Classifications

• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
  • A23D9/00—Other edible oils or fats, e.g. shortenings, cooking oils
  • A23D9/007—Other edible oils or fats, e.g. shortenings, cooking oils characterised by ingredients other than fatty acid triglycerides
• • 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
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
  • A23D9/00—Other edible oils or fats, e.g. shortenings, cooking oils
  • A23D9/007—Other edible oils or fats, e.g. shortenings, cooking oils characterised by ingredients other than fatty acid triglycerides
  • A23D9/013—Other fatty acid esters, e.g. phosphatides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D11/00—Solvent extraction
  • B01D11/02—Solvent extraction of solids
  • B01D11/0288—Applications, solvents
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D11/00—Solvent extraction
  • B01D11/02—Solvent extraction of solids
  • B01D11/0292—Treatment of the solvent
• • 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

Definitions

• the invention relates to the field of production of defatted oils and cakes from a biological substrate by a solid / liquid extraction process.
• the solid / liquid extraction method comprises a solid / liquid extraction step involving a solvent to obtain a liquid fraction comprising an oil and the solvent.
• Solid residues also called cake
• solid residues are mainly used in animal feed, and increasingly in human food, mainly as a protein supplement, but also as a metabolizable energy source.
• hexane is the most widely used solvent in the solid / liquid extraction process because it has advantageous properties. Indeed, hexane allows a high yield extraction of the oil (> 97%) and allows to leave less than 3% of residual oil in the solid substrate, which prevents the latter from becoming rancid. Hexane is easy to separate from the extracted oil, it has a suitable boiling point (ie high enough to limit losses during extraction but low enough to limit energy consumption during its separation from oil extracted and during its recycling), it is stable and has good lipid selectivity.
• hexane has significant drawbacks. It is of petroleum origin, it is neurotoxic and is classified as toxic for reproduction of category 2. It is also toxic for the aquatic environment of category 2.
• the present invention therefore aims to provide an industrial solid / liquid extraction process which makes it possible to produce a crude oil rich in polyphenol and / or a defatted oil cake.
• the Applicant has developed a process which meets this need.
• the invention relates to a process for producing a crude oil rich in polyphenol from a biological substrate comprising a step of:
• the solvent comprises 2-methyloxolane and water
• the mass percentage of water in the solvent during step a) of extraction is from 0.3% to 20%.
• solid / liquid extraction means obtaining a liquid fraction and a solid residue from a solid biological substrate using a liquid solvent as solvent for extraction.
• solid / liquid extraction can be carried out by decoction, infusion, digestion, percolation, leaching or maceration.
• a liquid / liquid extraction step is not a solid / liquid extraction step within the meaning of the present invention because it does not use a solid biological substrate; moreover, the physico-chemical characteristics involved in a solid / liquid extraction step and in a liquid / liquid extraction step are different.
• crude oil means an unrefined oil, ie which has not undergone a chemical or mechanical refining step, also called physical, after its extraction by a solid / liquid process .
• the method according to the invention makes it possible to produce a crude oil richer in polyphenol than the crude oil produced by the methods using anhydrous hexane or 2-methyloxolane.
• "crude oil rich in polyphenol” means a crude oil comprising one or more polyphenols and whose mass concentration of polyphenols is greater than or equal to 100 ppm, in particular from 320 ppm to 2000 ppm, more particularly from 350 ppm to 1500 ppm, more particularly still from 400 ppm to 1200 ppm.
• polyphenol means a class of molecules characterized by the presence of several phenolic groups arranged in complex structures.
• Crude oil may also include a tocopherol.
• Tocopherols have antioxidant properties which advantageously protect crude oil from oxidation and therefore from rancidity. In addition tocopherols have beneficial effects on health, in particular in prevention against cardiovascular diseases. Crude oil comprising a tocopherol can therefore have beneficial effects on health, in particular in prevention against cardiovascular diseases.
• the mass concentration of tocopherol in crude oil can be greater than or equal to 350 ppm, in particular from 825 ppm to 10,000 ppm, more particularly from 1,500 ppm to 5,000 ppm, more particularly still from 2,000 ppm to 3,000 ppm.
• this mass concentration of tocopherol is greater than the mass concentration of tocopherol in a crude oil produced by processes using anhydrous hexane or 2-methyloxolane.
• the mass concentration of tocopherol in the crude oil can be greater than or equal to 350 ppm, in particular from 825 ppm to 10,000 ppm, more particularly from 1,500 ppm to 5,000 ppm, more particularly still from 2000 ppm to 3000 ppm, with the exception of the crude oil produced from the biological substrate which is rapeseed, the mass concentration of tocopherol in the crude oil can be from 825 ppm to 10,000 ppm, more particularly from 1500 ppm to 5000 ppm, more particularly still from 2000 ppm to 3000 ppm.
• Crude oil may also include 2-methyloxolane.
• the mass concentration of 2-methyloxolane in the crude oil can be from 0.5 ppm to 500 ppm, in particular from 50 ppm to 300 ppm.
• the method according to the invention uses a solvent comprising 2-methyloxolane (CAS No. 96-47-9) and water.
• 2-methyloxolane is not classified as toxic to the environment and is of biobased origin because its raw material is typically from bagasse of cane sugar or corn cobs.
• 2-methyloxolane is non-toxic when ingested for the amounts envisaged. Indeed, a published test of 3 months in ingestion on rats showed a dose in observed adverse effect ("NOAEL - Non Observed Adverse Effect Limit", according to English terminology) of 250 mg / kg body weight / day against 23 mg / kg bodyweight / day for hexane (Parris et al. Regulatory Toxicology and Pharmacology 87 (2017) 54-63 and Opinion of the European Scientific Committee for Food published on June 17, 1994).
• the mass percentage of water in the solvent is from 1% to 15%, more particularly from 4% to 6% during step a) of extraction.
