WO2021058647A1 - Procédé de production de stérols et/ou de tocophérols avec récupération de sous-produits - Google Patents

Procédé de production de stérols et/ou de tocophérols avec récupération de sous-produits Download PDF

Info

Publication number
WO2021058647A1
WO2021058647A1 PCT/EP2020/076723 EP2020076723W WO2021058647A1 WO 2021058647 A1 WO2021058647 A1 WO 2021058647A1 EP 2020076723 W EP2020076723 W EP 2020076723W WO 2021058647 A1 WO2021058647 A1 WO 2021058647A1
Authority
WO
WIPO (PCT)
Prior art keywords
sterols
phase
methanol
sterol
optionally
Prior art date
Application number
PCT/EP2020/076723
Other languages
English (en)
Inventor
Valerie Eychenne
Yannick Basso
Olivier VALLEJO
Original Assignee
Basf Se
Basf Health And Care Products France S.A.S.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Se, Basf Health And Care Products France S.A.S. filed Critical Basf Se
Priority to CA3145091A priority Critical patent/CA3145091A1/fr
Priority to CN202080067968.XA priority patent/CN114450386A/zh
Priority to EP20785451.4A priority patent/EP4034620A1/fr
Publication of WO2021058647A1 publication Critical patent/WO2021058647A1/fr

Links

Classifications

    • 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
    • C11B13/00—Recovery of fats, fatty oils or fatty acids from waste materials
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
    • C11C3/10—Ester interchange
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
    • A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
    • A23L33/105—Plant extracts, their artificial duplicates or their derivatives
    • A23L33/11—Plant sterols or derivatives thereof, e.g. phytosterols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
    • C07D311/70—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4 with two hydrocarbon radicals attached in position 2 and elements other than carbon and hydrogen in position 6
    • C07D311/72—3,4-Dihydro derivatives having in position 2 at least one methyl radical and in position 6 one oxygen atom, e.g. tocopherols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J9/00—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of more than two carbon atoms, e.g. cholane, cholestane, coprostane
    • 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
    • C11B11/00—Recovery or refining of other fatty substances, e.g. lanolin or waxes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/74—Recovery of fats, fatty oils, fatty acids or other fatty substances, e.g. lanolin or waxes

