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    • 专利摘要:
    MEMBRANE-BASED PROCESSES FOR SELECTIVE FRACTIONATION ESSENTIAL OILS. The present invention relates to a process for (1) reducing impurities, that is, undesirable natural components such as waxes and undesirable synthetic materials such as pesticides and other environmental pollutants, or (2) fractioning the natural components present in an essential oil using at least one selective membrane.
    公开号:BR112014027647B1
    申请号:R112014027647-1
    申请日:2013-03-20
    公开日:2020-12-22
    发明作者:Andrew Boam；Andrea Meniconi；Xiaoping Wu
    申请人:Evonik Operations Gmbh；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a process of (1) reduction of impurities, that is, undesirable natural components such as waxes and undesirable synthetic materials such as pesticides and other environmental pollutants, or (2) fractionation of natural components present in an essential oil using at least one selective nanofiltration membrane.
    [0002] Essential oils are produced from plant materials through three main routes, distillation, extraction with an appropriate hydrophobic solvent and compression (physical crushing) depending on the location of the oil within the plant material and the inherent properties of the oil. In all cases, the production technique generates a solution containing a mixture of compounds. In many cases, the essential oil must be removed from a second aqueous phase that is present as a result of the production process. In addition, valuable oil components must often be additionally separated from undesirable materials present in the oil produced to generate the desired final product.
    [0003] Essential oils, including citrus oils, contain a wide range of high-value chemical species, many of which have valuable organoleptic properties that are used in the food and beverage industry and the flavor industry and fragrances, for example. In many applications, the removal of certain natural and synthetic impurities is the main processing step for crude essential oil. Natural impurities include components that form a solid waxy material or after an extended period of storage or when the oil is cooled, these include but are not limited to, high molecular weight hydrocarbons or esters, coumarins, sterols , flavonoids, etc. In addition, the synthetic impurities that can be present in the crude oil and these include but are not limited to organic compounds extracted from packaging materials (eg phthalates) and pesticides (eg insecticides, fungicides, etc.).
    [0004] One of the primary steps in the processing of many essential oils is the removal of "wax" (see, Industrial Engineering and Chemistry Research 47 (2008), 9573-9580). The current state of the art for removing "wax" is a process known as inversion. Winterization is a process known to those skilled in the art that involves cooling the oil to low temperatures, usually in the range of -10 ° C to -40 ° C, allowing wax crystals to form and grow as the temperature drops , and then setting the wax crystals under gravity. Due to the slow speed of wax formation and the low difference in density between solid wax and crude oil, this process can take several weeks to complete and can be carried out in several stages (with the different stages optionally operating). at different temperatures). The wintering product can also be centrifuged to remove any residual wax. The multi-stage nature of this process, combined with the low temperatures involved and an extensive process time scale, makes this an energy-intensive and very tedious process to be performed.
    [0005] An additional tedious task in the processing of many essential oils is the reduction of impurities present in the essential oil. As impurities constitute a wide variety of chemical species, they cannot be reduced with just one unit operation, so the current state of the art for removing synthetic impurities occurs through a series of independent unit operations that include the use of adsorbents or washing the oil with various aqueous chemical solutions. Suitable adsorbents are known to those skilled in the art and include diatomaceous earth, activated carbon, silica and resin beads. However, the effectiveness of these adsorbents in reducing synthetic impurities is limited and can reduce the yield of valuable components. The aqueous chemical products wash only the species of interest in the crude oil that can be ionized to form salts with the components in aqueous solution (for example, see EP0656932 and US2007237844A1), these salts are insoluble in the crude essential oil, and the form of salt from the impurities is removed in the aqueous washing solution, thus reducing the concentration of the impurities in the crude essential oil. However, this approach is effective only for impurity compounds that can be ionized or that can be extracted in an aqueous phase.
    [0006] The use of membranes to concentrate the valuable components of essential oil in an aqueous solvent or organic solvent system has been reported. For example, Peev et al. (Chemical Engineering Research and Design, 89 (2011), 2236-2243) discloses the use of nanofiltration membranes in organic solvents for the concentration of an extract of rosmarinic acid from lemon balm. Tylkowski et al. (Journal of Membrane Science 348 (2010), 124-130) report the use of nanofiltration membranes in organic solvents to concentrate an aqueous ethanolic extract of propolis. This disclosure uses the fact that free fatty acids are more easily dissolved in ethanol than triglycerides to produce an ethanol extract enriched in free fatty acids. After that, a membrane is used to separate the free fatty acids from the ethanolic extract.
    [0007] The processes described above are designed to purify plant extracts comprising only some components of an essential oil, but not all essential oil. Such vegetable extracts cannot be compared with raw materials comprising all essential oil, that is, all essential oil components.
    [0008] Carlson et al. (Journal of Supercritical Fluids 34 (2005), 143-147) disclose the application of reverse osmosis membranes to separate supercritical carbon dioxide from limonene. Sarmento et al. (Journal of Membrane Science 237 (2004), 71-76) also inform the use of reverse osmosis membranes to concentrate the essential oils of supercritical carbon dioxide. The reports released demonstrate the ability of membranes to conserve and concentrate essential oils from a solvent matrix.
    [0009] Dupuy et al. (Journal of Membrane Science 378 (2011), 203-213, Flavor and Fragrance Journal 26 (2011), 192-203) also inform the application of membranes in the form of membrane contactors to provide an emulsion-free extraction of the components of essential oil of lemon oil in aqueous ethanolic solutions. In this process, the quality of the separation is governed by the aqueous ethanolic extraction solvent and not by the properties of the membrane. The membrane stabilizes the interface between the lemon oil and the aqueous ethanolic solution.
    [00010] The recovery of aroma compounds from essential oil from solid / liquid matrices using membrane technology is also known. Pervaporation can be applied to recover aroma compounds under mild conditions (for example Figoli et al. (Desalination 199 (2006) 111-112 and Desalination, 193 (2005), 160-165).
    [00011] Han et al. applied microfiltration membranes to the separation of water-essential oil mixtures (Zhongguo Zhongyao Zazhi 36 (1) (2011), 41-44). The separation generates an aqueous eluted material and the essential oil is concentrated as a second phase in the material concerned. Sakamoto et al. (Food Science and Technology Research, 9 (1) (2003), 11-16) describes a similar separation of a two-phase water / essential oil mixture using ultrafiltration with ceramics and microfiltration membranes to generate an aqueous eluted material and a material retained containing a second phase of the essential oil.
    [00012] EP2205710 for Givaudan describes a membrane-based process for degreasing citrus oils. The process described in the patent uses ultrafiltration or microfiltration membranes to remove wax compounds from citrus oils, such that they do not generate additional solid wax when left to stand at 4 ° C for 48 hours. Citric oil is cooled to approximately 10 ° C before filtration to improve the ease with which wax compounds can be filtered.
    [00013] Essential oils cover a wide range of variation of non-lipid derivatives of natural oils from vegetable matter, for example, citrus oils, rosemary oil, lemon grass oil, lavender oil, eucalyptus oil, etc. Considering the wide variety of raw materials, crude essential oils contain the desired components of the essential oil (for example, terpenic hydrocarbons, aldehydes, alcohols, esters, etc.) as well as a range of undesirable impurities, for example, compounds wax (often associated with cuticle formation in the raw material), pesticide residues (from agricultural cultivation of the raw material). These undesirable materials are often challenging or tedious to separate from the desired compounds and often multi-step and energy-consuming processes are required to generate the desired products. In addition, the most valuable compounds in essential oil are often thermally sensitive, and it is a significant challenge to isolate these compounds in high yield without causing thermal damage.
    [00014] Thus there remains a need in the art for a more efficient process to remove impurities or fractionated compounds from an essential oil such as a citrus oil.
    [00015] The problem with the present invention was, therefore, to provide a process for refining essential oils that do not have the drawbacks of the prior art processes discussed above or have such drawbacks only to a small degree.
    [00016] A special problem of the present invention was to provide a process that can achieve the combined effect of one, two, three or more of the conventional processing steps applied to essential oils (for example, degreasing, color removal (adsorption) , fractionation, pesticide removal) in a single process. The disclosed process should therefore simplify and / or speed up the production of an essential oil and potentially improve the performance and quality of the oil.
