 34 can be fully removed as a stream of ester product 36 and further processed or sold for their own value, as shown in Figure 1. As an example without limitation, esters 34 can encompass various triglycerides that could be used as a lubricant. Based on the quality of separation between

<img file="MX348233B_D0054.tif" />

IMPI olefins and esters, asters 34 can comprise some olefin heavy υυιιιμϋηοΙιίυΓΤΓΗΐΓ carried with the triglycerides. In other embodiments, the esters 34 can be further processed in a biorefinery or other chemical or fuel processing unit known in the art, thus producing various products such as biodiesel or specialty chemicals that have a higher value than that of triglycerides, for example. Alternatively, in some embodiments, the esters 34 may be partially removed from the system and sold, with the remainder further processed in the biorefinery or other chemical or fuel processing unit known in the art.

In some embodiments, the ester stream 34 is sent to a transesterification unit 70. Within the transesterification unit 70, the esters 34 reacted with at least 38 alcohol in the presence of a transesterification catalyst. In some embodiments, the alcohol comprises methanol and / or ethanol. In some embodiments, the transesterification reaction is carried out at about 60-70 ° C and about 1 atm. In some embodiments, the transesterification catalyst is a homogeneous sodium methoxide catalyst. Varying amounts of catalyst can be used in the reaction, and, in some embodiments, the transesterification catalyst is present in the amount of about 0.5-1.0% by weight of the esters 34.

The transesterification reaction can produce products

IMPI

MEXICAN INSTITUTE

DE LA MOHEDA D

INDUSTRIAL

<img file="MX348233B_D0055.tif" />

transesterifications 72 including saturated and / or unsaturated fatty acid methyl esters (FAME), glycerin, methanol, and / or free fatty acids. In some embodiments, the transesterified products 72, or a fraction thereof, can encompass a biodiesel source. In some embodiments, the transesterified products 72 comprise 9DA esters, 9UDA esters, and / or 9DDA esters. Non-limiting examples of the 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 radical of a metatesized glyceride is extracted from the glycerol backbone to form a 9DA ester.

In some embodiments, a glycerin alcohol can be used in reaction with a stream of glyceride. This reaction can produce monoglycerides and / or diglycerides.

In some embodiments, the transesterified products 72 from the transesterification unit 70 may be sent to a liquid-liquid separation unit, where the transesterified products 72 (i.e., FAME, free fatty acids, and / or alcohols) are separated from the glycerin. Furthermore, in some embodiments, the glycerin by-product stream can be 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.

In some embodiments, the transesterified products 72 are _S8 IMPI ^^ 'MSTTTVTO MBX1CANO

OF THE PWPtBDAD 15 ^

ÍNtH / STRLAL further processed in a water washing unit. In this unit, the transesterified products are subjected to a liquid-liquid extraction when washed with water. Excess alcohol, glycerin, and water are removed from the transesterified products 72. In some embodiments, the water wash step is followed by a drying unit in which excess water is removed in addition to the desired mixture of esters (i.e., 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.

In some embodiments, specialty chemicals (eg, 9DA) can be further processed in an oligomerization reaction to form a lactone, which can serve as a precursor to a surfactant.

In some embodiments, the transesterified products 72 from the transesterification unit 70 or specialty chemicals from the water washing unit or drying unit are sent to an ester distillation column 80 for subsequent separation of various individuals 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 some embodiments, the 9DA ester 82 can be individually distilled or separated from the remaining mixture 84 of transesterified products or specialty chemicals. In certain

IMPI

ΙΗΤΤΤΤυΤΌ MIX1CANC

Dt LA FROHEDAT

INDUSTRIAL

<img file="MX348233B_D0056.tif" />

process conditions, the ester 9DA 82 should be the lightest component in the transesterified product or specialty chemical stream and exits the top of the ester distillation column 80. In some embodiments, the remaining mixture 84, or components Heavier, transesterified products or specialty chemicals may be separated at the lower end of the column. In some embodiments, this stream of funds 84 can potentially be sold as biodiesel.

The 9DA esters, 9UDA esters and / or 9DDA esters can be processed after the distillation step in the ester distillation column. In some embodiments, under known operating conditions, the 9DA ester, 9UDA ester and / or 9DDA ester may then undergo a hydrolysis reaction with water to form 9DA, 9UDA and / or 9DDA, alkali metal salts and alkaline earth metal salts of the above, individually or in combinations of these.

In some embodiments, the fatty acid methyl esters of the transesterified products 72 can react with each other to form other specialty chemicals such as dimers.

Figure 2 depicts some modalities for processing natural oil into fuel compositions and specialty chemicals. As described above, the natural oil and / or low molecular weight olefin feedstock in Figure 2 may undergo a pretreatment step prior to the metathesis reaction. In figure 2, the

<img file="MX348233B_D0057.tif" />

IMPI TNSTmiTO MEXICAN DE LA RXOREBAC INDUSTRIA!

Natural oil feedstock 112 reacts with itself ^ or combined with a low molecular weight olefin 114 in a metathesis reactor 120 in the presence of a metathesis catalyst. In some embodiments, in the presence of a metathesis catalyst, natural oil 112 undergoes a self-metathesis reaction with itself. In other embodiments, in the presence of the metathesis catalyst, natural oil 112 undergoes a cross-metathesis reaction with low molecular weight olefin 114. In some embodiments, natural oil 112 undergoes both auto-metathesis and cross-metathesis reactions. in parallel metathesis reactors. The self-metathesis and / or cross-metathesis reaction forms a metathesis product 122 wherein the metathesis product 122 consists of olefins 132 and esters 134.

In some embodiments, the low molecular weight olefin 114 is in the range of C₂ to C₆. As a non-limiting example, in some embodiments, the low molecular weight olefin 114 can be composed of at least one of the following: ethylene, propylene, butene-1,2-butene, isobutene, 1-pentene, 2-pentene, 3 -pentene, 2-methyl-1-butene, 2-methyl-2-butene, 3-methyl-1-butene, cyclopentene, 1-hexene, 2-hexene, 3-hexene, 4-hexene, 2-methyl-1-pentene, 3 -methyl-1-pentene, 4-methyl-l-pentene, 2-methyl-2-pentene, 3-methyl-2-pentene, 4-methyl-2-pentene, 2-methyl-3-pentene, and cyclohexene. In some embodiments, the low molecular weight olefin 114 consists of at least one of styrene and vinyl cyclohexane. In some embodiments, the low molecular weight olefin 114 may be composed of al

<img file="MX348233B_D0058.tif" />

IMPI ¡NTTTTUTO MEJUCAN · DI LA nomDA · INDUSTRIAL minus one of ethylene, propylene, 1-butene, 2-butene and isebutone. In some embodiments, the low molecular weight olefin 114 comprises at least one alpha-olefin or terminal olefin in the C range.₂ to C ™.

In some embodiments, the low molecular weight olefin 114 comprises at least one low molecular weight olefin branched in the range of C₄ to C₁₀. Unlimited examples of branched low molecular weight olefins include isobutene, 3-methyl-1-butene, 2-methyl-3-pentene, and 2,2-dimethyl-3-pentene. In some embodiments, low molecular weight branched olefins can help achieve desired performance properties for the fuel composition, such as turbine fuel, kerosene, or diesel.

As noted, it is possible to use a mixture of several linear or branched low molecular weight olefins in the reaction to achieve the desired metathesis product distribution. In some embodiments, a mixture of butenes (1-butene, 2-butene, and isobutene) can be employed as the low molecular weight olefin 114.

In some embodiments, recycle streams from downstream separation units may be introduced to metathesis reactor 120 in addition to natural oil 112 and, in some embodiments, low molecular weight olefin 114 to improve the performance of the target fuel composition and / or transesterification target products.

After the metathesis unit 120 and before the hydrogenation unit 125, in some embodiments, the metathesis product 122

<img file="MX348233B_D0059.tif" />

may be introduced to an adsorbent bed to facilitate -ta¹ septnátlúl l Utíl 'product of metathesis 122 of the metathesis catalyst. In some embodiments, the adsorbent is a clay. The clay will adsorb the metathesis catalyst, and after a filtration step, the metathesis product 122 can be sent to the hydrogenation unit 125 for further processing. In some embodiments, the adsorbent is a water soluble phosphine reagent (eg, THMP). The catalyst can be separated from the reaction mixture with a water soluble phosphine through known liquid-liquid extraction mechanisms by decanting the aqueous phase from the organic phase. In other embodiments, the addition of a reagent to deactivate or remove the catalyst could be used, with a representative reagent being an isomerization suppressing agent in accordance with current teachings.

As shown in Figure 2, the metathesis product 122 is sent to a hydrogenation unit 125, where the carbon-carbon double bonds in the olefins and esters are partially to fully saturated with hydrogen gas 124. As described above, hydrogenation can be carried out according to any method known in the art for hydrogenating compounds containing the double bond such as olefins and esters present in metathesis product 122. In some embodiments, in hydrogenation unit 125, hydrogen gas 124 reacted with metathesis product 122 in the presence of a hydrogenation catalyst to produce a product

7₃ Hydrogenated IMPI tNSTmrFO MU1CANC DEUntOHITY tNDITTRIAI 126 comprising partially fully paraffins / olefins and partially fully hydrogenated esters.