• the mass percentage of water in the solvent corresponds to the mass of water in the solvent divided by the total mass of the solvent at the inlet of the extractor in which the step a) of extraction is carried out.
• the mass percentage of water in the solvent can be determined by the Karl Fischer method.
• biological substrate means a solid material chosen from a plant, an alga, a microorganism and their mixtures, in particular a plant.
• the biological substrate is a vegetable
• the crude oil obtained according to the method according to the invention is called crude vegetable oil.
• the vegetable can be an oilseed, a protein crop or a mixture thereof.
• oilseeds mention may be made of rapeseed, sunflower, soy, peanut, sesame, walnut, almond, cotton, flax or their mixtures, in particular rapeseed, sunflower, soy or their mixtures.
• Examples of protein crops are peas, beans, lupine and their mixture.
• the biological substrate can be a plant chosen from almond, amaranth, peanut, argan, sea buckthorn, cashew, avocado, oats, borage, safflower , camelina, carrot, cocoa, cashew, hemp, rapeseed, copra, squash, cotton, croton, rose hips, fig, prickly pear, pomegranate, hops, illipe, jojoba, shea, flax, lupine, corn, hazel, walnut, coconut, flax, olive, evening primrose, palm kernel, paprika, pecan, pistachio, pepper, castor, rice, rosebush, sesame, soy, marigold, sunflower, Calophyllum inophyllum, madhuca, Queensland walnut, raspberry, blackcurrant, melon, grape, tomato, baobab, babassu, cranberry, chia, pumpkin, mustard, neem, Nigella Sativa,
• step a) of extraction can be carried out from the whole plant or from one or more parts of the plant, and in particular a part chosen from the root , the stem, the bark, the flower, the seed, the germ, the leaf, the bran, the fruit, the nut, the seeds, the nucleus.
• the organic substrate can be chosen from oat bran, raspberry seeds, blackcurrant seeds, pomegranate seeds, melon seeds, grape seeds, tomato seeds, seeds baobab, babassu seeds, cranberry seeds, chia seeds, corn seeds, cotton seeds, peanut seeds, rapeseed seeds, squash seeds, madhuca seeds, seeds mustard, neem seeds, Nigella Sativa seeds, niger seeds, poppy seeds, Perilla seeds, Plukenetia volubili seeds, pumpkin seeds, annatto seeds, rice bran, soybeans, taramira seeds, sunflower seeds, apricot kernels, plum kernels, peach kernels, Calophyllum inophyllum, walnuts, cashews, macadamia nuts, coconut, pecan, especially soybeans, colz seeds a, sunflower seeds, baobab seeds and their mixtures.
• the biological substrate is chosen from soybeans, rapeseed, sunflower seeds and their mixtures.
• the biological substrate is an alga
• it can be chosen from the genera Arthrospira, Haematococcus, Dunaliella, Chlorella, Nannochloropsis, Schizochytrium, Crypthecodinium, Culindrotheca, Isochrysis, Nannochloris, Nitzchia, Phaeodactylum, Chaetoceros and their mixtures.
• the biological substrate is a microorganism chosen from yeast, mold, bacteria, fungus or a mixture thereof.
• the yeast can typically be chosen from the genera Cryptococcus, Candida, Lipomyces, Rhodotorula, Saccharomyces, Trichosporon, Yarrowia and their mixtures.
• the biological substrate may have undergone, before the extraction step a), a preliminary preparation step.
• This preparation step can be, for example, a flattening also called flaking to obtain a flake, grinding, mechanical extraction to obtain a flake, pressure, centrifugation, cooking, lyophilization, enzymatic lysis, mechanical lysis , a maceration, a trituration to obtain an oil cake, an ultrasonic treatment, a microwave treatment, a drying or their mixtures or any combination of the said preparations.
• Step a) of extraction can typically be carried out in batch ("batch" in English) or continuously.
• step a) of extraction is carried out in a batch
• the biological substrate and the solvent are advantageously mixed in an extractor, such as a fixed bed extractor or an extractor with dispersed charge.
• an extractor such as a fixed bed extractor or an extractor with dispersed charge.
• the mass ratio biological substrate: solvent can be from 1: 1 to 1: 50, in particular from 1: 2 to 1: 20, more particularly from 1: 5 to 1 : 10.
• step a) of extraction is carried out continuously, the biological substrate arrives continuously in an extractor in a movable bed, such as extractors with movable compartments, movable baskets, conveyor chains or conveyor belt.
• the solvent is brought into contact with the biological substrate by circulation or percolation, typically against the current of the biological substrate.
• the mass ratio of biological substrate: solvent can advantageously be from 1: 0.5 to 1: 5, in particular from 1: 0.75 to 1: 3, more particularly from 1: 1 to 1: 1, 3.
• step a) of extraction is advantageously carried out at a temperature of 20 ° C to 100 ° C, in particular from 40 ° C to 80 ° C, more particularly from 55 ° C to 75 ° C.
• the extraction step a) is facilitated in these temperature ranges because they are compatible with the boiling point of the azeotrope 2-methyloxolane / water which is 71 ° C.
• the method according to the invention may further comprise a step b) of recovery of the liquid fraction comprising the crude oil and the solvent.
• the method according to the invention can comprise, in addition to step a) of extraction, the following steps:
• Step b) of recovery of the liquid fraction makes it possible to separate the liquid fraction from the solid residue.
• this step b) can be carried out by filtration.
• Step c) of separation can be carried out by liquid / liquid extraction, by steaming, by heating, by distillation or a combination thereof, in particular by steaming, by distillation or combinations thereof, especially by distillation.
• step c) of separation can be carried out in batch or continuously.
• Steps b) and c) are conventional steps in the processes for producing oils by solid / liquid extraction. Those skilled in the art will be able to adapt the operating conditions of these steps to carry them out.
