EP1227727A1 - Procede d'extraction d'huiles essentielles et de composes antioxydants a partir d'extraits de la famille des lamiacees, au moyen d'une technique d'evaporation a film enroule - Google Patents

Procede d'extraction d'huiles essentielles et de composes antioxydants a partir d'extraits de la famille des lamiacees, au moyen d'une technique d'evaporation a film enroule

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Publication number
EP1227727A1
EP1227727A1 EP00973514A EP00973514A EP1227727A1 EP 1227727 A1 EP1227727 A1 EP 1227727A1 EP 00973514 A EP00973514 A EP 00973514A EP 00973514 A EP00973514 A EP 00973514A EP 1227727 A1 EP1227727 A1 EP 1227727A1
Authority
EP
European Patent Office
Prior art keywords
extract
essential oils
extract product
organic solvent
residue
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.)
Withdrawn
Application number
EP00973514A
Other languages
German (de)
English (en)
Other versions
EP1227727A4 (fr
Inventor
James E. Haworth
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.)
Kemin Industries Inc
Original Assignee
Kemin Industries Inc
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 Kemin Industries Inc filed Critical Kemin Industries Inc
Publication of EP1227727A1 publication Critical patent/EP1227727A1/fr
Publication of EP1227727A4 publication Critical patent/EP1227727A4/fr
Withdrawn legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K36/00—Medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicines
    • A61K36/18—Magnoliophyta (angiosperms)
    • A61K36/185—Magnoliopsida (dicotyledons)
    • A61K36/48—Fabaceae or Leguminosae (Pea or Legume family); Caesalpiniaceae; Mimosaceae; Papilionaceae
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K36/00—Medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicines
    • A61K36/18—Magnoliophyta (angiosperms)
    • A61K36/185—Magnoliopsida (dicotyledons)
    • A61K36/53—Lamiaceae or Labiatae (Mint family), e.g. thyme, rosemary or lavender