Typical hydrogenation catalysts have already been described with reference to embodiments in Figure 1. Reaction conditions have also been described. In some embodiments, the temperature ranges from about 50 ° C to about 350 ° C, about 100 ° C to about 300 ° C, about 150 ° C to about 250 ° C, or about 50 ° C to about 150 ° C. . The desired temperature can vary, for example, with hydrogen gas pressure. In general, higher gas pressure could allow the use of a lower reaction temperature. Hydrogen gas is pumped into the reaction vessel to achieve a desired gas pressure H₂. In some embodiments, the gas pressure H₂ ranges from about 15 psig (1 atm) to about 3000 psig (204.1 atm), or about 15 psig (1 atm) to about 500 psig (34 atm). In some embodiments, the reaction conditions are medium, where the temperature is approximately between approximately 50 ° C and approximately 150 ° C and the pressure of the gas H₂ it is less than about 400 psig (28 atm). When the desired degree of hydrogenation is reached, the reaction mass is cooled to the desired temperature of filtration.

<img file="MX348233B_D0060.tif" />

During hydrogenation, the carbon-carbon double bonds are partially to fully saturated by the hydrogen gas 124. In some embodiments, the olefins in the metathesis product 122. imrnvTOMUiiCAi *

FROM LAHOHBDAI JJeTSFW 'ΙΗΝΚΤ ·! '.

they reacted with hydrogen to form a fuel composition comprising only or primarily paraffins. In addition, the esters of the metathesis product are fully or nearly fully saturated in hydrogenation unit 125. In some embodiments, the resulting hydrogenated product 126 includes only partially saturated paraffins / olefins and partially saturated esters.

In Figure 2, the hydrogenated product 126 is sent to a separation unit 130 to separate the product into at least two product streams. In some embodiments, the hydrogenated product 126 is sent to separation unit 130 or distillation column, to separate the partially to fully saturated paraffins / olefins, or fuel composition 132, from the partially to fully saturated esters 134. In some embodiments, a by-product stream formed by C₇s and cyclohexadiene may be removed in a side stream from separation unit 130. In some embodiments, fuel composition 132 may be composed of hydrocarbons with carbon numbers up to 24. In some embodiments, fuel composition 132 consists essentially of hydrocarbons. saturated.

In some embodiments, esters 134 can comprise partially to fully hydrogenated metathesis glycerides. In other words, the final lighter paraffins / olefins 132 are preferably separated or the higher products are distilled for processing into the fuel compositions, while the esters 134, compounds

IMPI

-, _r INSTITUTO MWICANO / 5 DtureoHeoA ·

INDUSTRIAL mainly of compounds with carboxylic acid / ester functionality, extracted as a cash flow. Based on the quality of the separation, it is possible that some ester compounds are carried into the upper paraffin / olefin stream 132, and it is also possible that some heavier paraffin / olefin hydrocarbons are carried into the ester stream 134.

In some embodiments, it may be preferable to isomerize the composition of fuel 132 to improve the quality of the product stream and target desired fuel properties such as evaporation point, freezing point, energy density, cetane number or distillation temperature of end point, among other parameters. Isomerization reactions are well known in the art, as described in US Patent No. 3,150,205; 4,210,771; 5,095,169; and 6,214,764. In some embodiments, as shown in Figure 2, the fuel composition 132 is sent to an isomerization reaction unit 150 where an isomerized fuel composition 152 is produced. Under typical reaction conditions, the isomerization reaction at this stage can also break down some of the compounds present in stream 132, which can further help to make an improved fuel composition with compounds within the desired carbon number range. such as 5 to 16 for a combustion turbine fuel composition.

In some embodiments, the fuel composition 132 or isomerized fuel composition 152 comprises about

<img file="MX348233B_D0061.tif" />

<img file="MX348233B_D0062.tif" />

IMPI

BISTrrUTO MIXlCAf *

I HEARD THE ΡΚΟΡΚΟΑΠ IMM'ITUIAl

15-25% by weight of C₇, about &lt;5% by weight of C8I ~ about 20-40% by weight of C9, about 20-40% by weight of C10, about &lt;5% by weight of Cu, about 15-25% by weight of C- i2, about &lt;5% by weight of C₁₃, about &lt;5% by weight of C14, about &lt;5% by weight of C15, about &lt;1% by weight of Ci₆, approximately &lt;1% in C₁₇, and about &lt;1% by weight of Ci₈+. In some embodiments, the fuel composition 132 or the isomerized fuel composition 152 comprises a heat of combustion of at least about 40, 41, 42, 43, or 44 MJ / kg (per ASTM 03338). In some embodiments, the fuel composition 132 or isomerized fuel composition 152 contains less than about 1 mg of sulfur per kg of fuel composition (measured by ASTM 05453). In other embodiments, the fuel composition 132 or isomerized fuel composition 152 comprises a density of about 0.70-0.75 (as measured by ASTM 04052). In other embodiments, the fuel composition 132 or isomerized fuel composition 152 has a final boiling point of about 220-240 ° C (measured by ASTM 086).

The fuel composition 132 or the isomerized fuel composition 152 may be used as a combustion turbine fuel, diesel or kerosene, depending on the characteristics of the fuels. In some embodiments, the fuel composition may contain by-products of hydrogenation,

<img file="MX348233B_D0063.tif" />

IMPI! RSTm »TO MEXICANO nc LA PROPTWAD industrial isomerization and / or metathesis reactions. The fuel composition 132 or isomerized fuel composition 152 can be further processed in a fuel composition separation unit 160 as shown in Figure 2. The separation unit 160 can be operated to remove any remaining by-products from the mixture. , such as hydrogen gas, water, C hydrocarbons₂-C₉ or Ci5 + hydrocarbons, thus producing a desired fuel product 164. In some embodiments, the mixture can be separated into the desired fuel product C₉-C₁₅ 164 and a fraction of light ends C₂-C₉ (or C₃-C₈) 162 and / or a C-i8 + 166 heavy-end fraction. Distillation can be used to separate the fractions. On the other hand, in other embodiments, such as for a naphtha or kerosene type combustion turbine fuel composition, the heavy end fraction 166 can be separated from the desired fuel product 164 by cooling the paraffins / olefins to about 40 ° C. , -47 ° C or -65 ° C and then removing the solid, heavy end fraction 166 by techniques known in the art such as filtration, decantation, or centrifugation.

With respect to the partially to fully saturated esters 134 from separation unit 130, in some embodiments, the esters 134 can be fully removed as a partially to fully hydrogenated ester product stream 136 and further processed or sold for their own value, as shown in Figure 2. As a non-limiting example, esters 134 comprise various triglycerides partially a

<img file="MX348233B_D0064.tif" />

INSTTTtrro ΜΒΙΟΛΝΟ DE. INDUSTRIAL MOHRITY

<img file="MX348233B_D0065.tif" />

fully saturated that could be used as a lubricant ..... Based on the quality of separation between the paraffins / olefins (fuel composition 132) and the asters, the asters 134 can be composed of some heavier components of paraffins and olefins carried with triglycerides. In other embodiments, the asters 134 can be 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 are of higher value than that of triglycerides, for example. Alternatively, the asters 134 can be partially removed from the system and sold, with the remainder further processed in the biorefinery or other chemical or fuel processing unit known in the art.

In some embodiments, the stream of ester 134 is sent to a transesterification unit 170. Within transesterification unit 170, the asters 134 react with at least one alcohol 138 in the presence of a transesterification catalyst. In some embodiments, the alcohol comprises methanol and / or ethanol. In some embodiments, the transesterification reaction is carried out at about 60-70 ° C and 1 atm. In some embodiments, the transesterification catalyst is a homogeneous sodium methoxide catalyst. Different amounts of catalyst can be used in the reaction, and, in some embodiments, the transesterification catalyst is present in the amount of about 0.5-1.0% by weight of the esters 134.

₇₉ IMPI ^ 'and INSTITUTO MEXICANO KfTOíJW'&gt; E LA EROTIEDaD VVwuSJsL INDtISTRIAl -

The transesterification reaction can produce transesterified products 172 including saturated and / or unsaturated fatty acid methyl esters (FAME), glycerin, methanol, and / or free fatty acids. In some embodiments, the transesterified products 172, or a fraction thereof, may comprise a source for the biodiesel. In some embodiments, the transesterified products 172 comprise esters of decenoic acid, esters of decanoic acid, esters of undecenoic acid, esters of undecanoic acid, esters of dodecenoic acid, and / or esters of dodecaonic acid. In some embodiments, in a transesterification reaction, a decanoic acid radical of a metathesis glyceride is removed from the glycerol backbone to form a decanoic acid ester. In some embodiments, a decenoic acid radical of a metathesis glyceride is extracted from the glycerol backbone to form a decenoic acid ester.

In some embodiments, a glycerin alcohol can be used in reaction with a stream of triglycerides 134. This reaction can produce monoglycerides and / or diglycerides.

