Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/16—Hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/1802—Organic compounds containing oxygen natural products, e.g. waxes, extracts, fatty oils
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/228—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen double bond, e.g. guanidines, hydrazones, semicarbazones, imines; containing at least one carbon-to-nitrogen triple bond, e.g. nitriles
  • C10L1/2286—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen double bond, e.g. guanidines, hydrazones, semicarbazones, imines; containing at least one carbon-to-nitrogen triple bond, e.g. nitriles containing one or more carbon to nitrogen triple bonds, e.g. nitriles
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
• • C—CHEMISTRY; METALLURGY
  • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
  • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
  • C12P7/00—Preparation of oxygen-containing organic compounds
  • C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P30/00—Technologies relating to oil refining and petrochemical industry
  • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

• a subject matter of the present invention is an aviation fuel (or kerosene) composed of a mixture of kerosene of oil origin and of a fuel derived from vegetable oils.
• kerosene in addition to its distillation range, are the density, the resistance to cold (melting point) and the flash point. There should also be added, to these characteristics, the energy requirement of the fuel, which is imperative for the satisfactory operation of the plane. This is because it is necessary to be able to have available a fuel having an energy requirement which is as high as possible while meeting the other characteristics.
• a high specific energy (energy requirement per kilogram) is important in order to minimize the energy consumption during takeoff when the tanks are full.
• a high energy density (energy requirement per liter) is important in order to minimize the volumes of tanks as any additional volume also implies an excess weight for the structure of the plane and tanks.
• the selection of one of these routes naturally depends on the “thermal and energy” properties of the fuels thus obtained but also on three important additional criteria, namely the compatibility of these fuels with the engines currently used, the accordance with the new standards with regards to the emission of CO 2 and the harmonization (noncompetition) with food crops.
• the application of the first criterion results in provisionally leaving aside hydrogen, which would involve the development of new reactors, that of the second synthetic fuels based on fossil carbon, due to the production of CO 2 and that of the third a selection from carbon-rich plants intended for the production of an energy biomass not competing with food.
• the alcohol route represented by ethanol and methanol, which are obtained by fermentation of sugars.
• Fuels based on such alcohols have been used, in particular in Brazil, for ground vehicles. They have also been used for light aviation but, due to their characteristics, they are simply not suitable for the manufacture of kerosene supplements or substitutes.
• FAME Fatty Acid Methyl Ester
• the fatty acids are obtained from the seeds of these plants, from which their triglycerides are extracted, which triglycerides provide, by hydrolysis, the corresponding fatty acids which are subsequently esterified with methanol.
• the esters can be obtained by direct transesterification of the vegetable oil in the presence of methanol, which results in a mixture of esters.
• FAEE that is to say the corresponding ethyl ester essentially represented by oleic acid ethyl ester, was prepared.
• first-generation biodiesels They form what is known as first-generation biodiesels.
• Second-generation biodiesels are also known, which products are obtained by hydrotreating the vegetable oils, resulting, by hydrogenation, in isomerized or nonisomerized long-chain hydrocarbons.
• the isomerization of the paraffins makes it possible to significantly reduce the cloud point, that is to say the temperature at which the paraffins begin to crystallize.
• Esterified or transformed fatty acids such as FAME, which are conventionally known as biodiesels, constitute a fraction having boiling points, on the one hand, which are too high and melting points, on the other hand, which are also too high, these characteristics being related directly to the chain length of the fatty acid, conventionally from 16 to 18 carbon atoms, in order to be able to be incorporated in large amounts in aviation fuel fractions.
• the problem to be solved is thus that of finding a fuel based on a renewable source which meets as best as possible the criteria (specifications) of aviation fuels and in particular the criteria of density, of boiling and melting points and of energy requirement.
• the invention is targeted at overcoming these disadvantages by providing aviation fuels composed of a mixture of a kerosene resulting from oil and of compounds chosen from nitriles and esters of medium fatty acids obtained from renewable monounsaturated fatty acids of natural origin, these medium fatty acids comprising from 7 to 12 carbon atoms per molecule.