• the method according to the invention may comprise, after step c), a step d) of recycling in step a) of extraction of all or part of the solvent recovered at the end of the step vs).
• step c) recycling the solvent recovered at the end of step c) makes it possible to reduce the economic cost of the raw material of the process according to the invention and therefore to improve its industrial viability.
• step d ') of reducing the mass percentage of water is particularly advantageous when the mass percentage of water in the solvent recovered at the end of step c) is greater than 20%, in particular greater than 15%, very particularly greater than 6%.
• all or part of the solvent recovered at the end of step c) is directly recycled in step a) of extraction during step d) of recycling.
• the method does not include, between step c) and step d), step d ') of reducing the mass percentage of water.
• This second variant is particularly advantageous when the mass percentage of water in the solvent recovered at the end of step c) is from 0.3% to 20%, in particular from 1% to 15%, more particularly from 4% at 6%.
• step d ') of reducing the mass percentage of water can be carried out by condensation, by decantation, by distillation or their combinations, in particular by condensation, by decantation or their combination, more particularly by decantation followed by distillation.
• an azeotrope comprising 89.4% by weight of 2-methyloxolane and 10.6% by weight of water at 71 ° C. during condensation.
• the mass percentage of water in the solvent can be from 1% to 25%, in particular from 5% to 20% and more particularly from 10% to 12% after the condensation. It may also be advantageous to dissolve the water in 2-methyloxolane directly during condensation or possible decantation, the solubility of the water in 2-methyloxolane being 4.1% at 20 ° C. and 4.6% at 60 ° C.
• the mass percentage of water in the solvent can be from 0.3% to 20%, in particular from 1% to 15%, more particularly from 4% to 6% after condensation or possible decantation.
• step d ') of reducing the mass percentage of water can be carried out by condensation followed by decantation and:
• the mass percentage of water in the solvent after condensation is from 1% to 25%, in particular from 5% to 20% and more particularly from 10% to 12%, and
• the mass percentage of water in the solvent after decantation is from 0.3% to 20%, in particular from 1% to 15%, more particularly from 4% to 6%.
• Crude oil can include impurities such as gums, waxes, free fatty acids, pigments, metallic traces, volatile odor compounds and mixtures thereof.
• the crude oil can therefore undergo a refining step to remove at least one of these impurities from the crude oil and recover a refined oil.
• this refined oil can be adapted, for example, for food use, for cosmetic use, for pharmaceutical use and / or for technical use.
• An embodiment of the invention is a method for producing a refined oil comprising a step of refining the crude oil recovered during step c) of the method for producing a crude oil according to the invention.
• the refined oil produced by the process for producing a refined oil according to the invention can comprise a tocopherol.
• a refined oil comprising a tocopherol can have beneficial effects on health.
• the mass concentration of tocopherol in the refined oil may be greater than or equal to 350 ppm, in particular from 825 ppm to 10,000 ppm, more particularly from 1,500 ppm to 5,000 ppm, more particularly still from 2,000 ppm to 3,000 ppm. For the same biological substrate, this mass concentration is greater than the mass concentration of tocopherol in a refined oil produced by processes using anhydrous hexane or 2-methyloxolane.
• the mass concentration of tocopherol in the refined oil can be greater than or equal to 350 ppm, in particular from 825 ppm to 10,000 ppm, more particularly from 1,500 ppm to 5,000 ppm, more particularly still from 2000 ppm to 3000 ppm, with the exception of the refined oil produced from the biological substrate which is rapeseed, the mass concentration of tocopherol in the crude oil can be from 825 ppm to 10,000 ppm, more particularly from 1,500 ppm to 5,000 ppm, more particularly still from 2,000 ppm to 3,000 ppm.
• the refined oil produced by the process for producing a refined oil according to the invention can comprise 2-methyloxolane.
• the mass concentration of 2-methyloxolane in the crude oil decreases during the refining stage.
• the mass concentration of 2-methyloxolane in the refined oil is very low.
• the mass concentration of 2-methyloxolane in the refined oil can be less than or equal to 5 ppm, in particular from 0.01 ppm to 3 ppm, more particularly from 0.1 ppm to 1 ppm.
• the refined oil produced by the process for producing a refined oil according to the invention does not include hexane.
• this refined oil is safer than a refined oil obtained by a conventional process using hexane because, unlike 2-methyloxolane, hexane is neurotoxic and is classified as toxic for reproduction of category 2.
• a refined oil with a mass concentration of 2-methyloxolane greater than 5 ppm has degraded organoleptic properties.
• the refined oil produced by the process for producing a refined oil according to the invention therefore advantageously has satisfactory organoleptic properties.
• the refining step can be a chemical refining step and / or a physical refining step.
• the chemical refining step can comprise at least one of the following substeps:
• the physical refining step can include at least one of the following substeps:
• distillation in particular vacuum distillation with steam injection, to remove volatile odorous compounds and free fatty acids, recovered in the form of distillate.
• the lecithins recovered during the degumming sub-step and the distillate recovered during the distillation step include polyphenols. They are therefore good for health.
• the lecithins recovered during the degumming sub-step can in particular be used as an emulsifier.
• the distillate recovered during the distillation step can for example be used in a pharmaceutical, nutraceutical or cosmetic composition. It can also be used as a food supplement.
• the method according to the invention also makes it possible to produce a solid residue.
• the invention relates to a process for producing a solid residue comprising in a step e) recovery of the solid residue obtained during step a) of solid / liquid extraction of the process of production of a crude oil rich in polyphenol according to the invention.
• solid residue means the defatted solid produced by the process for producing a solid residue according to the invention from the biological substrate.
• the solid residue is also called oil cake.
• the mass concentration of polyphenol in the solid residue produced by the process for producing a solid residue according to the invention is less than the mass concentration of polyphenols in a solid residue produced by a conventional process using hexane .