Definitions

  • the presently claimed invention relates to a method of obtaining phytosterols and/or tocopherols from residues of a distillation of the esters of vegetable oils, preferably from oil distillation residues from a transesterification of vegetable oils and also to a method of purification of a sterol-containing phase, in particular sterol crystals.
  • Phytosterols and their esters possess hypocholesterolaemic properties, i.e. these substances are capable of lowering the cholesterol level in the blood. Accordingly, they are used as food additives, for example for the production of margarine, frying oils, sausages, ice creams and the like.
  • the production of sterols and other unsaponifiable constituents, such as tocopherols for example, from distillates obtained in the deacidification of vegetable oils has already been variously described in the patent literature, cf. EP-A20610742 (Hoffmann-LaRoche), GB-A1 2,145,079 (Nisshin Oil Mills Japan) and EP-A1 0333472 (Palm Oil Research and Development Board).
  • the main sources of phytosterols are residues from tall oil processing and distillates from vegetable oil refining.
  • fatty acid methyl ester (FME) as a source for obtaining phytosterols and tocopherols which consists of distillation residues from the vegetable oil methyl ester production for the field of use of biodiesel hereinafter "fatty acid methyl ester" as “FME”; in the art also known sometimes named "FAME"
  • FME fatty acid methyl ester
  • distillation residues from the vegetable oil methyl ester production care should be taken to ensure that the matrix of concomitant components and contaminants, which can have a disruptive effect on the process for obtaining sterols and tocopherols with regard to achievable yields and purities, is different from the one in steam distillates.
  • the distillation residue contains for example phosphatides, coloring components, enriched long-chain FMEs and polymerization products from the distillation.
  • the processing of the distillation residues needs to be done differently from the processing of the steam distillates.
  • EP 0656894 B1 (Henkel) describes a process for the production of sterols in which a residue from the distillation of methyl esters consisting essentially of glycerides, sterols, sterol esters and tocopherols is transesterified with methanol in the presence of alkaline catalysts. After neutralization of the catalyst, removal of the excess methanol by distillation and, optionally, removal of the catalyst by washing, the sterols are crystallized by lowering the reaction temperature from about 65 to 20 °C. The thus obtained crystals are washed with methanol and water. Unfortunately, the yield of sterols is unsatisfactory.
  • EP 2635592 B1 discloses a method for obtaining phytosterols and tocopherols using multi-phase separation systems to isolate the sterol and/or tocopherol.
  • EP1179535 B1 and EP1179536 B1 disclose processes for the production of sterols using a two-step-transesterification to obtain sterols from vegetable oil distillates. Crystallization of the obtained sterols and washing with methanol and FME is disclosed as subsequent process steps in dependent claims.
  • EP1179536 B1 "methyl ester" is disclosed as employed solvent in the examples, the "methyl ester” actually used in the examples and disclosed in the description is the FME from the transesterifications of the vegetable oil.
  • EP1179535 B1 discloses in its examples the use of "FME”; in [0036] and [0042] EP1179535 B1 also discloses that the crystals obtained in examples a) and b) "are washed with suitable solvents". However, which solvents those actually might be is not disclosed.
  • EP1169335 B1 discloses a process for the crystallization of sterols from a specific mixture of methanol and FME in certain ratios and washing of the obtained crystals. Objective of this disclosure is to provide sterols in high yields and "good color quality". Key is according to this disclosure the optimum amount and ratio of methanol during crystallization and thus the crystallization temperature which is said to lead to the desired improvement. The obtained crystals are then washed with FME, which step is said to further improve the color quality of the sterol crystals obtained.
  • the yield, color and purity of the phytosterol is significantly influenced by the process used for the downstream processing of the vegetable oil distillate and the solvent used for purification.
  • the conditions of the process and the choice of solvent used for the purification process each play - independently - a significant role in improving the color of the phytosterol and reducing the amount of impurities without compromising on the yield of the final product.
  • the presently claimed invention relates generally to the production of phytosterols and more particularly to a process for the production of phytosterols from residues of the distillation of transesterified oils.
  • sterols In order to be able to obtain sterols in pure form, they have to be converted from the esterified to the free state. Otherwise, they are very difficult to separate from the components accompanying them.
  • the conversion into free sterols may be carried out, for example, by hydrolysis, saponification or transesterification.
  • the presently claimed invention is directed to the use of a transesterification mechanisms.
  • the presently claimed invention relates to a method of obtaining phytosterols and/ or tocopherols from residues of a distillation of the esters of vegetable oils, preferably from distillation residues from a transesterification of vegetable oils, in particular from the vegetable oil-based FME production for the biodiesel field of application, wherein the method comprises at least the steps of: a) a first basic transesterification stage, wherein a reaction of partial glycerides contained in the distillation residues is carried out in the presence of a basic catalyst and methanol, whereby two phases are formed, wherein one phase comprises to a large extent glycerin and the second phase comprises the basic catalyst and unreacted methanol, and FME, with thereafter the further optional steps i), ii) and/ or iii) of i) optionally separating methanol ii) optionally separating FME, iii) optionally separating the basic catalyst, b) separating the phase comprising glycer
  • a two-stage basic catalyzed transesterification of a FME distillation residue from the biodiesel production or other oil transesterification process, preferably from the biodiesel production, with an intermediate separation of a glycerin phase produced in the transesterification is accumulated for completion of the glyceride reaction is carried out in the second reaction stage without methanol- or catalyst- removal such removal by e.g. flashing, distillation or washing.
  • the glycerin phase produced after the first transesterification stage can advantageously be fed directly to a process, preferably a distillation process, for obtaining glycerin of desired grade and purity, such as being suitable for use in cosmetics and/ or pharmaceutical applications.
  • the presently claimed invention relates to a purification process, wherein the color of the final phytosterol product is significantly improved and/ or, preferably and, the amount of phytosterol ester as an impurity is significantly reduced.
  • the presently claimed invention relates to a significantly reduced solvent content in the final phytosterol product.
  • first”, “second”, “third” or “(a)”, “(b)”, “(c)”, “(d)”, “i”, “ii” etc. relate to steps of a method or use or assay there is no time or time interval coherence between the steps, i.e. the steps may be carried out simultaneously or there may be time intervals of seconds, minutes, hours, days, weeks, months or even years between such steps, unless otherwise indicated in the application as set forth herein above or below.
  • the steps are performed in the numerical or hierarchical order implied by it, i.e. at first a, then b, then c etc., first i), then ii), then iii) etc.
  • final sterol product signifies the phytosterol which is obtained after the purification steps.
  • (oil) distillate encompasses edible vegetable oil distillates (VODs) which are even preferred.
  • (oil) distillation residue encompasses transesterified oil distillation residues which are even preferred.
  • Said transesterified oil distillation residues are preferably fatty acid alkyl ester distillation residues, more preferably fatty acid methyl ester distillation residues in particular from the production of biodiesel.
  • partial glycerides encompasses all combinations of mono-, di- and/or triglycerides. In case of oil distillates as starting material, there are only or nearly only triglycerides and no mono- and diglycerides, whereas, in case of typical oil distillation residues, there are mainly triglycerides and diglycerides and only a few monoglycerides.
