EP2933322B1 - Method for the treatment of animal and vegetable waxes - Google Patents
Method for the treatment of animal and vegetable waxes Download PDFInfo
- Publication number
- EP2933322B1 EP2933322B1 EP15000877.9A EP15000877A EP2933322B1 EP 2933322 B1 EP2933322 B1 EP 2933322B1 EP 15000877 A EP15000877 A EP 15000877A EP 2933322 B1 EP2933322 B1 EP 2933322B1
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- wax
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- pesticides
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- 238000000034 method Methods 0.000 title claims description 22
- 239000012164 animal wax Substances 0.000 title claims description 6
- 241001465754 Metazoa Species 0.000 title claims description 3
- 239000012178 vegetable wax Substances 0.000 title description 5
- 239000001993 wax Substances 0.000 claims description 59
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 54
- 239000000575 pesticide Substances 0.000 claims description 30
- 235000013871 bee wax Nutrition 0.000 claims description 17
- 239000012166 beeswax Substances 0.000 claims description 17
- 239000002798 polar solvent Substances 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 9
- INISTDXBRIBGOC-CGAIIQECSA-N [cyano-(3-phenoxyphenyl)methyl] (2s)-2-[2-chloro-4-(trifluoromethyl)anilino]-3-methylbutanoate Chemical group N([C@@H](C(C)C)C(=O)OC(C#N)C=1C=C(OC=2C=CC=CC=2)C=CC=1)C1=CC=C(C(F)(F)F)C=C1Cl INISTDXBRIBGOC-CGAIIQECSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- FOANIXZHAMJWOI-UHFFFAOYSA-N bromopropylate Chemical compound C=1C=C(Br)C=CC=1C(O)(C(=O)OC(C)C)C1=CC=C(Br)C=C1 FOANIXZHAMJWOI-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 125000003158 alcohol group Chemical group 0.000 claims description 4
- 239000004203 carnauba wax Substances 0.000 claims description 4
- 235000013869 carnauba wax Nutrition 0.000 claims description 4
- UOAMTSKGCBMZTC-UHFFFAOYSA-N dicofol Chemical compound C=1C=C(Cl)C=CC=1C(C(Cl)(Cl)Cl)(O)C1=CC=C(Cl)C=C1 UOAMTSKGCBMZTC-UHFFFAOYSA-N 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- YVGGHNCTFXOJCH-UHFFFAOYSA-N DDT Chemical compound C1=CC(Cl)=CC=C1C(C(Cl)(Cl)Cl)C1=CC=C(Cl)C=C1 YVGGHNCTFXOJCH-UHFFFAOYSA-N 0.000 claims description 2
- 241000209094 Oryza Species 0.000 claims 2
- 239000012165 plant wax Substances 0.000 claims 1
- 238000000605 extraction Methods 0.000 description 11
- BXNANOICGRISHX-UHFFFAOYSA-N coumaphos Chemical compound CC1=C(Cl)C(=O)OC2=CC(OP(=S)(OCC)OCC)=CC=C21 BXNANOICGRISHX-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- JLYXXMFPNIAWKQ-GNIYUCBRSA-N gamma-hexachlorocyclohexane Chemical compound Cl[C@H]1[C@H](Cl)[C@@H](Cl)[C@@H](Cl)[C@H](Cl)[C@H]1Cl JLYXXMFPNIAWKQ-GNIYUCBRSA-N 0.000 description 8
- 239000005936 tau-Fluvalinate Substances 0.000 description 7
- INISTDXBRIBGOC-XMMISQBUSA-N tau-fluvalinate Chemical compound N([C@H](C(C)C)C(=O)OC(C#N)C=1C=C(OC=2C=CC=CC=2)C=CC=1)C1=CC=C(C(F)(F)F)C=C1Cl INISTDXBRIBGOC-XMMISQBUSA-N 0.000 description 7
- 238000010992 reflux Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- CVUGPAFCQJIYDT-UHFFFAOYSA-N 1-chloro-2-[2,2,2-trichloro-1-(4-chlorophenyl)ethyl]benzene Chemical compound C1=CC(Cl)=CC=C1C(C(Cl)(Cl)Cl)C1=CC=CC=C1Cl CVUGPAFCQJIYDT-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- JLYXXMFPNIAWKQ-UHFFFAOYSA-N gamma-hexachlorocyclohexane Natural products ClC1C(Cl)C(Cl)C(Cl)C(Cl)C1Cl JLYXXMFPNIAWKQ-UHFFFAOYSA-N 0.000 description 4
- 229960002809 lindane Drugs 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 244000020551 Helianthus annuus Species 0.000 description 2
- 235000003222 Helianthus annuus Nutrition 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- 239000004166 Lanolin Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 241000895647 Varroa Species 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 239000000642 acaricide Chemical group 0.000 description 1
- QXAITBQSYVNQDR-ZIOPAAQOSA-N amitraz Chemical group C=1C=C(C)C=C(C)C=1/N=C/N(C)\C=N\C1=CC=C(C)C=C1C QXAITBQSYVNQDR-ZIOPAAQOSA-N 0.000 description 1
