Classifications

• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS OR COOKING OILS
  • A23D9/00—Other edible oils or fats, e.g. shortenings or cooking oils
  • A23D9/007—Other edible oils or fats, e.g. shortenings or cooking oils characterised by ingredients other than fatty acid triglycerides
  • A23D9/013—Other fatty acid esters, e.g. phosphatides
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
  • C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
  • C11C1/007—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids using organic solvents
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS OR COOKING OILS
  • A23D9/00—Other edible oils or fats, e.g. shortenings or cooking oils
  • A23D9/02—Other edible oils or fats, e.g. shortenings or cooking oils characterised by the production or working-up
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23K—FODDER
  • A23K10/00—Animal feeding-stuffs
  • A23K10/30—Animal feeding-stuffs from material of plant origin, e.g. roots, seeds or hay; from material of fungal origin, e.g. mushrooms
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23K—FODDER
  • A23K10/00—Animal feeding-stuffs
  • A23K10/30—Animal feeding-stuffs from material of plant origin, e.g. roots, seeds or hay; from material of fungal origin, e.g. mushrooms
  • A23K10/37—Animal feeding-stuffs from material of plant origin, e.g. roots, seeds or hay; from material of fungal origin, e.g. mushrooms from waste material
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
  • C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
  • C11B1/00—Production of fats or fatty oils from raw materials
  • C11B1/02—Pretreatment
  • C11B1/04—Pretreatment of vegetable raw material
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
  • C11B1/00—Production of fats or fatty oils from raw materials
  • C11B1/10—Production of fats or fatty oils from raw materials by extracting
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
  • C11B3/00—Refining fats or fatty oils
  • C11B3/001—Refining fats or fatty oils by a combination of two or more of the means hereafter
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
  • C11B3/00—Refining fats or fatty oils
  • C11B3/02—Refining fats or fatty oils by chemical reaction
  • C11B3/04—Refining fats or fatty oils by chemical reaction with acids
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
  • C11B3/00—Refining fats or fatty oils
  • C11B3/10—Refining fats or fatty oils by adsorption
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
  • C11B3/00—Refining fats or fatty oils
  • C11B3/12—Refining fats or fatty oils by distillation
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
  • C11B3/00—Refining fats or fatty oils
  • C11B3/12—Refining fats or fatty oils by distillation
  • C11B3/14—Refining fats or fatty oils by distillation with the use of indifferent gases or vapours, e.g. steam
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
  • C11B3/00—Refining fats or fatty oils
  • C11B3/16—Refining fats or fatty oils by mechanical means
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
  • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
  • C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
• • 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
  • C12P7/6436—Fatty acid esters
  • C12P7/6445—Glycerides
• • 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
  • C12P7/6436—Fatty acid esters
  • C12P7/6445—Glycerides
  • C12P7/6458—Glycerides by transesterification, e.g. interesterification, ester interchange, alcoholysis or acidolysis
• • 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
  • Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
  • Y02P60/80—Food processing, e.g. use of renewable energies or variable speed drives in handling, conveying or stacking
  • Y02P60/87—Re-use of by-products of food processing for fodder production

Definitions

• the present invention relates to a novel process capable of extracting and enhancing the majority of the components of the lesquerella seed.
• the present invention more particularly relates to a flexible process, capable of providing in one and the same device, depending on the demand, either of lesquerella oil, or of the lesquerolic ester, but also of recovering the other products of the seed of Lesquerella (hereinafter 'co-products') in directly recoverable form:
• the present invention aims in particular at promoting the esterérolic esters for the manufacture of new monomers, and new polyamides derived from lesquerella, by the production of 11-amino undecanoic acid, a monomer used in the synthesis of polyamide 11, of the 13 amino tridecanoic acid, or dodecanedioic diacid.
• the present invention aims to provide a method for improving the oil extraction yield, the quality of Lesquerella crude oils, and providing a deoiled cake.
• deoiled cake means a cake containing less than 3% of oil, preferably less than 1% of oil.
• the present invention is preferably aimed at obtaining a yield of at least 90% of oil extraction, preferably at least 95%.
• the present invention also aims to provide such a process in which the by-products of extraction, such as cake, phospho lipids and gums are directly recoverable.
• the fatty acid esters are prepared, after a step of solvent extraction of the oil from the seeds of oleaginous plants, by transesterification of this oil in the presence of alcohol and of catalyst, leading to the obtaining of an ester phase and a glycerol phase.
• This is the process for obtaining fatty acid esters, in 2 stages, for a biodiesel application, described in the patent document WO2005 / 030911 of Petroleo Brasileiro SA-Petrobras. The method described is only performed in batch mode (stirred bed reaction). The process is carried out from seeds of oleaginous plants rich in oils (having a triglyceride content ranging from 15 to 70% by weight) and after having husked the seeds.