• the solid residue produced by the process for producing a solid residue according to the invention comprises a polyphenol and a residual oil, the mass concentration of polyphenol in said solid residue being less than or equal to 3000 ppm, in particular 10 ppm to 1500 ppm, more particularly from 50 ppm to 500 ppm and the mass concentration of residual oil in said solid residue being less than or equal to 5%, in particular from 0.1% to 3%, more particularly from 0.3% at 2%.
• the solid residue produced by the process for producing a solid residue according to the invention advantageously has a mass concentration of residual oil lower than a solid residue produced by a conventional process using hexane or a process using anhydrous 2-methyloxolane.
• a "residual oil” included in the solid residue is an oil extracted according to the process described in standard NF EN ISO 734: Feb 2016.
• Step e) of recovery of the solid residue makes it possible to separate the liquid fraction from the solid residue. Typically this step e) can be carried out by filtration.
• the solid residue may comprise solvent for the process according to the invention, in particular 2-methyloxolane.
• the solid residue can therefore undergo a desolvation step f) after step e) to recover on the one hand the solvent and on the other hand a desolvated solid residue.
• Another embodiment of the invention is a process for producing a desolvated solid residue comprising a step f) of desolvation of the solid residue recovered during step e) of the process for producing the solid residue according to the invention for recovering on the one hand the solvent and on the other hand the desolvated solid residue.
• the desolvation step f) can be carried out by heating the solid residue then injecting steam into the heated solid residue, optionally accompanied by placing under vacuum.
• the vapor may be a vapor of the solvent according to the invention, a superheated vapor of the solvent according to the invention, a vapor of anhydrous 2-methyloxolane, a superheated vapor of anhydrous 2-methyloxolane, a vapor of water, a superheated vapor of water and their mixtures, in particular a superheated vapor of the solvent according to the invention or a superheated vapor of anhydrous 2-methyloxolane, more particularly a superheated vapor of the solvent according to the invention.
• a desolvation step reduces the mass concentration of 2-methyloxolane present in the solid residue.
• the desolvated solid residue comprises 2-methyloxolane and the mass concentration of 2-methyloxolane can typically be less than 1000 ppm, in particular from 10 ppm to 500 ppm, very particularly from 100 ppm to 300 ppm.
• the mass concentration of residual oil in the desolvated solid residue is less than or equal to 5%, in particular from 0.1% to 3%, more particularly from 0.3% to 2%.
• the solid residue can undergo a pretreatment step before step f) of desolvation such as an additional wetting to adjust the water content in the solid residue.
• this additional wetting step can facilitate the desolvation of the solid residue.
• a person skilled in the art will know how to adapt this additional wetting step as a function of the desired water content in the solid residue.
• the desolvated solid residue can then be transformed into a by-product intended, for example, for animal feed or human food.
• Another embodiment of the invention is therefore a process for producing a by-product comprising a step g) of processing the desolvated solid residue recovered during step f) of the process for producing a solid residue desolvated according to the invention to produce the by-product.
• the by-product produced by the process for producing a by-product according to the invention is particularly suitable for feeding animals, in particular cattle. In fact it is degreased, because it comes from the solid residue, and does not disturb the digestion of animals, in particular cattle. In addition, this by-product is safer than a by-product obtained by a conventional process using hexane because, unlike 2-methyloxolane, hexane is neurotoxic and is classified as toxic for reproduction category. 2.
• the by-product can be chosen from a flour, a protein concentrate, protein isolate, a textured protein and their mixtures.
• the term "flour” means the by-product from the grinding, milling or spraying of the solid residue in order to obtain a powder.
• protein concentrate means a by-product resulting from the treatment of the solid residue by solid extraction. liquid so as to remove the sugars and anti-nutritional factors, so as to obtain a solid fraction containing approximately 60 to 70% of proteins.
• protein isolate means a by-product obtained from treatment in an aqueous medium via a succession of steps of the solid residue so as to obtain a solid fraction containing approximately 90% protein.
• textured protein means a by-product resulting from the treatment by extrusion of a flour or a protein concentrate.
• the transformation step g) can be chosen from a grinding step, a solid-liquid extraction step, a protein solubilization step, a protein precipitation step, a step centrifugation, an extrusion step, a protein modification step, a functionalization step of proteins or their mixtures.
• the processing step g) can be a grinding step.
• the transformation step g) can be a solid-liquid extraction step using a hydro-alcoholic mixture.
• step g) of transformation can be a succession of steps of solubilization and precipitation of proteins at specific pH so as to selectively remove the sugars and fibers initially present in the solid residue.
• the transformation step g) can be an extrusion step from a flour or a protein concentrate.
• Step g) of transformation can reduce the mass concentration of 2-methyloxolane.
• the by-product comprises 2-methyloxolane and the mass concentration of 2-methyloxolane is less than 1000 ppm, in particular less than 500 ppm, very particularly from 0.5 ppm to 50 ppm.
• the mass concentration of 2-methyloxolane in the by-product may depend on the by-product.
• the mass concentration of 2-methyloxolane in flour can be less than 1000 ppm, in particular less than 500 ppm, very particularly from 5 ppm to 50 ppm.
• the mass concentration of 2-methyloxolane in the protein concentrate, in the protein isolate or in the textured protein can typically be less than 30 ppm, in particular from 0.5 ppm to 20 ppm, very particularly from 8 ppm to 12 ppm.
• the mass concentration of residual oil in the by-product is less than or equal to 5%, in particular from 0.1% to 3%, more particularly from 0.3% to 2%.
• the method according to the invention may further comprise a step h) of recycling in step a) of extraction of all or part of the solvent recovered during step f) of desolvation .
• step h all or part of the solvent recovered at the end of step f) of desolvation undergoes, before step h) of recycling, a step h ') of reduction of the mass percentage of water.