• fatty nitriles and fatty esters having a medium chain length, might, by virtue of their characteristics of density, of boiling and melting points and of energy requirement, constitute a fraction which is particularly advantageous as aviation fuel.
• a subject matter of the invention is an aviation fuel comprising from 1 to 100% by weight of a fraction of a compound, obtained by chemical conversion starting from natural and renewable, optionally hydroxylated, monounsaturated fatty acids with a chain length at least equal to 14 carbon atoms, chosen from nitriles and esters of medium fatty acids comprising from 7 to carbon atoms per molecule, and from 0 to 99% by weight of a kerosene resulting from oil meeting the world specifications for aviation fuels.
• this fraction of the compound will represent from 20 to 99% by weight and the kerosene meeting the world specifications from 1 to 80% by weight.
• the fraction of the compound will be composed of a mixture of at least one of the nitrile and/or ester compounds and of at least one olefin and/or alkane comprising from 6 to 13, preferably from 7 to 12, carbon atoms per molecule, of natural origin, resulting from chemical conversions analogous to that applied to said natural and renewable, optionally hydroxylated, monounsaturated fatty acids.
• the portion of the olefin and/or alkane in the mixture constituting the fraction of the compound will represent from 10 to 50% by weight of the mixture.
• alkanes or olefins will be found in the final aviation fuel by the side of analogous molecules originating from the kerosene. However, it will be possible to distinguish them from one another due to the origin of the renewable hydrocarbons, which will comprise a 14 C fraction.
• the aldehyde is converted to acetal, or an acid, ester, nitrile, alcohol, alkane or olefin.
• esters of medium fatty acids will preferably comprise an odd number of carbon atoms, 7, 9 or 11.
• the esters composed of 10 or 12 carbon atoms will preferably be in the form of an ⁇ -unsaturated ester.
• the compounds in their nitrile form will be in a saturated or monounsaturated form.
• the fatty nitrile comprising 12 carbon atoms will preferably be ⁇ -unsaturated.
• These fatty nitriles can comprise, according to some manufacturing processes, in addition to the nitrile functional group, another functional group, either ester or nitrile. These compounds can be introduced into the fuel if their characteristics (density, phase change temperatures and energy requirement) are sufficient not to have to subject them to a further and expensive conversion.
• the alcohol radical participating in the ester functional groups will comprise from 1 to 4 carbon atoms.
• this radical will be methyl in order to confer, on the compound, its best properties in the fuels of the invention.
• the ⁇ -olefins and alkanes exhibit certain characteristics (very low melting point, low density, high specific energy) which can constitute an excellent source for being incorporated as supplement of the mixture in a kerosene fraction. They make it possible in particular to compensate for the failings of certain compounds, such as esters, as regards density and specific energy.
• the combination of a nitrile compound and of an olefin or of an alkane will confer the same advantages on the mixture. The production of these two components can occur during the same reaction process provided that the fatty acid treated is in the nitrile form.
• This solution is more advantageous than the normal solution, which consists in completely hydrogenating the vegetable oils, in that it consumes less hydrogen and also contributes to lowering the boiling points and solidification temperatures.
• the compounds of ester and/or nitrile type participating in the makeup of the fuel are obtained from monounsaturated fatty acids of natural and renewable origin. These fatty acids are higher acids, that is to say comprising at least 14 carbon atoms per molecule.
• fatty acids are in particular myristoleic (C 14 ⁇ ), palmitoleic (C 16 ⁇ ), petroselinic (C 18 ⁇ ), oleic (C 18 ⁇ ), vaccenic (C 18 ⁇ ), gadoleic (C 20 ⁇ ), cetoleic (C 22 ⁇ ) and erucic (C 22 ⁇ ) acids and the monohydroxylated fatty acids ricinoleic (C 18 ⁇ OH) and lesquerolic (C 20 ⁇ OH) acids.
• the compounds participating in the makeup of the aviation fuel of the invention are obtained from natural oils (or fats) which are treated by hydrolysis or methanolysis in order to obtain fatty acids or their methyl esters as a mixture with glycerol, from which they are separated before chemical treatment. It is also possible to form the fatty nitriles directly from vegetable oils. It is particularly advantageous to form the nitrile from the oil when the latter is rich in free fatty acids, as in the case of used natural cooking oils or that of certain natural oils. It is preferable, in order to obtain the nitriles, to use fatty acids as starting material.
