• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    Concentrated pesticide-free limonene essential oil. The present invention relates to a process for obtaining pesticide-free limonene essential oil, which comprises the following steps: A) obtaining limonene essential oil B) obtaining a limonene condensate by evaporating the limonene oil obtained in stage a) The present invention also relates to the pesticide-free limonene essential oil obtained by said process and to the use thereof as a food, chemical, pharmaceutical or cosmetic ingredient. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2557954A1
    申请号:ES201531839
    申请日:2015-12-18
    公开日:2016-01-29
    发明作者:Juan CUELLO MARTÍNEZ；José CUELLO GARCÍA；Juan Francisco CUELLO GARCÍA
    申请人:Cugargestion Man S L；Cugargestion Management Sl；
    IPC主号:
    专利说明:

    DESCRIPTION
    CONCENTRATE OF ESSENTIAL OIL OF LEMON FREE OF PESTICIDES Field of the invention
    The present invention relates to an emulsifiable concentrate of pesticide-free limonene oil, a method of obtaining it and the use of pesticide-free limonene oil in different industries such as agriculture, chemistry, cosmetics, Food and pharmaceutical.
    State of the art
    The incorporation of technological advances to agriculture, has allowed today in 10 days products with greater quality, more quantity and requiring the use of fewer resources can be grown. The development of products that more efficiently manage the health of crops and take care of the health of consumers and the environment, is a necessary condition in a modern agriculture, which is immersed in a change of trend towards Ecological production leaving aside the use of pesticides and harmful substances.
    Phytosanitary products are part of modern agriculture protecting crops from pests and diseases that stalk them. There is a huge variety of phytosanitary products in the market. However, their use is increasingly restricted and controlled. The evolution of regulations in the use of phytosanitary products is accompanied by a notable evolution in the technology in the manufacture and use of phytosanitary products. Obtaining safe and reliable products for the farmer, the environment and the consumer, as well as compliance with the increasingly demanding and restrictive evolving regulations proposed in the European Union is essential in this sector.
    At present there is a change of trend worldwide, not a fad, in terms of the increasing consumption of products grown under the name of organic, biological or organic products.
    Limonene is a natural substance that is extracted from the oil of the husks of the citrus fruits and that gives the characteristic smell to them. It belongs to the group of terpenes, specifically to limonoids, which constitute one of the largest classes of functional foods and phytonutrients, functioning as antioxidants.
    Limonene is finding widespread use in the chemical, food and cosmetic industry. It is also used, for example, in resin solvents, pigments, inks, paints, in the manufacture of adhesives, as an additive in fragrances, in cooling fluids,
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    as odor control, etc. It is also used by the pharmaceutical and food industries as a flavoring and flavoring, being used, for example, in the production of artificial flavors of citrus and in the manufacture of sweets, chewing gum, drinks and spices.
    Limonene is also used as an insecticide to repel or kill ants, as described in patent ES 2224386.
    US 4379168 describes different pesticidal compositions containing limonene as the main ingredient.
    However, the use of limonene for certain industries is in turn limited by the substances and pesticides used in agriculture when growing citrus. In addition, the use of these pesticides is difficult to control given the diverse origin of the different items used in obtaining the essential oil of orange and lemon from which limonene is extracted.
    There is therefore a need to provide a pesticide-free limonene, which is of high quality and can be used for the agricultural, chemical, cosmetic, food and pharmaceutical industries.
    Brief Description of the Invention
    The present invention solves the problems of the state of the art since it provides a method of obtaining a limonene oil free of pesticides.
    Thus, in a first aspect, the present invention relates to a process for obtaining pesticide-free limonene oil (hereinafter, process of the present invention), which comprises the following steps:
    a) obtaining limonene essential oil,
    b) obtaining a limonene condensate by evaporating the citric oil obtained in step a)
    In the present invention limonene refers to limonene both in its D-limonene form and in its L-limonene form.
