WO2000064922A1 - Systeme de solvants alcanol, methylethylcetone, eau utilise pour la separation des sterols - Google Patents

Systeme de solvants alcanol, methylethylcetone, eau utilise pour la separation des sterols Download PDF

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Publication number
WO2000064922A1
WO2000064922A1 PCT/IB2000/000539 IB0000539W WO0064922A1 WO 2000064922 A1 WO2000064922 A1 WO 2000064922A1 IB 0000539 W IB0000539 W IB 0000539W WO 0064922 A1 WO0064922 A1 WO 0064922A1
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WIPO (PCT)
Prior art keywords
desmethylsterols
sterols
alkanol
solvent
weight ratio
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PCT/IB2000/000539
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English (en)
Inventor
Antti Hamunen
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Sterol Technologies Ltd.
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 Sterol Technologies Ltd. filed Critical Sterol Technologies Ltd.
Priority to AU39839/00A priority Critical patent/AU3983900A/en
Publication of WO2000064922A1 publication Critical patent/WO2000064922A1/fr

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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
    • C11B13/005—Recovery of fats, fatty oils or fatty acids from waste materials of residues of the fabrication of wood-cellulose (in particular tall-oil)
    • 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
    • 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 present invention relates to a method for separation of commercially important sterols from neutral substances comprising those fractions of wood originated extractives which are soluble in organic solvents.
  • neutral substances are included in e.g. tall oil and tall oil pitch.
  • Sterols useable in pharmaceuticals and foods need to be purified to quite a high degree to exclude undesired components.
  • undesired components include a-sitosterol (citrostadienol), other methylsterols, dimethylsterols and triterpene alcohols e.g. betuline.
  • U.S. 5,670,669 discloses a method of separating tocopherols (vitamin E) from a mixture containing tocopherols and sterols, the mixture being essentially free of higher fatty acids.
  • the tocopherols and sterols are separated by the crystallization of the sterols using a solvent blend comprised of a major amount of a low polarity organic solvent, a minor amount of a high polarity organic solvent, and a minor amount of water.
  • the preferred low polarity organic solvents are the higher alkanes, mono-ketones such as acetone, 2- butanone or 2-octanone, mono-aldehydes, mono-esters and higher mono-hydric alcohols such as n-propanol, iso-propanol, n-butanol, sec-butanol, n-hexanol or 2-ethylhexanol.
  • the preferred high polarity organic solvents are the low molecular weight, oxygenated hydrocarbons, preferably the lower alkanols.
  • the solvent blend is preferably comprised of 90-99.5 % of the low polarity solvent and 0.5-10% of the high polarity solvent, with the water preferably being present in an amount essentially equal to the high polarity organic solvent.
  • ⁇ -sitosterol is separated from an ⁇ -sitosterol- containing sterol mixture by crystallizing it from an organic solvent including one of 1 ,2-dichloroethylene, methyl ethyl ketone and ethyl acetate, or mixtures thereof, and also including the addition of water.
  • the formed crystals are collected by filtration.
  • the drawback with this method is that the filtration is difficult to perform, because the crystals are not structurally clear and therefore, the yield and the purity of the product is not acceptable.
  • sterols are separated from extracted and dried neutral substances using methanol or ethanol, or a mixture thereof, or a mixture of methyl ethyl ketone and water as a solvent.
  • the neutral substances are mixed in the solvent, heated until dissolved, and the mixture is cooled to room temperature or below to precipitate the desired sterols, which are then filtered and washed with a suitable solvent.
  • washing solvents acetone or a mixture of methanol and acetone are mentioned.
  • U.S. 2,843,610 discloses the use of a methanol-containing solvent medium composed of 9-100% by volume of methanol, 0-90% by volume of acetone or methyl ethyl ketone and 0-10% by volume of water, to crystallize sterols from sterol-containing materials such as deoderizer sludges, fatty acid distillation residues, tall oil still bottoms (i.e. , pitch) and soap stocks. It has been found that these starting materials cannot be used to crystallize sterols having a high purity.
  • a method for the purification of 4-desmethylsterols from undesired neutral components comprising the treatment of neutral substances containing 4- desmethylsterols and undesired neutral components with a solvent mixture comprising methyl ethyl ketone, a lower alkanol and water.