• the conversions of the long-chain monounsaturated fatty acids/esters/nitriles are based on a fractioning of the long-chain molecule at the double bond. This fractioning will be carried out either by a cross metathesis reaction with ethylene (ethenolysis), or by oxidative cleavage of the double bond under the action of a strong oxidizing agent and in particular by oxidative ozonolysis, or by thermal cracking for hydroxylated fatty acids.
• the ethenolysis reaction is often accompanied by an isomerization of the substrate and/or the products, which has the effect of resulting in a mixture of products.
• the mixture of products is entirely compatible with the targeted application, which dispenses with the search for a catalyst which would not be at all isomerizing.
• the isomerization for example in the case of the ethenolysis of the ester of oleic acid, has the effect of resulting in the formation of a mixture of esters of approximately 10 carbons and of a mixture of olefins, also of approximately 10 carbons.
• a fuel comprises, besides kerosene, x % of a nitrile or ester compound (obtained via a metathesis) of “n” carbon atoms, this will mean that this compound will be a mixture composed of nitriles or esters comprising from n ⁇ 2 to n+2 carbon atoms with a majority of compounds comprising n carbon atoms.
• the cross metathesis can be carried out with acrylonitrile with formation, besides the ⁇ -unsaturated nitrile, of nitrile-ester difunctional compounds.
• Myristoleic acid is subjected to an ethenolysis (cross metathesis with ethylene) according to the following reaction (the formulae are expressed in the acid form for the sake of simplicity of the account, even if the reaction involves the ester or the nitrile):
• the C 6 ⁇ -olefin is optionally subjected to a cross metathesis reaction with the acrylonitrile in order to obtain a C 7 unsaturated nitrile according to the reaction:
• the C 7 saturated nitrile is obtained by hydrogenation.
• the C 6 olefin can be introduced into the fuel mixture; it is also compatible with the application and can be hydrogenated to give hexane, itself also compatible.
• the second product (acid) from the reaction forms, after esterification, a C 10 ⁇ -unsaturated ester which can be used as is (or its formed saturated by hydrogenation) but which can also be converted via cross metathesis with acrylonitrile, according to a reaction analogous to that described above for the C 6 ⁇ -olefin, to give a C 11 unsaturated nitrile-ester.
• Palmitoleic acid is subjected to an ethenolysis according to the following reaction:
• the C 8 ⁇ -olefin is optionally subjected to a cross metathesis reaction with acrylonitrile in order to obtain a C 9 unsaturated nitrile according to the reaction:
• the C 9 saturated nitrile is obtained by hydrogenation.
• the C 8 olefin can be incorporated in the fuel mixture. It can be hydrogenated beforehand.
• the acid resulting from the ethenolysis reaction results in the same ester or nitrile-ester as in the case of myristoleic acid.
• Petroselinic acid is subjected to an ethenolysis according to the following reaction:
• the C 13 unsaturated olefin can be incorporated as is as a mixture with the ester.
• the C 7 ⁇ -unsaturated acid results in the corresponding ester by esterification.
• a metathesis reaction with acrylonitrile a C 8 unsaturated nitrile-ester is obtained.
• a cross metathesis with methyl acrylate By carrying out a cross metathesis with methyl acrylate, a C 8 unsaturated ester is obtained.
• Oleic acid is subjected to an ethenolysis with the following reaction:
• the C 10 unsaturated ⁇ -olefin is optionally subjected to a cross metathesis reaction with acrylonitrile in order to obtain a C 11 unsaturated nitrile according to the reaction:
• the C 11 saturated nitrile is obtained by hydrogenation.
• the C 10 olefin can be incorporated in the fuel mixture. It can be hydrogenated beforehand.
• the C 10 ⁇ -unsaturated acid resulting from the ethenolysis can be esterified. The hydrogenation of the ester thus obtained makes it possible to obtain a C 10 ester.
• a C 11 unsaturated nitrile-ester is obtained.
