• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to extraction of phytosterols from alkaline tall oil soap which is obtained from the Kraft process black liquor by skimming. In the method according to the present invention, phytosterols are extracted using dibromomethane, bromoform or a combination thereof.
    公开号:SE1650109A1
    申请号:SE1650109
    申请日:2016-01-29
    公开日:2017-07-30
    发明作者:Kavakka Jari
    申请人:Stora Enso Oyj；
    IPC主号:
    专利说明:

    EXTRACTION OF PHYTOSTEROLS Field of the invention The present invention relates to extraction of phytosterols from alkaline tall oilsoap which is obtained from the Kraft process black liquor by skimming. ln themethod according to the present invention, phytosterols are extracted usingdibromomethane, bromoform or a combination thereof.
    Background Tall oil soap (TOS) is a by-product of the Kraft process. The soap consistsmainly of sodium salts of fatty acids, sodium salts of diterpenic (rosin) acids,free fatty acids, free rosin acids and unsaponifiable neutral compounds suchas fatty alcohols, sterols, steryl esters and waxes. The water content of neatsoap is typically 25 to 45%, such as 30 to 35%. The pH of the soap is typicallyin the range of 12 to 13, arising from the presence of entrained black liquor. lnindustrial practice, soap is routinely acidulated with sulphuric acid to producecrude tall oil (CTO), an article of commerce. Sterols, in particular phytosterols,have several uses, including the use as food additives and as precursors forsteroids. Several methods have been reported for the isolation of sterols fromtall oil soap. The general method involves the extraction of neat soap with avariety of organic solvents. The presence of entrained black liquor promotesand stabilizes the unwanted water-oil emulsion, which is known to beextremely difficult to break. Consequently, the efficiency of solvent extractionof neat soap for the isolation of sterols is greatly reduced. Holmbom et al.teach in US Patent 3,965,085 the extraction of a mixture of acetone-watersoap slurry, with a water-immiscible solvent such as hexane. The aqueousphase contains mainly sodium salts of fatty and resin acids. The organicphase contains mostly unsaponifiables including sterols. ln US Patent4,044,031, Johansson et al. teach the dissolution of soap in a water- immiscible mixture comprising hexane and acetone, extraction of the water-immiscible phase with another solvent mixture comprising methanol, hexane,acetone and water, and isolation of sterols from the methanolic phase byevaporative crystallization. ln US Patent 5,770,749, Kutney et al. teach theuse of a mixture of ketones, hydrocarbons and water to extract sterols fromsoap. The hydrocarbon extract is further processed with methanol. However,the complexity of recovering the multi- component spent solvent is veryproblematic in these processes. Also, recycling highly water soluble solvents such as acetone and methanol from water mixtures is very complicated.
    Futher examples of methods of obtaining phytosterols are described inUS2005/0107582, WO2009/106696 and CA2319230.
    There is thus a need for a more efficient method of obtaining phytosterolsfrom tall oil soap.
    Summary of the invention lt has been found that any of the solvents dibromomethane and bromoformcan selectively extract phytosterols from tall oil soap without a need for anyemulsion breaking polar organic solvent.
    Thus, the present invention is directed to a method for extracting phytosterols from tall oil soap comprising the steps of a) obtaining tall oil soap,b) mixing the tall oil soap with a solvent selected from dibromomethane,bromoform or a combination thereof, and c) recovering phytosterols from the solvent extract. ln one embodiment of the present invention, step c) involves separation ofphases followed by distillation of the selected solvent with elevatedtemperature at normal or reduced pressure. ln one embodiment of the present invention, step c) involves precipitation ofthe phytosterols. The precipitation can be achieved through reducing thetemperature or concentrating the sample or by addition of an anti-solvent orany combination thereof. ln one embodiment of the present invention, the phytosterols recovered instep c) are purified by cooling or evaporative crystallization. ln one embodiment of the present invention, dibromomethane is used asextraction solvent. ln one embodiment of the present invention, bromoform is used as anextraction solvent. ln one embodiment of the present invention, a combination of bromoform anddibromomethane is used as extraction solvent. ln one embodiment of the present invention, the solvent is recycled. Theextraction solvent in the phytosterol fraction can be recycled after isolation ofthe phytosterols. The extraction solvent adsorbed in the aqueous phase can be recycled through acidulation, phase separation and subsequent distillation.