  • a method for selectively separating 4-desmethylsterols from undesired neutral components comprising adding to neutral substances containing 4-desmethylsterols and undesired neutral components a solvent mixture comprising methyl ethyl ketone, a lower alkanol and water to obtain a mixture, heating the mixture to dissolve the neutral substances, cooling the heated mixture to selectively crystallize 4-desmethylsterols , separating the obtained 4-desmethylsterol crystals, e.g. by centrifugation or filtration, and optionally subjecting the separated crystals to at least one of following additional treatment steps: washing and recrystallizing.
  • a method for selectively separating 4-desmethylsterols from undesired neutral components comprising providing a solution comprising neutral substances containing 4- desmethylsterols and undesired neutral components including undesired sterols dissolved in a solvent, crystallizing sterols from the solution, separating the obtained sterol crystals, e.g. by centrimgation or filtration, selectively washing the separated sterol crystals with a solvent mixture comprising methyl ethyl ketone, a lower alkanol and water for removing undesired sterols, separating the desired 4-desmethylsterols, e.g. by filtration, and optionally recrystallizing the 4-desmethylsterols.
  • a method for selectively separating 4-desmethylsterols from undesired neutral components comprising providing a solution comprising neutral substances containing 4- desmethylsterols and undesired neutral components including undesired sterols dissolved in a solvent, crystallizing sterols from the solution, separating the obtained sterol crystals, e.g. by centrifugation or filtration, optionally washing the obtained sterol crystals, selectively recrystallizing the sterols from a solvent mixture comprising methyl ethyl ketone, a lower alkanol and water, to obtain desired 4- desmethylsterol crystals, and optionally washing the 4-desmethylsterol crystals.
  • the neutral substances can be obtained e.g. by extracting from soaps. Any soap of wood origin may be used. Neutral substances suitable as starting material in the method according to the invention may therefore be obtained from extracts of wood origin such as crude soap from the sulfate cellulose process or pitch soap obtained from tall oil. Any soap from the mentioned sources may be used as raw-material for producing the neutral substances used as starting material in the present invention. However, the method is particularly suitable for soaps obtained from the pulping of wood which contains hardwood.
  • any known isolation method may be used, e.g. extraction or distillation.
  • the extraction may preferably be performed using hydrocarbons alone or together with a ketone or an alcohol.
  • the use of hydrocarbons alone is particularly suitable when performing the extraction at a temperature high enough to avoid emulsion formation.
  • the weight ratio of methyl ethyl ketone : lower alkanol : water is preferably 50-75 : 15-40 : 5-15, and more preferably 60-70 : 20-35 : 5-10. Most preferably, the weight ratio can be about 70 : 20 : 10.
  • the sum of the three components in the solvent mixture is preferably 100.
  • the solvent components can be added one at a time or be mixed together before use in the purification.
  • the claimed treatment with the solvent mixture can comprise at least one of following treatment steps : crystallization, washing and recrystallization.
  • the purification method of the present invention comprises two or more of these treatment steps, they can be carried out in optional order.
  • the obtained end product is practically free (e.g., contains less than 2 % , more preferably less than 1 %) of possible methyl and dimethyl sterols and triterpene alcohols (e.g. citrostadienol , cycloartols , betulinol) which may be present in the wood raw material and also still in the neutral substances.
  • the end product contains practically pure 4-desmethylsterols, including sitosterol and campesterol, and their corresponding saturated forms, sitostanol and campestanol.
  • undesired neutral components all material included in the neutral substances other than the 4-desmethylsterols.
  • the undesired neutral components include e.g. other sterols like 4-methyl- and 4,4'-dimethylsterols, fatty alcohols and terpene alcohols.
  • Preferred lower alkanols to be used in the invention are methanol and ethanol.
  • Methanol is especially preferred, because of its higher specificity.
  • the solvent mixture has the composition as defined above.
  • the weight ratio of neutral substances : solvent mixture is preferably 1 : 0.5-15, and more preferably 1 : 1.5-8.
  • the crystallization is performed preferably at about 0-40 °C, and more preferably at ambient temperature, i.e. about 20-25 °C. Typically, the yield is lower, but the purity is higher when higher crystallization temperatures are used, and vice versa.
  • the crystals may be washed with a suitable solvent e.g.