• This method comprises a preliminary step of conditioning the seeds, during which the seeds are shelled and cleaned with a vibrating sieve, and the cleaned seeds are dried so as to reduce their moisture content to less than 0.5% by weight. .
• the dried seeds are introduced into a reactor with anhydrous alcohol; this heterogeneous mixture is converted into a homogeneous suspension by means of a stirrer. Only then is a basic catalyst introduced into the reactor.
• This reaction mixture is then heated for 30 to 90 minutes at a temperature of 30 to 78 ° C, resulting in the transesterification of triglycerides to esters with a high conversion rate of between 98 and 100%.
• this method has the following drawbacks:
• Lesquerella oil is higher than that of other seeds, such as castor oil.
• the oil content of Lesquerella seeds is low, that is, less than 30%.
• the oil content is more than 40% in castor seed, more than 30% in jatropha seed, and more than 42% in rapeseed.
• the desquerella seed is also poorer in the hydroxylated fatty acid (55%) of lesquerolic acid vs 85% ricinoleic acid in castor). Because of its lower content of hydroxylated fatty acids, Lesquerella oil is significantly less extractable by an alcohol than castor oil, for example.
• the morphology of the seed makes its conditioning more complex in order to obtain a flake, which prevents optimal percolation of the solvent and does not allow efficient extraction with an alcohol alone.
• the document WO2010076527 describes a process in which the trituration and the transesterification reaction of the triglycerides present in castor oil are carried out in one step from castor oil, so as to lead to the simultaneous production of a cake, glycerol and esters of fatty acids, especially ricinoleic acid.
• the document WO2011092430 describes a reactive trituration process adapted to Jatropha seeds, in which a double flattening is carried out. Jatropha seeds do not impose the same constraints - they contain less phospholipids and gums - than those of Lesquerella.
• rapeseeds in WO2009013349 are also unsuitable for Lesquerella seeds, the rapeseed is free from gums and low in phospholipids.
• the very woody hull of rapeseed and jatropha seeds provides rigidity and mechanical strength to the flake, which is not the case for Lesquerella seeds and is problematic.
• Lesquerella seeds (about 10 mm for castor and Jatropha, 2 mm for rapeseed, and less than 1 mm for Lesquerella) requires a suitable process
• the present invention therefore aims to provide a simple process, which has the least possible steps and overcomes the aforementioned drawbacks, to produce lesquerol ester in a yield of at least 70%.
• the present invention also aims to provide such a method for simultaneously co-producing a deoiled cake and rid of its anti-nutritional elements, this directly from Lesquerella seeds.
• the present invention proposes to provide a desquerella seed treatment method which limits the number of seed treatment stages, with a view to continuous industrial application, aimed at producing either desquerella oil or esters.
• Lesquerolic acid which allows to produce cakes valorizable in animal feed, by maintaining a nutritional value to the cake and by eliminating the anti-nutritional elements.
• the object of the invention is to find the conditions of such a process which make it possible to use the same industrial device to alternatively produce crude oil or esterolic esters, and to further provide co-products. of the seed of lesquerella to valorize them.
• the Applicant has now found a process capable of fulfilling all these requirements, and even of making new products:
• the subject of the present invention is therefore a process for trituration of desquerella seeds in the presence of a mixture of light alcohol and co-solvent, which makes it possible, according to the addition or otherwise of a basic catalyst to the mixture, to carry out either (without addition of catalyst) the extraction of lesquerella oil, or (with the addition of catalyst) the extraction of oil and the simultaneous transesterification of the triglycerides present in the lesquerella oil to lead to the obtaining of esters of fatty acids, in particular of lesquerolic acid (14-hydroxy-cis-1-eicosenoic acid).
• the subject of the invention is a process for extracting from lesquerella seeds, said seeds having an acidity level of less than 6 mg KOH / g, said process comprising the following steps:
• ii) a step of contacting the conditioned seeds with an anhydrous light alcohol and a co-solvent under conditions of temperature and duration sufficient to allow extraction of the vegetable oil and a cake.
• step ii) is followed by a step iii) of separating the gums from the crude oil by centrifugation to obtain a degummed oil.
• step iii) is followed by a step iv) of separating the phospholipids from the degummed oil by refining the degummed oil.
• the refining of the oil comprises at least one of the following steps:
• said method comprises the following steps:
• This particular process according to the invention makes it possible to react "in planta” the mixture of alcohol-co-solvent and catalyst with the oil contained in the heart of the seed.
• Alcohol acts as both a solvent and a reagent.
• the term "lesquerella seeds” is intended to mean seeds of Lesquerella plants, alone or as a mixture with seeds from at least one other oleaginous, oleoproteinous or proteinaceous plant, including seeds of salt. seeds or seed mixture producing an oil containing at least 10% by weight of lesquerolic acid. It would not be outside the scope of the invention when the seeds used in the process according to the invention come in whole or in part from genetically modified plants producing desquerolic acid, alone or as a mixture with oleaginous plants which are possibly genetically modified. .