    [00017] Another problem was to provide a flexible process that would allow impurities to be removed from an essential oil and / or be used for the fractionation of at least one component of the oil, resulting in the formation of an enriched concentrated solution of at least one component Natural. This can lead to the production of new products.
    [00018] A special problem of the present invention was to provide a process to purify essential oils in a more economical way from wax and synthetic impurities, while avoiding as much as possible the negative effects on the product's flavor / fragrance profile. essential oily.
    [00019] The additionally special problems are: - Ensuring sufficient high capacities (flow rates) - Separating flavor / fragrance substances from synthetic impurities that have a molecular weight of the same dimension, ie 130 to 300 Da. - Reduce the steps compared to prior art processes. - Reduce energy (working at room temperature) - Have a stable process free from clogging the membrane.
    [00020] Additional problems not explicitly described above are obvious to someone skilled in the art in view of the description, claims, examples and drawings of the present application.
    [00021] The problems of the present invention are solved by a process according to claim 1 of the present invention. Preferred embodiments are claimed in dependent claims and / or are described in detail in the subsequent descriptions, examples and figures.
    [00022] Particularly the present description refers to a process for (1) reduction of impurities, that is, undesirable natural components such as waxes and undesirable synthetic materials such as pesticides and other environmental pollutants, or (2) fractionation of the natural components present in an essential oil comprising (a) optionally mixing the solvent essential oil with an organic to form a solution; (b) contacting the essential oil or solution with at least one selective nanofiltration membrane, wherein a retained material is formed comprising at least one essential oil compound and forms of eluted material comprising at least one essential oil compound such that the composition of the retained material and the elution solutions are different; and (c) optionally removing the organic solvent from the retained material to form a purified oil.
    [00023] This solution was not obvious in view of the aforementioned prior art, particularly in view of Givaudan (EP2205710) who recommends using ultrafiltration membranes (cutting molecular weight in the range of 2,000 Da to 2,000,000 Da) or microfiltration (pore diameter 0.2 micron and larger). Obviously Givaudan believed that the application of nanofiltration would adversely affect the flavor / fragrance profile of the essential oil product (the valuable organoleptic compounds are typically in the range of 130 to 300 Da molecular weight). The inventors of the present invention, however, can show that this is not the case.
    [00024] Another unexpected effect of the present invention was that nanofiltration membranes have much better degreasing properties compared to microfiltration or ultrafiltration membranes. The successful degreasing test applied by Givaudan (supporting for 48 hours at 4 ° C) is too soft to define successful degreasing. Degrease a citric oil with the process of the invention, versus a Givaudan ultrafiltration membrane, when applying a more rigorous test -20 ° C for degreasing the test sample, where at - 20 ° C a solution of one The ultrafiltration process is cloudy, while the solutions produced according to the invention are transparent.
    [00025] Another unexpected advantage of the present invention was that a sufficient flow of up to at least 5 L.m-2.h-1 can be achieved. This is beneficial for an economic process.
    [00026] There is no freezing or "wintering" required for the present invention. It is also not necessary to cool the essential oil solution to 10 ° C or lower. The process of the invention can be operated at room temperature, which saves time and energy.
    [00027] In contrast to the state of the art processes, the process of the invention allows to reduce process steps and although the synthetic impurities have a molecular weight <500 Da, it allows simultaneously to degrease and remove the synthetic impurities. This is another important and unexpected advantage.
    [00028] It should be understood that both the preceding general description and the following detailed description are only examples and explanations and are not restrictive of disclosure, as claimed. Brief Description of Drawings
    [00029] Figure 1 is a schematic of the cross-flow nanofiltration system, as used in Example 1.
    [00030] Figure 2 shows the results of UV absorbance at 432 nm to measure the color resistance of the samples from the feed, elution and material retained from orange oil filtration in one step with a PuraMem (R) S380 membrane.
    [00031] Figure 3 shows UV absorbance values at 432 nm to measure the color resistance of the samples from the feed, elution and material retained from orange oil filtration five times with PuraMem (R) S380 membrane
    [00032] Figure 4 UV shows absorbance values at 720 nm to measure the wax content of the samples in the feed, elution and material retained from orange oil filtration five times with PuraMem (R) S380 membrane.
    [00033] Figure 5 is a schematic diagram of a METcell cross-flow filtration system containing four cross-flow filtration cells.
    [00034] Figure 6 shows an example of orange oil fractionation mass balance in one step based on 100 kg of orange oil in the feed. description
    [00035] Particular aspects of the invention are described in greater detail below. The terms and definitions used in this application and as explained here are intended to represent the meaning within this disclosure. The patent and scientific literature mentioned here and referenced above are hereby incorporated by reference. The terms and definitions provided here, if in conflict with the terms and / or definitions incorporated by the reference, are the terms and definitions that must be used to interpret this disclosure.
    [00036] The singular forms "one / one" and "o / a" include the references of the plural unless the context dictates otherwise.
    [00037] The term "approximately" and "about" means to be almost the same when referring to a number or value. As used herein, the term "approximately" should generally be understood to encompass ± 30%, preferably ± 20%, particularly preferred ± 10% and especially preferred ± 5% of a specified amount, frequency or values.
    [00038] The term "essential oil" as used in the present description is to be understood as meaning that derived from hydrophobic oils of vegetable matter, which contain less than 40% by weight, preferably less than 30% by weight, particularly preferred less than 20% by weight, very particularly preferred less than 10% by weight, especially preferred less than 5% by weight, very especially preferred less than 1% by weight and much more preferred 0% by weight of lipids or oils of lipids. Lipids are compounds based on fatty acids and derivatives of fatty acids. Lipid oils are defined as oils based on fatty acids and derivatives of fatty acids (such as glyceride oils), while many essential oils have a terpene hydrocarbon base. Examples of essential oils include citrus oils, mint oils, cedar oil, eucalyptus oil, clove oil, etc. Examples of vegetable lipid oils include sunflower oil, olive oil, peanut oil, soy oil, corn oil, etc. In some embodiments, the term "essential oil" should also be used to cover mixtures of more than one "essential oil".
    [00039] In more detail an essential oil is a concentrated hydrophobic liquid containing volatile aroma compounds extracted from plants. Essential oils are composed mainly of spices and lesser amounts of alcohols, aldehydes, esters, phenols, and other compounds that communicate certain odors or flavors. They are usually obtained from plants, leaves, flowers, roots, buds, thin branches, rhizomes, heartwood, bark, resin, seeds and fruits. Essential oils are usually found in special secretory glands or cells within plants. Aromatic substances are formed and stored in certain organs of a plant as a by-product or because of its metabolism. Each essential oil contains its own design of chemical entities that is absolutely unique to that specific oil.
    [00040] Different techniques are known for obtaining essential oils from plants. Essential oils as used for the raw material in the present invention are produced by distillation, compression, or solvent extraction with hydrophobic solvents or supercritical solvents. Essential oils are used in perfumery, aromatherapy, cosmetics, incense, medicine, household cleaning products, and for flavoring drinks and food. They are valuable commodities for the fragrance and food industries. They should not be confused with essential fatty acids or with plant extracts prepared with more polar solvents comprising only the most polar components of essential oil.
    [00041] In a first preferred embodiment of the invention, essential oils are oils according to ISO 9235, that is, they are products obtained from a natural raw material of vegetable origin: or by steam distillation; or by mechanical processes of the citrus fruit epicarp; or by dry distillation after separation of the aqueous phase, if any, by physical processes.
    [00042] In a second preferred embodiment of the present invention, essential oils comprise essential oils according to the first preferred embodiment and also essential oils that can be obtained by mechanically compressing plant materials other than citrus fruits.
    [00043] In a third preferred embodiment of the present invention, essential oils cover the essential oils of the first and second preferred embodiments and also the essential oils that are obtained by extracting the plant material with supercritical solvents, preferably CO2 supercritical.
    [00044] In a fourth preferred embodiment of the present invention, essential oils comprise the essential oils of the first, second and third preferred embodiments and also the essential oils that are obtained by extracting plants with an apolar solvent, ie solvent with a dielectric constant, measured as the ratio of the electrical capacity of a condenser filled with the solvent to the electrical capacity of the empty condenser (at room temperature), less than or equal to 15, preferably less than or equal to 10 , particularly preferred less than or equal to 5 and very particularly preferred less than or equal to 3. The list of solvent dielectric constants is available, for example, in A. Maryott et al., "Table of Dielectric Constants of Pure Liquids ", Department of American Trade, National Bureau of Stan- dards Circular 514, 1951.