    In a particular embodiment, the process of the present invention comprises a stage after step b) consisting of obtaining a second limonene condensate by evaporating the limonene condensate obtained in step b).
    In a more particular embodiment of the present invention, evaporation is carried out at a temperature between 90-140 ° C and at a pressure of 40-100 mbar.
    With the process of the present invention, in addition to obtaining a pesticide-free limonene essential oil, the limonene richness is increased by more than 2%.
    In a second aspect, the present invention relates to a pesticide-free limonene essential oil (hereinafter, limonene essential oil of the present invention) obtained by the process of the present invention.
    In another aspect, the present invention refers to the use of limonene essential oil of the present invention, as a food, chemical, pharmaceutical and cosmetic ingredient in addition to agricultural use as a phytosanitary.
    In the present invention by ingredient, it refers to a substance that is part of a mixture.
    In another aspect, the present invention relates to the use of limonene essential oil of the present invention for the preparation of a phytosanitary emulsifiable concentrate.
    In another aspect, the present invention relates to a phytosanitary emulsifiable concentrate (emulsifiable concentrate of the present invention) comprising the limonene essential oil of the present invention
    In a particular embodiment, the emulsifiable concentrate of the present invention optionally comprises an emulsifier and / or paraffin oil.
    In another aspect, the present invention relates to a phytosanitary composition (hereinafter, composition of the present invention) comprising the emulsifiable concentrate 20 of the present invention and water.
    Detailed description of the invention
    Example 1: obtaining the essential oil of limonene.
    There are different methods to obtain the essential oil of limonene from citrus, but the procedure of the present invention was performed with an essential oil of limonene from the commercial house Citromil.
    Example 2: obtaining pesticide-free limonene oil
    The procedure began with the evaporation in a rotary evaporator (Buchi Lbortechnik) of a sample consisting of 500 ml of limonene oil obtained in example 1, containing limonene.
    The product was subjected to a pressure of 40 mbar and a temperature of 99 ° C, obtaining two phases, on the one hand a phase with the condensate and on the other hand, a phase with the concentrate.
    A sample of each phase was taken and a multi-residue analysis CG / QQQ was performed, the results are shown in table 1.
    Then the condensate obtained in the first evaporation was subjected to a second evaporation in a rotary evaporator (Buchi Lbortechnik), with the same conditions of 5 pressure and temperature of the first evaporation, obtaining a condensate that was analyzed in the laboratory, the results are shown in table 1.
    The procedure was repeated in the same way twice (trial 1 and trial 2), both tests giving the same results.
    The results obtained show that the condensates obtained by evaporation of limonene do not have pesticides.
     RESIDUE  LOT 60073 (500 ml) TEST 1: T = 992c, P = 40 mbar TEST 2: T = 942c, P = 40 mbar
     DISTILLED 1 (464 ml)  CONCENTRATE 1 (36 ml) DISTILLED 2 (464 ml) CONCENTRATE 2 (32 ml)
     Methyl Chlorpyrifos  0.589 mg / kg LC: 0.010 mg / kg <0.010 mg / kg LC: 0.010 mg / kg 7.539 mg / kg LC: 0.010 mg / kg <0.010 mg / kg LC: 0.010 mg / kg 7.389 mg / kg LC: 0.010 mg / kg
     Chlorpyrifos  3,716 mg / kg LC: 0.010 mg / kg <0.010 mg / kg LC: 0.010 mg / kg 42,511 mg / kg LC: 0.010 mg / kg <0.010 mg / kg LC: 0.010 mg / kg 41,315 mg / kg LC: 0.010 mg / kg
     Propiconazole  0.053 mg / kg LC: 0.010 mg / kg <0.010 mg / kg LC: 0.010 mg / kg 0.752 mg / kg LC: 0.010 mg / kg <0.010 mg / kg LC: 0.010 mg / kg 0.722 mg / kg LC: 0.010 mg / kg
     Orthophenylphenol  1,019 mg / kg LC: 0.010 mg / kg 0.031 mg / kg LC: 0.010 mg / kg 10,729 mg / kg LC: 0.010 mg / kg 0.030 mg / kg LC: 0.010 mg / kg 10,320 mg / kg LC: 0.010 mg / kg
     Pyrimethanil  0.936 mg / kg LC: 0.010 mg / kg <0.010 mg / kg LC: 0.010 mg / kg 9.673 mg / kg LC: 0.010 mg / kg <0.010 mg / kg LC: 0.010 mg / kg 9.607 mg / kg LC: 0.010 mg / kg
     Pyriproxyfen  <0.010 mg / kg LC: 0.010 mg / kg <0.010 mg / kg LC: 0.010 mg / kg 0.186 mg / kg LC: 0.010 mg / kg <0.010 mg / kg LC: 0.010 mg / kg 0.206 mg / kg LC: 0.010 mg / kg
    Table 1: Result
    ades of evaporation tests
    The same test was repeated but the sample was subjected to different temperatures (120 ° C, 130 ° C and 140 ° C at a constant pressure and the concentrate at 150 ° C. The data is shown in Table 2.