• Oleaginous plants are grown specifically for their high-fat oil-rich seeds or fruits from which food, energy or industrial oil is extracted.
• Protein plants belong to the botanical group of legumes whose seeds are rich in proteins.
• Oil-protein crops are legumes whose seeds also contain oil.
• the diameter of the lesquerella seeds used in the process of the invention is typically less than 1 mm.
• the seeds used in the process of the invention are fresh seeds which have not been preheated.
• Harvested seeds are simply dried in the harvester to promote storage. They may possibly undergo one or more fungicidal treatments.
• the first step of the process according to the invention consists in conditioning the seeds of Lesquerella, used alone or mixed with other seeds of oleaginous plants, oleo-proteinaceous or proteaginous. This conditioning is carried out on whole, unshelled seeds.
• the objective of the seed conditioning is to make the oil as accessible as possible to alcohol, without, however, greatly affecting its mechanical strength. This avoids the formation of a paste and fines, respectively detrimental to the implementation of a continuous process and the final purification of the products. Furthermore, the conditioned seed must allow easy passage of the reaction fluid (alcohol mixture - cosolvent and optional basic catalyst) according to a simple phenomenon of percolation.
• the seeds are conditioned by a sequence of operations comprising a single flattening step and at least one drying step thereof.
• This flattening (also called flaking) of Lesquerella seeds in a single operation is preferably carried out by means of smooth rolls.
• a simple flattening is carried out in the case of the invention for two reasons.
• the seeds are so small that it is not necessary to make two flattenings.
• the gums contained in Lesquerella seeds are polyols complexed by divalent cations. These gums are soluble in water and are extracted by alcohols. To limit the production of co-extracted gums with the esters, so one only flattening.
• the fresh seeds are flattened on a smooth roller mechanical flattener.
• the rolls used are smooth because the Lesquerella seeds are small (less than 1 mm in size), while the fluted rollers are rather adapted to much larger seeds.
• the packaging further comprises a drying operation of the seeds thus flattened.
• the drying operation is carried out at a temperature between 80 and 120 ° C, preferably between 90 and 110 ° C.
• the flattened seeds are dried, for example in a thermoregulated ventilated oven or in a continuous belt dryer or rotary hot air dryer.
• the drying time and the temperature are chosen so as to obtain a decrease in the moisture content of the seeds at values of less than or equal to 2% by weight.
• the drying is carried out rapidly after flattening, in less than one hour, preferably after 5 to 10 minutes, at a temperature sufficient to reduce the moisture content of the seeds to 2% by weight or less.
• the residual moisture of the seed is determined by thermogravimetry: the seed is ground beforehand and the ground material obtained is dried at 105 ° C. in a thermobalance until the weight is stabilized.
• the water content is expressed as a percentage of the raw material.
• the seeds packaged as described above are brought into contact with an anhydrous light alcohol and a co-solvent.
• the mass ratio (alcohol-cosolvent) / seeds is in the range from 1 to 10.
• This contacting is carried out under conditions of temperature and duration sufficient to allow the extraction of the vegetable oil and lead to obtaining a mixture:
• Crude oil comprising fatty acids, including lesquerolic acid, gums and phospho lipids, and
• the light alcohol used in stage ii) is a lower aliphatic alcohol, that is to say an alcohol whose carbon number is included in the range. from 1 to 8, preferably from 1 to 5, or even better from 1 to 4.
• the light alcohol is advantageously selected from methanol, ethanol, isopropanol, n-propanol, butanol, isobutanol, 2-ethylhexanol, and mixtures thereof, and preferably is methanol.
• the co-solvent used in stage ii) is selected from the group: hexane, heptane, benzene, bicyclohexyl, cyclohexane, decalin, decane, gasoline, petroleum ether, kerosene, kerdane, gas oil, kerosene, methylcyclohexane, naphtha (Texsolve V), Skellite, Tetradecane, Texsolve (B, C, H, S, S-2, S-66, S-LO, V), supercritical CO2, propane or butane pressurized, natural solvents such as terpenes (limonene, alpha and beta pinene)), ethers such as dimethyl ether, diethyl ether, ketones such as acetone and mixtures of all these solvents.
• the co-solvent used in the process of the invention is hexane.
• the volume ratio of light alcohol / cosolvent according to the process of the invention is in the range of from 0.5 to 2.
• the light alcohol is methanol and the co-solvent is hexane .
• step ii) comprises the following steps:
• the recovered liquid is within the meaning of the invention, an oil or ester suspension in an alcohol / cosolvent phase.
• step ii) further comprises a step of washing the cake with the alcohol / cosolvent mixture, said washing being carried out by at least 3 successive washes at a temperature in the range of 30 to 50 ° C.