Definitions

  • the invention relates generally to a method for removing by wipe or rolled film evaporation essential oils and antioxidants from extracts of organic material, more particularly organic material from the Lamiaceae (or Labiatae) family, including rosemary (Rosemannus officinalis).
  • the fraction containing antioxidants is suitable for addition to animal feeds and human food.
  • the essential oils are pharmaceutical grade.
  • Tocopherols have a potent ability to inhibit lipid peroxidation in vivo by trapping peroxy-radicals (Burton, G. W., and K. U. Ingold (1989), in Vitamin E: Biochemistry and Health Implications, edited by A. T. Diplock, L. J. Machlin, L. Packer and W. A. Pryor, The New York Academy of Sciences, New York, pp. 7- 22).
  • Various herbal extracts for use as natural antioxidants are being explored. Possibilities include the extraction of rosemary or other botanical sources. Such new antioxidants may play a role in combating carcinogenesis as well as the aging process, and may be applicable in the nutraceutical industry.
  • rosemary extracts which are reported to be highly effective in retarding lipid oxidation and protecting living cells from the damaging oxidative stress (Chen, Q., H. Shi and C-T Ho (1992), "Effects of rosemary extracts and major constituents on lipid oxidation and soybean lipoxygenase activity", J Am Oil Chem Soc 69: 999-1002; Wong, J. W., K. Hashimoto and T. Shibamoto (1995), "Antioxidant activities of rosemary and sage extracts and vitamin E in a model meat system", J Agric Food Chem 43: 2707-2712).
  • Essential oils are volatile oils that are the aroma and flavor components of organic material. They are used in a variety of products such as incense, aromatherapy oils, perfumes, cosmetics, pharmaceuticals, beverages, and foods. The market for these oils demands consistent high quality and reliable supplies at competitive prices. Essential oils are typically commercially extracted from organic material such as rosemary using steam distillation. In this prior art process, the antioxidants are destroyed, and thermal degeneration of the essential oils may occur. An improved method for the simultaneous extraction of both antioxidant compounds and essential oils form species of the family Lamiaceae is described in pending patent application Serial No. 09/206,458, which was filed December 7, 1998, and is incorporated herein by this reference.
  • TFE tetrafluoroethane
  • extracts of organic material that have a high level of antioxidant activity and further contain much of the essential oils present in the organic material.
  • the essential oils are pro-oxidants, however, and further may limit the amount of the extract that may be used in certain antioxidant applications due to the odor of the essential oils.
  • essential oils of some species have a high market value apart from the antioxidant compounds. Accordingly, there is a need to remove and preserve the essential oils from the extract without substantially degrading the activity of the antioxidant compounds. There is also a need to purify further the antioxidant compounds, particularly camosic acid, that may be present in the extract.
  • This invention is directed to a method of removing antioxidants and essential oils from the extract products of organic materials while preserving the activity of the compounds.
  • a purpose of the present invention is to provide a method using rolled film evaporation for removing antioxidants and essential oils from extracts of plants of the family Lamiaceae, particularly rosemary, that yields a fraction containing the essential oils of the plant material and a fraction that contains the antioxidant compounds present in the extract substantially free from odor and suitable for incorporation into animal feeds and human foods.
  • a further purpose of the present invention is to provide a method for removing antioxidants and essential oils from extracts of rosemary in high yields and high purity.
  • the organic material used during testing was dried, finely ground rosemary of the Arp variety. It is anticipated that the organic material can be any plant of the Lamiaceae family, and more broadly, any plant material that contains antioxidants and essential oils. It is also expected that any parts of the plant which contain the desired components may be extracted, as well as any form of the plant material (e.g., whole, ground, fresh, or dried).
  • Tetrafluoroethane (1 ,1,1 ,2) was used in the solvent blend. Tetrafluoroethane has a boiling point of -27° C. The technology utilizes the vapor pressure of the solvent at room temperature and allows extraction under mild conditions, therefore minimizing the oxidative decomposition of camosic acid during the extraction process. Tetrafluoroethane is substantially apolar and is preferably blended with acetone in the extractions of rosemary described here. The advantages of TFE show that it is non-flammable, has a low boiling point, is environmentally acceptable (very low toxicity), and is easily handled.
  • the organic material and solvent blend are added together in a 1 :3 (organic material: solvent blend) or higher (i.e., 1 :4, 1 :5, etc.) weight ratio to perform the extraction step in any vessel which will be compatible with the components.
  • the vessel Since the TFE is preferably added in liquid form, the vessel has to be a pressure vessel that will withstand pressures equal to those required to maintain the TFE in liquid form.
  • the extraction has been carried out at ambient temperatures, but the pressure and temperature may be varied, so long as the TFE and organic solvents remain in liquid form.
