WO2000012533A1 - Isolation et purification de sterols de la fraction des neutres de poix de tall oil par cristallisation directe, phase duelle - Google Patents

Isolation et purification de sterols de la fraction des neutres de poix de tall oil par cristallisation directe, phase duelle Download PDF

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Publication number
WO2000012533A1
WO2000012533A1 PCT/US1999/014135 US9914135W WO0012533A1 WO 2000012533 A1 WO2000012533 A1 WO 2000012533A1 US 9914135 W US9914135 W US 9914135W WO 0012533 A1 WO0012533 A1 WO 0012533A1
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WO
WIPO (PCT)
Prior art keywords
neutrals
tall oil
sterols
hydrocarbon
sterol
Prior art date
Application number
PCT/US1999/014135
Other languages
English (en)
Inventor
Zhiquan Q. Yan
Jane F. Byrne
Thomas J. Cuff
Philip L. Robinson
Raymond S. Vincente
Original Assignee
Westvaco Corporation
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 Corporation filed Critical Westvaco Corporation
Priority to AU49583/99A priority Critical patent/AU4958399A/en
Publication of WO2000012533A1 publication Critical patent/WO2000012533A1/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 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 bottoms, or pitch, fraction of distilled 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 pitch which, upon said purification and subsequent modification, are useful as a dietary supplement in foods to reduce cholesterol levels in humans.
  • CTO Crude Tall Oil
  • CTO and Crude Sulfate Turpentine are major, renewable, chemical raw materials obtained from the kraft (sulfate) pulping of various coniferous trees.
  • Coniferous trees, especially pine contain resin acids in the free form, long chain fatty acids, and volatile terpenes . These materials, which are a major part of the wood extractives, are released from the wood during the kraft pulping process.
  • 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 sodium soap of these mixed acids rise to the surface and can be skimmed off.
  • This material is referred to as "soap skimmings" or "tall oil soap.”
  • 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 fraction.
  • the de-pitched 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 pitch is a class of commercially significant compounds known as sterols, including sitosterol. It is commonly known, however, that a typical method to obtain these sterols is via solvent extraction of tall oil soap, which is practiced 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 specialty 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 ultimately achieved by isolating the sterol component of the neutrals fraction of saponified tall oil pitch in the manner disclosed and claimed herein.
  • the first step in the invention sterol isolation process is accomplished by extracting the neutrals from saponified tall oil pitch. Then the extracted neutrals phase in a hydrocarbon, preferably heptane, is mixed with an alcohol solvent, preferably methanol, at a relatively high temperature (preferably greater than 50°C) . To this hydrocarbon/neutrals/alcohol solution is then added small amounts of water of a temperature higher than that of the hydrocarbon/neutrals/alcohol solution to result in two phases.
  • a hydrocarbon preferably heptane
  • an alcohol solvent preferably methanol
  • hydrocarbon/alcohol/neutrals/ water solution is allowed to cool slowly, with agitation, to facilitate crystallization of sterols.
  • the sterol crystals are isolated and washed with hydrocarbon solvent .
  • the Figure represents a flow diagram of the claimed process of isolation and purification of sterols from single-solvent extraction neutrals of tall oil pitch by direct crystallization—dual phase.
  • the invention direct crystallization, dual phase, process involves controlling the growth of sterol crystals from a solution of extracted, or distilled, tall oil pitch neutrals in a hydrocarbon solvent, preferably heptane.
  • a hydrocarbon solvent preferably heptane.
  • an alcohol solvent preferably methanol
  • Water also of a relatively higher temperature (preferably greater than 60°C, more preferably greater than 70°C) is then added to the hydrocarbon/methanol/neutrals solution to produce two liquid phases.
  • the mixture of the two liquid phases is cooled slowly, resulting in the crystallization of the sterols from the neutrals portion of the hydrocarbon/neutrals phase.
  • the two liquid phases are filtered to recover the sterol crystals.
  • Sterol yields up to 80.3%, based on the weight of sterols recovered divided by the available sterols in the neutrals, were achieved. Also, purities of up to 98.4% were achieved, with negligible contamination .
  • the direct crystallization, dual phase, process is seen to involve adding water to the relatively high temperature hydrocarbon/alcohol/neutrals solution to result in two liquid phases.
  • the mixture is allowed to cool slowly, during which time the sterols crystallize.
  • the mixture is then filtered to recover the sterol crystals.
  • the sterols are recovered from a hydrocarbon solution of the pitch- extracted neutrals of tall oil processing.
  • the neutrals may be derived from various sources, such as tall oil soaps or tall oil pitch. Also, such neutrals may be recovered by various means, the more obvious of which include distillation or solvent extraction.
  • the hydrocarbon employed likewise, may be one (or a mixture) of several organic solvents. A preferred hydrocarbon solvent is heptane.
  • extraction neutrals are prepared and concentrated in the laboratory, but the neutrals could remain in residual heptane from the solvent extraction operation.
  • a temperature of 50-60°C is sufficient to dissolve the neutrals in the lab; however, optimization of the invention process involves raising the temperature of the heptane stream phase to a higher temperature.
  • an alcohol preferably methanol, at the same or higher temperature, to create a heptane/sterol/methanol phase.
  • water at a higher temperature preferably greater than 60°C, more preferably greater than 70°C, is added to result in two separate liquid phases .
  • the dual-phase solution is allowed to cool slowly, preferably with sufficient agitation to keep the slurry well stirred throughout.
  • the sterol crystals are filtered using a jacketed Buchner funnel, and the resulting filter cake is washed with copious amounts of heptane.
  • the jacketed Buchner funnel is kept at near 40°C using a water bath. This keeps the temperature of the filter cake from cooling excessively during filtration, which can lead to contamination.
  • Final crystallization temperature is from 20-30°C, preferably 25°C.
  • a method for the isolation of sterols from sulfate pulping process tall oil pitch comprising the steps of: (a) saponifying the tall oil pitch; (b) separating the neutral fraction from the saponified tall oil pitch;
  • the blended solution is allowed to cool to a final temperature from about 20 °C to about 40°C to produce sterol crystals
  • hydrocarbon solvent is selected from the group consisting of straight- and branched- chain hydrocarbons with from 5 to 10 carbons;
  • hydrocarbon solvent is selected from the group consisting of pentane, hexane, heptane, iso-octane, and mixtures thereof;
  • the alcohol solvent is selected from the group of aliphatic alcohols consisting of methanol, ethanol, butanol, iso-propanol, and mixtures thereof;
  • step (a) is greater than 60 °C; (8) the method of claim 1 wherein the temperature in step (a) is greater than 70°C;