    [00045] In the third and fourth preferred embodiments of the present invention, crude products are obtained after the extraction of vegetable material with the nonpolar solvent. In many cases these extracts are called "concrete" and can contain significant amounts of waxes, resins and other lipophilic plant material. The concrete can be directly dissolved in an organic solvent and used for the process of the present invention; on the other hand, it can be additionally treated in mechanical or extractive purification steps to obtain an organic solution of the essential oil that is used in the present invention.
    [00046] In general, crude essential oils or pre-purified essential oil obtained by the processes described above can be used as raw material for the process of the present invention.
    [00047] The term "fatty acid" includes, for example, saturated and unsaturated short- and long-chain hydrocarbons (for example, monounsaturated and polyunsaturated) comprising a carboxylic acid group. Fatty acid derivatives include esters, glycerides, phosphoesters, etc., from fatty acid.
    [00048] It should be understood that the term "fractionation" as used in this description means that the concentration of a given species in solution is different in the retained material and in the elution solutions generated by applying the process described here. It will be understood by someone skilled in the art that this means that a given species could be "fractionated" or in solutions of elution or retained material, and, moreover, that "fractionation" as defined herein it can incorporate enrichment, depletion, complete removal and complete capture of a species in any of the retained and eluted material solutions.
    [00049] The term "nanofiltration" as used in this disclosure should be used as meaning a synthetic membrane that provides a cut of nominal molecular weight in the range of 150 g.mol-1 to 1,500 g.mol-1, where the cut to the nominal molecular weight means the molecular weight at which the membrane provides a 90% rejection of a series of polystyrene oligomers (eg nominal polystyrene polymer standards Mp 1,000 (part number PL2012- 3010) and nominal Mp of 580 (part number PL2012 - 2010) from Agilent Technologies) according to the method described in See Toh et al., (Journal of Membrane Science, 291 (1-2) (2007), 120- 125). Nanofiltration membranes differ from ultrafiltration membranes (cutting molecular weight in the range of 2,000 Da to 2,000,000 Da) and microfiltration membranes (pore diameter 0.2 micron and larger).
    [00050] The term "natural impurity" as used in this disclosure should be understood as meaning any chemical species that is occurring naturally in the raw material, but that is not a desired species in the final form of the essential oil. Typical examples can include waxes (as they can lead to unwanted fogging in the oily product), colored compounds (which cannot be desired if the oil is to be mixed into a product of a different color), sterols and vitamins.
    [00051] The term "rejection" is defined by equation (1), where CPi is the concentration of species i in elution solution, "eluent" is the liquid that has passed through the membrane, and CRi is the concentration of species. cies i in retained solution, "retained material" which is the liquid that did not pass through the membrane. It will be understood by someone skilled in the art that a rejection of 0% implies that the membrane does not offer any separation of species i, and a rejection of 100% implies that species i are completely retained. It will be additionally recognized by someone skilled in the art who provides the rejection of species A not equal to the rejection of species B so the species can be fractionated, as defined here.

    [00052] The term "synthetic impurity" as used in this disclosure should be understood as meaning any chemical species that is not occurring naturally in the raw material from which the essential oil is produced. It will be understood by someone skilled in the art that synthetic impurities can incorporate both artificial and naturally occurring compounds that are applied as pesticides or are present as environmental pollutants.
    [00053] The term "waxes" as used in the present disclosure should be understood as meaning naturally occurring species in the essential oil that are capable of communicating the haze to the oily product at temperatures below 20 ° C. Typical wax compounds found in essential oils include long-chain aliphatic hydrocarbons (typically C14 or longer), long-chain alcohols (typically C14 or longer), and ketones, aldehydes, acids, diols, etc. and coumarins, sterols, flavonoids. Essencial oils
    [00054] The term essential oil has already been defined in paragraphs 38 to 46 above. Further details on essential oils and their use are provided in the following paragraphs.
    [00055] An essential oil according to the present disclosure is derived from plant material. In some embodiments of the present disclosure, the essential oil may comprise a mixture of more than one essential oil. The essential oil can be derived from several different parts of the plant, including, as a non-limiting example, fruits, seeds, bark, wood, rhizome, leaves, resin, flowers, bark and root.
    [00056] The preferred essential oils are derived from the genus Citrus. Particularly preferred essential oils are selected from oils derived from lime orange, orange, lemon, lime, grapefruit, bergamot, lime, pomelo, cider, mandarin, mandarin, pear orange, rangpur, lime, clementine, yuzu , kaffir file, ugli.
    [00057] Essential oils include as a non-limiting example, pepper oil, juniper oil, cumin oil, cinnamon bark oil, camphor oil, rosewood oil, ginger oil, basil oil, eucalyptus oil, lemon grass oil, peppermint oil, rosemary oil, mint oil, tea oil, frankincense oil, chamomile oil, clove oil, jasmine oil, lavender oil, oil rose oil, ylang ylang oil, bergamot oil, grapefruit oil, lemon oil, lime oil, orange oil, and valeriaine oil.
    [00058] Essential oils are a rich source of a wide variety of natural compounds that find numerous applications. Bakkali et al. (Food and Chemical Toxicology 46 (2008) 446-475) reviews many uses of essential oils, these including bactericidal, viricidal, fungicidal, antiparasitic, insecticidal, medicinal, cosmetic, and flavor / fragrance applications. For example, many components of essential oils alter the cell wall composition of common bacterial / fungal pathogens that can be lethal to the microorganism or that make the action of other antimicrobial compounds much easier. An additional example of the benefits of essential oils includes their antioxidant and pro-oxidant capabilities, which can help protect cells, but also eliminate damaged cells by enhancing apoptosis.
    [00059] Several essential oils also contain compounds with potent pharmaceutical activities. These include artemisinin, which is an antimalarial compound derivative of Artemisia annua, hyperforin, which is an antidepressant drug derivative of Hypericum perforatum, as well as various sterols ("Supercritical Fluid Extraction of Nutricochemicals and Bioactive Compounds", editor. JL Martinez (2008) ISBN 978-0-8493-7089-2).
    [00060] Other essential oils are mainly used as sources of compounds for flavor / fragrance applications. These are mainly citrus oils such as orange oils, lemon oil, lime oil, bergamot oil, etc. but also oils such as lavender oil and rose oil are used in these applications. Membrane
    [00061] Selective membranes suitable for use in accordance with the present description, include polymeric and ceramic membranes, and a mixture of polymeric / inorganic membranes.
    [00062] At least one selective membrane used in the process of the present invention can be formed of any polymeric or ceramic material that provides a separation layer capable of fractioning the essential oil content or separating the desired essential oil content from at least one natural and / or synthetic impurity present in the essential oil. For example, at least one selective membrane can be formed of or comprise a material chosen from polymeric materials suitable for making nanofiltration membranes, preferably including polyethylene, polypropylene, polytetrafluoroethylene (PTFE), polyvinylidene difluoride (PVDF), polysulfo - na, polyethersulfone, polyacrylonitrile, polyamide, polyimide, polyamideimide, polyetherimide, cellulose acetate, polyaniline, polypyrrole, polyetheretherketone (PEEK), polybenzimidazole, and mixtures thereof. At least one selective membrane can be made by any technique known in the art, including agglomeration, stretching, etching (track etching), leaching in mold, interfacial polymerization, or phase inversion. In a preferred embodiment, at least one selective membrane can be cross-linked or treated as a way to improve its stability to the reaction solvents. For example, as a non-limiting example, the membranes described in GB2437519, the contents of which are incorporated herein by reference, can be used in the present description.
    [00063] In an additional preferred embodiment, at least one selective membrane is a crosslinked or no crosslinked composite material comprising a support and a selectively permeable thin layer. The selectively permeable thin layer, for example, can be formed of or comprise a material chosen from modified elastomer-based polysiloxane including polydimethoxysiloxane-based elastomers (PDMS), ethylene diene-based elastomers propylene (EPDM), elastomers based on poly-norbornene, elastomers based on polyoctamer, elastomers based on polyurethane, elastomers based on butadiene and butyl nitrile rubber, natural rubber, butyl rubber based elastomers, polychloroprene-based elastomers (Neoprene), epichlorohydrin elastomers, polyacrylate elastomers, polyethylene, polypropylene, poly-tetrafluoroethylene (PTFE) -based, polyvinylidene difluoride (PVDF), polyether blocks , polyurethane elastomers, cross-linked polyether, polyamide, polyaniline, polypyrol, and mixtures thereof.