• This first variant is particularly advantageous when the mass percentage of water in the solvent recovered at the end of the desolvation step f) is greater than 20%, in particular greater than 15%, very particularly greater than 6%.
• the process does not include, between stage f) of desolvation and stage h) of recycling, of stage h ') of reduction of the mass percentage of water.
• This second variant is particularly advantageous when the mass percentage of water in the solvent recovered at the end of the desolvation step f) is from 0.3% to 20%, in particular from 1% to 15%, more particularly from 4% to 6%.
• Step h ') of reducing the mass percentage of water is carried out under the same conditions as step d') of reducing the mass percentage of water.
• all or part of the solvents recovered during steps c) and f) can be mixed and all or part of their mixture can be recycled in step a) of extraction in step i ) recycling.
• all or part of the solvents recovered during steps c) and f) can be mixed and all or part of their mixture can undergo a step i ') of reducing the mass percentage of water before be recycled in step a) of extraction in a step i) of recycling.
• step i) the method does not include, between steps c) and f) and step i), step i ') of reducing the mass percentage of water.
• Step i ') of reducing the mass percentage of water is carried out under the same conditions as step d') of reducing the mass percentage of water.
• the process for producing a crude oil according to the invention comprises the following steps:
• step d) recycling in step a) of all or part of the solvent recovered during step c) after a step d) of reduction of the mass percentage of water in all or part of the solvent recovered at the end of the step c) by condensation followed by decantation and:
• the mass percentage of water in the solvent after condensation is from 1% to 25%, in particular from 5% to 20% and more particularly from 10% to 12%, and
• the mass percentage of water in the solvent after decantation is from 0.3% to 20%, in particular from 1% to 15%, more particularly from 4% to 6%.
• the process for producing a desolvated solid residue according to the invention comprises the following steps: a) solid / liquid extraction of the biological substrate with the solvent to obtain on the one hand a fraction liquid comprising the crude oil and the solvent and on the other hand a solid residue,
• step f) desolvation of the solid residue recovered during step e) to obtain on the one hand the solvent and on the other hand the desolvated solid residue
• step h) recycling in step a) of all or part of the solvent recovered during step f).
• the process for producing a by-product according to the invention comprises the following steps:
• step h) recycling in step a) of all or part of the solvent recovered during step f).
• the method for producing a crude oil according to the invention makes it possible to produce a crude oil advantageously rich in polyphenol and which can comprise 2-methyloxolane.
• the invention also relates to a crude oil rich in polyphenol derived from a biological substrate, said crude oil comprising one or more polyphenols, 2-methyloxolane, and being characterized in that the mass concentration of polyphenol is greater or equal to 100 ppm, in particular said crude oil is capable of being obtained by the process for producing a crude oil according to the invention.
• the term “crude oil rich in polyphenol” means a crude oil comprising one or more polyphenols and the mass concentration of polyphenol of which is greater than or equal to 100 ppm, in particular from 320 ppm to 2000 ppm, more particularly from 350 ppm to 1500 ppm, more particularly still from 400 ppm to 1200 ppm.
• the mass concentration of 2-methyloxolane in the crude oil can be from 0.5 ppm to 500 ppm, in particular from 50 ppm to 300 ppm.
• Crude oil may also include a tocopherol.
• the mass concentration of tocopherol in the crude oil can be greater than or equal to 350 ppm, in particular from 825 ppm to 10,000 ppm, more particularly from 1,500 ppm to 5,000 ppm, more particularly still from 2,000 ppm to 3,000 ppm.
• this mass concentration of tocopherol is greater than the mass concentration of tocopherol in a crude oil produced by processes using anhydrous hexane or 2-methyloxolane.
• the mass concentration of tocopherol in the crude oil can be greater than or equal to 350 ppm, in particular from 825 ppm to 10,000 ppm, more particularly from 1,500 ppm to 5,000 ppm, more particularly still from 2000 ppm to 3000 ppm, with the exception of the crude oil produced from the biological substrate which is rapeseed, the mass concentration of tocopherol in the crude oil can be from 825 ppm to 10,000 ppm, more particularly from 1500 ppm to 5000 ppm, more particularly still from 2000 ppm to 3000 ppm.
• the biological substrate is as described above in connection with the process for producing a crude oil according to the invention.
• Crude oil can advantageously be good for health because it is rich in polyphenol and can include a tocopherol.
• the crude oil can be adapted, for example, for food use, for cosmetic use, for pharmaceutical use and / or for technical use.
• the subject of the present invention is the use of this crude oil for the preparation of a composition such as a food composition, a cosmetic composition and a pharmaceutical composition.
• the process for producing a refined oil according to an embodiment of the invention advantageously makes it possible to produce a refined oil comprising a tocopherol so that this refined oil can have beneficial effects on the health.
• an object of the invention is a refined oil obtained from a biological substrate comprising a tocopherol, the mass concentration of tocopherol in the refined oil being greater than or equal to 500 ppm, in particular said refined oil is capable of 'be obtained by the process for producing a refined oil according to an embodiment of the invention.
• the mass concentration of tocopherol in refined oil can be greater than or equal to 350 ppm, in particular from 825 ppm to 10,000 ppm, more particularly from 1,500 ppm to 5,000 ppm, more particularly still from 2,000 ppm to 3,000 ppm .
• this concentration mass by tocopherol is greater than the mass concentration by tocopherol in a refined oil produced by processes using anhydrous hexane or 2-methyloxolane.
• the mass concentration of tocopherol in the refined oil can be greater than or equal to 350 ppm, in particular from 825 ppm to 10,000 ppm, more particularly from 1,500 ppm to 5,000 ppm, more particularly still from 2000 ppm to 3000 ppm, with the exception of the refined oil produced from the biological substrate which is rapeseed, the mass concentration of tocopherol in the crude oil can be from 825 ppm to 10,000 ppm, more particularly from 1500 ppm to 5000 ppm, more particularly still from 2000 ppm to 3000 ppm.