In some embodiments, the transesterified products 172 from the transesterification unit 170 can be sent to a liquid-liquid separation unit, where the transesterified products 172 (i.e., FAME, free fatty acids and / or alcohols) are separated from glycerin. Additionally, in some embodiments, the glycerin by-product stream may be processed in a secondary separation unit, in

<img file="MX348233B_D0066.tif" />

where the glycerin and any remaining alcohol are removed to the transesterification unit 170 for further processing.

In some embodiments, the transesterified products 172 are further processed in a water wash unit. In this unit, the transesterified products undergo a liquid-liquid extraction when washed with water. The excess alcohol, glycerin and water are extracted from the transesterified products 172. In some embodiments, the water wash step is followed by a drying unit in which excess water is removed in addition to the desired mixture of esters (ie, specialty chemicals). Such hydrogenated specialty chemicals include non-limiting examples such as decenoic acid, decanoic acid, undecenoic acid, undecanoic acid, dodecenoic acid, dodecanoic acid, and mixtures thereof.

As shown in Figure 2, the transesterified products 172 from the transesterification unit 170 or specialty chemicals from the water washing unit or drying unit can be sent to an ester distillation column 180 for subsequent separation of various individual or groups of compounds. This separation may include, but is not limited to, the separation of decenoic acid esters, decanoic acid esters, undecenoic acid esters, undecanoic acid esters, dodecenoic acid esters and / or dodecanoic acid esters. In some embodiments, a decanoic acid ester or decenoic acid ester 182 can be distilled or individually separated from the remaining mixture 184 of

<img file="MX348233B_D0067.tif" />

transesterified products or de- ^ speetalidach chemicals — Under certain process conditions, the decanoic acid ester or decenoic acid ester 182 should be the lightest component in the transesterified product or specialty chemical stream and comes out the top from the ester distillation column 180. In some embodiments, the remaining mixture 184, or heavier components, of the transesterified products or specialty chemicals may be separated at the lower end of the column. In some modalities, this stream of funds 184 can potentially be sold as biodiesel.

Decanoic acid esters, decanoic acid esters, undecenoic acid esters, undecanoic acid esters, dodecenoic acid esters and / or dodecanoic acid esters can be processed after the distillation step in the ester distillation column. In some embodiments, under known operating conditions, the decenoic acid ester, decanoic acid ester, undecenoic acid ester, undecanoic acid ester, dodecenoic acid ester and / or dodecanoic acid ester can then undergo a hydrolysis reaction with water to form decenoic acid, decanoic acid, undecanoic acid, undecenoic acid, dodecenoic acid and / or dodecanoic acid.

As noted, natural oil auto-metathesis or cross-metathesis between natural oil and low molecular weight olefins occurs in the presence of a metathesis catalyst. The catalyst phrase

<img file="MX348233B_D0068.tif" />

INSTITUTO MEXICANO DE LA INDUSTUIAl

<img file="MX348233B_D0069.tif" />

Metathesis includes any catalyst or system that catalyzes a metathesis reaction. Use any known or future developed metathesis catalyst, individually or in combination with one or more additional catalysts. Exemplary non-limiting metathesis catalysts and process conditions are described in WO 2009/020667 A1 (eg pages 18-47). A number of the indicated metathesis catalysts are manufactured by Materia, Inc. (Pasadena, CA).

The metathesis procedure can be performed 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 minimize unwanted by-products. The metathesis procedure can be performed 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 gas diluent is typically an inert gas, meaning that the gas does not interact with the metathesis catalyst to substantially prevent catalysis. For example, particular inert gases are selected from the group consisting of helium, neon, argon, nitrogen, individually or in combinations thereof.

In some embodiments, the metathesis catalyst is dissolved in a solvent prior to performing the metathesis reaction. In some 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, etc .; halogenated aromatic hydrocarbons, such as chlorobenzene and dichlorobenzene; aliphatic solvents, including pentane, hexane, heptane, cyclohexane, etc .; and chlorinated alkanes, such as dichloromethane, chloroform, dichloroethane, etc. In some embodiments, the solvent comprises toluene.

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

The metathesis reaction can be run under any desired pressure. Generally, it is 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 range of the pressure will normally decrease as the boiling point of the cross-metathesis reagent

<img file="MX348233B_D0070.tif" />

increases. Total pressure can be set to be greater than ... about 0.1 atm (10 kPa), in some modes more than about 0.3 atm (30 kPa), or more than about 1 atm (100 kPa). Typically, the reaction pressure is no greater than about 70 atm (7000 kPa), in some embodiments no greater 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).

By way of non-limiting example, referring to Figure 1, methods for inhibiting isomerization of an olefin metathesis product in accordance with current teachings can be implemented prior to introduction of metathesis product 22 to separation unit 30 (e.g. example, a distillation column) and / or in one or more additional steps in the process. By way of further non-limiting example, referring to Figure 2, methods for inhibiting the isomerization of an olefin metathesis product in accordance with current teachings can be implemented prior to introduction of metathesis product 122 to separation unit 130 and / or the hydrogenation unit 125 and / or in one or more additional steps in the process. Furthermore, in some embodiments, when the isomerization suppressing agent has sufficient thermal stability (for example, a phosphite ester having a sufficiently high molecular weight), the isomerization suppressing agent can be left in the mixture comprising the olefin metathesis product and carried for a

<img file="MX348233B_D0071.tif" />

additional processing (for example to the separation units shown, respectively, in Figures 1 and 2 of United States Patent Application Publication No. 2011/0113679 A1 and / or to one or more additional units in these systems or systems analogs).

In some embodiments, as shown in Figure 3, methods for suppressing the isomerization of an olefin metathesis product in accordance with current teachings may further optionally comprise a polar solvent wash - in other words, extracting the mixture to which it is applied. has added an isomerization suppressing agent with a polar solvent. However, as described above, in some embodiments it may not be possible, necessary and / or desirable to remove an isomerization suppressing agent in accordance with the present teachings via extraction with a polar solvent prior to further processing, which in some modalities include but are not limited to processing that involves heating.

In some embodiments, the metathesis mixture (e.g., a clean mixture comprising, in some embodiments, natural oil, residual metathesis catalyst, olefin metathesis product, and optionally low molecular weight olefins) is substantially immiscible with the polar solvent, which form two layers. For convenience, these immiscible layers are described herein as aqueous and organic, although in some embodiments, the so-called aqueous layer may comprise a polar solvent other than or in addition to water. In some

<img file="MX348233B_D0072.tif" />

IMPI instituto mqucanc Dt THE PROPERTY ΙΝΓ umiAL modalities, extraction by polar solvent (eg. Java.do.coii_agjjXL—. can serve to remove at least a portion of the isomerization suppressing agent, particularly but not exclusively when the isomerization suppressing agent is at least partially hydrolyzable (e.g., in some embodiments, a phos ester having a low molecular weight , including but not limited to trimethyl phosphite, triethyl phosphite, and a combination thereof) - which in some embodiments, it can result in the conversion of an isomerization suppressing agent in accordance with the present teachings (eg, an ester of an oxo phosphorous acid) to a corresponding acid.

In some embodiments, when extraction with a polar solvent is desired, the extraction comprises high shear mixing although such 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 shear). The current teachings are in no way restricted to a particular type or duration of the mix. However, for purposes of illustration, in some embodiments, the extraction comprises mixing the polar solvent and mixing together for at least about 1 minute. In some embodiments, the mixture and polar solvent are mixed together for at least 2 minutes, in some embodiments for at least 5 minutes, in some embodiments for at least 10 minutes, in some embodiments for at least about 15 minutes.

<img file="MX348233B_D0073.tif" />

minutes, in some modalities at least approximately? Q m¡niÍtnc_r - .

some modes for at least about 25 minutes, some modes for at least about 30 minutes, some modes for at least about 35 minutes, some modes for at least about 40 minutes, some modes for at least about 45 minutes, in some modalities at least approximately 50 minutes, in some modalities for at least approximately 55 minutes and in some modalities for at least approximately 60 minutes.

When extraction with a polar solvent is desired, current 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 greater than the weight of the mixture. In some embodiments, the amount by weight of polar solvent (eg, water) added to the extraction mixture is less than the weight of the mixture. In some embodiments, the proportion by weight of the mixture a is added to the mixture is at least

<td>approximately</td><td> 1:1,</td><td>in</td><td>some</td><td>modalities</td><td>by</td><td>the</td><td>less</td>

<td>approximately</td><td> 2:1,</td><td>in</td><td>some</td><td>modalities</td><td>by</td><td>the</td><td>less</td>

<td>approximately</td><td> 3:1,</td><td>in</td><td>some</td><td>modalities</td><td>by</td><td>the</td><td>less</td>

<td>approximately</td><td> 4:1,</td><td>in</td><td>some</td><td>modalities</td><td>by</td><td>the</td><td>less</td>

<td>approximately</td><td> 5:1,</td><td>in</td><td>some</td><td>modalities</td><td>by</td><td>the</td><td>less</td>

IMPI

MEXICAN INSTITUTE

I&gt; C INDUSTRIAL RATIO

<td>approximately</td><td> 6:1,</td><td>in</td><td>some</td><td colspan="3">modaIidade &amp;. .by .. Jo. ^ menoo</td>

<td>approximately</td><td> 7:1,</td><td>in</td><td>some</td><td>modalities</td><td>by</td><td>least</td>

<td>approximately</td><td> 8:1,</td><td>in</td><td>some</td><td>modalities</td><td>by</td><td>least</td>

<td colspan="7">approximately 9: 1 and in some modalities for less approximately</td>

10:1.