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

L'invention concerne l'isolation du composant stérol de la fraction des neutres de poix de tall oil saponifiés. L'isolation de stérol est effectuée par une extraction liquide-liquide des neutres dérivés des poix de tall oil et entraîne une phase hydrocarbonée (de préférence heptane), à une température relativement élevée (de préférence supérieure à 50 °C), à laquelle on ajoute en petites quantités un solvant alcool, de préférence du méthanol. Ensuite, on ajoute à la solution hydrocarbure/alcool/neutres de l'eau à une température élevée, de préférence de 60 à 70 °C pour engendrer la formation de deux phases distinctes. La solution mélangée est refroidie lentement, par agitation, pour faciliter la cristallisation de stérols. Les stérols sont isolés par filtration puis lavés par un solvant hydrocarboné pour obtenir un rendement élevé et une grande pureté.
PCT/US1999/014135 1998-08-27 1999-07-12 Isolation et purification de sterols de la fraction des neutres de poix de tall oil par cristallisation directe, phase duelle WO2000012533A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU49583/99A AU4958399A (en) 1998-08-27 1999-07-12 Isolation and purification of sterols from neutrals fraction of tall oil pitch by direct crystallization, dual phase

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US14152998A 1998-08-27 1998-08-27
US09/141,529 1998-08-27

Publications (1)

Publication Number Publication Date
WO2000012533A1 true WO2000012533A1 (fr) 2000-03-09

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AR (1) AR013050A1 (fr)
AU (1) AU4958399A (fr)
WO (1) WO2000012533A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105037473A (zh) * 2015-07-20 2015-11-11 宜春大海龟生命科学有限公司 一种从塔尔油中提纯精制甾醇的方法
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 (9)

* 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
US3887537A (en) * 1973-09-18 1975-06-03 Japan Synthetic Rubber Co Ltd Process for recovering fatty acids and/or rosin acids
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
CS250645B1 (cs) * 1985-12-29 1987-04-16 Reiner Seifert Způsob izolace sterolů z vedlejších produktů výroby sulfátové buničiny

Patent Citations (9)

* 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
US3887537A (en) * 1973-09-18 1975-06-03 Japan Synthetic Rubber Co Ltd Process for recovering fatty acids and/or rosin acids
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
CS250645B1 (cs) * 1985-12-29 1987-04-16 Reiner Seifert Způsob izolace sterolů z vedlejších produktů výroby sulfátové buničiny

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 111, no. 2, 10 July 1989, Columbus, Ohio, US; abstract no. 9173, SEIFERT, REINER ET AL: "Streamlined recovery of sterols from pulp byproducts" XP002116666 *
CHEMICAL ABSTRACTS, vol. 85, no. 26, 27 December 1976, Columbus, Ohio, US; abstract no. 194404, NEKRASOVA, V. B. ET AL: "Determination of the optimal parameters for saponification of tall oil pitch" XP002116667 *
DATABASE PAPERCHEM2 [online] KARPUS, G. G. ET AL: "COMPARISON OF LTA (LENINGRAD ACADEMY OF WOOD TECHNOLOGY) METHODS FOR OBTAINING STEROIDS FROM SULFATE SOAP AND TALL OIL PITCH", XP002116668, retrieved from STN Database accession no. 6176 *
IZV. VUZ, LESNOI ZH., (1976) VOL. 19, NO. 1, PP. 115-118. [RUSS.]. *
IZV. VYSSH. UCHEBN. ZAVED., LESN. ZH. (1976), 19(4), 113-16 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105037473A (zh) * 2015-07-20 2015-11-11 宜春大海龟生命科学有限公司 一种从塔尔油中提纯精制甾醇的方法
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

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AR013050A1 (es) 2000-11-22
AU4958399A (en) 2000-03-21

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