  • the method for removing the organic material from the solution was filtration. Any suitable separation process known to one skilled in the art which does not interfere with the other steps of the method may be used.
  • the removal of the solvent blend has been accomplished by evaporation.
  • the TFE and organic solvent(s) may be removed by any suitable method known to one skilled in the art as well.
  • a thin film evaporator has been found to be particularly suitable for this process.
  • the extract after removal of the TFE, methanol and acetone, is passed through a rolled film evaporator under vacuum at a temperature in the range of about 65 °C to about 120 °C, and preferably between about 80 °C and 90 °C.
  • the remaining volatile components of the extract include the essential oils of the organic material. These volatile compounds are evaporated in the rolled film evaporator and collected in distillate fractions. The residue is a viscous oily product that contains many of the antioxidant compounds that were present in the organic material.
  • the residue is essentially odor free and can therefore be used in applications where the extract containing the essential oils was found to be unsatisfactory, for example in protecting the fats in dog food from oxidation.
  • the residue has a high percentage of antioxidant compounds.
  • the residue contains between about 10% and about 50% camosic acid, and typically about 30% camosic acid.
  • the distillate is found to include the essential oils, as before, but it also exhibits antioxidant activity. It is believed that the antioxidant compounds present in the extract, for example, camosic acid and/or camosol, are evaporated at the higher temperatures and therefore are present in the distillate.
  • the essential oils resulting from rolled film evaporation at the lower temperature range are of very high purity (pharmaceutical grade) and surprisingly high yields (compared to previous extraction methods for obtaining essential oils).
  • the distillate at the higher temperature range is a product that contains the essential oils but also exhibits antioxidant activity.
  • Fig. 1 is a process diagram of the preferred embodiment of the extraction method of the present invention.
  • Fig. 2 is a chart of the antioxidant efficacy of a sample of rosemary extracted according to described Method 1 compared with the residues following rolled film evaporation under a variety of conditions.
  • Fig. 3 is a chart of the antioxidant efficacy of the residues from Fig. 2 compared with residues following rolled film evaporation of the residue under a variety of conditions.
  • Fig. 4 is a chart of the antioxidant efficacy of a number of residues and distillates following rolled film evaporation of the residues from Fig. 2.
  • Fig. 5 is a chart of the antioxidant efficacy of residues before and following combination with soybean oil and processing by rolled film evaporation.
  • Fig. 6 is a chart of the antioxidant efficacy of tocopherols, the antioxidant fraction following rolled film evaporation of a 65% extract 35% soy bean oil mixture, and of the antioxidant fraction following a second pass through the rolled film evaporator.
  • Fig. 7 is a chart of the antioxidant efficacy of tocopherols, a solvent blend extract, a soybean oil/solvent blend extract mixture, and residues collected after a first and after a second pass through the rolled film evaporator.
  • Fig. 8 is a GC/MS chart of a commercially available essential oil extract of rosemary.
  • Fig. 9 is a GC/MS chart of an essential oil fraction of an extract of rosemary prepared according to the present invention.
  • Fig. 10 is a GC/MS headspace chart of a solvent blend extract of rosemary prepared according to the present invention prior to being processed through the rolled film evaporator.
  • Fig. 1 1 is a GC/MS headspace chart of a residue fraction of a solvent blend extract of rosemary prepared according to the present invention after the essential oil fraction has been removed by being processed through the rolled film evaporator
  • the process includes an extraction vessel 10 where the organic material 12 is extracted using the solvent blend preferably at a pressure equal to that necessary to keep the TFE in liquid form and at ambient temperature.
  • the solvent blend is premixed in a solvent blend tank 14 before being added to the extraction vessel 10 where the organic material 12 has been added.
  • the solvents are added to the solvent blend tank 14 from fresh supply tanks, acetone tank 16, methanol tank 18, and TFE tank 20, or alternatively, recycled from the end separation techniques.
  • the mixture is passed through a filter 22.
  • the filtered extract then passes through a thin film evaporator 24 where the TFE and methanol/acetone are removed as gasses and the remaining extract passes to the next step.
  • the removed TFE and methanol/acetone are recycled back through a cold-trap 26 that is at a temperature to liquefy the methanol and acetone but not the TFE.
  • the liquefied co-solvents are returned to the solvent blend tank 14.
  • the gaseous TFE is moved by a compressor 34 through a second cold trap 36 which liquefies the TFE, whereupon it is returned to the TFE tank 20 for reuse.
  • the solvent-free extract then passes through a rolled film evaporator 28 where the antioxidant 30 and essential oil 34 fractions of the extract are collected.
  • Example 1 The invention identifies methods of removing the essential oils from extracts of organic material, particularly TFE extracts of species of the family Lamiaceae, and to a method of producing essential oils that have antioxidant properties.