• Oleic acid can also be subjected to an oxidative cleavage, such as an oxidative ozonolysis, according to the following (simplified) reaction (the oxidative ozonolysis involves an oxygen source after the formation of the ozonide in order for the decomposition of the latter to result in two acid groups):
• the C 9 ester is obtained after esterification of the monoacid.
• Vaccenic acid is subjected to an ethenolysis according to the following reaction:
• the C 8 unsaturated ⁇ -olefin is optionally subjected to a cross metathesis reaction with acrylonitrile in order to obtain a C 9 unsaturated nitrile according to the reaction:
• the C 9 nitrile is obtained by hydrogenation.
• the C 10 olefin can be incorporated in the fuel mixture. It can be hydrogenated beforehand.
• the C 12 ⁇ -unsaturated acid resulting from the ethenolysis can be esterified in order to obtain the C 12 ⁇ -unsaturated ester.
• Vaccenic acid can also be subjected to an oxidative cleavage, such as an oxidative ozonolysis, according to the following (simplified) reaction:
• the C 7 is obtained and, on the other hand, the C 11 diester is obtained.
• This C 11 diester can be converted to nitrile, either completely, in order to form a dinitrile, or partially, in order to arrive at the nitrile ester.
• the dinitrile can also be formed from the diacid.
• Gadoleic acid is subjected to an ethenolysis according to the following reaction:
• the C 12 unsaturated ⁇ -olefin is optionally subjected to oxidative cleavage, such as an ozonolysis, according to the following (simplified) reaction:
• the C 11 acid resulting from the ozonolysis is esterified to give C 11 ester and can, if appropriate, be converted to C 11 nitrile.
• the C 12 olefin can be incorporated in the fuel mixture. It can be hydrogenated beforehand.
• the C 10 ⁇ -unsaturated acid is esterified and then, if appropriate, hydrogenated to give C 10 saturated ester, it being possible, in either case, for the ester or acid functional group to be converted to a nitrile functional group.
• This acid after esterification with methanol, for example, can also be subjected to a cross metathesis reaction with acrylonitrile in order to obtain a C 22 unsaturated nitrile-ester according to the reaction:
• the C 11 nitrile-ester is obtained by hydrogenation.
• Cetoleic acid is subjected to an ethenolysis according to the following reaction:
• the C 12 ⁇ -unsaturated ⁇ -olefin is optionally subjected to an oxidative cleavage, such as an ozonolysis, according to the following (simplified) reaction:
• the C 11 acid is esterified to give C 11 ester which can, if appropriate, be converted to C 11 nitrile.
• the C 12 ⁇ -unsaturated acid is esterified and then, if appropriate, hydrogenated to give C 12 saturated ester, it being possible for the ester or acid functional group in either case to be converted to a nitrile functional group.
• Erucic acid is subjected to an ethenolysis according to the following reaction:
• the C 10 unsaturated ⁇ -olefin is optionally subjected to a cross metathesis reaction with acrylonitrile in order to obtain a C 11 unsaturated nitrile according to the reaction:
• the C 11 nitrile is obtained by hydrogenation.
• the C 10 unsaturated ⁇ -olefin can also be subjected to an oxidative cleavage, such as an ozonolysis, according to the following (simplified) reaction:
• the C 9 acid is esterified to give C 9 ester which can, if appropriate, be converted to C 9 nitrile.
• the C 10 olefin can be incorporated in the fuel mixture. It can be hydrogenated beforehand.
• Erucic acid can be subjected to an oxidative cleavage, such as oxidative ozonolysis, according to the following (simplified) reaction:
• the C 11 acid is converted to C 11 ester.
• the methyl ester of ricinoleic acid is subjected to cracking according to the reaction:
• the C 7 aldehyde is easily converted to C 7 acid by oxidation and then to C 7 nitrile, the formation of the aldehyde functional group being an intermediate phase in the conversion of the carboxyl functional group to a nitrile functional group.
• the C 7 aldehyde can also be converted to dimethyl acetal by the action of methanol, which product can be incorporated in the fuel mixture in the same way as for the olefins or alkanes mentioned above.