  • the presently claimed invention relates to a method of obtaining phytosterols and/ or tocopherols from residues of a distillation of the esters of vegetable oils, preferably from distillation residues from a transesterification of vegetable oils, in particular from the vegetable oil-based FME production, specifically for the biodiesel field of application, with the following embodiments 1 to 4 defining the general invention, and the further description below those embodiments disclosing further features and more details of the process steps, preferred options and alternatives still encompassed by the present invention:
  • Method of obtaining phytosterols and/or tocopherols from residues of a distillation of the esters of vegetable oils preferably from distillation residues from a transesterification of vegetable oils, in particular from the vegetable oil-based FME (FAME) production, more preferably from the production of biodiesel
  • the method comprises at least the steps of: a) providing a starting material containing unsaponified matter which is a residue from the work-up of vegetable oils, such residue containing sterols and usually also tocopherols, wherein the starting material which contains at least 5, preferably at least 10, more preferably at least 15, even more preferably at least 20 weight % of sterols, b) optionally subjecting the starting material to a concentration step to increase the content of sterols compared to the initial content, preferably to a content of at least 25, more preferably at least 30, even more preferably at least 40 and most preferably to at least 50 wt.% of sterols in the concentrated residue, by subjecting the residue to
  • residues of a distillation of the esters of vegetable oils comprises a residue derived from an oil selected from the group consisting of soybean oil, sunflower oil, rapeseed oil, coconut oil, palm oil, palm kernel oil, and mixtures thereof.
  • the oil distillation residue comprises a residue derived from rapeseed oil such as high eruic acid rapeseed oil or CANOLA oil.
  • Step a) - Starting material The starting material for the presently claimed process may be obtained using known processes as outlined herein above using the known prior art processes.
  • the starting material thus is a residue from the work-up of vegetable oils, such residue containing sterols and usually also tocopherols.
  • Such residue is obtained by several esterification and transesterifications, treatment with acid etc., all of which is known in the art.
  • One such process is the known process to produce biodiesel, i.e. fatty acid methyl ester.
  • this residue resulting from such vegetable oil processing and work-up including that from the bio-diesel process is meant with the term "residue”.
  • Such residue as a starting material for the present process contains "unsaponified matter”, such unsaponified matter containing sterols and usually also tocopherols, with the content in the starting material being at least 5, preferably at least 10, more preferably at least 15, even more preferably at least 20 weight % of sterols, however usually at the lower end with about 5 to 15wt% sterols.
  • Such residues may be obtained as outlined herein above, using the known prior art processes.
  • Especially suitable residues are such from the work-up of vegetable oils containing sterols and usually also tocopherols. These residues are obtained by several esterification and transesterifications, treatment with acid etc., all of which is known in the art.
  • One such known process is the process to produce biodiesel, i.e. fatty acid methyl ester.
  • the oil distillation residue comprises a residue derived from an oil selected from the group consisting of soybean oil, sunflower oil, rapeseed oil, high erucic acid rapeseed oil (HEAR), low eruric acid rapeseed oil (CANOLA; CANadian Oil Low eruic Acid), coconut oil, palm oil, palm kernel oil, and mixtures thereof, more preferably, the oil distillation residue comprises a residue derived from soybean oil, sunflower oil, rapeseed oil such as HEAR or CANOLA, even more preferably, the oil distillation residue comprises a residue derived from sunflower oil, rapeseed oil, preferably HEAR.
  • an oil selected from the group consisting of soybean oil, sunflower oil, rapeseed oil, high erucic acid rapeseed oil (HEAR), low eruric acid rapeseed oil (CANOLA; CANadian Oil Low eruic Acid), coconut oil, palm oil, palm kernel oil, and mixtures thereof
  • the oil distillation residue
  • residues are preferably residues from coconut oil, from palm kernel oil, from palm oil, from soybean oil, from sunflower oil, from rapeseed oil such as from HEAR and/ or CANOLA, more preferably from soybean oil, sunflower oil, rapeseed oil such as HEAR, even more preferably from sunflower oil and/or rapeseed oil, and especially HEAR, with acid values of 0 to 10, preferably from 0 to 6 and contain mixtures of di- and triglycerides, FMEs, sterol esters, wax esters and free sterols, preferably 1 to 7 % by weight triglycerides, 3 to 15 % by weight diglycerides, 15 to 40 % by weight FMEs, 40 to 50 % by weight, in particular 42 to 47 % by weight sterol esters, 3 to 4 % by weight wax esters and 3 to 15 % by weight free sterols and small quantities of mono glycerides.
  • FMEs di- and triglycerides
  • oil distillates are used as raw materials for the production of sterols.
  • These distillates are preferably such of coconut oil, of palm kernel oil, of palm oil, of soybean oil, of sunflower oil, of rapeseed oil such as from HEAR and/ or CANOLA, more preferably of soybean oil, sunflower oil, rapeseed oil such as from HEAR, even more preferably of sunflower oil and/or rapeseed oil from HEAR, containing 45 to 65 % by weight triglycerides and 35 to 55 % by weight sterol esters summing up to 100 %.
  • Such residue may be further concentrated.
  • the residue as outlined before can be concentrated to a content of "unsaponified matter" of about more than 20 such as 35 to 60, preferably 40 to 55 and more preferably 45 to 50 weight percent of unsaponified matter relative to the total weight of concentrated residue (hereinafter "concentrated residue").
  • concentration can be achieved by submitting the residue as obtained to a transesterification reaction using methanol as solvent and reactant and sodium methylate as catalyst. The aim is to convert remaining glycerides in the residue to methyl esters. Following that transesterification, the formed glycerin is to be removed by standard means, e.g. decanting.
  • This process of transesterification with following glycerin removal can be repeated once or twice or more, but one repetition usually is enough and thus a preferred embodiment.
  • Excess methanol is then to be removed, followed by optional further removal of remaining glycerin which can form again as separate phase during or after the removal of methanol.
  • the formed methyl ester can be removed, by e.g. distillation. This thus also increases the yield of the fatty acid methyl ester, i.e. biodiesel.
  • This process of concentration is an optional process step which can be employed prior to the "first transesterification” which then follows to convert the sterols present in the "unsaponified matter" in the residue or concentrated residue to purified sterols which can then be crystallized and further purified.
  • Step c) Initial purification step by adsorption
  • the residue or - in case the optional step of concentration the residue is performed - concentrated residue can be subjected to the purification using adsorbents such as clays, earths and oxides.
  • adsorbents such as clays, earths and oxides.
  • Suitable adsorbents are well-known, e.g. the Trisyl-grades (e.g. from the company Grace).
  • This treatment allows for an improvement of the color, lowering the content of soaps, and/ or absorbing trace metals and/ or metal ions, preferably all of those improvements, by choosing suitable adsorbents.
  • This treatment may be performed at ambient or elevated temperature. In view of the high viscosity of the residue or concentrated residue, treatment at elevated temperature is preferable.
  • Suitable temperatures are ambient to about 100 degree Celsius, with temperatures of around 60 to 90 °C being preferred mainly to a good combination of viscosity and energy cost needed.
  • Suitable treatment duration may be anything from 10 minutes to several hours, e.g. even 5 to 10 hours. Duration mainly depends on the degree of removal desired and the amount of contaminants present in the residue or concentrated residue. Preferably durations are about 1 to 10 hours, more preferably 1 to 5 hours, even more preferable 1 to 3 hour, most preferably about 2 hours at 75 to 90°C.
  • This process of initial purification by adsorption is an optional process step which can be employed prior to the "first transesterification” which then follows to convert the sterols present in the "unsaponified matter" in the residue or concentrated residue to purified sterols which can then be crystallized and further purified.