    Detailed description The term "phytosterol" is intended to mean a sterol derived from plants andencompasses all plant sterols and the saturated forms of phytosterols thereof(i.e., phytostanols). Plant sterols fall into one of three categories: 4-desmethylsterols (lacking methyl groups); 4-monomethylsterols (one methylgroup); and 4,4-dimethylsterols (two methyl groups) and include, but are notlimited to, sitosterol (e.g., [alpha] and [beta] sitosterol), campesterol, stigmasterol, taraxasterol, and brassicasterol. The term "phytostanol" is intended to mean a saturated phytosterol and encompasses, but is not limitedto, sitostanol (e.g., [alpha] and [beta] sitostanol), campestanol, stigmastanol,clionastanol, and brassicastanol. Phytosterols isolated by the methods of the invention may be quantified by any means known in the art. ln one embodiment of the present invention, the dibromomethane, bromoformor a combination thereof is mixed with tall oil soap and the solvent fraction isremoved through phase separation achieved e.g. with mixer settler,centrifugation or with temperature change or any combination thereof and the phytosterols are recovered by removal of the solvent by distillation. lt has been observed that regardless of the selected extraction solvent, thevolume of aqueous fraction was increased by 20-40°/> after first extraction dueto the adsorption of extraction solvent to the lipophilic carboxylic acid salts in aqueous phase.
    As the boiling points of the solvents are low, the adsorbed solvent can berecovered later by acidulation, phase separation and subsequent distillation.According to UPLC/HPLC-analysis, a selective extraction of phytosterols canbe accomplished with any of the two solvents listed above or a combinationthereof. After the phase separation and evaporation of the brominated solventthe crude phytosterol mixture can be purified by crystallization, using methodsknown in the art. Finally, the phytosterol depleted tall oil soap can be acidifiedto produce tall oil with high acid number.
    The phytosterol crystallization can be performed using methods known in theart, including cooling, concentration by removing some of the solvent bydistillation, evaporation to dryness followed by introduction of a solvent orsolvent mixture in which the phytosterols only dissolve at elevated temperature followed by cooling or through seeding with phytosterol crystals.
    The phytosterol depleted tall oil soap can be acidified to produce the tall oil inwhich there would be residual extraction solvent originating from adsorption to the aqueous phase during the extraction. As there is only trace amount ofwater left in the tall oil after acidulation of the soap followed by a phaseseparation, it can be distilled to remove the residual extraction solvent. Afterthis distillation, both the phytosterols as well and the extraction solvent have been removed from the tall oil.
    The extraction according to the present invention may be carried out atambient temperature (room temperature), alternatively under moderateheating to a temperature below about 90 °C.
    The process according to the present invention may be carried out as a batch pFOCGSS OI' 8.3 8. COntlnUOUS DFOCGSS. ln view of the above detailed description of the present invention, other modifications and variations will become apparent to those skilled in the art.However, it should be apparent that such other modifications and variationsmay be effected without departing from the spirit and scope of the invention.
    权利要求:
    Claims (1)
    [1] 1. Claims A process for extracting phytosterols from tall oil soap comprisingthe steps of a) obtaining tall oil soap, b) mixing the tall oil soap with a solvent selected from dibromomethane, bromoform or a combination thereof, andc) recovering phytosterols from the solvent extract. A process according to claim 1, wherein step c) involvesseparation of phases followed by distillation of the selectedsolvent with elevated temperature at normal or reducedpressure. A process according to claim 2, wherein step c) involvesprecipitation of the phytosterols. A process according to any one of claims 1 to 3, wherein thephytosterols recovered in step c) are purified bycrystallization. A process according to any one of claims 1 to 4, whereindibromomethane is used as solvent. A process according to any one of claims 1 to 4, whereinbromoform is used as solvent. A process according to any one of claims 1 to 4, wherein acombination of bromoform and dibromomethane is used assolvent. A process according to any one of claims 1-7, wherein thesolvent is recycled after isolation of the phytosterols and theextraction solvent adsorbed in the aqueous phase is recycledthrough acidulation, phase separation and subsequentdistillation.