  • solvents selected from the group consisting of hydrocarbons, more preferably short chain hydrocarbons containing 1-10 carbon atoms, preferably 5-8 carbon atoms, such as straight chain hydrocarbons (preferably pentane , hexane , heptane or octane) , branched chain hydrocarbons, hydrocarbons containing cyclic structures like cyclohexane or methylcyclohexane or hydrocarbon mixtures comprising any of these, lower alkanols such as methanol and/or ethanol and ketones such as methyl ethyl ketone. Water may also be added to the solvents.
  • hydrocarbons more preferably short chain hydrocarbons containing 1-10 carbon atoms, preferably 5-8 carbon atoms, such as straight chain hydrocarbons (preferably pentane , hexane , heptane or octane) , branched chain hydrocarbons, hydrocarbons containing cyclic structures like cyclohex
  • a solvent mixture comprising methyl ethyl ketone, a lower alkanol and water may be used. More preferably the solvent mixture has the composition as defined above.
  • a preferred solvent mixture comprises 50-75% by weight of MEK, 15-40% by weight of methanol and 5-15% by weight of water.
  • the solvents can be added one at a time or be mixed together before use.
  • a more preferred solvent mixture contains about 60-70% of MEK, about 20-35 % of MeOH and about 5-10% of water, and the most preferred about 70% of MEK, about 20% of MeOH and about 10% of water.
  • a mixture is used with the same composition as the one used in the crystallization step to avoid the need for many different solvent systems in the process as a whole.
  • the end product contains too much undesired material (with or without the use of washing steps as indicated above), it can be recrystallized.
  • the recrystallization may be performed after a washing step or directly after the crystallization.
  • the recrystallization may be performed by any known method, but preferably in the same manner as the first crystallization.
  • the amount by weight of the solvent added to the sterol crystals is suitably somewhat higher than in the first crystallization, e.g. 5 to 15 times the amount of sterol crystals.
  • a solvent mixture of the same composition as in the first crystallization may be used.
  • a third aspect of the present invention is to perform the crystallization in any prior known manner (e.g. as disclosed in U.S. 4,420,427, hereby incorporated by reference), and then perform the washing step using the solvent mixture according to the invention, i.e. a solvent comprising MEK, a lower alkanol and water.
  • the solvent mixture used for washing preferably has the composition as defined above.
  • a preferred solvent mixture comprises 50-75% by weight of MEK, 15-40% by weight of methanol and 5-15% by weight of water.
  • the solvents can be added one at a time or be mixed together before use.
  • a more preferred solvent mixture contains about 60-70% of MEK, about 20-35 % of MeOH and about 5-10% of water and the most preferred about 70% of MEK, about 20% of MeOH and about 10% of water.
  • a recrystallization step, if needed, may also be included in the procedure after the washing step. In the recrystallization step, preferably a solvent mixture is used with the same composition as the one used in the washing step to avoid the need of many different solvent systems in the process.
  • a fourth aspect of the present invention is to recrystallize the desired sterols from the solvent mixture according to the present invention, i.e. a solvent comprising MEK, a lower alkanol and water, if the product still contains undesirable amounts of the undesired sterols.
  • a method for selectively separating 4-desmethylsterols from undesired neutral components comprising (a) providing a solution comprising neutral substances containing 4- desmethylsterols and undesired neutral components including undesired sterols dissolved in a solvent,
  • the solvent mixture used in the recrystallization preferably has the composition as defined above.
  • a preferred solvent mixture comprises 50- 75 % by weight of MEK, 15-40% by weight of methanol and 5-15 % by weight of water.
  • the solvents can be added one at a time or be mixed together before use.
  • a more preferred solvent mixture contains about 60-70% of MEK, about 20-35% of MeOH and about 5-10% of water and the most preferred about 70% of MEK, about 20% of MeOH and about 10% of water.
  • the crystallization of the desired sterols from the neutral substances may be performed in any known manner (e.g. as disclosed in U.S. 4,279,827 or U.S. 4,420,427, each hereby incorporated by reference) prior to the recrystallization.
  • a washing step may also be included in the procedure either before or after the recrystallization. In the washing step, preferably a solvent mixture is used with the same composition as the one used in the recrystallization step to avoid the need of many different