    [00064] In an especially preferred embodiment of the present invention, at least one selective nanofiltration membrane or the nanofiltration compound membrane is used comprising a polyimide, particularly preferred is a polyimide subject to post-formation crosslinking and impregnation with a low volatility compound. Most particularly preferred are polyimides according to GB2437519 and Soroko et al. (Journal of Membrane Science, 381 (1-2) (2011), 152-162) the levels of which are incorporated here by reference.
    [00065] Particularly preferred are nanofiltration membranes in organic solvents coated with silicone especially based on polyimide nanofiltration membranes. Most membranes that are particularly preferred in the example described in DE10 2009 07 351 or disclosed in WO2012010889, the contents of which are incorporated herein by reference, can be used in the present disclosure. The inventors have especially found that when using nanofiltration membranes of organic solvent coated with silicone, degreasing and reduction to the concentration of certain synthetic impurities can be carried out under ambient temperature conditions and above environments free from clogging. of membrane or the organoleptic properties of the essential oil that is affected.
    [00066] Without being bound by any theory, the inventors are of the opinion that the silicone coating minimizes the deposition of wax compounds on the membrane surface, thus minimizing the clogging that leads to the stable performance of the membrane over the time.
    [00067] Another advantage that silicone coated membranes seem to achieve compared to uncoated membranes is that the diffusion nature of the mass transport solution in silicone linings means that these membranes offer discrimination between the components of the essential oil and certain synthetic impurities of similar molecular weight that are not reached to this degree with phase inversion membranes.
    [00068] In another embodiment, at least one selective membrane is prepared from an inorganic material such as, for example, silicon carbide, silicon oxide, zirconium oxide, titanium oxide, and zeolites, using any technique known to those skilled in the art. technique such as agglomeration, leaching, or sol-gel processing.
    [00069] In an additional embodiment, at least one selective membrane comprising a polymer membrane with organic or inorganic matrices dispersed in the form of powdered solids present in amounts up to 20% by weight of the polymer membrane. Molecular carbon matrices can be prepared by pyrolysis of any suitable material as described in US Patent No. 6,585,802. Zeolites as described in US Patent No. 6,755,900 can also be used as an inorganic matrix. Metal oxide, for example, titanium dioxide, zinc oxide, and silicon dioxide can be used, as can the materials available from Evonik Industries AG (Germany) under their trademarks AEROSIL and ADNANO. Varied metal oxide such as mixtures of cerium, zirconium, and magnesium can also be used. In at least one embodiment, the arrays will be of particles smaller than 1.0 microns in diameter, for example, less than 0.1 microns in diameter, such as less than 0.01 microns in diameter.
    [00070] It is particularly preferred in all embodiments of the present invention that at least one selective membrane having a cut in molecular weight ranging from approximately 150 g.mol-1 to approximately 1,500 g.mol-1, preferably from approximately 200 g.mol-1 to approximately 800 g.mol-1 and particularly 200 g.mol-1 less than or equal to 600 g.mol-1 is used in the process of the invention.
    [00071] In a special embodiment, more than one membrane, respectively, more than one membrane separation step are comprised in the process of the invention. In this particular embodiment, it is particularly preferable that two different membranes that have two different molecular weight cuts are used. Very particularly preferred, at least one membrane having a molecular weight cut between 400 g.mol-1 and 1,500 g.mol-1, especially between 500 g.mol-1 and 800 g.mol-1 and at least one membrane with a cut of different molecular weight between 150 g.mol-1 and 600 g.mol-1, especially between 200 g.mol-1 and 500 g.mol-1 is used. That the ranges of variation mentioned before the overlap does not mean that the membranes are identical, on the contrary it must be understood that a membrane with a cut of molecular weight of 400 g.mol-1 can be combined with a membrane presenting a cut of molecular weight of 600 g.mol-1. Impurities
    [00072] Essential oils may contain undesirable natural impurities or undesirable synthetic impurities, which must be removed from the essential oil for its desired use. The disclosed method can effectively remove a wide variety of natural and synthetic impurities, thereby producing oils suitable for your desired applications.
    [00073] The process disclosed here describes the separation of impurity from an essential oil, resulting in oil presenting levels of impurity within desired and / or regulatory limits for, for example, human consumption.
    [00074] The concentration and composition of impurities found in the essential oil may vary. For example, an essential oil composition can vary based on the species from which the oil derives and the part of the plant from which the oil derives, the geographical location where the plant is grown, the harvest season, etc. In some instances, the targeted impurities may be missing or below the detection limit, but if the oil is concentrated, the impurities can also be concentrated.
    [00075] The impurities present in the essential oil can be natural or synthetic impurities such as, as a non-limiting example, environmental pollutants, pesticide residues, extractable from the packaging, plant sterols, lipophilic hormones, waxes, colored components, oxidation products, vitamins, and components that create undesirable odor and taste in the oil, such as aldehydes and / or ketones. In at least one modality, the removal of colored components results in an oil that improves in color, and the removal of components that create an undesirable odor and taste results in an oil with an improved organoleptic profile.
    [00076] The term "environmental pollutants" includes, but is not limited to, for example, biphenyl polychlorinated (PCBs), polychlorinated diphenyl ethers (PBDEs), polycyclic aromatic hydrocarbons (PAHs), hexachlorocyclohexanes (HCHs), dichlorohydrophenyltrichlorohydrate (DDT), dioxins, furans, non-ortho-PCBs, and metals.
    [00077] The term "pesticide residues" includes as a non-limiting example, pesticides and their degradation products. Chlorinated pesticides include, for example, lindane, endrine, dieldrine, aldrin, isodrine, heptachloro-exo-epoxide, heptachloro-endo-epoxide, trans-chlorodane, cis-chlorodane, oxy-chlorodane, chlorodane, hepta-chloro endosulfan-1, and mirex. Other types of the pesticide include organophosphate pesticides, such as, as a non-limiting example, pesticides parathion, malathion, methyl parathion, chlorpyrifos, diazinon, dichlorvos, phosmet, phenitrothion tetrachlorvinphos, and methyl azinphos, and carbamate, as a non-example form limiting aldi-carb, carbofuran (Furadan), carbaryl (Sevin), ethienocarb, and phenobu- carb.
    [00078] "Natural impurities" may include as a non-limiting example, sterols, lipophilic hormones, and natural colors, for example, belonging to carotenoids.
    [00079] Extracts from the packaging may include, as a non-limiting example, compounds such as plasticizers (eg phthalates), resin components disconnected, polymer polymer material disconnected, lubricants, etc. Process to Reduce Impurities and Process to Partition Natural Components
    [00080] Some embodiments of the present description refer to a process for reducing the impurities of an essential oil using at least one selective membrane. In addition, some of the modalities of the present disclosure relate to a process of fractionation of at least one natural component of an essential oil using at least one selective membrane.
    [00081] According to a modality, the fractionation of undesirable natural and synthetic impurities can be achieved by contacting the oily solution with at least one selective membrane that retains the undesirable impurities, that is, in the form of a retained material, and allows the elution of the desired compounds from the essential oil, that is, in the form of eluate. The content permeates through the membrane due to, for example, a transmembrane pressure. In at least one embodiment, the transmembrane pressure ranges from 0.1 to 10 MPa. Preferably the transmembrane pressure can range from 0.5 to 7.5 MPa, particularly preferred from 1 to 6 MPa.
    [00082] The fractionation of the essential oil can be achieved by contacting the oily solution with at least one selective membrane. The essential oil is then fractionated with at least one species showing a different concentration in the retained solution compared to the elution solution. The content permeates through the membrane due to, for example, a transmembrane pressure. In at least one embodiment, the transmembrane pressure ranges from 0.1 to 10 MPa. Preferably the transmembrane pressure can vary from 0.5 to 7.5 MPa, particularly preferably from 1 to 6 MPa.