In some embodiments, when extraction with a polar solvent is desired, methods for inhibiting isomerization of an olefin metathesis product in accordance with current teachings further comprise allowing a sedimentation period after polar solvent washing to promote separation of the olefin. phase. Current teachings are in no way limited to any particular length of the settling period. However, for illustration purposes, in some embodiments, the settling period is at least about 1 minute. In some embodiments, the settling period is at least about 2 minutes. In some embodiments, the settling period is at least about 5 minutes. In some embodiments, the settling period is at least about 10 minutes. In some embodiments, the settling period is at least about 15 minutes.

In some embodiments, when extraction with a polar solvent is desired, methods for suppressing isomerization of an olefin metathesis product in accordance with current teachings may further optionally comprise separating an organic phase from an aqueous phase,

IMFI

OQ INSmVTOMIXJCANO

WJSTUAL DELAWOPTEDAD as shown in Figure 3. In some embodiments, although not exclusively when the isomerization suppressing agent is at least partially hydrolyzable, most of the isomerization suppressing agent is distributed in the aqueous phase. In some embodiments, the majority of olefin metathesis products are distributed in the organic phase. In some embodiments, most of the isomerization suppressing agent is distributed in the aqueous phase and most of the olefin metathesis product is distributed in the organic phase.

In some embodiments, when extraction with a polar solvent is desired, such that an organic phase is separated from an aqueous phase, and when the residual metathesis catalyst in the mixture comprises ruthenium, a majority of the ruthenium is carried in an organic phase and a minority of ruthenium is distributed in an aqueous phase. In some embodiments, at least about 51% of the ruthenium is extracted in an organic phase. In some embodiments, at least about 60% of the ruthenium is extracted in an organic phase. In some embodiments, at least about 65% of the ruthenium is extracted in an organic phase. In some embodiments, at least about 70% of the ruthenium is extracted in an organic phase. In some embodiments, at least about 75% of the ruthenium is extracted in an organic phase. In some embodiments, at least about 80% of the ruthenium is extracted in an organic phase. In some embodiments, at least about 85% of the ruthenium is extracted in an organic phase. In some embodiments, at least about 90% of the ruthenium is extracted in a

<img file="MX348233B_D0074.tif" />

<img file="MX348233B_D0075.tif" />

organic phase. ,

In some embodiments, it is observed that removing excess isomerization suppressing agent from a cross-metathesis oil by washing it with water may be accompanied by a loss in overall isomerization suppression efficiency. While it is not wished to be bound by any particular theory or intended to limit in any way the scope of the appended claims or their equivalents, it is presently believed that the reduction in suppression of isomerization sometimes observed after a water wash it is simply a management artifact. On the other hand, it is currently thought that the effect can be mitigated and / or eliminated by using slightly different experimental conditions including but not limited to the use of higher concentrations of isomerization suppressing agent, handling of the material obtained from the treatment of suppression under an inert atmosphere (eg nitrogen) and / or the like.

In some modes, as shown in Figure 3, A method in accordance with current teachings for suppressing isomerization of an olefin metathesis product produced in a metathesis reaction comprises (a) adding an isomerization suppressing agent to a mixture that includes the olefin metathesis product and residual metathesis catalyst from the metathesis reaction under conditions sufficient to passivate at least a portion of the residual metathesis catalyst; (b) processing the mixture to provide a fraction comprising the olefin metathesis product and / or a derivative thereof, wherein the

<img file="MX348233B_D0076.tif" />

IMPI

MIlUCANO INSTITUTE

OF THE FROP11TY

INDUSTRIAL isomerization suppressing agent is not eliminated from the "^ ntes clül *" processing. The isomerization suppressing agent comprises (i) a salt and / or ester of an oxo phosphorous acid, and / or (ii) a derivative of oxo phosphorous acid in which at least one PH bond has been replaced by a PC bond, and / or (iii) a salt and / or an ester of the derivative. In some embodiments, the ester of an oxo phosphorous acid is substantially insoluble in water. In some embodiments, the residual metathesis catalyst comprises ruthenium. In some embodiments, the fraction comprising the olefin metathesis product and / or a derivative thereof is composed primarily thereof (for example, the olefin metathesis product and / or derivative thereof represent at least about 51% in fraction weight, in some embodiments at least about 65% by weight, in some embodiments at least about 70% by weight, in some embodiments at least about 75% by weight, in some embodiments at least about 80% by weight, in some embodiments at least about 85% by weight, in some embodiments at least about 90% by weight, and in some embodiments at least about 95% by weight.

In some embodiments, processing the mixture comprises heating. In some embodiments, processing the mixture comprises heating to a temperature of at least about 100 ° C, in some embodiments at least about 125 ° C, in some embodiments at least

IMPI rmrnvro mmjcano DE LA PROREDAD INDUSTRIAL

<td>approximately</td><td>150 ° C,</td><td>in some</td><td>modalities</td><td>to the</td><td>less</td>

<td colspan="6">approximately 175 ° C, in some modes at least about 200 ° C, in some modes at least approximately 225 ° C, and in some modes at least about 250 ° C. In some embodiments, the processing involves distillation. In some modalities, the processing comprises transesterification. In some modalities, the processing</td>

comprises distillation and transesterification.

In some embodiments - particularly, though not exclusively those involving metathesis-based methods for refining natural oil feedstocks - methods for suppressing isomerization of an olefin metathesis product in accordance with current teachings further comprise separating the metathesis product. of olefins in a metathesis triacylglyceride fraction (m-TAG) and an olefin fraction, as shown in Figure 3. A majority of the triacylglyceride fraction is composed of molecules that comprise one or more carbon-carbon double bonds and optionally one or more additional functional groups, while a majority of the olefinic fraction is comprised of molecules that comprise one or more bonds. unsaturated carbon carbon and no additional functional groups.

In some embodiments, particularly though not exclusively those involving metathesis-based methods for refining natural oil raw materials, methods for suppressing the

<img file="MX348233B_D0077.tif" />

Mexican IMPÍ iNrrmrro gave the INDUSTRIAL rbotiscad isomerization of a nlefin metathesis product rnnfnrme to the current teachings also include the transesterification of the triacylglyceride fraction to produce one or a plurality of transesterification products, as shown in figure 3. In some In embodiments, the transesterification products comprise fatty acid methyl esters (FAME). In some embodiments, particularly though not exclusively those involving metathesis-based methods for refining natural oil feedstocks, methods for suppressing isomerization of an olefin metathesis product in accordance with current teachings further comprise separating the transesterification products from one phase. containing glycerol, as shown in Figure 3.

In some embodiments, particularly though not exclusively those involving metathesis-based methods for refining natural oil raw materials, methods for suppressing isomerization of an olefin metathesis product in accordance with current teachings further comprise separating the metathesis product from olefins in a triacylglyceride fraction and an olefinic fraction, transesterification of the triacylglyceride fraction to produce one or a plurality of transesterification products (eg, FAME) and separate the transesterification products from a glycerol-containing phase, as shown in Figure 3. In some embodiments, the residual catalyst of metathesis in the mixture comprises ruthenium. In some

MEXICAN INSTITUTE

OF THE INDUSTRIAL MOMÍBAD modalities, a majority of the ruthenium is distributed among what-contains glycerol and the transesterification products.

In some embodiments, a method of refining a natural oil in accordance with current teachings comprises: (a) providing a raw material comprised of a natural oil; (b) reacting the raw material in the presence of a metathesis catalyst to form a metathesis product comprising a definition and an ester; (c) passivating the metathesis catalyst with an agent selected from the group consisting of (i) a salt and / or an ester of an oxo phosphorous acid, (ii) a derivative of oxo phosphorous acid in which at least one PH bond has been replaced by a PC bond, (iü) a salt and / or ester of the derivative, and (iv) combinations thereof; (d) separating the olefin in the metathesis product from the ester in the metathesis product; and (e) transesterifying the ester in the presence of an alcohol to form a transesterified product and / or hydrogenation of the olefin to form a partially or fully saturated hydrogenated product.