     RESIDUE  BATCH 60073 (500 ml) TEST 3: T = 120 ° c P = 100 mbar TEST 3: T = 130 ° c P = 100 mbar TEST 3: T = 140 ° c, P = 100 mbar TEST 3: T = 150 ° c P = 100 mbar
     DISTILLED 1 (460 ml)  DISTILLED 2 (10 ml) DISTILLED 3 (5ml) CONCENTRATED 1 (27 ml)
     Methyl Chlorpyrifos  0.589 mg / kg LC: 0.010 mg / kg <0.010 mg / kg LC: 0.010 mg / kg 0.010 mg / kg LC: 0.010 mg / kg 0.020 mg / kg LC: 0.010 mg / kg 12.541 mg / kg LC: 0.010 mg / kg
     Chlorpyrifos  3,716 mg / kg LC: 0.010 mg / kg <0.010 mg / kg LC: 0.010 mg / kg 0.027 mg / kg LC: 0.010 mg / kg 0.082 mg / kg LC: 0.010 mg / kg 78.924 mg / kg LC: 0.010 mg / kg
     Propiconazole  0.053 mg / kg LC: 0.010 mg / kg <0.010 mg / kg LC: 0.010 mg / kg <0.010 mg / kg LC: 0.010 mg / kg <0.010 mg / kg LC: 0.010 mg / kg <0.010 mg / kg LC: 0.010 mg / kg
     Orthophenylphenol  1,019 mg / kg LC: 0.010 mg / kg 0.027 mg / kg LC: 0.010 mg / kg 0.106 mg / kg LC: 0.010 mg / kg 0.123 mg / kg LC: 0.010 mg / kg 15.337 mg / kg LC: 0.010 mg / kg
     Pyrimethanil  0.936 mg / kg LC: 0.010 mg / kg <0.010 mg / kg LC: 0.010 mg / kg 0.010 mg / kg LC: 0.010 mg / kg 0.025 mg / kg LC: 0.010 mg / kg 11.402 mg / kg LC: 0.010 mg / kg
     Pyriproxyfen  <0.010 mg / kg LC: 0.010 mg / kg <0.010 mg / kg LC: 0.010 mg / kg <0.010 mg / kg LC: 0.010 mg / kg <0.010 mg / kg LC: 0.010 mg / kg 0.159 mg / kg LC: 0.010 mg / kg
     Table 2: Resu  All evaporation tests
    Example 3: Use of pesticide-free limonene oil for the preparation of a phytosanitary emulsifiable concentrate
    As active material, a pesticide-free limonene oil obtained in example 2 was used and paraffin oil was added as an adjuvant, which improved the adhesion and persistence of phytosanitary broths. As paraffin oil does not affect bees, or other beneficial living things, this phytosanitary is suitable for organic farming.
    10 After numerous field trials, the following results were obtained in citrus:
    - For doses higher than 2.6 liters of limonene essential oil per 1000 liters of phytosanitary broth, a progressive paralysis of the growth and vigor of the tree occurs as the dosage increases. For high doses burns in the leaves of the tree.