    [00083] According to an additional modality, the essential oil is mixed with an organic solvent to form a homogeneous solution of oil and solvent. Mixing can be carried out by any technique known to someone skilled in the art, such as, for example, via a static mixer connected in series, a dynamic mixer connected in series, and / or a mixing vessel containing a mechanical stirrer. Preferably, the solution may contain the essential oil in an amount ranging from 1 to 95% v / v, particularly preferred from 5 to 50% v / v.
    [00084] The term "organic solvent" when applied to the solvents used to prepare the mixture of essential oil and organic solvent includes, for example, an organic liquid with a molecular weight less than 300 Daltons. The term "solvent" includes a mixture of organic solvents, as well as a mixture of organic solvents and water.
    [00085] Preferred examples are solvents including aromatic hydrocarbons, aliphatic hydrocarbons, ketones, glycols, chlorinated solvents, esters, ethers, amines, nitriles, aldehydes, alcohols, phenols, amides, carboxylic acids, alcohols, furans, lactones and dipolar aprotic solvents, and mixtures thereof and with water.
    [00086] Other preferred examples are, solvents include toluene, xylene, benzene, stryrene, anisole, chlorobenzene, dichlorobenzene, chloroform, dichloromethane, dichloroethane, methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), acetone, ethylene glycols, ethanol, methanol, isopropanol, propanol, butanol, hexane, heptan, cyclohexane, dimethoxyethane, methyl tert -butyl ether (MTBE), diethyl ether, adiponitrile, N, N-dimethylformamide, dimethylsulfoxide, N, N-dimethylacetamide, dioxane, nitromethane, nitrobenzene, pyridine, carbon disulphide, tetrahydrofuran, methyl - tetrahydrofuran, N-methyl pyrrolidone, N-ethyl pyrrolidone, acetonitrile, and mixtures thereof and with water.
    [00087] Particularly preferred solvents are selected from a group consisting of methanol, ethanol, isopropanol, ethyl acetate, acetone, hexane, heptane, ethylene glycols, and mixtures thereof and with water.
    [00088] The reduction of undesirable natural and synthetic impurities can be achieved by contacting the solvent and oil solution or the essential oil with at least one selective nanofiltration membrane that retains the undesirable impurities, that is, in the form of a retained material, and allows elution of the desired compounds from the essential oil, that is, in the form of eluate. The content permeates through the membrane due to, for example, a trans-membrane pressure. In at least one embodiment, the trans-membrane pressure ranges from 1 to 100 bar. Preferably, the trans-membrane pressure can vary from 5 to 75 bar, particularly preferred from 10 to 60 bar.
    [00089] The fractionation of the essential oil can be achieved by contacting the solvent and oil solution with at least one selective nanofiltration membrane. The essential oil is then fractionated with at least one species showing a different concentration in the retained solution compared to the elution solution. The content permeates through the membrane due to, for example, trans-membrane pressure. In at least one embodiment, the trans-membrane pressure ranges from 1 to 100 bar. Preferably the trans-membrane pressure can vary from 5 to 75 bar, particularly preferably from 10 to 60 bar.
    [00090] In one aspect, the present description provides a process for reducing natural impurities (for example, waxes, oxidation products, and colored components) and synthetic impurities (for example, pesticide residues, extractables from packaging, etc. .) present in an essential oil applying the nanofiltration membrane, comprising the steps of: (i) supplying an essential oil; (ii) supply of at least one selective permeable nanofiltration membrane with a first surface and a second surface; (iii) separating the oil from the impurities by transferring the essential oil from the first to the second surface through at least one nanofiltration membrane contacting the essential oil with the first surface, where the pressure on the first surface is greater than the pressure on the second surface, and where the membranes are selectively permeable membranes such that the membrane rejection (RImp) of impurities is superior to the rejection (Rleo) of oily species.
    [00091] In an additional aspect, the present description provides a process for reducing natural impurities (for example, waxes, oxidation products, and colored components) and synthetic impurities (for example, pesticide residues, extractables from packaging, etc.) present in a solution of a solvent and an essential oil applying the nanofiltration membrane, comprising the steps of: (i) providing a homogeneous solution of an organic solvent and an essential oil; (ii) supply of at least one selective permeable nanofiltration membrane with a first surface and a second surface; (iii) the separation of the oil solution from the impurities by transferring the essential oil solution emerges from the first to the second surface through at least one nanofiltration membrane through the contact of the essential oil solution with the first surface, in that the pressure on the first surface is higher than the pressure on the second surface, and that the membranes are selectively permeable membranes in such a way that the rejection of the membrane (RImp) of impurities is superior to the rejection (Rleo) of oily species.
    [00092] The disclosed method can also be used to fractionate at least one natural component in the essential oil, such as one or more of the terpenic or oxygenated components of the essential oil, fat-soluble vitamins, plant sterols, and / or colored components, using the selective nanofiltration membranes released, resulting in the formation of a concentrate comprising at least one natural component in a higher concentration than in the raw material of essential oil. The fractionation is performed by applying the nanofiltration membrane, comprising the steps of: (i) supplying an essential oil; (ii) supply of at least one selective permeable nanofiltration membrane having a first surface and a second surface; (iii) separation of one or more components to be fractionated from other components of the essential oil from the components that pass emerging from the first to the second surface through at least one nanofiltration membrane through the contact of the essential oil with the first surface , where the pressure on the first surface is higher than the pressure on the second surface, and where the nanofiltration membranes are selectively permeable membranes such that the membrane rejection (RComp) of the components to be fractionated is not the same as rejection (Rleo ) of the other oil components.
    [00093] In an additional embodiment, the disclosed method can also be used to fractionate at least one natural component in the essential oil, such as one or more of the terpenic or oxygenated components of the essential oil, fat-soluble vitamins, plant sterols, and / or colored components, using the selective nanofiltration membranes disclosed, resulting in the formation of a concentrate comprising at least one natural component in a higher concentration than in the raw material of the essential oil in which the essential oil is dissolved in an organic solvent. The fractionation is performed by applying the nanofiltration membrane, comprising the steps of: (i) supplying a solution of an organic solvent and an essential oil; (ii) supply of at least one selective permeable nanofiltration membrane having a first surface and a second surface; (iii) separation of one or more components to be fractionated from other components of the essential oil solution by passing the components from the first to the second surface through at least one nanofiltration membrane by contacting the essential oil solution with the first surface, in that the pressure on the first surface is higher than the pressure on the second surface, and that the nanofiltration membranes are selectively permeable membranes in such a way that the membrane rejection (RComp) of the components to be fractionated is not the same as rejection (Róleo ) of the other oil components.
    [00094] In an additional embodiment, the process of the invention comprises subjecting the material retained from the oil or solution and / or the eluted oil or solution to at least one additional processing step, preferably at least one additional separation step by membrane.
    [00095] In a particularly preferred modality, the process disclosed here can be applied in multiple stages. As a non-limiting example, a second stage additionally comprises the supply of the material retained from a first filtration that was performed to reduce the concentration of an impurity; the first retained solution passing through at least one additional selective membrane, preferably also a nanofiltration membrane, in which a second retained material and a second eluent are formed in which an additional reduction of impurities has been carried out. In yet another embodiment, the process disclosed here additionally comprises the eluted supply of a first filtration that was performed to reduce the concentration of an impurity; and passing the elution solution through at least one additional selective membrane, preferably also a nanofiltration membrane, in which a second retained material and a second eluent are formed in which an additional reduction of impurities has been carried out.
    [00096] Optionally, the processed essential oil can be treated with at least one adsorbent process to remove additional components and / or remaining impurities. As a non-limiting example, the processed essential oil is treated with activated carbon, which, for example, can additionally remove the environmental pollutants present in the essential oil. In additional steps, the essential oil can be subjected to additional separation processes to improve fractionation or remove additional impurities. Additional purification processes may include, for example, liquid-liquid extraction, fractional distillation, high pressure liquid chromatography, supercritical chromatography, or resin or ion exchange adsorption depending on the application.
    [00097] Components of some essential oils are known to be vulnerable to thermal degradation. In comparison with other known methods for removing natural and synthetic impurities, the method disclosed here can be carried out effectively under conditions of temperature close to the environment or sub-environment. Many of the other known methods of removing impurity involve higher temperatures, which can be dangerous for thermally sensitive components, that is, thermally sensitive components are converted into the different chemical species that reduces their yield and can also modify organoleptic properties or effectiveness of essential oil. The process of the present invention can preferably be carried out at 10 to 50 ° C.