• the refined oil of the invention can also comprise 2-methyloxolane.
• This refined oil is safer than a refined oil produced by a conventional process using hexane because, unlike 2-methyloxolane, hexane is neurotoxic and is classified as toxic for reproduction category 2.
• the mass concentration of 2-methyloxolane in the refined oil can be less than or equal to 5 ppm, in particular from 0.01 ppm to 3 ppm, more particularly from 0.1 ppm to 1 ppm.
• a refined oil whose mass concentration of 2-methyloxolane is greater than 5 ppm has degraded organoleptic properties.
• the refined oil according to the invention therefore advantageously has satisfactory organoleptic properties.
• the biological substrate is as described above in connection with the process for producing a crude oil according to the invention.
• Refined oil that includes a tocopherol can be beneficial for health.
• the refined oil can be adapted, for example, for food use, for cosmetic use, for pharmaceutical use.
• the subject of the present invention is the use of this refined oil for the preparation of a composition such as a food composition, a cosmetic composition and a pharmaceutical composition.
• the process for producing a refined oil according to an embodiment of the invention also makes it possible to produce lecithins and / or a distillate comprising a polyphenol.
• an object of the invention is lecithins from a biological substrate comprising a polyphenol, in particular said lecithins are capable of being obtained by the process for the production of a refined oil according to an embodiment of the 'invention.
• the biological substrate is as described above in connection with the process for producing a crude oil according to the invention.
• the lecithins include polyphenols. They are therefore good for health.
• lecithins can in particular be used as an emulsifier.
• An object of the invention is a distillate from a biological substrate comprising a polyphenol, in particular said distillate is capable of being obtained by the process for producing a refined oil according to one embodiment of the invention.
• the biological substrate is as described above in connection with the process for producing a crude oil according to the invention.
• the distillate can for example be used in a pharmaceutical, nutraceutical or cosmetic composition. It can also be used as a food supplement.
• the subject of the present invention is the use of this distillate for the preparation of a composition such as a pharmaceutical composition, a nutraceutical composition or cosmetic composition.
• the present invention relates to the use of this distillate as a food supplement.
• the method for producing a solid residue according to an embodiment of the invention advantageously makes it possible to produce a solid residue depleted in polyphenols and comprising a low mass concentration of residual oil.
• an embodiment of the invention is a solid residue derived from a biological substrate comprising a polyphenol and a residual oil, the mass concentration of polyphenol of which is less than or equal to 3000 ppm, in particular from 10 to 1500 ppm, more particularly from 50 to 500 ppm and whose mass concentration in residual oil is less than or equal to 5%, in particular from 0.1% to 3%, more particularly from 0.3% to 2%, in particular said solid residue is capable of being obtained by the process for producing a solid residue according to an embodiment of the invention.
• the biological substrate is as described above in connection with the process for producing a crude oil according to the invention.
• the residual oil included in the solid residue is as defined above in connection with the process for producing a solid residue.
• the solid residue can also comprise 2-methyloxolane.
• the solid residue does not include hexane.
• the solid residue can then be transformed into a by-product intended, for example, for animal feed or human food.
• the present invention also relates to the use of this solid residue for the preparation of an animal or human food composition.
• one embodiment of the invention is a desolvated solid residue derived from a biological substrate comprising 2-methyloxolane and whose mass concentration of 2-methyloxolane is less than 1000 ppm, in particular from 10 ppm to 500 ppm, very particularly from 100 ppm to 300 ppm, in particular said desolvated solid residue is capable of being obtained by the process for the production of a desolvated solid residue according to an embodiment of the invention.
• the mass concentration of residual oil in the desolvated solid residue is less than or equal to 5%, in particular from 0.1% to 3%, more particularly from 0.3% to 2%.
• the desolvated solid residue does not include hexane.
• the biological substrate is as described above in connection with the process for producing a crude oil according to the invention.
• the desolvated solid residue can then be transformed into a by-product intended, for example, for animal feed or human food.
• Another subject of the present invention is the use of this desolvated solid residue for the preparation of an animal or human food composition.
• the invention also relates to a by-product derived from a biological substrate comprising 2-methyloxolane and whose mass concentration in 2-methyloxolane is less than 1000 ppm, in particular less than 500 ppm, very particularly from 0.5 ppm to 50 ppm, in particular said by-product is capable of being obtained by the process for producing a by-product according to one embodiment of the invention.
• the by-product can be chosen from a flour, a protein concentrate, protein isolate, a textured protein, and their mixtures.
• the mass concentration of 2-methyloxolane in the by-product may depend on the by-product.
• the mass concentration of 2-methyloxolane in flour can be less than 1000 ppm, in particular less than 500 ppm, very particularly from 5 ppm to 50 ppm.
• the mass concentration of 2-methyloxolane in the protein concentrate, in the protein isolate or in the textured protein can typically be less than 30 ppm, in particular from 5 ppm to 20 ppm, very particularly from 8 ppm to 12 ppm .
• the mass concentration of residual oil in the by-product is less than or equal to 5%, in particular from 0.1% to 3%, more particularly from 0.3% to 2%.
• the by-product does not include hexane.
• the biological substrate is as described above in connection with the process for producing a crude oil according to the invention.
• the by-product being particularly suitable for food, in particular animal food
• the present invention also relates to the use of this by-product for the preparation of a food composition, in particular a food composition. animal.
• the mass concentration of polyphenols in crude oil, in solid residue, in lecithins and in distillate is determined according to the method known as "Folin Ciocalteu” described by Slinkard and Singleton in publication “Total Phenol Analysis: Automation and Comparison with Manual Methods” published in the journal “American Journal of Enology and Viticulture 28, no 1 (January 1, 1977): 49-55".
