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WO2000004039A1 - Isolation et purification de sterols a partir de la fraction de substances neutres de poix de tallol par precipitation par decantation unique - Google Patents

Isolation et purification de sterols a partir de la fraction de substances neutres de poix de tallol par precipitation par decantation unique Download PDF

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Publication number
WO2000004039A1
WO2000004039A1 PCT/US1999/014139 US9914139W WO0004039A1 WO 2000004039 A1 WO2000004039 A1 WO 2000004039A1 US 9914139 W US9914139 W US 9914139W WO 0004039 A1 WO0004039 A1 WO 0004039A1
Authority
WO
WIPO (PCT)
Prior art keywords
neutrals
sterols
tall oil
sterol
hydrocarbon
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/US1999/014139
Other languages
English (en)
Inventor
Philip L. Robinson
Thomas J. Cuff
Jane F. Byrne
Zhiquan Q. Yan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Westvaco Corp
Original Assignee
Westvaco Corp
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 Westvaco Corp filed Critical Westvaco Corp
Priority to AU49587/99A priority Critical patent/AU4958799A/en
Publication of WO2000004039A1 publication Critical patent/WO2000004039A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • 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)
    • 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 is related to methods of isolating and purifying the valuable constituents from Crude Tall Oil (CTO) recovered from the black liquor residue of wood pulping processes, primarily used in making paper. More particularly, the present invention is related to methods of extraction of valuable constituents from the neutrals fraction of CTO. Most particularly, the present invention is related to methods of isolation and purification of extracted or distilled constituents of the neutrals fraction of CTO which, upon said purification and subsequent modification, are useful as a dietary supplement in foods to reduce cholesterol levels in humans . Description of Related Art
  • the black liquor residue from wood pulping contains valuable chemicals, which make up the CTO, with various industrial applications.
  • the black liquor contains the soaps of rosin and fatty acids, as well as sodium lignate and the spent cooking chemicals for reuse.
  • the CTO is recovered by partially evaporating the black liquor, for concentration purposes, and then skimming off the tall oil soaps which float to the top of a skimming tank.
  • the soap skimmings are converted to CTO by reaction with sulfuric acid and then separated from the simultaneously-formed spent acid by batch cooking, continuous centrifuging, or continuous decanting.
  • the CTO is normally divided into various fractions by distillation which first extracts the pitch (or bottoms) .
  • the depitched CTO is then separated into fractions of heads, tall oil rosin (TOR) , tall oil fatty acids (TOFA) , and distilled tall oil (DTO) .
  • a major ingredient of the neutral fraction of CTO, concentrated in the pitch fraction thereof, is a class of compounds known as sterols, including sitosterol. It is known, however, that a better place to obtain these sterols is via solvent extraction of tall oil soap, which is done commercially in Scandinavia.
  • U.S. Patent No. 5,502,045 disclosed the use (by ingestion) of a ⁇ -sitostanol fatty acid ester for reducing serum cholesterol level.
  • the patent's assignee, Raisio a Finnish manufacturer of foodstuffs, grain, and specially chemicals, has developed a cholesterol-reducing margarine called Benecol ® .
  • the active ingredient (in cholesterol reduction) in Benecol ® is the claimed fat-soluble stanol ester which prevents cholesterol from being absorbed into the human digestive system.
  • the stanol ester is produced from plant-derived sterols (phytosterols) via hydrogenation and trans-esterification reactions. Cholesterol reductions (LDL and HDL) of 10-15% are common for individuals with diets containing Benecol ® .
  • the above-stated objects of the invention are achieved by isolating the sterol component of the neutrals fraction of saponified tall oil pitch.
  • the isolation is accomplished by a liquid-liquid extraction where the hydrocarbon extraction stream is washed with an aqueous methanol solution to remove methanol- soluble impurities. After the hydrocarbon and aqueous phases are separated, water is added to the hydrocarbon phase to facilitate crystallization of sterols.
  • the Figure represents a flow diagram of the claimed process of isolation and purification of sterols from the neutrals fraction of tall oil pitch by single decantation precipitation.
  • the first step in the isolation and purification of sterols from an extracted neutrals fraction of tall oil pitch by a preferred embodiment of the invention process involves dissolving the concentrated (solventless) neutrals in a hydrocarbon solvent, preferably heptane, in a ratio between 2 and 5 parts hydrocarbon to 1 part neutrals fraction.
  • a solution of an alcohol solvent, preferably methanol, and water are combined with the neutrals in heptane at 40-50°Cso that impurities, presumably dimer fatty acids, can be removed selectively from the neutrals solution.
  • the higher temperature prevents sterols from crystallizing in the heptane phase during the washing procedure.
  • phase separation has occurred, the sterol-rich heptane phase is isolated and allowed to cool to room temperature.
  • the single decantation precipitation (SDP) process begins with dissolving the dry (solventless) neutrals by heating to near reflux in heptane at ratios between two and five parts heptane to one part SSE neutrals.
  • a blend of methanol (1 to 4 parts) and water (0.1 to 0.5 parts) are combined with the heptane solution of neutrals at 40°C.
  • the heptane phase Once the heptane phase has been isolated, it is allowed to cool to the final crystallization temperature where water (1 part) is added quickly with a specified agitation rate and agitation time for precipitation.
  • the sterol granules that precipitate are filtered from the two liquid phases, and the solid is washed with an additional two parts heptane on the Buchner funnel. The sterols are then dried, weighed, and analyzed for mass yield, sterol yield, and sterol purity.
  • the key variables listed in the stated general procedure are the heptane content, methanol content, water content, crystallization temperature, crystallization agitation time, and crystallization agitation rate.
  • the high, low, and center point values are listed for each variable in Table II.
  • ( a ) Parts refers to the relative weight ratio of the variable to the amount of neutrals used in the experiment. For example, experiments performed with the high heptane value were run with five parts heptane to one part neutrals. The results from 22 additional experiments for the SDP process (Examples 10-31) are given in Table III, below. The mass yields range from 0 to 85.2%; sterol yields range from 0 to 78.4%; and the purities range from 0 to 98.4%. Unfortunately, two experiments (runs 9 and 16) produced an emulsion that did not settle well, therefore, very low sterol yields were obtained. The data show that these two experiments are atypical. Both runs were done with high heptane, high methanol, and low wash water conditions, which obviously leads to problems .
  • a method for the isolation of sterols from the neutrals fraction of tall oil pitch comprising the steps of:
  • hydrocarbon solvent is selected from the group consisting of pentane, hexane, heptane, and iso-octane;
  • a method for the isolation of sterols from a hydrocarbon solution of tall oil pitch neutrals comprising the steps of:

Landscapes

  • 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

Des stérols issus de la fraction de substances neutres de poix de tallöl sont isolés et purifiés par extraction liquide-liquide, processus dans le cadre duquel le courant d'extraction d'hydrocarbure est lavé à l'aide d'une solution aqueuse au méthanol afin d'enlever des impuretés solubles dans le méthanol. Après séparation des phases, hydrocarbure et aqueuse, on ajoute de l'eau à la phase hydrocarbure afin de faciliter la cristallisation des stérols.
PCT/US1999/014139 1998-07-14 1999-07-12 Isolation et purification de sterols a partir de la fraction de substances neutres de poix de tallol par precipitation par decantation unique Ceased WO2000004039A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU49587/99A AU4958799A (en) 1998-07-14 1999-07-12 Isolation and purification of sterols from neutrals fraction of tall oil pitch by single decantation precipitation

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US11500298A 1998-07-14 1998-07-14
US09/115,002 1998-07-14

Publications (1)

Publication Number Publication Date
WO2000004039A1 true WO2000004039A1 (fr) 2000-01-27

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1999/014139 Ceased WO2000004039A1 (fr) 1998-07-14 1999-07-12 Isolation et purification de sterols a partir de la fraction de substances neutres de poix de tallol par precipitation par decantation unique

Country Status (3)

Country Link
AR (1) AR019778A1 (fr)
AU (1) AU4958799A (fr)
WO (1) WO2000004039A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000064923A1 (fr) * 1999-04-27 2000-11-02 Sterol Technologies Ltd. Procede d'isolation de phytosterols a partir de substances neutres mettant en oeuvre des systemes de solvant a base d'hydrocarbure et d'alcool
JP2016222926A (ja) * 2008-03-10 2016-12-28 サンパイン アーベーＳｕｎｐｉｎｅ Ａｂ 残留植物油ストリームからの植物性ステロールの再生
CN111875659A (zh) * 2020-08-21 2020-11-03 宜春大海龟生命科学有限公司 一种植物甾醇提纯方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2530810A (en) * 1949-08-23 1950-11-21 Pittsburgh Plate Glass Co Separation of unsaponifiable matter from tall oil residue
US3691211A (en) * 1970-12-07 1972-09-12 Procter & Gamble Process for preparing sterols from tall oil pitch
US3840570A (en) * 1970-12-07 1974-10-08 Procter & Gamble Process for preparing sterols from tall oil pitch
US4044031A (en) * 1976-07-02 1977-08-23 Ake Allan Johansson Process for the separation of sterols
US4298539A (en) * 1979-11-19 1981-11-03 Farmos-Yhtma Oy Process for the isolation of β-sitosterol
EP0057075A1 (fr) * 1981-01-27 1982-08-04 Farmos-Yhtyma Oy Procédé d'isolation de bêta sitostérol d'un mélange de stéroides
US4524024A (en) * 1983-02-10 1985-06-18 The Badger Company, Inc. Processes of recovering fatty acids and sterols from tall oil pitch

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2530810A (en) * 1949-08-23 1950-11-21 Pittsburgh Plate Glass Co Separation of unsaponifiable matter from tall oil residue
US3691211A (en) * 1970-12-07 1972-09-12 Procter & Gamble Process for preparing sterols from tall oil pitch
US3840570A (en) * 1970-12-07 1974-10-08 Procter & Gamble Process for preparing sterols from tall oil pitch
US4044031A (en) * 1976-07-02 1977-08-23 Ake Allan Johansson Process for the separation of sterols
US4298539A (en) * 1979-11-19 1981-11-03 Farmos-Yhtma Oy Process for the isolation of β-sitosterol
EP0057075A1 (fr) * 1981-01-27 1982-08-04 Farmos-Yhtyma Oy Procédé d'isolation de bêta sitostérol d'un mélange de stéroides
US4524024A (en) * 1983-02-10 1985-06-18 The Badger Company, Inc. Processes of recovering fatty acids and sterols from tall oil pitch

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000064923A1 (fr) * 1999-04-27 2000-11-02 Sterol Technologies Ltd. Procede d'isolation de phytosterols a partir de substances neutres mettant en oeuvre des systemes de solvant a base d'hydrocarbure et d'alcool
JP2016222926A (ja) * 2008-03-10 2016-12-28 サンパイン アーベーＳｕｎｐｉｎｅ Ａｂ 残留植物油ストリームからの植物性ステロールの再生
CN111875659A (zh) * 2020-08-21 2020-11-03 宜春大海龟生命科学有限公司 一种植物甾醇提纯方法
CN111875659B (zh) * 2020-08-21 2021-10-08 宜春大海龟生命科学有限公司 一种植物甾醇提纯方法

Also Published As

Publication number Publication date
AR019778A1 (es) 2002-03-13
AU4958799A (en) 2000-02-07

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