  • the extracts without the surfactant tend to have components that evaporate so quickly that the product is atomized as it enters the evaporator.
  • the surfactant improves the viscosity of the extract so that it flows better through the evaporator and may also form an improved, more uniform thin film over the cylinder of the evaporator. Any oil or surfactant, or other compound, which contributes similar properties to the extract could alternatively be used.
  • the product subjected to rolled film evaporation comprised 2015 g, of which 932.0 g were the TFE-solvent blend extract of rosemary, 932.0 g of ATMOS 300 surfactant, and 151 g water.
  • This product was passed through a KDL-9 rolled film evaporator purchased from UIC, Inc., Chicago, Illinois, in two passes at the temperatures and conditions as set out in Table 1.
  • Fig. 2 illustrates the oxygen absorption of the starting product, identified as 1 1-11, as well as that of the residues of the five samples taken in the first pass through the rolled film evaporator.
  • the chart shows that the later four residues, identified as R12 - R15, had much higher antioxidant activity than the control or starting product and the first residue, identified as Rl 1.
  • Figs. 3 and 4 illustrate the oxygen absorption of the combined residues from the first pass, identified as R2FEED and the residues and distillates taken during the second pass through the rolled film evaporator.
  • R2FEED the first pass
  • R21 and R22 the residues and distillates taken during the second pass
  • R21 and R22 the residues and distillates taken during the second pass
  • the oxygen bomb data of the distillates collected during the second pass are illustrated with the third and fourth residues collected during the second pass.
  • the sixth distillate, D26 has an antioxidant activity that is much improved over the earlier distillates taken at lower temperatures.
  • Example 2 For Experiment 2, two extracts of rosemary were prepared using the process as previously described, wherein one extract was obtained using a solvent blend comprising 85.7% TFE / 7.14% methanol / 7.14% acetone (identified as Zwag 1), and the second extract was obtained using a solvent blend comprising 80% TFE / 13.3% methanol / 6.7% acetone (identified as Zwag 2).
  • the two extracts were combined to form an extract for processing in the rolled film evaporator.
  • Five hundred grams of soybean oil was mixed with 550 g of the combined extract samples (52.4% extract / 47.6% soybean oil). This mixture was run through the rolled film evaporator under the conditions set out in Table 2.
  • Sample 75 comprised of 75% of the solvent blend extract and 25% soybean oil
  • Sample 65 comprised of 65% of the solvent blend extract and 35% soybean oil.
  • Example 4 The residue collected in the final stage of Experiment 3 was run through the evaporator a second time in an effort to remove more of the volatile materials in the extract. The results are reported in Table 4.
  • Oxygen bomb data on the starting material (identified as 30-1) and the residue collected in sample tube #2 (identified as 30-R2) are reported in Fig. 6.
  • Example 5 An experiment was run to determine if the addition of water to the samples would improve the characteristics of the samples. Two samples were prepared, one comprising 65% of the solvent blend extract and 35% ATMOS 300, and the other with 5% water added (61.75% extract / 33.25% ATMOS / 5.0% water). The samples were run through the evaporator. No significant effect on the removal of the essentials oils from the extract was observed. One explanation for seeing no effect may be that the extract samples already contained a significant amount of water.
  • Example 6 From previous experiments, it was determined that the presence of water in the starting extract samples was preventing operation of the evaporator under conditions needed to remove a sufficient amount of the essential oils from the extract. Specifically, at the evaporator temperature and high vacuum needed to remove the essential oils, the samples would spatter and/or foam vigorously upon entering the evaporator and would frequently require disassembly and cleaning of the evaporator before it could be used again. An experiment was run that first used less aggressive conditions in the evaporator to remove most of the water (and/or other volatile contaminants), followed by a second pass through the evaporator of the residue collected during the first pass, wherein the evaporator would be set to the more aggressive conditions needed to assure removal of the essential oils from the extract.
  • a sample was prepared containing 65% of the solvent blend extract and 35% soybean oil. It was run through the evaporator at the conditions as set out in Table 5.
  • Example 7 An experiment was conducted to compare the gas chromatograph / mass spectroscopy graphs of the essential oils obtained in the distillate collected from the rolled film evaporator with such graphs taken from a plurality of essential oil of rosemary products available in the commercial marketplace. Such essential oil products are produced by the use of steam distillation.
  • chromatogram of a sample of the essential oil distillate collected from the process of the present application is depicted in Fig. 9. These chromatograms demonstrate that the essential oil fraction recovered using the process of the present invention should perform as a suitable substitute for commercially available oil of rosemary products.