  • the first transesterification stage is carried out with a content of basic catalyst, preferably sodium methylate, but for example also sodium hydroxide (NaOH) or potassium hydroxide (KOH) could be used instead or together, in the range from 0.1 % to 0.3 %, preferably in the range from 0.18 % to 0.22 % and with a methanol content in the range from 12 % to 18 %, preferably in the range from 14 % to 16 % and the second transesterification stage with a content of catalyst in the range from 0.5 % to 1 %, preferably in the range from 0.6% to 0.8%, and with a methanol content in the range from 20% to 38%, preferably in the range from 34% to 36%, wherein the added quantity of basic catalyst is standardized to an addition of sodium methylate and, if appropriate, should be adapted to the use of other basic catalysts.
  • a content of basic catalyst preferably sodium methylate
  • NaOH sodium hydroxide
  • KOH potassium hydroxide
  • the method according to the presently claimed invention can be operated in a particularly cost-effective and recycling-friendly manner, because for example only small quantities of methanol must be supplied for methanol recovery.
  • glycerin is added in an amount in the range from 0.2% to 7.2%, preferably in the range from 0.5% to 6.0%, and particularly preferably in the range from 1.0% to 5.5%, in each case based on the mass of the total batch.
  • the second transesterification reaction is carried out at a temperature range of 25 °C to 150 °C depending on the pressure and time conditions.
  • the first transesterification stage is carried out at a temperature in the range from room temperature (e.g. 25 °C) to 100 °C, preferably to 95, more preferably to 90 and even more preferably to 88°C, preferably in the range from 40 °C to 75 °C and particularly preferably in the range from 55 °C to 70 °C, such as at a temperature of 60 to 65 °C, and furthermore in particular at normal pressure.
  • the reaction may be performed depending on the temperature and pressure chosen under reflux or without reflux. When methanol is chosen which is the most favorable alcohol to be employed, this means that the reaction is performed at the boiling temperature of methanol or slightly below when operating at ambient pressure. By this a good temperature control can be implemented.
  • This embodiment of the invention enables an energy-saving and cost- efficient performance of the method, because high heating costs are avoided and the respective transesterification reactions can be preferably carried out inter alia at normal pressure, so that expensive pressurized reactors and complex and expensive generation and maintenance of the temperatures and pressures, such as are necessary in the prior art, can be omitted.
  • this embodiment is preferred over the following two embodiments for this process step.
  • the transesterification reaction of the partial glycerides is preferably carried out over a period of 5 to 20 minutes and more particularly 8 to 15 minutes at a temperature of 110 to 160, more preferably at 115 to 145° C. and more particularly at a temperature of 120 to 130° C at a pressure of 2 to 10 bar.
  • Steps i), ii) and iii) of step d) are described in the following section.
  • the glycerin phase may be preferably be removed without previous separation of FME, methanol and/ or catalyst, more preferably the glycerin phase may be removed without previous separation of FME, methanol and catalyst.
  • the glycerin phase is removed from the reaction mixture of the transesterification reaction without prior removal of methanol, fatty acid ester and catalyst.
  • the basic catalyst used according to the presently claimed invention can be used and recycled without any environmental or food-related problems, wherein in an advantageous manner, unlike for example in the aforesaid U.S. Pat. No. 5,424,457, there should be no fear of heavy metal contamination in the produced products, in this case phytosterols and/ or tocopherols.
  • the basic catalyst is optionally separated from the reaction mixture resulting from the first transesterification process.
  • reaction mixture resulting from the first transesterification reaction is submitted to the following additional process steps: i) depletion of methanol by e.g. flashing and/ or distillation, ii) depletion of FME by e.g. flashing and/ or distillation, with the steps i) and ii) being performed either first step i) and then step ii) or both steps i) and ii) being performed together or with some overlap, i.e. that step ii) starts before step i) is finished, and iii) removal of the catalyst by e.g. absorption on suitable absorbents such as suitable Trisyl-grades (e.g. from Grace) and the like, optionally by adding suitable acids during or before adding the adsorbent.
  • suitable absorbents such as suitable Trisyl-grades (e.g. from Grace) and the like
  • the glycerin phase preferably the glycerin phase resulting from the reaction mixture after having performed the further process steps i), ii) and iii) of previous step d) and only then having separated the glycerin-phase, from the first transesterification stage can advantageously be fed directly to a process for obtaining glycerin of any desired grade and purity, such process preferably being a multi stage distillation process using typically, known equipment and conditions.
  • the second transesterification reaction is carried out at a temperature range of 25 °C to 150 °C depending on the pressure and time conditions.
  • the second transesterification stage is carried out at a temperature in the range from room temperature (e.g. 25 °C) to 100 °C, preferably to 95°C, more preferably to 90°C and even more preferably to 88°C, preferably in the range from 40 °C to 75 °C and particularly preferably in the range from 55 °C to 70 °C, such as e.g. 60 or 65 °C, and furthermore in particular at normal pressure.
  • the reaction may be performed depending on the temperature and pressure chosen under reflux or without reflux. When methanol is chosen - which is the most favorable alcohol to be employed - this means that the reaction is performed at the boiling temperature of methanol or slightly below when operating at ambient pressure.
  • This embodiment of the invention enables an energy-saving and cost-efficient performance of the method, because high heating costs are avoided and the respective transesterification reactions can be - preferably - carried out inter alia at normal pressure, so that expensive pressurized reactors and complex and expensive generation and maintenance of the temperatures and pressures, such as are necessary in the prior art, can be omitted.
  • this embodiment is preferred over the other embodiments for the second transesterification step requiring other temperatures and pressures and thus durations.
  • the low reaction temperature during the first and/or the second transesterification stage contributes to a reduction in the operating costs relative to known methods and thus also improves the economy of the method relative to previously customary methods.
  • the duration of the reaction has to be prolonged compared to high temperatures, as otherwise no satisfying yields are obtainable.
  • the net benefit in terms of energy saving depends on the complete outline of the process, the equipment employed and the temperature and duration of the reactions, as a simply reduction in time leads to higher reaction temperature (if the yield should stay the same) or lower yields (if the duration stays the same).
  • a further advantage of the transesterification which can be carried out according to the presently claimed invention without pressure also resides in the fact that costly safety measures, which are necessary in the event of the use of pressure vessels, can be omitted, when the method is applied, since all operations are carried out at normal or atmospheric pressure, and, due to the low reaction temperatures, in an energy-efficient manner and quickly.
  • the reaction at around the boiling temperature of the solvent/ reactant employed for the transesterification i.e. the alcohol such as methanol, ethanol etc.
  • permits a good temperature control as excessive temperatures can be avoided as then the alcohol component will boil and thus cool down the reaction mixture again to the desired temperature.
  • the obvious advantage of performing at ambient pressure and lower temperatures is the omittance of (more expensive) pressurized equipment but with the drawback of usually longer reaction times needed to obtain the same yield of conversion.
  • the second transesterification reaction takes place over a period of about 2 to 10, preferably over a period of 4 to 10 hours and more particularly 5 to 8 hours at temperatures of 90 to 145° C. and more particularly 120 to 130°C and under a pressure of 2 to 10 bar.
  • the obvious advantage of this embodiment is the very high conversion to be achieved at relatively short times.