As noted above, the use of THMP as an isomerization suppressant, particularly on an industrial scale, is problematic due to its commercial availability and prices, the fact that a carcinogenic by-product, formaldehyde, typically accompanies its preparation, and the potential that exists. to generate gas H₂ explosive if conditions become too basic. In addition to these drawbacks, the present inventors have found that when THMP (as opposed to an isomerization suppressing agent in accordance with the present

<img file="MX348233B_D0078.tif" />

IMPI

INSTITUTO MU1GANO DE LA P &amp; OFIWaD fNDUSTtUL teachings) is used for the suppression of isomergae + en-ele- olefins, particularly when the amount of residual metathesis catalyst is low (for example, in some modalities less than about 1000 ppm, in some modalities less than about 500 ppm, in some modes less than about 250 ppm, and in some modes less than about 100 ppm), Recovery of transition metals from the residual metathesis catalyst can be complicated by the distribution of transition metals (eg, ruthenium) among multiple phases without appreciable concentration or convergence of the transition metals in any phase. For example, when THMP is used as an isomerization suppressing agent in a metathesis-based method for the refinement of a natural oil feedstock, as described above, ruthenium is found to be widely distributed among a wash stream. of water on the one hand and a phase containing glycerol and the transesterification products on the other hand. In some studies, about 50% of the total ruthenium was carried in a water wash stream with the remaining Ru distributed between a glycerol-containing phase and the transesterification products. While it is not wished 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 noted that the difficulty in concentrating most of the transition metals in one particular current when THMP is used as the ₉6 IMPI

INSTITUTO MEXICANO DE LA PltfUEDAP inWstriae isomerization occurs mainly when the amount of rutenigLgL5er ,,. recovered is small (eg, about 1% by weight or less). In contrast, when a large amount of ruthenium is involved (eg, about 1% by weight or more) and THMP is used as an isomerization suppressing agent, a majority of the ruthenium can be successfully concentrated in an aqueous phase and removed.

In some embodiments, for purposes of simplifying the metal recovery procedure, it would be desirable if the metal to be reclaimed (for example, in some embodiments, ruthenium) was concentrated primarily in one phase and, in some embodiments, if that phase was located downstream in the general procedure. Thus, for embodiments in which the isomerization suppressing agent has sufficient thermal stability (for example, a phosphite ester having a sufficiently high molecular weight), such that it can be left in the mixture comprising the metathesis product of olefins and carry with further processing at high temperatures (e.g. 250 ° C), A method in accordance with the present teachings provides an additional advantage over the use of THMP in that direct aqueous scrubbing is not required in the process, and the catalyst metal can be more easily concentrated in and recovered from various common background fractions. down in the procedure.

<img file="MX348233B_D0079.tif" />

Furthermore, thermally stable isomerization suppressing agents according to the present teachings have θζ IMPI ^

MEXICAN INSTTTVTO

OF INDUMIAL NOHUMD reduced its tendency to break down into lower molecular weight phosphorus-containing compounds (eg, phosphine, etc.) that can potentially contaminate metathesis products. Furthermore, considering that it is often desirable to wash a suppressor such as THMP out of a metathesis mixture prior to subjecting the mixture to distillation and / or other high temperature processing to avoid introducing the suppressor into hot areas of the process where it may occur decomposition and / or resulting product and / or recycled stream contamination, The thermally and hydrolytically stable isomerization suppressing agents described herein can be carried out without water washing, which greatly simplifies metathesis-based methods for refining natural oil feedstocks, by eliminating the need for (i) a water wash ( mixed), (ii) separation (decantation) and (ii) recovery (evaporator).

The following representative examples and procedures illustrate features in accordance with current teachings and are provided by way of illustration only. They are not intended to limit the scope of the appended claims or their equivalents.

EXAMPLES

EXAMPLE 1

An 18.9 I Parr reactor vessel with steel jacket

ÍM P í

INSTITUTO M &amp; XICANL!

DE LA PROMIAD CV¿3K INDUSTRIAL stainless, dry, clean equipped with a superior stirrer induction tube and internal heating / cooling coils, temperature probe, sampling valve and upper gas release valve was purged with argon at 15 psig ( 1 atm). Soybean oil (SBO, 2.5kg, 2.9 mol, Costco, MWn = 864.4 g / mol, 85 wt% unsaturation as determined by GC, 1 hour with bubbled argon in 18.9 I container) was added in the Parr reactor. 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 psig (0.7 atm). The dip tube valve in the reactor was connected to a cylinder with 1-butene (Airgas, CP grade, pressure suppression 33 psig (2.3 atm),&gt; 99% by weight) and was repressurized to 15 psig (1 atm) of 1-butene. The reactor was vented again at 10 psig (0.7 atm) to remove residual argon in space. The SBO was stirred at 350 rpm and 9-15 ° C under 18-28 psig (1.2-1.9 atm) of 1-butene until 3 mol of 1-butene per olefin bond SBO was transferred into the reactor (approximately 2.2 kg of 1-butene for about 4-5 hours). A toluene solution of [1,3-Bis- (2,4,6-trimethylphenyl) -2imidazolidinylidenejdichlororuthenium (3-methyl-2-butenylidene) (tricyclohexylphosphine) (C827, Matter) was prepared 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 SBO olefin bond) and was added to the reactor via the reactor dip tube pressurizing the space within the Fischer-Porter vessel to 50-60 psig (3.5-4.2 atm) with argon.

<img file="MX348233B_D0080.tif" />

The Fischer-Porter container and dip tube were rinsed with. 30 g of additional 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 space 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, 880 CG pure flow) and a magnetic stir bar. The reaction mixture was treated 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 cooled to 40 ° C and filtered through a sintered glass filter. An aliquot of the product mixture was found by gas chromatography analysis (after transesterification with 1% w / w NaOMe in methanol at 60 ° C) contained approximately 22% by weight of methyl 9-decenoate, approximately 16 % by weight of methyl 9-dodecenoate, about 3% by weight of methyl 9-octadecenoate and weight of about 3% by weight of methyl 9-octadecenoate (by gas chromatography). These results compare favorably with the calculated equilibrium yields of 23.4% by weight of methyl 9-decenoate, 17.9% by weight of methyl 9-dodecenoate, 3.7% by weight of dimethyl 9octadecenoate and 1.8% by weight of 9 -methyl octadecenoate.

<img file="MX348233B_D0081.tif" />

γμρι

INSTITUTO MEXICANO MIAFSOHEDAD INDUSTRIAL

100

EXAMPLE 2

By the general procedures described in Example 1, a reaction was carried out with 1.73 kg of SBO and 3 mol of 1-butene / SBO double bond. An aliquot of the product mixture was found by gas chromatography analysis after transesterification with 1% w / w NaOMe in methanol at 60 ° C contained approximately 24% by weight of methyl 9decenoate, 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 gas chromatography).

EXAMPLE 3

By the general procedures described in Example 1, a reaction was carried out with 1.75 kg of SBO and 3 mol of 1-butene / SBO double bond. An aliquot of the product mixture was found by gas chromatography analysis after transesterification with 1% w / w NaOMe in methanol at 60 ° C contained approximately 24% by weight of methyl 9decenoate, approximately 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 determined by gas chromatography).

<img file="MX348233B_D0082.tif" />

101

<img file="MX348233B_D0083.tif" />

ΜΤΓΠνΤΟ MOUCANO nt the INDUSTRIAL norCDAD

EXAMPLE 4

By the general procedures described in Example 1, a reaction was carried out with 2.2 kg of SBO and 3 mol of 1-butene / double bond SBO, and 60 g of toluene used to transfer the catalyst was replaced with SBO. An aliquot of the product mixture was found by gas chromatographic analysis after transesterification with 1% w / w NaOMe in methanol at 60 ° C contained approximately 25% by weight of methyl 9decenoate, 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 gas chromatography).

EXAMPLE 5

A 12 liter, 3-neck glass round bottom flask that was equipped with a magnetic stir bar, heating mantle, and temperature regulator 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 a receiving flask was connected to the condenser. The hydrocarbon olefins were removed from the reaction product by vacuum distillation in the range of monitoring conditions: 22-130 ° C temperature

<img file="MX348233B_D0084.tif" />

102

IMPI

INSTITUTO MÍXICANC ·

OF THE INDUSTRIAL MIOHIOAD OF THE CONTAINER, 19-70 ° C Destfiaetérry'qres'tóft-ete2000-160 head temperature ptorr. The weight of the material remaining after the volatile hydrocarbons were removed was 5.34 kg. An aliquot of the non-volatile product mixture was found by gas chromatography analysis after transesterification with 1% w / w NaOMe in methanol at 60 ° C contained 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 gas chromatography).

EXAMPLE 6

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% w / w NaOMe 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 about an hour, the mixture turned a homogeneous orange color (pH = 11 detected). After a total reaction time of 2 hours, the mixture was cooled to room temperature and two layers were observed. The organic phase was washed twice with 3 I of 50% (v / v) aqueous MeOH, separated and neutralized by washing with glacial HOAc in MeOH (1 mol HOAc / mol NaOMe) at a detected pH 6.5,

103

<img file="MX348233B_D0085.tif" />

IMPI

INSTTrVK) MEXICAN rw INDUSTRIAL RONITY producing 5.03 kg.

EXAMPLE 7

A 12 I, 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 heating mantle. The column attached to the flask was a 5 cm x 91 cm glass column containing 0.40 cm Pro-Pak ™ stainless steel supports. The distillation column was attached to a fractional distillation head to which a 1 I preweighed round bottom flask was fitted for collection of distillation fractions. Distillation was carried out under vacuum at 100-120 ptorr. A reflux ratio of 1: 3 was used to isolate methyl 9-decenoate (9-DAME) and methyl 9-dodecenoate (9-DDAME). A reflux ratio of 1: 3 referred to 1 drop collected for every 3 drops sent back to the distillation column. Samples collected during distillation, vacuum distillation conditions, and content of fractions 9-DAME and 9-DDAME as determined by ge, are shown in Table 1. Combination fractions 2-7 produced 1.46 kg. of methyl 9-decenoate with a purity of 99.7%. After collecting fraction 16, 2.50 kg of material remained in the distillation vessel: it was found by gas chromatography to contain approximately 14% by weight of 9-DDAME,

<img file="MX348233B_D0086.tif" />

104

IMPI twrnvro mokano DI LA NoriBDAD fND'.lTSIAL about 42% by weight of methyl palmitate, and ^ joxinaadai »epite · 12% by weight of methyl stearate.