• the C 11 ⁇ -unsaturated ester, methyl w-undecylenate, resulting from the cracking can be hydrolyzed to give w-undecylenic acid.
• the hydrogenation of the ester thus obtained makes it possible to obtain the C 11 ester.
• This ⁇ -undecylenic acid can be converted to ⁇ -undecylenic nitrile.
• a metathesis reaction with acrylonitrile a C 12 unsaturated nitrile-ester is obtained.
• the C 7 aldehyde is easily converted to C 7 nitrile or converted to dimethyl acetal, as indicated above.
• An example of an industrial process which uses a fatty acid as starting material is that of the manufacture of fatty nitriles and/or amines starting from fatty acids extracted from vegetable or animal oils. This process, which is described in the Kirk-Othmer Encyclopedia, vol. 2, 4 th edition, page 411, dates from the 1940s.
• the fatty amine is obtained in several stages. The first stage consists of a methanolysis or a hydrolysis of a vegetable oil or of an animal fat, respectively producing the methyl ester of a fatty acid or a fatty acid. The methyl ester of the fatty acid can subsequently be hydrolyzed to form the fatty acid.
• nitrilation agent generally chosen from ammonia or urea and employ a metal oxide catalyst, such as ZnO or others.
• Heterogeneous catalysts have also been developed which are based on metals, such as rhenium, molybdenum and tungsten, deposited on alumina or silica.
• metals such as rhenium, molybdenum and tungsten
• immobilized catalysts that is to say catalysts whose active principle is that of the homogeneous catalyst, in particular ruthenium-carbene complexes, but which is immobilized on an inactive support.
• the object of these studies is to increase the selectivity of the reaction with regard to the side reactions, such as “homometathesis” reactions between the reactants brought together. They relate not only to the structure of the catalysts but also to the effect of the reaction medium and the additives which may be introduced.
• the metathesis reaction is generally carried out at a low temperature of between 20 and 100° C.
• One of the possible stages of the processes for the conversion of unsaturated fatty acids is the cleavage by attack at the double bond of the molecule in order to achieve a division of the double bond with formation of at least one terminal acid or aldehyde functional group.
• This cleavage can be carried out using strong oxidizing agents, such as KMnO 4 , ammonium chlorochromate, aqueous hydrogen peroxide solution and more particularly ozone, hence the term of ozonolysis widely employed. It can be carried out by cracking but only in the case where a hydroxyl radical is located in a position ⁇ to the double bond.
• oxidative cleavage depends on the objectives desired, either oxidative ozonolysis, resulting in the formation of the acid functional group, or reductive ozonolysis, if it is desired to stop at the aldehyde stage.
• oxidative cleavage will be chosen if the aim is the formation of the acid functional group or of a nitrile functional group.
• the first consists of a methanolysis of castor oil in a basic medium, producing methyl ricinoleate, which is subsequently subjected to pyrolysis in order to produce, on the one hand, heptanaldehyde and, on the other hand, methyl undecylenate.
• the latter is changed to the acid form by hydrolysis.
• Transesterification with methanol makes it possible to obtain the methyl ester, as described in the patent application FR 2 918 058.
• the ricinoleic acid triglyceride (castor oil) is transesterified by an excess of methanol in the presence of sodium methoxide.
• the ester is then vaporized at 225° C. and subsequently mixed with superheated steam (620° C.).
• the reaction is brief, approximately ten seconds.
• the methyl undecenoate is subsequently purified, first of all by cooling in the medium, which makes possible the extraction of the water, and then by a series of distillations, which makes possible the separation of the ester and of the reaction by-products.
• the mixture is cracked in the presence of steam at a temperature of 620° C.
• the degree of the conversion of the methyl ester is 70%.
• the light fraction is subsequently separated at atmospheric pressure and that mainly composed of heptanaldehyde is subsequently separated by distillation at reduced pressure.
• the fraction composed predominantly of the methyl ester of undecylenic acid is distilled under a vacuum of 0.01 atm.
• the fraction rich in methyl esters of oleic and linoleic acids is distilled from the fraction comprising the unconverted methyl ester of ricinoleic acid, which is optionally recycled to the cracking stage.