• step ii) comprises a step of neutralizing miscella with the aid of a strong acid, such as sulfuric acid, the acid content representing from 0.1 to 1% compared to the dry extract of miscella before neutralization.
• a strong acid such as sulfuric acid
• non-reactive or “oil route” embodiment of the process according to the invention is preferred if it is desired to enhance the gums and phospholipids of lesquerella, in addition to the oil and the deoiled food cake.
• lesquerolic acid represents from 50 to 60% by weight of the crude oil obtained.
• the gums represent for their part from 0.5 to 3% by weight of the crude oil.
• the Lesquerella gums obtained according to the process of the invention are partially liposoluble and have an acidity level of greater than 5 mg KOH / g.
• Lesquerella gums can advantageously be valued as new gelling agents in food, cosmetic or pharmaceutical preparations. They can on the one hand constitute alternatives to xanthan gums obtained by biotechnology and on the other hand present rheological properties complementary to the current gums of the market (guar gum, locust bean, etc.).
• the crude oil obtained according to the process of the invention comprises at least 0.5% of hydroxylated phospholipids, that is to say having hydroxyl groups, and therefore comprise at least one hydroxylated chain.
• Lesquerella phospholipids have the advantage of being derived from non-genetically modified plant chains and can therefore be useful substitutes for soy lecithins.
• their hydroxylated nature brings new emulsifying properties.
• the dequered lesquerella cake according to the invention results directly from the implementation of the method according to the invention, its use in animal feeds not requiring additional steps and / or reagents.
• the cake resulting from the process of the invention contains less than 1% by weight of oil, based on the weight of the cake.
• food lesquerella cake is meant a Lesquerella cake with a total content of antinutrients less than 1% by weight, on the weight of the cake. Lesquerella cake is directly usable in animal feed.
• the deoiled Lesquerella cake obtained according to the invention also has the particularity of being rich in fibers, and it has a cellulose and / or starch content greater than 20% by weight.
• the Lesquerella seed is converted directly to the ester (methyl or ethyl) of lesquerolic acid by an adaptation of a reactive variant (simple addition of basic catalyst) of the process according to the invention.
• the seeds packaged as described above are brought into contact with an anhydrous light alcohol, a co-solvent and an alkaline catalyst under conditions of temperature and duration sufficient to allow the extraction and transesterification of the oil. plant and leading to obtaining a mixture comprising fatty acid esters and glycerol, and a food deoiled cake rich in gums and cellulose.
• the basic catalyst (the catalyst is independently named alkaline catalyst or basic catalyst in the present description), is selected from group: soda, alcoholic soda, solid soda, potash, alcoholic potash, solid potassium hydroxide, sodium or potassium methoxide, sodium or potassium ethylate, sodium and potassium propylate, sodium and potassium isopropoxide, and preferably sodium hydroxide.
• the reaction takes place in a fixed bed reactor.
• the fixed bed reactor is a thermoregulated percolation column equipped with a grid.
• a pump makes it possible to feed the column with an alcohol-cosolvent mixture and any basic catalyst.
• the alcohol, the co-solvent and the optional catalyst are therefore added simultaneously to the reactor, which is maintained at a temperature ranging from 30 to 75.degree. C., preferably at about 40.degree.
• the weight ratio catalyst / alcohol-co-solvent / seeds is preferably in the range 0/1 to 10/1 for the oil route; and in the range of 0.001 to 0.1 / 1 to 10/1, preferably in the range of 0.011 to 0.1 / 1 to 10/1, for the Ester route.
• the food is made at the head of bed; the reaction liquid then percolates through the bed and is recovered in a reserve located downstream, under the bed. By pumping, the liquid is returned to the headboard to diffuse back into the bed.
• the duration of the recirculation cycle of the alcohol / cosolvent / optional catalyst mixture is 15 to 60 minutes, preferably 20 to 40 minutes. At the end of the cycle, the liquid supply is stopped. Part of the liquid still present in the soaked seeds is then recovered by simple dripping.
• the column is fed with the mixture of anhydrous alcohol and co-solvent which diffuses again by percolation without subsequent recirculation.
• the quantity of mixture is injected during a given period (of the order of 4 to 10 minutes), the liquid then being drained for a period of 10 to 20 minutes.
• the miscella preferably undergoes a neutralization step (any residual basic catalyst and / or soaps formed) by addition of acid.
• An evaporation step (generally by distillation at a temperature of about 40 to 60 ° C.) of solvents (alcohol and cosolvent) of the miscella leads to either the crude oil (non-reactive case) or to a mixture of phases consisting of a lighter phase rich in esters and a denser phase rich in glycerol (reactive case).