  • transesterification steps are: i) optionally separating and removing methanol from the reaction mixture obtained from the transesterification step; ii) optionally separating and removing FME from the reaction mixture obtained from the previous step, iii) optionally separating and removing the basic catalyst from the reaction mixture obtained from the previous step, and/ or iv) separating and removing the phase comprising glycerin from the reaction mixture obtained from the previous step.
  • step (g) when water is added in step (g), it is added in an amount in the range from 15% to 25%, preferably from 18% to 22%, and particularly preferably in the range from 19.5% to 20.5%, in each case based on the mass of a total batch, in order in particular to set a mass ratio of sterol: FMEs: methanol: water of substantially 1 : 2.5-3 : 2.2-2.5 : 0.8-1.2.
  • the steps of optionally separating and removing methanol from the mixture obtained from the step of adding water; optionally separating and removing FME from the mixture obtained from the previous step, optionally separating and removing the basic catalyst from the mixture obtained from the previous step, and/ or separating and removing the phase comprising glycerin from the mixture obtained from the previous step, as described for the previous step f) could be applied again after the end of step g).
  • the same rationales, measures etc. are applied as already described above for such measures within the paragraph on the first transesterification, to obtain the same results as described there and thus to further purify the mixture prior to the next process step.
  • the crystal structure of the required phytosterol crystals can be significantly improved by compliance with a maturation period, which in turn has a perceptible positive effect on improved filtration properties of the crystals and also yields of crystals.
  • the maturation period is in particular in the range from 1 hour to 48 hours, preferably in the range from 2 hours to 36 hours and particularly preferably in the range from 4 hours to 12 hours.
  • Successful crystallization typically requires a free sterol concentration of at least 20 to 25%. Sterol concentrations of > 40% can be achieved by the process according to the presently claimed invention. Should the concentration still be below a value which does not allow reasonable crystallization, it is increased by distilling off the fatty acid esters produced in the "transesterification of the sterol esters" process step. The procedure involved corresponds to the "fatty acid ester distillation” step. If the transesterification of the sterol esters was carried out under pressure and the metal soaps precipitated were removed by adsorption, FME is added as solvent. In this case, the quantity of FME is again 30 to 200% by weight and preferably 50 to 100% by weight, based on the amount of product used in the transesterification of the sterol esters.
  • the presently claimed invention relates to the purification of the sterol fractions which, apart from the lower alcohol, mainly contain methyl esters, takes place in a known manner, i.e. the hot mixtures (ca 50- 70 °C.) are slowly cooled to form the phytosterol crystals, which are formed at a temperature of from 15 °C to 50 °C, preferably 20 °C to 45 °C, more preferably 25 °C to 35 °C, even more preferably 20 °C to 30 °C, in a crystallizer.
  • alkaline catalyst from the transesterification present in the mixture can be neutralized beforehand, for example by addition of citric acid or other suitable organic or inorganic acids that are also suitable or acceptable for the intended use of the sterols later on; preferably, such neutralization is omitted if the feed for the crystallization allows for.
  • the lower alcohol is selected from the group consisting of methanol, ethanol and isopropyl alcohol.
  • the lower alcohol is methanol.
  • the alcohol may contain small amounts of water, but preferably is essentially water-free.
  • the ratio of sterol: methanol is in the range of 1: 0.1 to 1: 5, preferably 1: 0.5 to 1:3, more preferably 1:0.5 to 1:2.5.
  • the sterol containing phase which primarily contains sterol crystals, may subsequently be washed with methanol, wherein the quantity of methanol is in the range from 20% to 800 %, preferably in the range from 125% to 600%, more preferably in the range from 200% to 400% in each case based on the mass of the sterol crystal phase.
  • the sterol containing phase which primarily contains sterol crystals ,may subsequently be washed with methanol, wherein the quantity of methanol is in the range from 50% to 800%, preferably in the range from 125% to 700%, more preferably in the range from 200% to 550% in each case based on the mass of the sterol crystal phase, wherein this methanol washing is optionally preceded by a displacement washing of the sterol crystals with methyl ester, in particular vegetable oil methyl ester such as, for instance, methyl ester of rapeseed oil and/ or soya oil and/ or sunflower oil and/ or coconut oil and/ or palm oil and/ or cottonseed oil and/ or corn germ oil, at a proportion in the range from 50% to 500%, preferably in the range from 75% to 400%, and particularly preferred in the range from 100% to 350%, in each case relative to the mass of the sterol crystal phase.
  • methyl ester in particular vegetable oil methyl ester such as, for instance, methyl este
  • the phytosterol crystals are formed at a temperature of from 15°C to 50 °C, preferably 20°C to 45°C, more preferably 25 °C to35 °C even more preferably 20 °C to 30 °C, such as 20 °C, 21 °C, 22 °C, 23 °C, 24 °C, 25 °C, 26 °C, 27 °C, 28 °C, 29 °C, 30 °C, 31 °C, 32 °C, 33 °C, 34 °C or 35 °C.
  • the phytosterol crystals are formed at a temperature of from 15 °C to 50 °C, and more preferably at every temperature in between 15 to 50°C.
  • part of the mother liquor is recycled, for example to the crystallization process, after filtration of the crystal suspension.
  • the return stream is fed to the system together with the fatty acid esters in the "catalyst removal (II)" process step.
  • Another way of recycling the mother liquor is to introduce it into the first (a) or second (c) transesterification step.
  • the recycle ratio of the mother liquor depends to a very large extent on the starting material and hence on the composition of the mother liquor. It may be in the range from 0.1 to 5.0. A recycle ratio of 0.2 to 3.0 is preferably established.
  • Step (i) - Separation of phases the separation of the phases is carried out by means of a filter, a screen or a decanter centrifuge or the like apparatus suitable for separating liquid/ solid (or solid-containing) phase-mixtures, wherein a filter centrifuge or a decanter is preferably used, with a filter centrifuge being more preferred.
  • a filter or a decanter centrifuge in practice a filter cake can be obtained with a significantly lower residual moisture (“moisture” meaning the content of solvent(s) employed) than would be possible for example with differential pressure filtration or other filtration techniques.
  • a 3-phase decanter is also very suitable for separating the multi-phase system consisting of a sterol-containing phase, a glycerin-containing and a methanol-containing phase and a tocopherol-containing phase, wherein the phase containing sterol crystals or the sterol crystals themselves form the heaviest phase and can be separated off or pre-thickened well by means of the 3-phase decanter, whilst simultaneously the FME phase and the water phase containing glycerin and methanol can be obtained separately.
  • the separation of the sterol crystals by means of a discontinuously operating filter centrifuge also offers the possibility of carrying out cake washing immediately after the filtration.
  • the free sterols obtained from crystallization (in step (h)) and phase separation in step i) may be further (re-) crystallized to obtain sterol crystals of higher purity, by re-dissolution in the same solvent/ solvent mixture used for the first crystallization. Then, again, the obtained crystals have to be separated as disclosed before for step i).
  • the separated sterol crystals are subjected to further purification.
  • the sterol crystals are further purified using a solvent or solvent system.
  • the sterol crystals obtained in step h) and - if performed - step j), either in a separate process step or a combined process step - are purified using an organic solvent, a solvent mixture of more than one organic solvents and optionally but not preferred also containing water, or - more preferred - an azeotropic solvent mixture of at least one protic polar solvent and an at least one aprotic polar solvent.
  • the purification of the sterol fraction occurs in the presence of a solvent system which comprises at least one polar aprotic solvent.