    [00098] It will be understood by someone skilled in the art that the disclosed method also relates to a process to reduce the amount of at least one component in an essential oil composition that thus generates a concentrate of at least one component. The resulting concentrates comprising at least one desired natural component can be used directly as a product directly, or can be used as an intermediate that is subjected to additional separation processes, such as, for example, chromatographic or crystallization methods .
    [00099] It will be understood by someone skilled in the art that the modalities described above are not limiting examples and in the spirit of this description the modalities can also be combined and applied in different sequences to achieve a desired product composition of essential oil. Resulting Compositions
    [000100] The present disclosure also refers to compositions that result from the process disclosed here. Such compositions can include the retained material, the purified oil, and / or the eluted material.
    [000101] For example, in at least one embodiment, the described process produces the degreased essential oil. In at least one other modality, the disclosed process produces a 90% reduction in at least one impurity, for example, pesticide residues, in relation to the essential oil feed.
    [000102] In an additional embodiment, the color of the essential oil is reduced, for example, from brown to pale yellow.
    [000103] In yet another embodiment, the essential oil is processed to reduce the concentration of impurities in the oil. In such an embodiment, the disclosed process may produce a composition, such as retained material, comprising an increased concentration of at least one of plant sterols, fumarocoumarins, hormones, and natural colors, such as beta-carotene, compared to essential oil for food.
    [000104] In yet another modality, the essential oil is processed to fractionate a component of the essential oil. In such an embodiment, the disclosed process may produce a composition, such as retained material, comprising an increased concentration of at least one of the essential oil components such as α-, β-sinensal or nootkatona, compared to essential oil for food.
    [000105] The examples disclosed below are provided for a deeper understanding and clarification of the present invention. They, however, cannot be construed to restrict the scope of the invention in any way. EXAMPLES Example 1 - One-step orange oil removal.
    [000106] A METcell dead-end filtration cell (Evonik Memory Extraction Technology Ltd, United Kingdom) containing a nanofiltration PuraMem (R) S380 membrane card in organic solvent (Evonik Membrane Extraction Technology Ltd., UK) for this experiment, see Figure 1 of a schematic diagram of the METcell dead end filtration system. PuraMem (R) S380 is a silicone coated membrane prepared according to DE10 2009 047 351 with a cut of nominal molecular weight of 600 g.mol- 1. The membrane was prepared for use for filtration of 200 mL of the liquid. monene (Sigma-Aldrich, Germany) at room temperature and 3 MPa of filtration pressure to remove the conditioning agent (preservative) from the PuraMem (R) S380 membrane.
    [000107] Once the membrane was prepared, the filtration cell was emptied and refilled with 100 ml of orange oil in one step. The orange oil in one step was filtered at a temperature of 30 ° C and a filtration pressure of 3 MPa. 75 mL of the oil was eluted and collected in 25 mL aliquots.
    [000108] The color resistance of the orange oil samples was determined using a UV spectrophotometer to measure the absorbance at a wavelength of 432 nm. Figure 2 shows the UV absorbance measured in the feed oil, the retained portion of the orange oil and the three aliquots eluted. The color resistance in the eluted samples was reduced from approximately 16 absorbance units in the feed oil to approximately 1 absorbance unit in the eluted samples. At the same time, the color resistance in the retained material has increased from approximately 16 absorbance units to 23 absorbance units, which is consistent with only a small proportion of the colored compounds that are transported through the membrane during filtration. These results demonstrate the potential to reduce the color of essential oils, including citrus oils, especially orange oil. Example 2 - Removing the orange oil color in five steps.
    [000109] A METcell dead-end filtration cell (Evonik Memory Extraction Technology Ltd, United Kingdom) containing a nanofiltration PuraMem (R) S380 membrane card in organic solvent (Evonik Membrane Extraction Technology Ltd., UK) for this experiment, see Figure 1 for. a schematic diagram of the METcell dead end filtration system. PuraMem (R) S380 is a silicone coated membrane prepared according to DE10 2009 047 351 with a cut of nominal molecular weight of 600 g.mol-1. The membrane was prepared for use by filtering 200 mL of limonene (Sigma-Aldrich, Germany) at room temperature and 3 MPa of filtration pressure to remove the conditioning agent (preservative) from the PuraMem (R) S380 membrane.
    [000110] Once the membrane was ready, the filtration cell was emptied and refilled with 100 ml of orange oil five times. The orange oil was filtered five times at a temperature of 30 ° C and a filtration pressure of 3 MPa. 65 mL of the oil was eluted; the first 25 mL eluted were collected as an "Eluted 1" aliquot; the next 20 mL eluted were collected as a second aliquot ("Eluted 2"), and; the following 20 mL were collected as the third and final aliquot ("Eluted 3").
    [000111] The color resistance of the orange oil samples was determined using a UV spectrophotometer to measure the absorbance at a wavelength of 432 nm. Figure 3 shows the measured UV absorbance of the feed oil, the retained portion of the orange oil and the three aliquots eluted. The color resistance in the eluted samples was reduced from approximately 85 absorbance units in the feed oil to 5 to 10 absorbance units in the eluted samples. At the same time, the color resistance in the retained material increased from approximately 85 absorbance units to 230 absorbance units, which is consistent with only a small proportion of the colored compounds that are transported through the membrane during filtration. These results demonstrate the potential to reduce the color of the essential oil concentrate (multiple steps), including citrus oils in five steps, especially orange oil. Example 3 - Removal of natural impurity (wax) from orange oil.
    [000112] A METcell dead-end filtration cell (Evonik Memory Extraction Technology Ltd, United Kingdom) containing a nanofiltration PuraMem (R) S380 membrane card in organic solvent (Evonik Membrane Extraction Technology Ltd., UK) for this experiment, see Figure 1 of a schematic diagram of the METcell dead end filtration system. PuraMem (R) S380 is a silicone coated membrane prepared according to DE10 2009 047 351 with a cut of nominal molecular weight of 600 g.mol-1. The membrane was prepared for use by filtering 200 mL of limonene (Sigma-Aldrich, Germany) at room temperature and 3 MPa of filtration pressure to remove the conditioning agent (preservative) from the PuraMem (R) S380 membrane.
    [000113] Once the membrane was prepared, the filtration cell was emptied and refilled with 100 ml of orange oil five times. The orange oil was filtered five times at a temperature of 30 ° C and a filtration pressure of 3 MPa. 65 mL of the oil was eluted.
    [000114] The wax content of the orange oil samples was determined after the oil samples were cooled for at least 24 hours at -24 ° C by assessing turbidity of the solutions using a UV spectrophotometer to measure absorbance at a length 720 nm waveform. Figure 4 shows the UV absorbance measured in the feed oil, in the retained portion of the orange oil and in the eluted orange oil. The wax content of the eluted samples was reduced from approximately 0.54 unit of absorbance in the feed oil to 0.18 unit of absorbance in the eluted samples. At the same time, the wax content of the retained material increased from approximately 0.54 absorbance unit to approximately 1.18 absorbance unit, which is consistent with a large proportion of the wax compounds that are retained by the membrane during filtration. These results demonstrate the potential to reduce the wax content of essential oils, including citrus oils in five stages, orange oil especially in five stages. This example, together with Example 2 also confirms, that both wax and colored impurities can be removed from the orange oil. Example 4 - Fractionation of components in orange oil in one step.
    [000115] A METcell cross-flow filtration system (Evonik Membrane Extraction Technology Ltd, United Kingdom) containing DuraMem (R) S XP2 membrane coupons from organic solvent nanofiltration (Evonik Membrane Extraction Technology Ltd.) was used for this experiment, see Figure 5, a schematic diagram of the cross flow filtration system METcell. DuraMem (R) S XP2 is a silicone coated membrane prepared in accordance with DE10 2009 047 351 with a cut-in nominal molecular weight of approximately 350 g.mol-1. The membrane was prepared for use by filtering 200 ml of limonene (Sigma-Aldrich, Germany) through the membrane card at room temperature and 3 MPa of filtration pressure to remove the conditioning agent (preservative) from the DuraMem (R) S XP2 membrane .