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  • Health & Medical Sciences (AREA)
  • Natural Medicines & Medicinal Plants (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Alternative & Traditional Medicine (AREA)
  • Biotechnology (AREA)
  • Botany (AREA)
  • Medical Informatics (AREA)
  • Medicinal Chemistry (AREA)
  • Microbiology (AREA)
  • Mycology (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Epidemiology (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)
  • Fats And Perfumes (AREA)

Abstract

Selon l'invention on peut augmenter l'activité antioxydante spécifique d'extraits de romarin Rosemarinus officinalis en utilisant, dans le processus d'extraction, un mélange de tétrafluoroéthane et d'un solvant organique. Un mélange de tétrafluoroéthane, d'acétone et de méthanol améliore le rendement total, tandis qu'un mélange de tétrafluoroéthane et d'acétone, tout en étant plus efficace, produit comparativement des rendements moindres. A l'aide de ces procédés, on peut produire un extrait liquide, huileux et antioxydant qui se mélange facilement avec un produit liquide, tel que de l'huile de soja, et qui est utile en tant que complément alimentaire pour l'animal et l'homme, et on peut simultanément produire, avec des rendements importants, des huiles essentielles de qualité pharmaceutique.
EP00973514A 1999-10-14 2000-10-13 Procede d'extraction d'huiles essentielles et de composes antioxydants a partir d'extraits de la famille des lamiacees, au moyen d'une technique d'evaporation a film enroule Withdrawn EP1227727A4 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US15968699P 1999-10-14 1999-10-14
US159686P 1999-10-14
PCT/US2000/028356 WO2001026472A1 (fr) 1999-10-14 2000-10-13 Procede d'extraction d'huiles essentielles et de composes antioxydants a partir d'extraits de la famille des lamiacees, au moyen d'une technique d'evaporation a film enroule

Publications (2)

Publication Number Publication Date
EP1227727A1 true EP1227727A1 (fr) 2002-08-07
EP1227727A4 EP1227727A4 (fr) 2004-07-07

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EP00973514A Withdrawn EP1227727A4 (fr) 1999-10-14 2000-10-13 Procede d'extraction d'huiles essentielles et de composes antioxydants a partir d'extraits de la famille des lamiacees, au moyen d'une technique d'evaporation a film enroule

Country Status (3)

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EP (1) EP1227727A4 (fr)
AU (1) AU1201701A (fr)
WO (1) WO2001026472A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6855349B2 (en) * 1998-12-07 2005-02-15 Kemin Industries, Inc. Method for simultaneous extraction of essential oils and antioxidants from Labiatae species and the extract products thereof
RU2305588C2 (ru) * 2004-10-15 2007-09-10 Поль Эмануилович Бланк Способ обработки жидкой среды и устройство для его осуществления
WO2011056826A2 (fr) * 2009-11-04 2011-05-12 E. I. Du Pont De Nemours And Company Procédés et compositions pour l'extraction de composés de flaveur et de fragrance et la solubilisation d'huiles essentielles
EP2753311B1 (fr) * 2011-09-09 2020-07-29 Kemin Industries, Inc. Formulations d'antioxydants
CN103018369B (zh) * 2012-12-17 2014-06-25 江苏大学 液化石油气萃取产品中溶剂残留的检测方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2184341A (en) * 1985-12-20 1987-06-24 Kalamazoo Holdings Inc Herb extract and its preparation
EP0717925A1 (fr) * 1994-12-20 1996-06-26 Societe Des Produits Nestle S.A. Matière végétale issue d'épices à haute teneur en antioxydants
WO2000033859A1 (fr) * 1998-12-07 2000-06-15 Kemin Industries, Inc. Procede d'extraction simultanee d'huiles essentielles et d'antioxydants a partir d'especes de lamiaceae
WO2000053206A1 (fr) * 1999-03-11 2000-09-14 Kemin Industries, Inc. Romarin contenant des extraits antioxydants a efficacite elevee
US20030185916A1 (en) * 1998-05-20 2003-10-02 James Haworth Method of extracting antioxidants from lamiaceae species and the extract products thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62204756A (ja) * 1986-03-04 1987-09-09 大研医工株式会社 薬剤揮散方法および装置
US5017397A (en) * 1990-04-25 1991-05-21 Uy Nguyen Process for extracting antioxidants from Labiatae herbs

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2184341A (en) * 1985-12-20 1987-06-24 Kalamazoo Holdings Inc Herb extract and its preparation
EP0717925A1 (fr) * 1994-12-20 1996-06-26 Societe Des Produits Nestle S.A. Matière végétale issue d'épices à haute teneur en antioxydants
US20030185916A1 (en) * 1998-05-20 2003-10-02 James Haworth Method of extracting antioxidants from lamiaceae species and the extract products thereof
WO2000033859A1 (fr) * 1998-12-07 2000-06-15 Kemin Industries, Inc. Procede d'extraction simultanee d'huiles essentielles et d'antioxydants a partir d'especes de lamiaceae
WO2000053206A1 (fr) * 1999-03-11 2000-09-14 Kemin Industries, Inc. Romarin contenant des extraits antioxydants a efficacite elevee

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO0126472A1 *

Also Published As

Publication number Publication date
AU1201701A (en) 2001-04-23
WO2001026472A1 (fr) 2001-04-19
EP1227727A4 (fr) 2004-07-07

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