  • the step k) of the purification of the sterol fraction occurs in the presence of at least one polar aprotic solvent which is ethyl acetate, methyl ethyl ketone and methyl acetate, dichloromethane, N- methyl pyrrolidone, tetrahydrofuran, acetone, dimethylformamide, acetonitrile, dimethyl sulfoxide, heptane and/ or hexane, with ethyl acetate, methyl ethyl ketone, methyl acetate, acetone, heptane and/ or hexane being preferred, and with ethyl acetate, methyl ethyl ketone and/ or methyl acetate being even more preferred, with methyl acetate being most preferred.
  • at least one polar aprotic solvent which is ethyl acetate, methyl ethyl ketone and methyl acetate, dich
  • the purification of the sterol fraction occurs in the presence of at least one polar aprotic solvent which is ethyl acetate, acetone, methyl ethyl ketone and/ or methyl acetate.
  • polar aprotic solvent which is ethyl acetate, acetone, methyl ethyl ketone and/ or methyl acetate.
  • methyl acetate is used as the sole polar aprotic solvent.
  • the purification of the sterol fraction occurs in the presence of at least one polar aprotic solvent and at least one polar protic solvent which are mixed together and/ or form an azeotrope in the solvent system.
  • the polar protic solvent is water, ethanol, methanol, isopropyl alcohol, butanol and/ or acetic acid.
  • the polar protic solvent is water, ethanol, methanol and/ or isopropyl alcohol.
  • methanol is used as the sole polar protic solvent.
  • the polar aprotic solvent is present in the range of 25 to 75% by weight, based on the amount of phytosterol, preferably in the range of 30 % to 50 % by weight, based on the amount of phytosterol, and every value in between 30 % to 50 %, based on the amount of phytosterol, with ethyl acetate, acetone, methyl ethyl ketone and/ or methyl acetate being the preferred polar aprotic solvent (s), and methyl acetate being more preferred as the sole polar aprotic solvent.
  • the polar protic solvent is present in the range of 5 to 50 % by weight, based on the amount of phytosterol, preferably in the range of 10 to 30 % by weight, based on the amount of phytosterol, and every value in between 10 % to 30 %, based on the amount of phytosterol, with methanol being the preferred polar protic solvent.
  • the phytosterol is provided in the form of a 10% by weight solution in pyridine,
  • the final sterol product has a Gardner color number of less than 4.0, when measured for a 10 wt.% of sterol in pyridine.
  • the final sterol product has a Gardner color number of less than 3.0, preferably less than 2.0, more preferably less than 1.5, when measured for a 10 wt.% of the sterol in pyridine.
  • the solvent content in the purified phytosterol is less thanlOO ppm, preferably less than 50 ppm, more preferably less than 20 ppm, and even more preferably less than 10 ppm such as 5 or 1 ppm, and every value in between 100 and 1 ppm, based on the total weight of the purified phytosterol.
  • the sterol ester content in the purified phytosterol is less than 10 % by weight, preferably less than 5 % by weight, more preferably less than 2 % by weight, even more preferably less than 1 % by weight, and most preferably less than 0.5 % by weight, such as 0.1, 0.05 % by weight and every value in between 5 and 0.05 % by weight, based on the total weight of the purified phytosterol.
  • Step 1) optional further drying the sterols
  • the washed sterol crystals can be dried using conventional dryers of all kinds, to remove remaining solvents. Application of reduced pressure helps to increase the removal of solvent traces.
  • This step serves as drying or "pre-drying", depending on the method employed and the desired content of residual solvent in the final sterol product to be obtained. The latter of course mainly depends on the intended use of the sterols.
  • the sterols obtained as sterol crystals may be further dried by e.g. stream stripping at a temperature of 130 to 200, preferably 150 °C to 170 °C, for 1 to 3 hours, to remove the solvent.
  • Step m) optional further purifying the sterols by melt-drying to remove trace amounts of solvents within the sterols
  • the (pre-)dried crystals can be melted preferably under reduced pressure to remove solvent traces enclosed within the crystals.
  • the residual content of solvents can be lowered even more so as to achieve certain higher product qualities being usable also for critical applications, e.g. direct applications to human beings in nutritional or pharmaceutical products.
  • Step n) optional subjecting the sterols to a particle-forming process to obtain sterol particles
  • the melted sterols from previous step m) need to be solidified. That could be done either by simple cooling with stirring of any kind, e.g. in an extruder, a paddle dryer and the like.
  • Other known methods for solidification of melts are prilling, in apparatuses such as prillers including jet-prillers, which can form droplets close to spherical shapes, or simply in dripping towers, in which molten material is dropped into colder air or gases, all such methods to finally obtained solid, particulate sterols, which are preferably in forms that do not show dusting but good fiowability and preferably a high density, to obtain sterols particulates with easy handling properties.
  • the sterols obtained - and preferably (pre-) dried - are subjected to a particle forming process, such as prilling, preferably jet-prilling, which is preferably done under liquid nitrogen, to obtain solid, close to spherical, low to non-dusting sterol particles of very low organic solvent-content, which are suitable for direct use including oral intake by humans.
  • a particle forming process such as prilling, preferably jet-prilling, which is preferably done under liquid nitrogen, to obtain solid, close to spherical, low to non-dusting sterol particles of very low organic solvent-content, which are suitable for direct use including oral intake by humans.
  • a further stage of obtaining tocopherols from the tocopherol-containing phase the FME phase of the multi-phase system, which contains the tocopherol in dissolved form, is preferably subjected to a distillation for separation off of the methyl ester, whereby it is possible to concentrate the tocopherol content in the FME phase to over 10 wt.% based on the amount of FME, in order to enable a simple further preparation of the tocopherols in a known manner.
  • the tocopherol is separated by known processes.
  • the tocopherol is purified by known methods.
  • the steps (p) and (q) could be optionally performed by known process steps, to obtain the substances in pure forms of the desired purity.
  • the process is suitable for various starting mixtures and does not involve the use of toxicologically and ecologically unsafe solvents.
  • the phytosterols are obtained with a Gardner color number of less than 4.
  • the phytosterols are obtained in a high yield with a very low content of sterol ester (i.e. less than 10%) by using the above described purification process.
  • the solvent content of the final product is low (less than lOOppm).
  • Examples 1 and 2 are as disclosed in EP 2635592B1
  • the batch is temperature-controlled at 65 °C. and in a first transesterification stage 37.5 g Na methylate (30% solution in methanol) and 818 g methanol are added and mixed in. After 50 minutes settling time 301.2 g glycerin-containing bottom phase are drawn off. The reaction in the partial glycerides is over 95%.
  • the suspension is filtered by means of a filter centrifuge, and the cake formed is subjected while still in the centrifuge to a first washing with 3.5 liters RME distillate and a second washing with 10.4 liters methanol.
  • a first washing with 3.5 liters RME distillate and a second washing with 10.4 liters methanol.
  • After drying of the filter cake moistened with methanol the result is 908 g of white sterol powder with a sterol content of over 98%, which corresponds to a yield (based on the total sterol content of the distillation residue) of over 82%.
  • the filtrate from the filtration of the suspension separates by itself into a light phase containing FMEs, sterols and tocopherols and into an aqueous phase containing methanol and catalyst.
  • Sterols and tocopherols are also dissolved in the washing RME phase, whilst no tocopherols are detectable in the washing methanol phase.
  • the batch is temperature-controlled at 65 °C. and in a first transesterification stage 36.3 g Na methylate (30% solution in methanol) and 873.5 g methanol are added and mixed in. After 50 minutes settling time 319.2 g glycerin-containing bottom phase is drawn off. The reaction in the partial glycerides is over 95%.
  • crystals were melt- dried to constant weight and subjected to particle forming by prilling.
  • example Cl and T1 refer to the same sterol batch originating from the same rapeseed methyl ester distillation residue. The same applies to C2 and T2, C3 and T3 as well as C4 and T4 (if applicable). Thus, example Cl has to be compared with example T1 and so on.
  • Table 1- Solvent used is azeotrope of ethyl acetate with methanol (laboratory scale)
  • Table 3 Solvent used is azeotrope of methyl acetate with methanol (laboratory scale)