    类似技术:
    公开号 | 公开日 | 专利标题
    WO2000027867A1|2000-05-18|Isolation and purification of sterols from neutrals fraction of tall oil pitch by single decantation crystallization
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    US4153622A|1979-05-08|Process for the recovery of β-sitosterol
    AU763546B2|2003-07-24|Process for the purification of sterols from hydrocarbon extracts using evaporative fractionation
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    RU2762561C1|2021-12-21|Method for producing phytosterols of high purity
    US6770767B1|2004-08-03|Method for the extraction and isolation of neutral substances from a soap
    US2729656A|1956-01-03|Isolation of sterols
    EP1190025B1|2003-03-05|Extraction and isolation method
    WO2000004039A1|2000-01-27|Isolation and purification of sterols from neutrals fraction of tall oil pitch by single decantation precipitation
    WO2000034305A1|2000-06-15|Isolation and purification of sterols from neutrals fraction of tall oil pitch by dual decantation crystallization
    WO2000012533A1|2000-03-09|Isolation and purification of sterols from neutrals fraction of tall oil pitch by direct crystallization, dual phase
    WO2000009535A1|2000-02-24|Isolation and purification of sterols from neutrals fraction of tall oil pitch by direct crystallization, single phase
    WO2000064922A1|2000-11-02|Alkanol, methyl ethyl ketone water solvent system for the separation of sterols
    Davis1949|Solvent Extraction of Unsaponifiable Matter From Crude Kraft Soap
    EP1389622A2|2004-02-18|Process for the purification of sterols from hydrocarborn extracts using evaporative fractionation
    JPH11158196A|1999-06-15|Extraction of tall oil alcohol component contained in tall oil skimming
    WO2000064923A1|2000-11-02|Process for the isolation of phytosterols from neutral substances using hydrocarbon and alcohol based solvent systems
    CA2245114A1|1999-02-14|Non-chromatographic process for selective crystallization of vegetable steroids
    同族专利:
    公开号 | 公开日
    US10597602B2|2020-03-24|
    SE540791C2|2018-11-13|
    US20190010420A1|2019-01-10|
    EP3408277A4|2019-09-04|
    EP3408277B1|2021-06-16|
    WO2017130127A1|2017-08-03|
    EP3408277A1|2018-12-05|
    CN108495859A|2018-09-04|
    CA3010923A1|2017-08-03|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2280815A|1940-03-20|1942-04-28|Squibb & Sons Inc|Method of obtaining sterols|
    US2573265A|1948-06-25|1951-10-30|Procter & Gamble|Isolation of sterols|
    US2839544A|1956-09-04|1958-06-17|Upjohn Co|Countercurrent extraction of steroids|
    US2963494A|1957-12-16|1960-12-06|Upjohn Co|Purification of sterols|
    US3840570A|1970-12-07|1974-10-08|Procter & Gamble|Process for preparing sterols from tall oil pitch|
    SE417107B|1973-06-29|1981-02-23|Bjarne Holmbom|PROCEDURE FOR PROCESSING SAPOR|
    US4044031A|1976-07-02|1977-08-23|Ake Allan Johansson|Process for the separation of sterols|
    FI57956C|1978-12-12|1980-11-10|Farmos Oy|FOER FARING ISOLERING AV BETA-SITOSTEROL MED LAOG ALFA-SITOSTEROLHALT|
    AT216395T|1994-09-29|2002-05-15|Univ British Columbia|STERIN COMPOSITIONS FROM WOOD DIGESTIVE SOAP|
    US20050107582A1|2003-07-30|2005-05-19|Alfred Wong|Method for the preparation of phytosterols from tall oil pitch|
    US6770767B1|1999-04-27|2004-08-03|Sterol Techologies Ltd.|Method for the extraction and isolation of neutral substances from a soap|
    CA2319230A1|2000-09-13|2002-03-13|Alfred Wong|Improved method of extraction of tall oil soap|
    US20060166951A1|2002-05-31|2006-07-27|Archer-Daniels-Midland Company|Compositions and methods for sterol isolation and purification|
    FI20070137A0|2007-02-15|2007-02-15|Raisio Benecol Oy|Method for the isolation of fatty acids, resin acids and sterols from tall oil pitch|
    FI20080174A0|2008-02-29|2008-02-29|Raisio Nutrition Ltd|A method for separating sterols and acids from tall oil pitch|
    JP6057313B2|2008-03-10|2017-01-11|サンパイン アーベーＳｕｎｐｉｎｅ Ａｂ|Regeneration of plant sterols from residual vegetable oil streams|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    SE1650109A|SE540791C2|2016-01-29|2016-01-29|Extraction of phytosterols|SE1650109A| SE540791C2|2016-01-29|2016-01-29|Extraction of phytosterols|
    CN201780007993.7A| CN108495859A|2016-01-29|2017-01-26|Phytosterol is extracted from tall oil soap using the solvent selected from methylene bromide, bromofom, tetrabromomethane or combinations thereof|
    CA3010923A| CA3010923A1|2016-01-29|2017-01-26|Extraction of phytosterols from tall oil soap using a solvent selected from dibromomethane, bromoform, tetrabromomethane or a combination thereof|
    PCT/IB2017/050408| WO2017130127A1|2016-01-29|2017-01-26|Extraction of phytosterols from tall oil soap using a solvent selected from dibromomethane, bromoform, tetrabromomethane or a combination thereof|
    EP17743812.4A| EP3408277B1|2016-01-29|2017-01-26|Extraction of phytosterols from tall oil soap using a solvent selected from dibromomethane, bromoform, tetrabromomethane or a combination thereof|
    US16/073,437| US10597602B2|2016-01-29|2017-01-26|Extraction of phytosterols from tall oil soap using a solvent selected from dibromomethane, bromoform, tetrabromomethane or a combination thereof|
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