• Folin Ciocalteu described by Slinkard and Singleton in publication “Total Phenol Analysis: Automation and Comparison with Manual Methods” published in the journal “American Journal of Enology and Viticulture 28, no 1 (January 1, 1977): 49-55”.
• Those skilled in the art know how to adapt this method to the sample analyzed and for its implementation on a 96-well microplate reader (FLUOstar Omega, BMG LABTECH, France).
• the operating conditions are as follows: 0.50 ⁇ 0.01 g of sample to be analyzed are weighed in a 20 mL bottle, specially designed for the "HeadSpace" technique (23 x 77 mm), then 7.0 mL of ultrapure water and 1.0 mL of DMF (N, N-dimethylformamide) are added to the bottle. The bottle is then closed hermetically using a cap fitted with a suitable septum. The bottle is then shaken vigorously for 30 seconds before analysis.
• the mass concentration of 2-methyloxolane in the analyzed sample of protein isolate is determined using a calibration curve performed over a range of mass concentrations of suitable 2-methyloxolane.
• the operating conditions are as follows: the solid residue is first ground using a ZM 200 centrifugal mill (Retsch GmbH) equipped with a 0.2 mm sieve. Then 0.5 ⁇ 0.01 g of the ground sample to be analyzed is weighed in a 20 mL bottle, specially designed for the "HeadSpace" technique (23 x 77 mm). Then 2.0 mL of water is added precisely to the bottle before closing it tightly with a cap fitted with a septum. The bottle is left to stand for at least 5 min before analysis.
• the method for determining the mass concentration of polyphenols in crude oils is the so-called “Folin Ciocalteu” method, described by Slinkard and Singleton in the publication “Total Phenol Analysis: Automation and Comparison with Manual Methods ”published in the journal“ American Journal of Enology and Viticulture 28, no 1 (January 1, 1977): 49-55 ”, with the modifications described below to implement it on a 96-well microplate reader (FLUOstar Omega , BMG LABTECFI, France). All the reagents and solvents used are of suitable analytical quality.
• the polyphenols contained in the crude oil are previously extracted by the following method: 1 g of oil is diluted in 1 ml of hexane, then the solution is extracted by 3 successive extractions with 3 ml of a methanol / water mixture ( 60% vol / 40% vol). After each extraction, the 2 phases are agitated and then separated by centrifugation (10,000 rpm-1/10 min / 20 ° C) and the liquid alcoholic phase is collected (any deposits, precipitates or potentially formed solid particles are not not taken). The 3 hydroalcoholic phases are combined and then washed with 1 ml of hexane. The phases are separated by centrifugation then the hydro-alcoholic phase is transferred to a 10 ml volumetric flask, and the volume is made up to the mark with the methanol / water mixture (60% vol / 40% vol).
• the absorbance of each well is read by the UV-Visible detector of the microplate reader at 750 nm at 25 ° C after 1 h of agitation in the dark in the device.
• a standard curve was established using 8 aqueous solutions of gallic acid (Sigma-Aldrich) in a concentration range from 0 to 100 mg / L of gallic acid, according to the same protocol. analysis defined for the samples, the difference being that the solution comprising the phase and the methanol / water mixture is replaced by one of the 8 aqueous solutions of gallic acid.
• PVPP polyvinylpolypyrrolidone
• the supernatant is then removed and then filtered using a syringe filter (0.25 ⁇ m) before being analyzed according to the same protocol as the solution not treated with PVPP.
• the absorbance value of this solution treated with PVPP will be used as "blank", it will be subtracted from the value obtained previously.
• the absorbance value thus obtained is used to calculate the mass concentration of polyphenols in the sample, from the equation of the calibration line.
• the mass concentration of polyphenols in the sample is expressed in pg of gallic acid (EAG, abbreviated) / g of crude oil, or equivalent, in ppm.
• the method for determining the mass concentration of tocopherols in crude oils and in refined oils is standard NF EN ISO 9936: June 201 6 ..
• the method for determining the mass concentration of 2-methyloxolane in the refined oil is implemented using the conventional technique of analytical chemistry known as "GC-HeadSpace" (Chromatography in gas phase with removal of the headspace), under the conditions described below.
• GC-HeadSpace Chromatography in gas phase with removal of the headspace
• the calibration curve has been drawn, according to the classical principles of chemistry analytical, by adding known quantities of a solution containing 2-methyloxolane and heptane, in a refined oil devoid of 2-methyloxolane, so as to obtain mass concentrations in oil of 0.51; 1.02; 2.05; 5.12 and 10.25 pg / g.
• Example 1 according to the invention: the solvent comprises 2-methyloxolane and water
• Example 1 -1 the substrate is the soybean
• the appliance is adjusted so as to operate according to the "Soxhlet Standard" mode, without rinsing or drying, with a number of cycles fixed at 20 and a heating power fixed at 10.
• the level detector is placed approximately 1 cm above the "high” level of the plant substrate and the refrigerant is supplied with cold water (8 ° C).
• the solvent is then brought to a boil using the built-in hot plate. After the 20 cycles are complete, all the solvent containing the extracted oil is collected in the receiving cup, while the solid residue remains inside the extraction cartridge.
• the solvent containing the extracted oil is left to cool for approximately 20 min at room temperature before being transferred to a 250 ml flask.
• the solvent is then evaporated using a rotary evaporator under reduced pressure (150 rpm; 50 ° C; 180 mbar, then 1 mbar to finish).
• the crude oil thus obtained is weighed and then cooled under a light flow of nitrogen for 10 minutes before being transferred to a sealed tube and then stored in the freezer at -20 ° C while awaiting analyzes.
• Example 1 -2 the substrate is rapeseed
• the operating protocol is the same as in Example 1-1, the difference being that the starting substrate is the whole rapeseed (supplier: OLEAD; provenance: Gironde (France); harvest: 2016; water: 5.2% +/- 0.15) and that the Soxhlet extraction cartridges used are made of cellulose and not glass.