TABLE 1

<td># of distillation fractions</td><td>Temp. head (° C)</td><td>Temp. container (° C)</td><td>Empty (gtorr)</td><td>Weight (g)</td><td>9-DAME (% by weight)</td><td>9-DDAME (% by weight)</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> 2</td><td> 45-46</td><td> 106</td><td> 110</td><td> 32.4</td><td> 99</td><td> 0</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> 4</td><td> 49-50</td><td> 110-112</td><td> 120</td><td> 283</td><td> 99</td><td> 0</td>

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

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

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

<td> 8</td><td> 51</td><td> 114</td><td> 110</td><td> 76</td><td> 97</td><td> 1</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> 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> 12</td><td> 76</td><td> 135-136</td><td> 110</td><td> 38</td><td> 0</td><td> 79</td>

<td> 13</td><td> 76</td><td> 136-138</td><td> 110</td><td> 52.4</td><td> 0</td><td> 90</td>

<td> 14</td><td> 76</td><td> 138-139</td><td> 110</td><td> 25.5</td><td> 0</td><td> 85</td>

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

<td> 16</td><td> 78</td><td> 140</td><td> 110</td><td> 426</td><td> 0</td><td> 100</td>

EXAMPLE 8

A reaction was carried out by the general procedures described in Example 1 with the following modifications: 22 kg of SBO, 7 mol of propene / mol of double bond SBO and 200 mg [1,3-Bis- (2,4,6tr ¡Methylphenyl) -2-¡midazolid¡n¡ldene] dichlororutene (benzylidene) (tricyclohexyphosphine) [catalyst C848, Materia Inc., Pasadena, California, USA, 90 ppm (w / w) vs. SBO] at a reaction temperature of 40 ° C were used. The passage of the

105 ^UI0 ixyrnVTOMüUCMjo n_F THE WOMAN

INDUSTRY! ** · ----'— catalyst removal using bleaching clay-tamó + en-fue ^ ·· ^ replaced by the following: after venting excess propene, the reaction mixture was transferred to a flask of 3-neck round bottom to which tris (hydroxymethyl) phosphine (THMP, 1.0 M in isopropanol, 50 mol THMP / mol C848) was added. The resulting cloudy yellow mixture was stirred for 20 hours at 60 ° C, transferred to a 6 I separatory funnel and extracted with 2 x 2.5 I deionized HaO. The organic layer was separated and dried over Na₂SW₄ anhydrous for 4 hours, then filtered through a sintered glass filter containing a bed of silica gel.

EXAMPLE 9

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

<img file="MX348233B_D0087.tif" />

106

IMPI

INM HITO MMU CANO

SAY THE ntOHWAD

INDUSTRIAL

The hydrocarbon olefins were removed from the combined reaction product described above by vacuum distillation by the general procedure described in Example 5. The weight of material remaining after the volatile olefins were removed was 4.0 kg. . An aliquot of the non-volatile product mixture was found by gas chromatography analysis after transesterification with 1% w / w NaOMe in methanol at 60 ° C contained 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 gas chromatography).

EXAMPLE 10

Two reactions were carried out by the general procedures described in Example 8, except that 3.1 kg of SBO and 280 mg of C848 catalyst were used for each reaction. After removal of the catalyst, the reaction products of the two preparations were combined, yielding 5.28 kg of material. An aliquot of the combined product mixture was found by gas chromatography analysis after transesterification with 1% w / w NaOMe in methanol at 60 ° C contained approximately 40% by weight of methyl 9-decenoate, approximately 13% by weight of methyl 9-undecenoate,

<img file="MX348233B_D0088.tif" />

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INSTITUTO MUlCANO Dt LA IROHLDAD INDUSTRIAL about 2% by weight of 9-octadecenedioate d ^ HymefiT ^ and about 1% by weight of methyl 9-octadecenoate (as determined by gas chromatography).

The hydrocarbon olefins were removed from the 5.28 kilograms of 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 4.0 kg. An aliquot of the non-volatile product mixture was found by gas chromatography analysis after transesterification with 1% w / w NaOMe in methanol at 60 ° C contained approximately 49% by weight of methyl 9decenoate, approximately 16% in weight of methyl 9-undecenoate, about 2% by weight of dimethyl 9-octadecenedioate, and about 3% by weight of methyl 9-octadecenoate (as determined by gas chromatography).

EXAMPLE 11

The general procedures described in example 10, two metathesis reactions were carried out with SBO, 7 mol cis-2-butene / mol double bond SBO and 220 mg of C848 catalyst / kg SBO. After removing the catalyst, the reaction products of the two preparations were combined, yielding 12.2 kg of material. An aliquot of the combined product mixture was found by gas chromatographic analysis

<img file="MX348233B_D0089.tif" />

108

ΙΜΡΪ ινϊτγπ / γο mimcano DS LA nüFÍEDAÜ industrial following transesterification with 1% w / w NaOMe- ^ wwetemt-rríf ^^ contained approximately 49% by weight of methyl 9-undecenoate, approximately 2% by weight of 9-octadecenedioate of dimethyl and about 1% by weight of methyl 9-octadecenoate (as determined by gas chromatography).

The hydrocarbon olefins were removed from the 12.2 kilograms of 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. An aliquot of the non-volatile product mixture was found by gas chromatography analysis after transesterification with 1% w / w NaOMe in methanol at 60 ° C contained approximately 57% by weight of methyl 9undecenoate, approximately 4% in weight of dimethyl 9-octadecenoate, and about 2% by weight of methyl 9-octadecenoate (as determined by gas chromatography).

EXAMPLE 12

By the general procedures described in Example 1, approximately 7 kg of cross-metathesis product was produced by reacting SBO with 3 mol of 1-butene / mol of double bond SBO using 43 mg of C827 catalyst / kg of SBO, then removal of the catalyst with THMP. An initial 2.09 kg portion of the metathesis product was

<img file="MX348233B_D0090.tif" />

109

IMPI Mexican institute DE LA FROFIEDAD ÍNDUSTMAt hydrogenated at 136 ° C and 400 psig (28 atm) of H₂ until -Gocé filled it * with hydrogen in a 3.78 I batch autoclave using 105 g of Johnson-Matthey A-7000 Sponge Metal ™ catalyst. The resulting mixture was filtered hot (22-55 ° C), producing 1.40 kg of filtrate and 350 g of a mixture composed of the catalyst and the hydrogenated product. The entire mixture containing the catalyst was returned to the 3.78 I reactor along with a second 2.18 kg portion of the metathesis product and a second hydrogenation reaction was similarly carried out until hydrogen uptake ceased. 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 mixture of product 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, yield 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. Aliquots of the hydrogenated product were found by gas chromatographic analysis to contain approximately 30% by weight of C6-C n-paraffins.₁₈ and weight about 70% by weight triglycerides. The relative distribution of the n-paraffins 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 Cw, 0.6 (0.1)% by weight of Cu, 22.2 (23.6)% in

<img file="MX348233B_D0091.tif" />

110

IMPI

MEXICAN INSTITUTE OF CURRENCY tndustkuu.

C weight₁₂, 3.4 (3.7)% by weight of C13, 0.1 (0.0)% by weight of T'IjO (6.3)% "'by weight of C₁₅, 0.4 (0.4)% by weight of Ο-ιθ, 0.1 (0.0)% by weight of Ci₇ and 1.0 (1.6)% by weight of C- |₈.

The paraffin components were removed by renewed film evaporation of a 4.84 kg aliquot of the hydrogenated paraffin / triglyceride product. An initial renewed film evaporation was carried out at 75 ° C, 100 torr, 300 rpm and condensing temperature of 15 ° C using a feed rate of 300 g / h and produced a condensate which was subjected to a second film evaporation renewed 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 C14, 1.2% by weight of C15, 0.1% by weight of Ci₆, 0.0% by weight of C₁₇ 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 05453), 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 masterbatch in a fuel application such as diesel or combustion turbine fuel.

<img file="MX348233B_D0092.tif" />

111

EXAMPLE 13

An oligomerization reaction of 1-olefin / 1,4-diene (92% by weight of 1-decene, 4.5% by weight of 1,4-decadiene, 2% by weight of 1,4-undecadiene) that was produced from 1-octene palm oil cross-metathesis was performed on a 550 g scale with 1.1% in mol of ethyl aluminum dichloride (1M solution in hexane) /1.1% in mol of tere-butyl chloride for 3 hours at 10 ° C. The reaction mixture was quenched with water and 1M sodium hydroxide solution and stirred until colorless. 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 through short path vacuum distillation (100 ° C and 5 Torr) and the distribution of the products was determined and 97% mixed oligomers were obtained 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.