• the phase mixture is subjected to a decantation step (consisting, for example, of a static decantation in one or more decanters in parallel or in series, centrifugal decantation, combination of static or centrifugal decantation), making it possible to obtain a higher phase composed predominantly fatty esters of lesquerolic acid (+ cosolvent) and a lower phase mainly composed of glycerol and water (glycerin phase).
• a decantation step consisting, for example, of a static decantation in one or more decanters in parallel or in series, centrifugal decantation, combination of static or centrifugal decantation
• esters and glycerol are separated by centrifugation.
• the ester yield of the process according to the invention calculated on the basis of the ester mass obtained on the expected theoretical ester mass, is at least 70%, preferably at least 80%, preferably at least 90%> or even better at least 98%>.
• the ester phase is then subjected to a sequence aimed at recovering fatty esters of lesquerolic acid, comprising, in a known manner, a washing step with water followed by a drying step under vacuum.
• the esters are washed to neutrality according to the following steps: addition of hot water, centrifugation and then drying under vacuum at a temperature of between 80 and 100 ° C. and at a pressure in the range of from 10 to 100.degree. at 30 mbar.
• the process according to the invention further comprises at least one step of liquid / liquid extraction of said esters by means of the light alcohol counter-current of the co-solvent, leading to obtaining an enriched alcohol phase in lesquerolic acid esters, and a co-solvent phase containing the other fatty acid esters.
• the process according to the invention makes it possible to recover the majority of the recoverable products derived from Lesquerella seeds.
• the collected crude oil is subjected to an additional stage of purification of the oil.
• Lesquerella shares a high content of hydroxylated fatty acid with another plant: castor oil.
• Lesquerella oil advantageously replaces castor oil in many applications, for example in lubricants and polyurethanes, but also as a raw material for Polyamide 11 (PAU), for which Arkema is the only world producer.
• PAU Polyamide 11
• Triglycerides extracted from lesquerella can in particular replace castor oil in applications such as the production of dehydrated oil (conjugated double bonds) and the production of oxidized lesquerella oil. Thanks to its anti-irritant properties, Lesquerella oil can be advantageously used in face wipes. Other potential uses of Lesquerella oil include hair fortifiers, sunscreen agents, nucleating agents, lubricants and lubricant additives.
• Lesquerolic acid is intended primarily for the manufacture of dodecanedioic acid and 2-octanol by alkaline fusion, or for the manufacture of a mixture of n-heptaldehyde and tridecylenic acid by pyrolysis.
• the zinc salts of Lesquerolic Acid have antifungal properties.
• the hydrogenation of desquerolic acid produces 14-hydroxy-eicosanoic acid, homologous to the acid 12- hydroxy-stearic acid, and can be used in particular in high-performance greases, gelling agents, nucleating agents, and as a reagent for producing new esters, amides and polymers.
• the mixture of collected liquid phases is subjected to an additional step of neutralizing esterification, which consists in:
• the ester fraction obtained from the mixture comprising fatty acid esters and glycerol is particularly suitable for the production of 11-amino undecanoic acid, a monomer used in the synthesis of polyamide 11, 13 amino-tridecanoic acid, and diodide dodecanedioic acid. .
• the lesquerolic acid ester obtained is intended for the preparation of 13-amino tridecanoic acid.
• the lesquerolic acid ester resulting from the process according to the invention is directly used in the synthesis of 13-amino tridecanoic acid.
• the process of the invention also comprises the following steps: pyrolysis or cracking of the methyl ester of the lesquerolic acid, leading to the production of heptanal and methyl tridecenoate;
• the 13-amino tridecanoic acid obtained is intended mainly for the condensation synthesis of polyamide 13.
• the lesquerolic acid ester obtained according to the process of the invention is intended for the preparation of 11-amino undecanoic acid.
• the process of the invention further comprises the following sequence of reactions:
• the 11-amino undecanoic acid thus obtained is intended mainly for the condensation synthesis of polyamide 11.
• ester of desquerolic acid obtained according to the process of the invention is intended for the preparation of dodecanedioic diacid.
• the method according to the invention further comprises the following sequence of reactions:
• the diacid thus obtained is intended principally for the condensation synthesis of copolyamides comprising X.12 units or monomers, in which X represents a diamine and "12" represents dodecanedioic acid or else the synthesis of solvents, for example in the form of esters. It can also be used for the preparation of the corresponding diamine C12 (dodecane diamine).
• the other product directly from the process according to the invention is the lesquerella cake.
• the lean cake (deoiled) impregnated with alcohol is dried in a ventilated oven for 4 hours at a temperature of less than or equal to 200 ° C., preferably less than or equal to 150 ° C. and even more preferably less than or equal to 120 ° C. This drying step makes it possible to eliminate more quickly from the cake the possible residues of solvent (alcohol and co-solvent) used during the extraction, then to use said cake in the animal feed.