• Example 1 -3 the substrate is the grain of corn
• Example 1 -4 the substrate is cotton seed
• a crude oil is obtained by solid / liquid extraction from three different biological substrates with different solvents comprising 2-methyloxolane (stabilized with BHT, Sigma Aldrich) and distilled water, the mass percentage in water in each solvent being 1%, 4.5%, 10% or 20%.
• the edible oils extracted from these three oil seeds are among the most produced in the world excluding palm oil.
• Example 3-1 according to the invention: the substrate is soybean
• the biological substrate is soybean.
• About 50 g of shelled soybeans are ground using a knife mill to obtain particles less than 1 mm in size. 30 g of the powder obtained are weighed and introduced into a 250 ml glass flask surmounted by a condenser so as to be able to carry out a reflux extraction.
• the duration of the extraction is fixed at 2 hours from the first sign of reflux. After 2 hours, the heating is stopped and the mixture is allowed to cool to room temperature for 20 min.
• the contents of the flask are filtered on a cotton bed so as to separate on one side the solid residue from the solvent containing the oil, collected in a new 250 ml flask.
• the solvent is then evaporated using a rotary evaporator under reduced pressure (150 rpm; 50 ° C; 180 mbar, then 1 mbar to finish).
• the crude oil thus obtained is weighed and then the traces of residual solvent are removed by a light flow of nitrogen for 10 minutes.
• the oil is transferred to a sealed tube and then stored in the freezer at -20 ° C while waiting for the analyzes.
• Example 3-2 according to the invention: the substrate is rapeseed
• Example 3-2 The procedure of this Example 3-2 according to the invention is identical to Example 3-1 according to the invention with the exception of the substrate which is rapeseed.
• Example 3-3 according to the invention: the substrate is the sunflower seed
• Example 3-3 The procedure of this Example 3-3 according to the invention is identical to Example 3-1 according to the invention with the exception of the substrate which is the husked sunflower seed.
• the substrate is the soybean
• the substrate is rapeseed
• the substrate is the sunflower seed
• Example 4 Production of a defatted meal
• Example 4-1 the substrate is soy flakes and the solvent comprises 2-methyloxolane and 4.5% water.
• the solvent used is a mixture of 2-methyloxolane (stabilized with BHT, Sigma Aldrich) containing 4.5 g of distilled water per 100 g of solvent.
• the device is configured to operate according to the “Soxhlet Standard” mode, without rinsing or drying, with a duration fixed at 1 hour and a heating power equal to 12 so as to guarantee a number of filling cycles- emptying of the extraction chamber equal to 7 ⁇ 1 per hour.
• the condensers are supplied with tap water, with a flow sufficient to guarantee condensation of the solvent vapors that will be generated.
• the mass concentration of residual oil in the defatted cake is determined according to standard NF EN ISO 734: Feb 2016, implemented using the automatic extraction system (Extraction System B-811, Büchi) according to the "Continuous Extraction” mode corresponding to the so-called “Twisselmann” method, with a slight modification because the material to be analyzed is finely ground using a knife mill instead of a micro ball mill.
• Example 4-2 the substrate is rapeseed and the solvent comprises 2-methyloxolane and 4.5% of water.
• Example 4-3 the substrate is sunflower scales and the solvent comprises 2-methyloxolane and 4.5% water.
• the operating protocol and the biological substrates are the same as in Examples 4-1 to 4-3, the differences being that the solvent is anhydrous 2-methyloxolane and that the heating power is fixed at 12 so as to guarantee a number of filling-emptying cycles of the extraction chamber equal to 7 ⁇ 1 per hour.
• Example 5-1 according to the invention: the substrate is soybean and the solvent is a mixture of 2-methyloxolane and water.
• the extraction temperature was on average 57 +/- 6 ° C, the solvent / solid mass ratio was set at 1.8 kg / kg and the extraction time at 15 min per passage, ie 3 x 15 min in total.
• the solvent containing the extracted oil (mixture noted misella) was collected by filtration after each pass, then concentrated using a distillation column (80-85 ° C, under reduced pressure) and finally desolvated with using a rotary evaporator (Hei-VAP Advantage, Heidolph, Germany) under vacuum and at 60 ° C until the absence of solvent condensation, then 1 hour at 90 ° C.
• the desolvated extract is then centrifuged (4000 rpm / 4 min) in order to remove a solid fraction extracted by the 2-methyloxolane and water mixture but which has become insoluble in an oily medium.
• the crude oil obtained is then stored at -20 ° C before refining or analysis.
• the solid residue (degreased and filtered flakes) is desolvated in the same tank ("Guedu" filter dryer).
• the tank is connected to a vacuum generator and then heated to 55 ° C for 140 min, with the injection of a nitrogen stream (14-18 L / min) to help the desolvation.
• the solid residue is discharged, spread on a plate and exposed to ambient air for 1 day in order to remove the traces of residual solvent.
• the crude oil obtained then undergoes a conventional chemical refining step comprising a degumming step at neutral pH then at acidic pH, followed by a neutralization step, a bleaching step then a deodorization step to obtain an oil refined.
• Comparative Example 5-2 The substrate is soybean and the solvent is anhydrous 2-methyloxolane.
• the extraction operating protocol is identical to Example 5-1 according to the invention with the exception of the following points: the solvent is 2-methyloxolane anhydrous (not stabilized), the solvent / solid ratio is 2.9 kg / kg, the extraction temperature is 53 +/- 5 ° C.
• Comparative Example 5-3 The substrate is soybean and the solvent is hexane.
• the extraction operating protocol is identical to Example 5-1 according to the invention with the exception of the following points: the solvent is hexane (extraction quality), the solvent / solid ratio is 2.2 kg / kg, the extraction temperature is 52 +/- 3 ° C.

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