The above-mentioned examples use the following analytical methods, which are described below:

The volatile products were analyzed by gas chromatography and flame ionization detector (FID). Alkene analyzes were performed with an Agilent 6890 instrument and the following conditions: column = Restek Rtx-5, 30 mx 0.25 mm (ID) x 0.25 film thickness

<img file="MX348233B_D0093.tif" />

p.m; injector temperature: 250 ° C; detector temperature: ~ 28U ° ü; oven temperature = 35 ° C start temperature, 4 minute wait time, rise rate from 12 ° C / min to 260 ° C, 8 minute wait time; carrier gas = helium; average gas velocity = 31.3 ± 3.5% cm / sec (calculated); and the division ratio = -50: 1.

Products were characterized by peak comparison to known standards, along with supporting data from mass spectrum analysis (GCMS-Agilent 5973N). GCMS analysis was performed with a second GC column with Rtx-5 film thickness, 30 mx 0.25 mm (ID) x 0.25 pm, using the same method as the previous one.

Alkane analyzes were performed using an Agilent 6850 instrument and the following conditions: column = Restek Rtx-65, film thickness 30 mx 0.32 mm (ID) x 0.1 pm; injector temperature: 250 ° C detector temperature = 350 ° C; oven temperature = 55 ° C start temperature, 5-minute waiting time, 20 ° C / min rise rate up to 350 ° C, 10-minute waiting time; carrier gas = hydrogen; flow rate = 1.0 ml / min; and the division ratio = 40: 1.

Products were characterized by peaks for comparison with known standards. Fatty Acid Methyl Ester (FAME) analyzes were performed using an Agilent 6850 instrument and the following conditions: column = J &amp; W Scientific, DB wax, film thickness 30 mx 0.32 mm (ID) x 0.5pm, temperature injector = 250 ° C; detector temperature = 300 ° C; oven temperature = 70 ° C temperature

113

<img file="MX348233B_D0094.tif" />

initial, 1 minute waiting time, rate of increase ~ 48O ^ rate of increase of 3 ° C / min to 220 ° C, 10 minutes of waiting time; carrier gas = hydrogen; and flow rate = 1.0 ml / min.

The above examples collectively demonstrate the main steps outlined in the process outlines, showing the production of olefins, paraffins, triglycerides from metathesis, esters of unsaturated fatty acids and acids, and diacid compounds of natural oils that are useful as chemicals, solvents and fuel blending stocks.

Materials and methods for isomerization suppression experiments

Unless otherwise noted, all chemicals were used as received and without drying. The palm oil was obtained from Wilmar International Limited. Kirkland soybean oil was purchased from commercial sources. 1-Octene was purchased from Sigma Aldrich. Ruthenium catalyst C827 was obtained from Materia, Inc. Trilauryl phosphite (DOVERPHOS® 53), trisnonyl phenyl phosphite (DOVERPHOS® 4), dioleyl hydrogen phosphite (DOVERPHOS® 253), and triisodecyl phosphite (DOVERPHOS® 6) were supplied by Dover Chemical Corporation. TNPP How much with other phosphites) is also supplied by Galata Chemicals. Diethyl phosphite was purchased from Aldrich (98% purity). DEQUEST 0239 and DEQUEST 0520 were obtained from Thermphos International BV.

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Mexican Institute of Industrial Property

Unless otherwise specified, all of its results of isomerization were derived from a small-scale isomerization unit (SSI) as described below. By way of example, taking the amount of terminal-to-terminal migration as a non-limiting representative and example, the degree of isomerization can be calculated by first obtaining the quotient of (i) the amount of internal isomers as represented, for example, by the areas under the gas chromatography (GC) peaks corresponding to these internal isomers to (ii) the total amount of all terminal and internal isomers, as plotted, for example, by the areas below the GC peaks corresponding to these isomers and then multiplying this ratio by 100. Analogous calculations can be performed to determine the amount of internal to terminal migration and / or the amount of internal to internal migrations.

EXAMPLE 14

Small-scale isomerization studies (SSI)

The metathesis samples were heated at 250 ° C for one hour under nitrogen after the suppression treatment. Duplicate runs were carried out on the sample to be examined as well as a control sample that had not been treated. The degree of isomerization was determined by taking the total isomers of methyl 9-decenoate divided by the total amount of methyl decenoate multiplied by 100.

<img file="MX348233B_D0095.tif" />

<img file="MX348233B_D0096.tif" />

115

IMPI MEXICAN TRTTTVTO OF THE INDUCTIVE MOMEDAN!

The small-scale isomerization unit of cylindrical aluminum having several holes (for example, six to eight) drilled in it. The aluminum block is placed on a hot plate and heated to the required temperature. Small amounts (typically several grams) of the metathesis product are placed in glass tubes, which are then fitted with plastic heads providing an opening for a slight positive pressure of nitrogen to be present above the mixture. After purging the samples for 30 minutes under nitrogen, the mixtures are heated to 250 ° C (with or without agitation) for one hour by placing the glass tubes in the opening of the aluminum block. The resulting triacylglycerides (TAG) are then transesterified with methanol and the base and the resulting FAME are analyzed by gas chromatography. In some embodiments, methyl 9-decenoate is measured relative to the amount of its internal isomers (if any).

EXAMPLE 15

Preparation of a cross-metathesized olefin product

The octenilized palm oil was prepared as follows. In a molar ratio 3: 1-octene (33.33 g) was added to palm oil (50 g), which has a peroxide value below 2.0 (which can normally be obtained by heating the oil to about 200 ° C under a N2 bubble to thermally decompose peroxides). How to use

116 IMPI ^ iwrnrnw mhjcano bE THE INDUSTRIAL PRECEDITY Here, the molar ratio of cross agent (eg 1-octene) to oil refers to the molar ratio of double bond content. In the oil, the double bond content is calculated from the relative ratio of the major fatty acids present (each with its own olefin content), all of which can easily be determined by gas chromatography after transesterification. Thus, in this example, a 3: 1 molar ratio refers to having a 3: 1 ratio of cross-agent double bonds to total oil double bonds. The resulting material is then heated with stirring to 60 ° C with N spray.₂ for 30-45 minutes. Once the oxygen was removed, the nitrogen line was lifted into the headspace. Catalyst C827 (2.75 mg, approximately 55 ppm loading) was then added. The reaction was run for two hours with periodic oil sampling to determine the degree of conversion of the reaction.

EXAMPLE 16

Phosphite ester as an isomerization suppressing agent

To 25 grams of cross metathesized palm oil (3: 1 octenilized in a 55 ppm load of C827), a molar excess 20 times greater than DOVERPHOS® 53 was added (molar in relation to the amount of C827 present). This 20-fold molar excess refers to the amount of suppressing agent added compared directly to the amount (moles) of

<img file="MX348233B_D0097.tif" />

117

IMPI uwrnuiO μ canc&gt;

FROM THE ΡΚΟΡΤφΑΟ WOVSTPfA to the present catalyst. The addition did not result in any observable separation, which suggests that the added phosphite is oil soluble. The mixture was then heated at 90 ° C for one hour with stirring. The level of isomerization in the absence of any suppressing agent was measured at 5.0% and 5.8% (duplicate runs) using a small scale isomerization unit (SSI) run at 250 ° C for one hour. A portion of the deleted sample was treated with water (approximately 4: 1 oil: water) and then separated. The unwashed and water washed sample was tested for suppression.

Samples that were taken after a suppression reaction for one hour exhibited isomerization levels of 0.1% and 0.2% (duplicate runs) after running in the SSL unit. Samples washed with water exhibited similarly low levels of suppression (0.3% and 0.2%).

EXAMPLE 17

Phosphite ester as an isomerization suppressing agent

A large scale reaction analogous to that described in Example 16 above was performed using DOVERPHOS® 53 in a 20-fold molar excess over the catalyst. A cross-metathesized palm oil (175 grams, octenilized 3: 1 at 55 ppm C827 loading) was added to a 500 ml, three-necked, round-bottomed flask equipped with an inlet / outlet

<img file="MX348233B_D0098.tif" />

118

IMPI ιιπττυτο msxicanc OF THE INDUSTRIAL EKOFIEOAP of nitrogen and a distillation head. The sample got-and-shaken ^ - ^^^^

90 ° C under nitrogen. At temperature, DOVERPHOS® 53 (107.5 microliters) was added to the mixture. The mixture was then heated for one hour at temperature. Heating was then increased to a point where the internal oil temperature is 250 ° C. A sample was taken at this zero time and the flask was then heated under these conditions (with the distillation of light olefins) for two hours. Additional samples were taken at 80 and 120 minutes. Samples were fully transesterified and then run for GC isomerization level. Analysis showed that all samples (0, 80 and 120 minutes) had isomerization levels less than 0.4% by weight. Typical isomerization levels of non-suppressor material under similar conditions were 30 +%.

EXAMPLE 18

Phosphite ester as an isomerization suppressing agent

Decreasing the total amount of phosphite (e.g. from a 20-fold molar excess to a 10-fold molar excess) was found to result in good isomerization suppression but at somewhat higher levels recorded in the previous examples (e.g., typically up to 1%). A cross-metathesized palm oil (25 grams, octenilized 3: 1) was heated to 90 ° C under nitrogen. At approximately 80 ° C, a 1: 1 mixture by weight of DOVERPHOS® 4 in toluene (20

119

MEXICAN INSTITUTE

OF THE noRITY _TO industrial - - microliters). Toluene was added to cut the total viscosity of the phosphite that was used. After 15 minutes, a sample was taken for the SSL test. A second sample was taken after one hour. Both samples showed significant isomerization suppression. The results are summarized in Table 2 below.