• the process according to the invention can easily be carried out continuously on an industrial scale, for example by means of: a continuously operating mobile-strip extractor reactor (De Smet extractor type); a rotary filter or centrifuge.
• the trituration is preferably carried out with the alcohol and the co-solvent (and the optional catalyst) in countercurrent to the cake, on several consecutive stages.
• the cakes are obtained directly from the seeds, according to the process of the invention. These cakes are devoid of antinutritional elements (content less than 1% by weight on the weight of the cake), they retain their physical integrity (cohesion, mechanical resistance), they have a high fiber content (greater than 20% by weight on the weight of the cake) and an interesting nutritional value, which allows their use in animal feed.
• the method according to the invention uses the reactive route (with basic catalyst) in order to obtain a cake free of anti-nutritional elements (their content representing less than 0.1% by weight on the weight of the cake).
• the simultaneous action of sodium hydroxide and methanol destroys the sulfur compounds that are these anti-nutritional elements.
• the cakes obtained by the method of treating seeds of lesquerella according to the invention keep a nutritional interest and can be directly used in animal feed, without the risk of constituting physiological disorders in animals that consume them.
• the process according to the invention allows the manufacture of gums whose properties are close to xanthan and arabic gums, as well as the production of hydroxylated phospholipids from Lesquerella seeds.
• the Lesquerella seed is recovered according to the process of the invention by non-reactive trituration.
• the non-reactive route (“Oil route") allows the extraction of oil and gums and phospholipids after degumming (degumming) of the crude oil, with production of a cake very well deoiled.
• a step of vacuum distillation of the free fatty acids advantageously leads to the production of neutralized oil and a recoverable acid deodistillate.
• the gums are recovered by centrifugation of the oil, the phospholipids are recovered at the refining stages of the oil.
• the reactive mode (Ester route) of the process is less advantageous as regards the valorization of the gums and phospholipids, since in this case the phospholipids are found in the glycerin and a part of the gums remains in the cake, all with a lipid yield less interesting. It is then particularly difficult to separate the gums from the cake and phospholipids having an emulsifying effect, it is difficult to separate them from glycerin and these two products are thus affected.
• Another advantage of the process according to the invention compared to conventional processes lies in the small amounts of water used.
• crude oil refining operations are very water intensive.
• This water saving is a major asset in the development of this technology in developing countries and to a lesser extent in rich countries as water tends to become an increasingly expensive commodity. It is particularly important for plants such as Lesquerella that have the particularity to grow in arid areas and therefore poor in water.
• the present invention provides a flexible, economical method, and to value the entire seed Lesquerella.
• the present invention also relates to an industrial device for implementing the method according to the invention, characterized in that it comprises:
• step ii) means for contacting the conditioned seeds with a mixture of anhydrous light alcohol and co-solvent according to step ii), said contacting means further comprising a basic catalyst inlet circulated or interrupted according to the demand of lesquerol ester or of lesquerella oil respectively.
• Linoleic (Cl 8: 2) (Internal) 9.1 Densipoleic (C18: 2-OH) 0.1 Linolenic (C18: 3) and Arachic (C20: 0) 11.6 (3)
• Linolenic acid is the majority.
• Lesquerella seed is in the form of very small seeds (0-1 mm), much smaller than rapeseed. In fact, these seeds can not be shelled.
• Lesquerella seeds and cakes see Tables 1 and 1B on page 43: it is noted that the total of the fractions assayed in the Lesquerella seed is not equal to 100%. Also, the lignin as well as the sucrose sugars, fractions generally representing 10 to 20% of the cake, have not been quantified;
• the non-reactive trituration process was carried out in the presence of three solvents or group of solvents:
• the flakes are then dried for 16 hours at 100 ° C.
• the flakes are introduced into the brewing column.
• the miscella is then evaporated under vacuum at 90 ° C. under 20 mbar for 5 min.
• the oil and gums are separated by centrifugation.
• the oil yield is calculated on the basis of the mass of oil obtained versus the expected theoretical mass of oil.
• the oil is then washed to neutrality by adding hot water and centrifugation, and it is dried under vacuum at 90 ° C, 20 mbar for 5 min. The acid number and the composition of this oil are then measured.
• the gums are reprocessed with 20% sulfuric acid and a body of water.
• the mixture is heated at 90 ° C for 30min. After cooling, The organic phase is solubilized in hexane, washed to neutrality and dried.
• the yield of dry extract is the ratio of 100% of the dry extract obtained after evaporation of miscella to the sum of the theoretical quantities of theoretical oil.
• Linolenic acid is the majority.
• the flakes are then dried for 16 hours at 100 ° C.
• the flakes are introduced into the brewing column.
• the methanol / hexane mixture (50/50, m / m) is then circulated on the bed for 30 minutes at 40 ° C.