  • the most preferred application of the invention is to perform the crystallization of the 4-desmethylsterols from the neutral substances using a mixture of MEK , MeOH and water , an especially preferred solvent comprising 50-75% by weight of MEK, 15-40% by weight of MeOH and 5-15 % by weight of water.
  • a more preferred solvent mixture contains about 60-70% of MEK, about 20-35 % of MeOH and about 5-10% of water and the most preferred about 70% of MEK, about 20% of MeOH and about 10% of water.
  • An even more preferred application of the present invention is to also perform the washing step with a similar solvent.
  • the process may also include a recrystallization step, preferably using a solvent of the same composition.
  • Example 1 hexane/acetone/water extraction (according to U.S. 3,965,085, hereby incorporated by reference) was dissolved by refluxing in 40 g of a MEK/MeOH/water 70 : 20 : 10 blend and heating.
  • the 4-desmethylsterols content (sitosterol + sitostanol + campesterol + campestanol) of the unsaponifiables was 24.5 % and the citrostadienol content was 2.9% .
  • the solution was allowed to cool to 25 °C with gentle agitation.
  • the crystals formed were filtered in a Buchner funnel and dried. The purity of the crystals was 82% .
  • Reference example 1 10 g of the similar unsaponifiables as used in example 1 was dissolved in 40 g of a solvent consisting of MEK/ water 90 : 10. The crystallization was done in a similar way as in example 1 and the crystals formed were filtered in a Buchner funnel. Filtration of the crystals was difficult. The purity of the dried product was 79% .
  • the raw material of this example was the unsaponifiables separated from tall oil pitch (100% pine origin).
  • the pitch was first saponified at 170°C with NaOH, and then the unsaponifiables were extracted in a closed system using a hydrocarbon solvent at the saponification temperature and prevailing vapor pressure of the mixture.
  • the fraction of unsaponifiables (35 % sterols) was dissolved by refluxing into a solvent mixture consisting of 65% MEK, 30% MeOH and 5% water (10 g unsaponifiables/80 g solvent). Crystallization of the sterols took place when the mixture was allowed to cool to 25 °C for 1.5 hours by gentle mixing with a magnetic stirrer. The crystals were filtered and washed with a solvent similar to the crystallization solvent. 2.8 g of 96.5 % pure dry sterols was obtained.
  • Example 4 The raw material was the unsaponifiables of 100 % Pinus radiata tall oil soap.
  • the unsaponifiables were extracted from the soap using hexane/acetone solvent extraction (according to U.S. 3,965,085, incorporated by reference).
  • 10 g of unsaponifiables was dissolved into 80 g solvent (60% MEK, 35 % MeOH, 5 % water) as in previous examples and the mixture was cooled to 20°C for 2 hours. After filtration, washing with 80 g of a solvent similar to the crystallization solvent added in small portions at a time, and drying, 2.85 g of 95 % pure sterols was obtained.
  • the crystallization feed was the distillate fraction obtained from thin film evaporation of dried saponified pitch (according to U.S. 4,076,700, hereby incorporated by reference).
  • the distillate contained 25 % sterols, and about 30% free fatty and resin acids.
  • 1 part (100 g) was mixed with 3 parts of solvent mixture (70% MEK, 20% MeOH, 10% water) and heated until the mixture was a homogeneous solution. The solution was allowed to cool to 25 °C and was filtered and washed with a solvent similar to the crystallization solvent. 18.6 g of dry sterol blend (purity 95 %) was obtained.
  • the starting material and the solvent were the same as in example 5 as well as the crystallization and washing procedure, but for the ratio of solids/ solvent, which was 1 : 1.5.
  • the yield of 96% pure sterols was 18.1 g from 100 g of starting material.
  • the crystallization was done in the same manner as in example 4. After filtration the crystals were washed with heptane. The sterol yield was 2.7 g of a 94.8 % sterol blend.
  • Example 9 Pitch soap (Pinus taeda based, unsaponifiables 29.6% , sterols 41 % of the unsaponifiables) was extracted with a commercial hydrocarbon mixture (LIAV 110, Neste Oy) in a two-stage mixer-settler extraction equipment.
  • the feed ratios of dry soap : water : solvent were 1 : 2.4 : 4.7, and the total feed rate was 730 kg/hour.
  • the temperature in the settler vessels was 182°C and 184°C, and the pressures were 20.7 and 20 bars, respectively.
  • the sterol content of the unsaponifiables included in the hydrocarbon phase was 35 % .
  • the hydrocarbon phase was cooled to 20 °C and the precipitated sterols were separated by filtration (purity 80%).
  • the crystals were recrystallized from a solvent mixture consisting of 70% MEK, 20% MeOH and 10% water, the amount of crude sterols : solvent being 1 : 9 by weight.
  • the yield of dry crystals was 75% , and the purity was 96% .
  • the amount of crystals to solvent was 1 : 9 by weight. After filtration, the purity of the sterols was 87% .