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Botany (AREA)
  • General Health & Medical Sciences (AREA)
  • Mycology (AREA)
  • Nutrition Science (AREA)
  • Food Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Cosmetics (AREA)
  • Steroid Compounds (AREA)
  • Pyrane Compounds (AREA)

Abstract

L'invention concerne un procédé d'obtention de phytostérols et/ou de tocophérols à partir de résidus d'une distillation des esters d'huiles végétales, de préférence à partir de résidus de distillation issus d'une transestérification d'huiles végétales, ainsi qu'un procédé de purification d'une phase contenant des stérols, en particulier des cristaux de stérol.
PCT/EP2020/076723 2019-09-27 2020-09-24 Procédé de production de stérols et/ou de tocophérols avec récupération de sous-produits WO2021058647A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CA3145091A CA3145091A1 (fr) 2019-09-27 2020-09-24 Procede de production de sterols et/ou de tocopherols avec recuperation de sous-produits
CN202080067968.XA CN114450386A (zh) 2019-09-27 2020-09-24 用于生产甾醇和/或生育酚并回收副产物的方法
EP20785451.4A EP4034620A1 (fr) 2019-09-27 2020-09-24 Procédé de production de stérols et/ou de tocophérols avec récupération de sous-produits

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP19200109 2019-09-27
EP19200109.7 2019-09-27

Publications (1)

Publication Number Publication Date
WO2021058647A1 true WO2021058647A1 (fr) 2021-04-01

Family

ID=68072272

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2020/076723 WO2021058647A1 (fr) 2019-09-27 2020-09-24 Procédé de production de stérols et/ou de tocophérols avec récupération de sous-produits

Country Status (4)

Country Link
EP (1) EP4034620A1 (fr)
CN (1) CN114450386A (fr)
CA (1) CA3145091A1 (fr)
WO (1) WO2021058647A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114686297A (zh) * 2022-04-01 2022-07-01 中粮工科(西安)国际工程有限公司 一种高效保留核桃油中天然ve及植物甾醇的方法

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2145079A (en) 1983-08-17 1985-03-20 Nisshin Oil Mills Ltd Methyl-esterification of deodorisation distillates of oils
EP0333472A2 (fr) 1988-03-16 1989-09-20 PALM OIL RESEARCH & DEVELOPMENT BOARD Production de tocophénols et de tocotriénols de haute concentration à partir de produits secondaires de l'huile de palme
EP0610742A1 (fr) 1993-02-11 1994-08-17 F. Hoffmann-La Roche Ag Procédé d'obtention de tocophérols et de stérols à partir de sources naturelles
US5424457A (en) 1994-05-27 1995-06-13 Eastman Chemical Company Process for the production of sterol and tocopherol concentrates
EP0656894B1 (fr) 1992-08-27 1998-02-25 Henkel Kommanditgesellschaft auf Aktien Procede d'obtention de tocopherol et de sterol
EP1169335B1 (fr) 1999-04-09 2003-11-26 Cognis Deutschland GmbH & Co. KG Procede de preparation de phytosterines par cristallisation a partir de quantites reduites de methanol
EP1179535B1 (fr) 2000-08-07 2004-09-22 Cognis Deutschland GmbH & Co. KG Procédé pour l'extraction des sterines
WO2005051294A2 (fr) * 2003-11-19 2005-06-09 Carotech Inc. Extraction de phytonutriments provenant d'huiles
EP1179536B1 (fr) 2000-08-07 2008-01-16 Cognis IP Management GmbH Procédé d'isolation des stérols de résidus de la production des acides gras ou méthyl-esters
EP2635592A1 (fr) * 2010-11-03 2013-09-11 Verbio Vereinigte Bioenergie AG Procédé d'extraction de phytostérols et/ou de tocophérols à partir de résidus d'une distillation d'esters d'huiles végétales, de préférence à partir de résidus de distillation issus d'une transestérification d'huiles végétales