    [000116] Once the membrane was prepared, the filtration cell was emptied and refilled with 500 ml of orange oil in a step that had been processed with a Pura-Mem (R) S380 membrane according to Example 3 methodology for removing wax compounds. The orange oil was filtered in one step at a temperature of 30 ° C and a filtration pressure of 3 MPa. The eluted samples were collected and analyzed using an Agilent 6850 gas chromatograph adjusted with an FID detector. The gas chromatograph was adjusted with a CV 5 column (30 mx 0.25 mm diameter) from Agilent Technologies and subjected to the following temperature program -70 ° C for 1 minute, the ramp function from 70 ° C to 250 ° C at 30 ° C.min-1, ramp function from 250 ° C to 310 ° C at 20 ° C.min-1, stabilized and 310 ° C for 2 minutes. The injector temperature was 275 ° C and the detector temperature was 350 ° C.
    [000117] Table 1 shows the membrane rejection values of a chosen number of compounds in the oil calculated from the analytical results obtained from the gas chromatograph (the rejection is defined above in Equation 1). Table 1. Rejection of compounds chosen in orange oil in one step when filtered with DuraMem (R) S XP2 membrane.

    [000118] Most of the compounds present rejection values of 0%, this means that these species pass through the membrane unimpeded and are present in the final eluted material in the same concentration as in the feed material. However, it can be seen that certain compounds, for example, sinensal and waxes, have non-zero rejection values, this means that these species do not pass freely through the membrane and are concentrated in the retained solution, leading to the fractionation of these components. of orange oil. Figure 6 shows an example of how these non-zero membrane rejection values provide the fractionation of essential oil components between flows of retained material and eluted material, the mass balance being calculated using the rejection data provided in Table 1. This example demonstrates the potential for fractionated components of essential oil, orange oil in an elution step. Example 5 - Removal of synthetic impurity (pesticide residue) from orange oil.
    [000119] For this experiment, two pieces of equipment were used. In the first stage of the experiment, a 6.35 cm x 30.48 cm spiral wound membrane module containing the PuraMem (R) S380 membrane (Evonik Membrane Extraction Technology Ltd., United Kingdom) was used in a pilot plant nanofiltration. PuraMem (R) S380 is a silicone coated membrane prepared according to DE 10 2009 047 351 with a cut of nominal molecular weight of 600 g.mol-1. The membrane was prepared by filtering 5 L of limonene (Sigma-Aldrich, Germany) at room temperature and 3 MPa of filtration pressure to remove the conditioning agent (preservative) from the PuraMem (R) S380 membrane. For the second stage of the experiment, a METcell dead-end filtration cell (Evonik Membrane Extraction Technology Ltd, United Kingdom) containing a DuraMem (R) S XP2 nanofiltration membrane card in organic solvent (Evonik Membrane Extraction Technology Ltd.) was used for this experiment, see Figure 1 of a schematic diagram of the METcell no-exhaust filtration system. DuraMem (R) S XP2 is a silicone coated membrane prepared according to DE10 2009 047 351 with a cut of nominal molecular weight of approximately 350 g.mol-1. The membrane was prepared by filtering 200 ml of limonene (Sigma-Aldrich, Germany) through the membrane card at room temperature and 3 MPa of filtration pressure to remove the conditioning agent (preservative) from the DuraMem (R) S XP2 membrane .
    [000120] In the first stage of the experiment, 8.2 kg of orange oil was processed five times using the Pura-Mem (R) S380 membrane module in a spiral in the nanofiltration pilot plant. 5 kg of the oil were eluted at 3 MPa and 30 ° C. The mass flow of the initial eluate was 23.5 kg.m-2.h-1 and this was reduced to 10.7 kg.m-2.h-1 at the end of the experiment (after 5 kg had been eluted) reflecting the increased concentration of higher molecular weight compounds and increased viscosity in the retained material (eg colored waxes and compounds). Samples of the feed, retained material and eluted solutions were taken to determine the concentration of pesticides (pesticide residues) present in the solutions. The samples were analyzed for the pesticide composition by AQura GmbH using an LC-MS-MS liquid chromatography method. The results of the removal of pesticides chosen during filtration with PuraMem (R) S380 are shown in Table 2. Table 2 - Concentration of selected pesticides in the feed, in the retained material and in the eluted solutions and rejection of pesticides when the orange oil it is filtered five times with a PuraMem (R) S380 membrane.

    [000121] * ND-Not detected, below the detection limit.
    [000122] The data show that with the PuraMem (R) S380 Membrane a range of variation of the separation performance is achieved, for example both diphenoconazole and phosmet are almost completely removed from the oil with this membrane, while propargite and spirodiclofen pass through the membrane almost unimpeded. The solution eluted from this first experimental stage was additionally treated with a lower molecular weight cutting membrane (DoraMem (R) S XP2, cutting of nominal molecular weight of approximately 350 g.mol-1) to determine if the reductions Additional pesticide residue (pesticides) can be achieved.
    [000123] In the second stage of the experiment, three samples containing 100 g of the eluate produced by processing orange oil five times with the PuraMem (R) S380 spiral membrane module at the nanofiltration pilot plant were further processed using the DuraMem membrane (R) S XP2. 10 g of oil from each sample was eluted at 3.8 MPa and 30 ° C. The permeate mass flow was constant for all filtrations at approximately 1.7 kg.m-2.h-1. The samples of the feed and eluted solutions were taken to determine the concentration of pesticides (pesticide residues) present in the solutions, the assumption was made, the feed and the concentrations of retained material were the same, considering the small sample volume that was pervaded. The samples were analyzed for the pesticide composition by AQura GmbH using an LC-MS-MS liquid chromatography method. The results of removing pesticides chosen during filtration with DuraMem (R) S XP2 are shown in Table 3 Table 3 - Concentration of selected pesticides in the feed and eluted solutions and rejection of pesticides when orange oil previously filtered five times with PuraMem (R) S380 membrane is filtered with DuraMem (R) S XP2 membrane

    [000124] The data show that by applying a lower molecular weight to the DuraMem (R) S XP2 cutting membrane, additional removal of pesticides (pesticide residues) can be achieved. This example demonstrates the potential to remove pesticide residues from essential oil, including orange oil five times. In addition, this example demonstrates the potential benefits of processes that subsequently apply more than one selectively permeable membrane to address a given separation task.
    权利要求:
    Claims (17)
    [0001]
    1. Process for separating components into an essential oil, which is a natural non-lipid oil derived from vegetable matter and containing less than 40% by weight of lipids, which comprises: (i) providing, as a food nanofliteration, an essential oil or a solution comprising an essential oil and at least one organic solvent, by a method selected from: (a) steam distillation of a natural raw material of plant origin, followed by the separation of the essential oil from a aqueous phase, if present, (b) mechanical treatment of the citrus epicarp, followed by the separation of essential oil from an aqueous phase, if present, (c) dry distillation of a natural raw material of plant origin, followed by separation of essential oil of an aqueous phase, if present, (d) mechanical expression of the essential from plant material other than citrus fruits, (e) extraction of plant material with supercritical solvent; (f) extraction of plant material with a non-polar solvent having a dielectric constant, measured as the ratio between the electrical capacity of a condenser filled with the solvent and the electrical capacity of the condenser evacuated at room temperature, less than or equal to 15; (ii) providing a selectively permeable nanofiltration membrane with a first surface and a second surface; the referred process being characterized by the fact that: (iii) the nanofiltration feed is contacted with the first surface of the nanofiltration membrane selectively permeable to separate the essential oil by transferring one or more components of the essential oil or essential oil solution that emerges from the first to the second surface through the membrane, with the essential oil or the essential oil solution in contact with the first surface forming a retained material and the essential oil or essential oil solution contacting the second surface forms an eluate, the pressure on the first surface being higher than the pressure on the second surface, and the concentration of one or more components of the essential oil or the essential oil solution is reduced in the essential oil or essential oil solution contacting the first surface compared to the essential oil or initial essential oil solution.
    [0002]
    2. Process, according to claim 1, characterized by the fact that it also comprises subjecting the oil or the solution of the retained material and / or the eluted oil or solution to at least one additional processing step.
    [0003]
    3. Process, according to claim 1 or 2, characterized by the fact that it also comprises recovering any solvent content of the eluted and retained solutions.