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Steroid Compounds (AREA)

Abstract

L'invention concerne un procédé de purification de 4-desméthylstérols à partir de substances neutres renfermant lesdits 4-desméthylstérols et des composants neutres indésirables. Ledit procédé consiste à traiter les substances neutres à l'aide d'un mélange de solvants comprenant une méthyléthylcétone, un alcanol en C1-C6 et de l'eau.
PCT/IB2000/000539 1999-04-27 2000-04-27 Systeme de solvants alcanol, methylethylcetone, eau utilise pour la separation des sterols WO2000064922A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU39839/00A AU3983900A (en) 1999-04-27 2000-04-27 Alkanol, methyl ethyl ketone water solvent system for the separation of sterols

Applications Claiming Priority (2)

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US13130599P 1999-04-27 1999-04-27
US60/131,305 1999-04-27

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WO2000064922A1 true WO2000064922A1 (fr) 2000-11-02

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001053320A2 (fr) * 2000-01-21 2001-07-26 Forbes Medi-Tech Inc. Nouveaux composites cristallins comprenant des phytosterols et des phytostanols ou des derives desdits composes
WO2022117922A2 (fr) 2020-12-01 2022-06-09 Forchem Oyj Procédé de purification de stérols à partir de brai de tall-oil

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB895145A (en) * 1957-08-28 1962-05-02 Eastman Kodak Co Separation of sterols
US3691211A (en) * 1970-12-07 1972-09-12 Procter & Gamble Process for preparing sterols from tall oil pitch
US4420427A (en) * 1981-07-21 1983-12-13 Oy Kaukus Ab Process for the separation of sterols or mixtures of sterols
WO1995004731A1 (fr) * 1993-08-06 1995-02-16 Henkel Corporation Recuperation de tocopherols

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB895145A (en) * 1957-08-28 1962-05-02 Eastman Kodak Co Separation of sterols
US3691211A (en) * 1970-12-07 1972-09-12 Procter & Gamble Process for preparing sterols from tall oil pitch
US4420427A (en) * 1981-07-21 1983-12-13 Oy Kaukus Ab Process for the separation of sterols or mixtures of sterols
WO1995004731A1 (fr) * 1993-08-06 1995-02-16 Henkel Corporation Recuperation de tocopherols

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001053320A2 (fr) * 2000-01-21 2001-07-26 Forbes Medi-Tech Inc. Nouveaux composites cristallins comprenant des phytosterols et des phytostanols ou des derives desdits composes
WO2001053320A3 (fr) * 2000-01-21 2001-09-27 Forbes Medi Tech Inc Nouveaux composites cristallins comprenant des phytosterols et des phytostanols ou des derives desdits composes
WO2022117922A2 (fr) 2020-12-01 2022-06-09 Forchem Oyj Procédé de purification de stérols à partir de brai de tall-oil

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Publication number Publication date
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