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FI65440C (fi) * 1981-07-21 1984-05-10 Kaukas Ab Oy Foerfarande foer separering av beta-sitosterol med en laog alfa-sitosterolhalt
JP2003079390A (ja) * 2001-09-13 2003-03-18 Nisshin Oillio Ltd ステロールの製造方法
US20050214370A1 (en) * 2004-03-26 2005-09-29 Sarama Robert J Stable coating agent comprising sterol
CN101607977B (zh) * 2009-06-12 2011-06-29 天津工业大学 油脂脱臭馏出物渣油中提取纯化天然植物甾醇的方法和工艺
CN102807547B (zh) * 2012-07-14 2015-03-04 淮北志强油脂有限公司 一种从大豆油脱臭馏出物中提取维生素e和甾醇的新工艺
CN107325145B (zh) * 2017-07-24 2020-01-21 合肥工业大学 电磁诱导植物甾醇结晶纯化方法

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2145079A (en) 1983-08-17 1985-03-20 Nisshin Oil Mills Ltd Methyl-esterification of deodorisation distillates of oils
EP0333472A2 (fr) 1988-03-16 1989-09-20 PALM OIL RESEARCH & DEVELOPMENT BOARD Production de tocophénols et de tocotriénols de haute concentration à partir de produits secondaires de l'huile de palme
EP0656894B1 (fr) 1992-08-27 1998-02-25 Henkel Kommanditgesellschaft auf Aktien Procede d'obtention de tocopherol et de sterol
EP0610742A1 (fr) 1993-02-11 1994-08-17 F. Hoffmann-La Roche Ag Procédé d'obtention de tocophérols et de stérols à partir de sources naturelles
US5424457A (en) 1994-05-27 1995-06-13 Eastman Chemical Company Process for the production of sterol and tocopherol concentrates
EP1169335B1 (fr) 1999-04-09 2003-11-26 Cognis Deutschland GmbH & Co. KG Procede de preparation de phytosterines par cristallisation a partir de quantites reduites de methanol
EP1179535B1 (fr) 2000-08-07 2004-09-22 Cognis Deutschland GmbH & Co. KG Procédé pour l'extraction des sterines
EP1179536B1 (fr) 2000-08-07 2008-01-16 Cognis IP Management GmbH Procédé d'isolation des stérols de résidus de la production des acides gras ou méthyl-esters
WO2005051294A2 (fr) * 2003-11-19 2005-06-09 Carotech Inc. Extraction de phytonutriments provenant d'huiles
EP2635592A1 (fr) * 2010-11-03 2013-09-11 Verbio Vereinigte Bioenergie AG Procédé d'extraction de phytostérols et/ou de tocophérols à partir de résidus d'une distillation d'esters d'huiles végétales, de préférence à partir de résidus de distillation issus d'une transestérification d'huiles végétales
EP2635592B1 (fr) 2010-11-03 2017-08-16 Verbio Vereinigte Bioenergie AG Procédé d'extraction de phytostérols et/ou de tocophérols à partir de résidus d'une distillation d'esters d'huiles végétales, de préférence à partir de résidus de distillation issus d'une transestérification d'huiles végétales

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114686297A (zh) * 2022-04-01 2022-07-01 中粮工科(西安)国际工程有限公司 一种高效保留核桃油中天然ve及植物甾醇的方法

Also Published As

Publication number Publication date
EP4034620A1 (fr) 2022-08-03
CA3145091A1 (fr) 2021-04-01
CN114450386A (zh) 2022-05-06

Similar Documents

Publication Publication Date Title
CA2143441C (fr) Recuperation de tocopherol et de sterol
WO2007054759A1 (fr) Procede de fabrication de phytosterols de grande purete a partir d'un distillat desodorisant issu d'huiles vegetales
US6956125B2 (en) Processes for producing sterols from fatty acid production residues
CA2369977C (fr) Procede de preparation de phytosterines par cristallisation a partir de quantites reduites de methanol
US9884837B2 (en) Method for obtaining phytosterols and/or tocopherols from residue of a distillation of the esters of vegetable oils, preferably from distillation residue from a transesterification of vegetable oils
WO2021058647A1 (fr) Procédé de production de stérols et/ou de tocophérols avec récupération de sous-produits
US11781088B2 (en) Process for the production and purification of sterols
CN107586253B (zh) 一种制备亚油酸的方法
US20020082434A1 (en) Process for the production of sterols
US6762312B1 (en) Process for purification of phytosterol from fatty acids and their esters
EP1226156B1 (fr) Procede de production de phytosterols par saponification dans un solvant alcool/eau
EP1610628B1 (fr) Procede permettant la preparation d'une composition a haute teneur en sterol
WO2021058648A1 (fr) Procédé de purification de phytostérol
KR20160096074A (ko) 트리테르펜 에스테르의 농축
CN107614667A (zh) 从粗植物油回收生育酚/生育三烯酚、类胡萝卜素、甘油、固醇和脂肪酸酯及其方法
JP2004500478A (ja) 植物・動物由来製品工業の廃棄物及び副産物に存在する脂溶性ビタミン及びプロビタミン、成長因子、植物・動物ホルモンの抽出及び濃縮プロセス
JP2001131199A (ja) 植物ステロールの製法
JP2001131197A (ja) 植物ステロールの製法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20785451

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 3145091

Country of ref document: CA

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2020785451

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2020785451

Country of ref document: EP

Effective date: 20220428