This example demonstrates the concept that the pre-dissolution of the isomerization suppressing agent can be accomplished (eg, by dissolving a phosphite ester in a solvent) and, in some embodiments, may be desirable (eg, cutting the overall viscosity , better solubilize the phosphite ester, etc.).

In this experiment it was also observed that a reduction in reaction time from 60 minutes of treatment at 90 ° C to only 15 minutes provided similar isomerization suppression results. Thus, while it is not desired to be bound by any particular theory or intended to limit in any way the scope of the appended claims or their equivalents, it is presently believed that increased solubility in organic systems of an isomerization suppressing agent in accordance with the present teachings they can result in shorter residence times and / or lower reaction temperatures without substantially affecting the efficiency of isomerization suppression.

<img file="MX348233B_D0099.tif" />

IMPI

MEXICAN INSTITUTE

DI LA P1ton * AD INDUSTRIAL

120

EXAMPLE 19

Low molecular weight phosphite ester as isomerization suppressing agent

A cross-metaesthesized palm oil (15.1 grams, octenilized 1: 1) is bubbled with N₂ for 45 minutes. At this time, trimethyl phosphite (60 microliters) was added to the reaction mixture. The mixture was heated with stirring for one hour at 90 ° C. The level of isomerization of this material after reaction in the SSI unit (one hour at 250 ° C) is 0.4%. The unsuppressed control was found to undergo 25.9% isomerization when run on SSI, as shown in Table 2.

EXAMPLE 20

Phosphonate as an isomerization suppressing agent

To 20 grams of a cross metathesized palm oil (octenilized 3: 1) was added DEQUEST ® 539 (80 microliters, further diluted from the active ingredient of approximately 1M), representing an approximately 100 fold ratio of phosphonate to catalyst. The mixture was heated for one hour under nitrogen at 90 ° C. Then a sample was taken for SSI testing. The material was then washed with water and another sample of the washed material was taken for SSI. The

<img file="MX348233B_D0100.tif" />

shows that it has no washing with water showed a level of. , »» &lt;. wi · »·« * '**&gt; ~ ^ * * · ~ *** - ^^-^ ^J'*' - * -WWTi HIT ΙιβΓΓΓί '* 2.0% / 2.5% isomerization (duplicate runs) versus unsuppressed sample (40.3% isomerization), as shown by the data in Table 2. The sample washed with Water provides isomerization levels of 7.6% / 7.8% (runs doubled), which is still lower than the control but not as effective as leaving the phosphonates in the metatesized material.

EXAMPLE 21

Susceptibility of the isomerization suppressing agent to distillation

To determine whether an isomerization suppressing agent in accordance with the present teachings could distill under usual natural oil refining conditions (e.g. 250 ° C, 15 mm), DOVERPHOS® 6 (30 g) was charged to a flask of 100 ml three-neck round bottom equipped with a J-KEM® temperature controller probe and simple distillation head. The container temperature was set at 275 ° C under a reduced pressure of 10 mm Hg. No change in head temperature was detected at a vessel temperature of 255 ° C. At a pot temperature of 264 ° C, the head temperature increased over time to 210 ° C but no liquid distillate was observed. Reducing the vacuum to 5 mm Hg resulted in a small amount of liquid head (head of

215 ° C). At 2 mm Hg, a small amount of head was collected (bottoms of

<img file="MX348233B_D0101.tif" />

122

FWSTrrUTO MUVCANC; OF INDUSTRIAL PROPERTY

242 ° C and 222 ° C head). A total of 1.5 grams was collected (5% loading) ._ Running the same experiment with DOVERPHOS® 4 resulted in no head product at a bottom temperature of 280 ° C and a reduced pressure of 2 mm Hg (head of 160 ° C). While it is not intended to be bound by any particular theory or intended to limit in any way the scope of the appended claims or their equivalents, it is currently believed that heavier phosphite esters (eg, one or more phosphites described above) are likely to be stable under conditions. distillation oils such as can be found in natural refining oils and, therefore, these materials are not capable of contaminating distillates. This represents a significant advantage over the use of lower molecular weight materials that can be decomposed and / or co-distilled with products under usual refining conditions.

EXAMPLE 22

Susceptibility of the isomerization suppressing agent to transesterification conditions

Five different DOVERPHOS® materials were subjected to transesterification conditions (for example, methoxide / methanol for one hour at 60 ° C) to assess their susceptibility to transesterification conditions (for example, as it could be used to transesterify a triacylglyceride fraction to produce one or a

<img file="MX348233B_D0102.tif" />

123 plurality of transesterification products, as shown in Figure 3 and as described above). Two of the five materials cleared during the reaction (ie, made monophasic) with DOVERPHOS® 4 have apparently reacted and DOVERPHOS® 253 has apparently not reacted to any significant degree.

Three of the five materials - DOVERPHOS® 53, DOVERPHOS® 6, and DOVERPHOS® 613 - did not clear and remained biphasic. GC-MS analysis suggests that a reaction may have occurred albeit to an unquantified degree. Accordingly, while it is not wished to be bound by any particular theory or intended to limit in any way the scope of the appended claims or their equivalents, it is presently believed that in some embodiments, these isomerization suppressing agents will arise in the fraction of FAME shown in figure 3. Furthermore, while it is not wished to be bound by any particular theory or intended to limit in any way the scope of the appended claims or their equivalents, it is currently believed that if the reaction occurs (as is apparently the case with DOVERPHOS® 4), some of the reaction products could also end up in the glycerol phase.

Therefore, the choice of isomerization suppressing agent can be guided in consideration of the desired final fate for the agent within a particular process scheme. For example, in some embodiments, it is desirable to select an isomerization suppressing agent that does not end up contaminating a stream of product.

124

<img file="MX348233B_D0103.tif" />

wanted. In some embodiments - particularly, though, not exclusively those involving metathesis-based methods for refining natural oil feedstocks, as shown in Figure 3 - it is desirable to isolate the olefins formed in the metathesis reaction without contamination from the agent. of isomerization suppression (eg, a phosphite ester). In some embodiments, as shown in Figure 3, a subsequent transesterification of the triacylglyceride fraction can provide one or a plurality of transesterification products (eg, FAME and / or other esters) that are substantially devoid of phosphorous contamination. as a consequence of the phosphite ester remaining in the bottoms of the distillation (ie, not being transesterified) or being hydrolyzed.

<img file="MX348233B_D0104.tif" />

IMPI

125

TABLE 2

IND'TTWIAL

Results of isomerization suppression of phosphorous oxo acid esters

<td>Phosphorous esters</td><td>Molar excess over catalyst</td><td>Isom. (duplicates)</td><td>Isom. (control run not suppressed</td><td>Comments</td>

<td>DOVERPHOS® 53</td><td> 10</td><td>0.9, 1.0 (1 hr)</td><td>3.6 (lower level of isom)</td><td>Pretreatment is for one hour at 60 ° C</td>

<td>DOVERPHOS® 4 (trisnonylphenyl phosphite, TNPP)</td><td> 10</td><td> 1.1, 0.8</td><td> 22.7, 28.3</td><td>As the previous</td>

<td>Galata TNPP</td><td> 10</td><td> 0.3, 0.5</td><td> 6.5, 8.5</td><td>Change in supplier of TNPP and used cross-metathesized oil</td>

<td>Galata TNPP</td><td> 3</td><td>0.7 to 3.5 (four runs)</td><td> 15.9, 14.9</td><td>Mixed with employed shear</td>

<td>Trimethyl phosphite</td><td> 100</td><td> 0.4</td><td> 25.9</td><td>Direct addition to SSSI</td>

<td>Diethyl phosphite</td><td> 100</td><td> 0.5</td><td> 22.4</td><td>Direct addition to SSSI</td>

<td>DEQUEST® 539</td><td> 100</td><td> 2.0, 2.5</td><td> 40.3</td><td>Phosphonate Ester Blend</td>

All content of each document cited herein is hereby incorporated by reference, except that in the event of any inconsistent description or definition in this specification, the description or definition herein shall be deemed prevailing.

The above detailed description and accompanying drawings have been provided by way of explanation and illustration and are not intended to limit the scope of the appended claims. Many variations on₁₂₆¹ MEXICAN INSTITUTE

OF THE «TOWHJAt

INDUSTRIAL Ό — M:

Presently preferred embodiments illustrated in the -aLpceseate document will be apparent to one of ordinary skill in the art and remain within the scope of the appended claims and their equivalents.

It is to be understood that the elements and features recited in the appended claims may be combined in different ways to produce new claims which are also within the scope of the present invention. Thus, considering that the dependent claims annexed below may depend on only one dependent or independent claim, it is to be understood that these dependent claims, alternatively, may depend on the alternative of any previous claim either independently or dependently, and such that those new combinations they should be understood as forming part of this specification.

127

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