• the light fraction is composed predominantly of methyl esters of oleic and linoleic acids.
• Use may be made of any plant whose seeds give unsaturated fatty acids of greater than 14 carbon atoms.
• castor oil which comprises more than 80% by weight of ricinoleic acid
• Jatropha curcas oil which comprises from 30 to 50% by weight of oleic acid
• these plants have yields per hectare which are particularly high, rendering them very attractive. They can also grow in very difficult soils and under conditions of low rainfall, hence where few food plants can be cultivated, which also limits competition with food applications.
• Use is made, in this case, of a commercial oleic acid fraction comprising 76.8% of oleic acid.
• the acid fraction is distilled under vacuum in order to concentrate the oleic acid fraction up to a content of 85%.
• the nitrile preparation is a conventional industrial operation for the preparation of fatty amines.
• a conventional charge of 25 kg of ZnO as catalyst per 40 tonnes of fatty acid (i.e. 0.0625%) is used.
• the operation is carried out with an ammonia flow rate of 1000 Sm 3 /h (i.e. 0.417 l/min.kg).
• the temperature of the reactor is gradually increased by approximately 1° C./min from 160° C. up to 305° C.
• the injection of ammonia is begun from 160° C.
• the reaction is maintained under these conditions for approximately 13 hours, until the acid number is less than or equal to 0.1 mg of KOH/g.
• the temperature of the dephlegmator is maintained at 130° C.
• the acid number of the nitrile obtained is 0.030 mg KOH/g, the iodine number is 98 g I 2 /100 g and the distillation yield is 90%.
• the final product comprises approximately 85% of oleonitrile, 10% of stearic acid nitrile and 4% of palmitic acid nitrile.
• the oleonitrile of the preceding example is converted to 1-decene and decenoic acid nitrile by ethenolysis in the presence of the catalyst [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro[[2-(1-methylethoxy)phenyl]methylene]ruthenium, CAS [301224-40-8], the formula of which is given below.
• the operation is carried out in toluene at a concentration of 0.05M, with 0.5% of catalyst, at 50° C. After 22 hours, the conversion is more than 99% and the calculated selectivity is 42% for decene and 46% for decenenitrile.
• the mixture thus obtained has a density of 0.78 g/ml and a cloud point of ⁇ 50° C. It can be incorporated in kerosene according to the terms of the invention.
• the final acid number is 0.17 mg KOH/g.
• the crude product is purified by distillation as above. The distillation is carried out under a vacuum of 40 mbar, with a distillation yield of 83%.
• the NMR analysis of the product shows that the double bond of the undecylenic acid nitrile has in part moved (isomerization reaction during the reaction).
• the final product comprises 96% of 10-undecenenitrile and 4% of isomers (where the C ⁇ C double bond is no longer terminal).
• the mixture thus obtained has a density of 0.83 g/ml and a boiling point of 270° C. and can be incorporated in part in kerosene according to the terms of the invention.
• the light fraction resulting from the final distillation is composed predominantly of the methyl esters of oleic and linoleic acids.
• This fraction which represents approximately 15% of the castor oil, can be incorporated, in all or part, by the side of the methyl ester of 10-undecylenic acid, in the kerosene fraction.
• the mixture thus obtained comprising the methyl ester of undecylenic acid and the methyl esters of oleic and linoleic acids, has a density of 0.88 g/ml and a cloud point of ⁇ 20° C. It can be incorporated in part in kerosene according to the terms of the invention.
• the methyl ester of 10-undecylenic acid, used alone, can be incorporated in larger amounts in kerosene.
• This example illustrates the ethenolysis of methyl oleate.
• Use is made, for this reaction, of the complex catalyst [RuCl 2 ( ⁇ CHPh)(IMesH 2 )(PCy 3 )], the formula (A) of which is given below.
• the reaction is carried out in CH 2 Cl 2 , at a methyl oleate concentration of 0.05M and an ethylene concentration of 0.2M, at a temperature of 55° C. and for 6 hours, in the presence of the catalyst at a concentration of 5 mol %, with respect to the methyl oleate.
• the yields are determined by chromatographic analysis.