    [0004]
    4. Process, according to claim 2, characterized by the fact that it also includes the subjection of the oil or solution of retained material and / or the oil or solution eluted to at least one additional contact with a selectively permeable membrane , preferably a nanofiltration membrane, in which preferably two different membranes are used which have two different molecular weight cuts, especially preferably in which at least one membrane having a molecular weight cut between 400 g.mol-1 and 1500 g .mol-1, especially between 500 g.mol-1 and 800 g.mol-1 and at least one membrane with a different molecular weight cut between 150 g.mol-1 and 600 g.mol-1, especially between 200 g.mol-1 and 500 g.mol-1 are used.
    [0005]
    5. Process according to any one of claims 1 to 4, characterized by the fact that: the essential oil is derived from plants and is selected from oils produced from fruits, seeds, bark, wood, rhizome, leaves, residues na, flowers, bark and root and / or the essential oil derives from the genus Citrus and / or the essential oil is selected from oils that derive from lime orange, orange, lemon, lime, grapefruit, bergamot, common lime, cider, mandarin, tangerine, pear orange, rangpur, lime, clementine, yuzu, kaffir lime, ugli and / or the essential oil is selected from pepper oil, juniper oil, cumin oil, bark oil cinnamon, camphor oil, rosewood oil, ginger oil, basil oil, eucalyptus oil, lemongrass oil, peppermint oil, rosemary oil, mint oil, tea oil, frankincense oil, chamomile oil, clove oil, jasmine oil, lavender oil, rose oil, ylang ylang oil, bergamot oil, grapefruit oil a, lemon oil, lime oil, orange oil, and valerian oil.
    [0006]
    6. Process according to any one of claims 1 to 5, characterized by the fact that the process produces a reduction: in the wax content and / or in the color content and / or in at least one natural impurity and / or synthetic chosen from environmental pollutants, pesticide residues, extractable from packaging, waxes, vegetable sterols, lipophilic hormones, colored components, oxidation products, components that produce odor and / or undesirable taste in the oil mixture, or vitamins in the essential oil product compared to the initial essential oil.
    [0007]
    7. Process, according to claim 6, characterized by the fact that at least one natural or synthetic impurity comprises pesticide residues.
    [0008]
    8. Process according to any one of claims 1 to 7, characterized in that the retained material comprises an increased concentration of at least one component of the essential oil chosen from vitamins, plant sterols, lipophilic hormones, components colored, furanocoumarins, sesquiterpenes in relation to the fatty acid oil mixture.
    [0009]
    Process according to any one of claims 1 to 8, characterized in that the organic solvent used to prepare the mixture of the essential oil and organic solvent is chosen from aromatic hydrocarbons, aliphatic hydrocarbons, ketones, glycols, chlorinated solvents, esters, ethers, amines, nitriles, aldehydes, phenols, amides, carboxylic acids, alcohols, furans, lactones, and dipolar aprotic solvents, and mixtures thereof and with water and / or toluene, xylene, benzene , styrene, anisol, chlorobenzene, dichlorobenzene, chloroform, dichloromethane, dichloroethane, methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), acetone, ethylene glycols ethanol, methanol, isopropanol, propanol, butanol, hexane, heptane, cyclohexane, dimethoxyethane, methyl tert-butyl ether (MTBE), diethyl ether, adiponitrile, N, N-dimethylformamide, dimethylsulfoxide, N, N-dimethylacetamide, dioxane, nitromethane, n itrobenzene, pyridine, carbon disulfide, tetrahydrofuran, methyl tetrahydrofuran, N-methyl pyrrolidone, N-ethyl pyrrolidone, acetonitrile, and mixtures thereof and with water and / or methanol, ethanol, isopropanol, acetate ethyl, acetone, hexane, heptane, ethylene glycols, and mixtures thereof and with water.
    [0010]
    10. Process according to any one of claims 1 to 9, characterized by the fact that at least one selective nanofiltration membrane comprises a material chosen from polyethylene, polypropylene, polytetrafluoroethylene (PTFE), polyvinylidene difluoride (PVDF), polysulfone, polyethersulfone, polyacrylonitrile, polyamide, polyimide, polyamideimide, polyetherimide, cellulose acetate, polyaniline, polypyrrole, polyetheretherketone (PEEK), polybenzimidazole, and mixtures thereof.
    [0011]
    11. Process according to claim 10, characterized by the fact that at least one selective nanofiltration membrane comprises a polyimide, preferably a polyimide subjected to post-formation crosslinking and impregnation with a low volatility compound.
    [0012]
    12. Process according to any one of claims 1 to 11, characterized in that at least one selective nanofiltration membrane is a composite material comprising a support and a selectively permeable thin layer, preferably a layer selectively permeable thin film comprising a material chosen from modified polysiloxane based on elastomers including elastomers based on polydimethoxysiloxane (from PDMS), ethylene propylene diene propylene (EPDM) elastomers, polynorbornene-based elastomers, polyoctamer-based elastomers, polyurethane-based elastomers, butadiene and nitrile butadiene rubber-based elastomers, natural rubber, butyl rubber-based elastomers, polychloroprene-based elastomers (Neoprene ), epichlorohydrin elastomers, polyacrylate elastomers, polyethylene, polypropylene, polytetrafluoroethylene (PTFE) -based elastomers, polyvinylidene difluoride (PVDF) , block polyether amides (PEBAX), polyurethane elastomers, crosslinked polyether, polyamide, polyaniline, polypyrrole, and mixtures thereof, a selectively permeable thin layer comprising a polysiloxane based elastomer is particularly preferred.
    [0013]
    13. Process according to any one of claims 1 to 12, characterized in that at least one selective nanofiltration membrane comprises an inorganic material chosen from silicon carbide, silicon oxide, zirconium oxide , titanium oxide, and zeolites.
    [0014]
    14. Process according to any one of claims 1 to 13, characterized by the fact that at least one selective nanofiltration membrane comprises a polymer membrane with organic or inorganic matrices dispersed in the form of powdered solids present in amounts up to approximately 20% by weight of the polymer membrane.
    [0015]
    15. Process according to any one of claims 1 to 14, characterized by the fact that at least one selective nanofiltration membrane comprises nanofiltration membranes in silicone-coated organic solvents, preferably based on nanofiltration membranes. polyimide.
    [0016]
    16. Process according to any one of claims 1 to 15, characterized by the fact that at least one selective member has a cut in molecular weight ranging from 150 g / mol to 1,500 g / mol, preferably from 200 g / mol to 800 g / mol, and in particular 200 g / mol less than or equal to 600 g / mol.
    [0017]
    17. Process according to any of claims 1 to 16, characterized by the fact that the process for nanofiltration is carried out at a temperature ranging from approximately 10 ° C to approximately 50 ° C and / or with a pressure transmembrane ranging from approximately 1 MPa to 6 MPa (and / or the essential oil is dissolved in the organic solvent in a concentration ranging from 1% v / v to 95% v / v.
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    同族专利:
    公开号 | 公开日
    MX2014013474A|2015-05-07|
    WO2013167307A1|2013-11-14|
    US20190106654A1|2019-04-11|
    PH12014502480B1|2015-01-12|
    PH12014502480A1|2015-01-12|
    US10934501B2|2021-03-02|
    SG11201406975XA|2014-11-27|
    US20150118331A1|2015-04-30|
    AU2013258396B2|2017-07-06|
    EP2846900A1|2015-03-18|
    JP2015521219A|2015-07-27|
    EP3677328A1|2020-07-08|
    AU2013258396A1|2014-11-06|
    ES2804454T3|2021-02-08|
    CN104302384B|2017-04-12|
    CA2872721A1|2013-11-14|
    BR112014027647A2|2017-06-27|
    US10202562B2|2019-02-12|
    CA2872721C|2019-04-30|
    CN104302384A|2015-01-21|
    EP2846900B1|2020-05-27|
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    法律状态:
    2018-05-02| B25A| Requested transfer of rights approved|Owner name: EVONIK DEGUSSA GMBH (DE) |
    2019-09-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-05-12| B25D| Requested change of name of applicant approved|Owner name: EVONIK OPERATIONS GMBH (DE) |
    2020-10-13| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-12-22| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 20/03/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP12166953|2012-05-07|
    EP12166953.5|2012-05-07|
    PCT/EP2013/055833|WO2013167307A1|2012-05-07|2013-03-20|Membrane-based processes for selectively fractionating essential oils|
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