• the miscella is then withdrawn and the flock bed is then washed with 5 successive washes with the methanol / hexane mixture at 40 ° C (5 minutes per wash).
• miscella is then evaporated under vacuum at 90 ° C. under 20 mbar for 5 min.
• the oil and the gums are separated by centrifugation.
• the oil yield is calculated on the basis of the mass of oil obtained versus the expected theoretical mass of oil.
• the oil is then washed to neutrality by adding hot water and centrifugation, and then dried under vacuum at 90 ° C 20 mbar for 5min. The acid number and the composition of this oil are then measured.
• the yield of dry extract is the ratio of 100% of the dry extract obtained after evaporation of miscella to the sum of the theoretical quantities of theoretical oil.
• the phospholipid content of the oil is 1.3% (Table 5).
• the extracted oil is very acidic (IA> 11). It is very likely that the solubilized gums have significant acidity. In addition, we find the expected content of lesquerolic acid (52%).
• Linolenic acid is the majority.
• the test was carried out under the following conditions: 1. Flocking of fresh lesquerella seed on smooth roller flattener.
• the flakes are then dried for 16 hours at 100 ° C.
• the flakes are introduced into the brewing column.
• the ethanol is then circulated on the bed for 30 minutes at 50 ° C.
• the miscella is then withdrawn and the bed of flakes is then washed with 5 successive washes with ethanol at 50 ° C (5 minutes per wash).
• miscella is then evaporated under vacuum at 90 ° C. under 20 mbar for 5 min.
• the oil and the gums are separated by centrifugation.
• the oil yield is calculated on the basis of the mass of oil obtained versus the expected theoretical mass of oil.
• the oil is then washed to neutrality by adding hot water and centrifugation, and then it is dried under vacuum at 90 ° C. for 20 minutes. The acid number and the composition of this oil are then measured.
• the yield of dry extract is the ratio of 100% of the dry extract obtained after evaporation of miscella to the sum of the theoretical quantities of theoretical oil.
• the phospholipid content is 1.3% (Table 7).
• the corrected oil yield taking into account the phospholipid content is 59.6% (Table 7).
• the extracted oil is very acidic (IA> 13). Again, it is likely that the solubilized gums have significant acidity. In addition, we find the expected content of lesquerolic acid (53%).
• the fixed bed reaction is carried out under the following conditions:
• the flakes are then dried for 16 hours at 100 ° C.
• the flakes are introduced into the brewing column.
• the miscella is then evaporated under vacuum at 90 ° C. under 20 mbar for 5 min.
• the ester and glycerin are separated by centrifugation.
• the ester yield is calculated on the basis of the ester mass obtained versus the expected theoretical ester mass.
• the ester is then washed to neutrality by adding hot water and centrifugation, and then dried under vacuum at 90 ° C 20 mbar for 5min. The acid number and the composition of this ester are then measured.
• Table 8 Mass balance of the reactive trituration process of double-flattened lesquerella seed TEST 10-E28
• the yield of dry extract is the ratio of 100% of the dry extract obtained after evaporation of miscella to the sum of the theoretical quantities of ester and glycerin.
• the test was conducted under the following conditions: Flocculation of fresh lesquerella seed on smooth roller flattener.
• the flakes are then dried for 16 hours at 100 ° C.
• the flakes are introduced into the percolation column.
• the methanolic sodium hydroxide solution is then circulated on the bed for 30 minutes at 50 ° C.
• miscella is then withdrawn and the flock bed is then washed with 5 successive washes with methanol at 50 ° C (5 minutes per wash).
• miscella is then evaporated under vacuum at 90 ° C. under 20 mbar for 5 min.
• the ester and glycerin are separated by centrifugation.
• the ester yield is calculated on the basis of the ester mass obtained versus the expected theoretical ester mass.
• the ester is then washed to neutrality by adding hot water and centrifugation, and it is dried under vacuum at 90 ° C. for 20 minutes. The acid number and the composition of this ester are then measured.
• the yield of dry extract is the ratio of 100% of the dry extract obtained after evaporation of miscella to the sum of the theoretical quantities of ester and glycerin.
• ester obtained could not be washed. In the presence of water, a very stable emulsion is formed. The yield of 83.7% seems very overestimated because the ester is probably polluted by emulsifying molecules (glycerides or gums).
• the yield of dry extract is the ratio of 100% of the dry extract obtained after evaporation of miscella to the sum of the theoretical quantities of ester and glycerin.
• the yields of esters produced in the presence of 0.4 and 0.5% of catalyst are respectively between 83 and 66%.
• Table 12 Fatty acid profiles of tests 10-E30 and 10-E31
• a neutralization test was therefore performed on a miscella sample of test 10-E31.
• the neutralization is carried out as follows:
• Liquids (miscella + washes) are combined in a flask.