    15 - For doses below 2.6 liters of limonene essential oil per 1000 liters
    of phytosanitary broth, there is a progressive decrease in the effectiveness of the preparation as the dosage decreases.
    In conclusion, a dosage of 2, 6 l is adopted as optimal. Limonene essential oil / 1000 l. of phytosanitary broth.
    One liter of phytosanitary product contains 0.26 liters of limonene essential oil (26%) and 0.74 liters of paraffin oil (74%). The cost is 40 l / ha, considering about 270 trees per hectare as a reference.
     PHYTOSANITARY (1 liter)  COMPONENTS AND PROPORTIONS
     0.26 liters  Limonene essential oil 26%
     0.74 liters  74% paraffin oil
    5 The phytosanitary broth prepared for application contained 99% water and 1% phytosanitary product (0.26% Limonene essential oil + 0.74% paraffin oil).
    The yield of the phytosanitary broth prepared for adult trees is 12 to 16 liters per tree. About 4,000 l / ha of phytosanitary broth are needed considering about 270 trees per hectare as a reference.
    10 The application procedure was by means of an atomizer, applying it directly to the crops once the fruit set. Fine droplet was used to distribute the product well over the surface of the plant where it was applied.
    Due to the insolubility of the limonene essential oil and the paraffin oil used as an adjuvant with the water of the phytosanitary broth, a special milkshake was made within 15 the tank during the application phase. Modern tanks do not have an effective shake system when using a recirculate of the broth. The lower density of the phytosanitary against water created the need for energy shaking of the culture broth to generate a uniform emulsion during application.
    Modified recirculation systems and / or whipping systems with rotating blades were used. There are atomization systems on the market prepared for this purpose, however, this machinery is not common and the tests were carried out by adapting the existing machinery.
    权利要求:
    Claims (7)
    [1]

    1. Procedure for obtaining essential oil of limonene free of pesticides, characterized in that it comprises the following stages:
    a) obtaining limonene essential oil
    5 b) obtaining a limonene condensate by evaporating the limonene oil obtained in step a)
    [2]
    2. Method according to claim 1, characterized in that it comprises a stage after stage b) consisting of obtaining a second limonene condensate by evaporating the limonene condensate obtained in stage b).
    Method according to any one of claims 1-2, wherein the evaporation is
    performed at a temperature between 90-140 ° C and at a pressure of 40-100 mbar
    [4]
    4. Pesticide-free limonene essential oil obtained by the method according to any of claims 1-3.
    [5]
    5. Use of the pesticide-free limonene essential oil according to claim 4, as a food, agricultural, chemical, pharmaceutical or cosmetic ingredient.
    [6]
    6. Use of the pesticide-free limonene essential oil according to claim 4, for the preparation of an emulsifiable phytosanitary concentrate.
    [7]
    7. Phytosanitary emulsifiable concentrate comprising a pesticide-free limonene essential oil according to claim 4.
    20 8. Phytosanitary emulsifiable concentrate according to claim 7, comprising
    emulsifiable compound and / or paraffin oil.
    [9]
    9. Phytosanitary composition comprising an emulsifiable concentrate according to any of claims 7-8 and water.
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    同族专利:
    公开号 | 公开日
    ES2557954B1|2016-10-21|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US4915707A|1987-10-21|1990-04-10|Lemco Energy, Inc.|Process for purifying limonene for fuel and the like|
    US20040092606A1|1997-04-30|2004-05-13|Mcpartland Tor|Ant spray containing D-limonene and methods of making and using same|
    US20100272835A1|2007-08-27|2010-10-28|Gang Shu|Use of volatile oil from plants in preparing medicaments for preventing and treating diabetes|
    CN104450202A|2014-12-31|2015-03-25|江西省科学院应用化学研究所|Preparation method of high-purity citrus peel essential oil|
    法律状态:
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    优先权:
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