• the methyl 9-decenoate CH 2 ⁇ CH—(CH 2 ) 7 —COOCH 3 and 1-decene yield is 55 mol %.
• the reaction is halted by adding a 1M solution of tris(hydroxymethyl)phosphine in isopropanol.
• the samples are then heated at 60° C. for 1 h, diluted in distilled water and extracted with hexane before analysis by gas chromatography.
• the analysis reveals a 1-decene yield of 30% and a methyl 9-decenoate yield of 30%.
• the mixture of methyl ester of decenoic acid and of 1-decene can be used directly as fraction which can be incorporated in kerosene. It is also possible to leave a portion of the methyl ester of oleic acid in the mixture, which means that it is not necessary to look for high purity for the 1-decene plus methyl ester of 10-undecylenic acid fraction.
• An equimolar mixture of methyl decenoate and 1-decene thus obtained has a density of 0.81 g/ml and a cloud point of ⁇ 52° C. It can be incorporated in kerosene according to the terms of the invention.
• oleic sunflower oil 82% of oleic acid, 10% of linoleic acid
• tungstic acid 5 g
• hydroxylated oil originating from a preceding synthesis.
• the temperature is increased up to 60-65° C. and then 280 ml of a 50% aqueous hydrogen peroxide solution are added in 3 hours while flushing the reactor with nitrogen in order to limit the presence of water in the reactor and thus the dilution of the aqueous hydrogen peroxide solution.
• the reaction is continued for 3 hours.
• the mixture formed on conclusion of the preceding stage is placed in a stirred autoclave.
• 300 g of a 1% aqueous cobalt acetate solution i.e. 0.4 mol % of Co, with respect to the diol produced in the preceding stage
• the temperature is adjusted to 70° C. and the reactor is placed under an air pressure of 12 bar.
• the start of the reaction is observed by the increase in temperature of the mixture because of the exothermicity of the reaction.
• the reaction then lasts 8 hours.
• the aqueous phase is separated under hot conditions.
• the aqueous phase is separated from the organic phase.
• the recoverable aqueous phase comprises the catalysts of the preceding stages.
• the organic phase of the oxidized oil comprises the triglycerides of azelaic acid produced by the reaction, as a mixture with pelargonic acid.
• the distilled organic phase makes possible the recovery of a 360 g fraction of pelargonic acid and other short fatty acids.
• the acid is subsequently esterified in the presence of methanol.
• This example illustrates the oxidative cleavage of oleic acid to give nonanoic acid by oxidative ozonolysis.
• Ozone obtained by a Welsbach T-408 ozone generator is bubbled in 25 ml of pentane until a blue color is observed.
• the pentane solution is maintained at ⁇ 70° C. with an acetone/dry ice bath.
• 20 mg of oleic acid dissolved in 5 ml of pentane and cooled to 0° C. are added to the ozone solution.
• the excess ozone is subsequently removed and the blue color disappears.
• the pentane is evaporated with a stream of dry nitrogen. During this stage, the temperature of the solution is maintained below 0° C. After evaporation of the pentane, 3 ml of methanol cooled to ⁇ 70° C.
• the initial step is to raise the temperature to approximately 60° C.
• the reaction of the decomposition of the ozonide begins, it is accompanied by a rise in the temperature.
• a stream of oxygen is continuously added, in order to maintain the temperature and to directly oxidize the products resulting from the decomposition of the ozonide.
• the procedure is carried out over 4 hours in order to limit the formation of decomposition products. It is important to maintain the reaction temperature slightly above the decomposition temperature of the ozonide during this stage. A temperature of 95° C. is used in this example.
• the nonanoic acid prepared according to example 7a is esterified by methanol with a stoichiometric excess of 100 in the presence of sulfuric acid as catalyst (2%). The reaction is carried out at reflux for 2 hours. At the end of the reaction, the methyl ester of nonanoic acid is isolated by extraction with the solvent, neutralization of the residual acids and then washing.
• the methyl ester thus obtained has a density of 0.87 g/ml and a cloud point of ⁇ 35° C. It can be incorporated in part in kerosene according to the terms of the invention.

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