• MeC18 content 3 + MeC20: 0 (%) 12.3 12.0 MeC20 content: l (%) 1,1 1,1
• the flakes are then dried for 16 hours at 100 ° C. 3.
• the flakes are introduced into the brewing column. 4.
• the sodium hydroxide solution in the methanol / hexane mixture (50/50) is then circulated on the bed for 30 minutes at 50 ° C.
• miscella is then withdrawn and the bed of flakes is then washed with 5 successive washes with a methanol / hexane (50/50) mixture at 50 ° C (5 minutes per wash).
• the miscella is then evaporated under vacuum at 90 ° C. under 20 mbar for 5 min.
• the ester and glycerin are separated by centrifugation.
• the ester yield is calculated on the basis of the ester mass obtained versus the expected theoretical ester mass.
• the ester is then washed to neutrality by adding hot water and centrifugation, and then dried under vacuum at 90 ° C 20 mbar for 5min. The acid number and the composition of this ester are then measured.
• the yield of dry extract is the ratio of 100% of the dry extract obtained after evaporation of miscella to the sum of the theoretical quantities of ester and
• esters are between 74 and 84% and these are more easily purifiable. Under these conditions, glycerine yields are higher (> 300%>, loaded with gums and / or soap). In the same way, the ester losses remain strong (11-15%, saponification) whereas the cakes are generally well exhausted ( ⁇ 1%> at the highest levels of catalyst);
• Table 18 Fatty acid profiles of tests 10-E45, 10-E46, 10-E46Bis and 10-E48
• a neutralization test was therefore performed on a miscella sample of the test.
• the neutralization is carried out as follows: 1. Liquids (miscella + washes) are combined in a flask.
• the yield of dry extract is the ratio of 100% of the dry extract obtained after evaporation of miscella to the sum of the theoretical quantities of ester and glycerin.
• the yield of dry extract is the ratio of 100% of the dry extract obtained after evaporation of miscella to the sum of the theoretical quantities of ester and glycerin.
• the flakes are then dried for 16 hours at 100 ° C.
• the flakes are introduced into the brewing column.
• the ethanolic sodium hydroxide solution is then circulated on the bed for 30 minutes at 50 ° C.
• the miscella is then withdrawn and the bed of flakes is then washed with 5 successive washings with ethanol at 50 ° C (5 minutes per wash).
• miscella is then evaporated under vacuum at 90 ° C. under 20 mbar for 5 min.
• the ester and glycerin are separated by centrifugation.
• the ester yield is calculated on the basis of the ester mass obtained versus the expected theoretical ester mass.
• the ester is then washed to neutrality by adding hot water and centrifugation, and it is dried under vacuum at 90 ° C. for 20 minutes. The acid number and the composition of this ester are then measured.
• the yield of dry extract is the ratio of 100% of the dry extract obtained after evaporation of miscella to the sum of the theoretical quantities of ester and glycerin.
• Table 1B Comparison of the composition of the Lesquerella seed, cakes from the reaction and non-reactive trituration processes according to the invention, and a soybean meal
• the deoiled and dehydrated Lesquerella cake from the process according to the invention have protein contents of greater than 30%. Also, the 2 cakes are less loaded than the values expected after drying and delipidation (31-32% against 48% theoretical). This difference can come from the presence in the cake of non-protein nitrogen in significant amount (nitrates or nitrites) or a solubilization of proteins in the miscella. This last hypothesis seems the most probable since the proteins of lesquerella are more succulated in basic medium.
• the reactive or non-reactive trituration process does not induce any significant change in the aminogram. However, the enrichment of the cake in some amino acids (alanine, glutamic acid, methionine + cystine, leucine, phenylalanine, valine, aspartic acid, arginine) is observed;
• lesquerella Compared to soybean meal, that of lesquerella is less rich in protein (31% versus 45%). It is also relative to relative concentrations, less rich in essential amino acids, especially cystine and methionine. That of lesquerella is more concentrated in cellulose and starch;
• cakes derived from the examples (above) of processes according to the invention contain less than 1% by weight of anti-nutritional elements.
• the high content of gums of desquerella seed (15%) is demonstrated during the reactive and non-reactive trituration tests according to the invention.
• the method according to the invention confirms the value of developing these gums which have properties similar to xanthan and arabic gums.
• the objective of this step is to concentrate the methyl mesterolate obtained at the output of a reactive trituration process.
• LM methyl laquerolate
• the monoglycerides are in turn reduced to a content of 5.8% in the methanolic phase;
• the LM content in the extracted ester is about 91%, more than 30 points that the raw material of departure;
• the monoglyceride content in the extracted ester remains stable at 1.4%.
• This concentrated ester may optionally be used to produce a synthetic oil enriched in hydroxylated acids.
• the method according to the invention improves both the extractability of lipids and esters of lesquerella seeds. It manages in particular to concentrate the lesquerolic acid.

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