- 229960002587 amitraz Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004204 candelilla wax Substances 0.000 description 1
- 235000013868 candelilla wax Nutrition 0.000 description 1
- 229940073532 candelilla wax Drugs 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- IUJAMGNYPWYUPM-UHFFFAOYSA-N hentriacontane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC IUJAMGNYPWYUPM-UHFFFAOYSA-N 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 235000019388 lanolin Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000000447 pesticide residue Substances 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229940127557 pharmaceutical product Drugs 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
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
- C11B11/00—Recovery or refining of other fatty substances, e.g. lanolin or waxes
-
- 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
- C11B11/00—Recovery or refining of other fatty substances, e.g. lanolin or waxes
- C11B11/005—Lanolin; Woolfat
Definitions
- the invention relates to a method for reducing pesticides in animal and vegetable waxes.
- Typical animal waxes are e.g. Beeswax or wool wax; among the vegetable waxes can be found e.g. Sugarcane wax, rice wax, carnauba wax or candelilla wax, just to name a few.
- Waxes are found in a variety of different products. In the case of pharmaceutical products in particular, it is necessary and, in the case of cosmetic products, at least desirable that the waxes processed there satisfy the criteria defined in the Pharmacopoeia, i. contain as possible no harmful foreign substances.
- Sensitive products are therefore mostly made from vegetable or animal wax originating from areas where no pesticides are used.
- US2456661A describes an extraction process of crude wax with n-propyl alcohol or isopropyl alcohol, using as a minimum three times the solvent.
- JPH 06200289 A describes an extraction process of crude wax with 1-4C alcohol in the liquid state in a ratio of 1: 3-1: 30.
- E KORTA ET AL "Determination of amitraz and other acaricide residues in beeswax", ANALYTICA CHIMICA ACTA, Vol. 475, No. 1-2, January 1, 2003 (2003-01-01), pages 97-103 discloses an analytical method still pesticides can be extracted from beeswax with methanol. The process is carried out with hard (unheated) wax. To 2g wax 15ml of methanol are added. This procedure requires the use of ultrasound.
- M Fernandez ET AL "Analytical Methods for Pesticide Residue Determination in Bee Products", Journal of Food Protection, March 25, 2002 (2002-03-25), pages 1502-1511 discloses an extraction process for pesticides (including fluvalinate). First, the beeswax and a polar solvent are mixed in the liquid state. The mixture is cooled so that the wax solidifies, but the solvent remains liquid, after which the solvent is removed.
- the object of the invention is to provide a method with which the proportion of undesirable harmful substances, in particular pesticides, can be gently reduced in wax.
- the wax to be purified is dissolved and then mixed with a polar solvent, wherein the polar solvent is alcohol, and the wax is mixed with the alcohol in the ratio of 20% to 80% alcohol. which is heated to a temperature above the melting temperature of the wax. The mixture is kept at this temperature for a defined period of time. The period of time should be sufficient to allow the solvent to extract as quantitatively as possible from that contained in the wax polar solvents soluble substances.
- the mixture agitates, for example shaken or otherwise agitated.
- fragrances are extracted from eg beeswax. These accumulate in the polar solvent, usually ethanol, and can be isolated from it in the form of a so-called absolute used in the perfume industry.
- Polar solvents which can be used in the context of the invention are, in particular, alcohols. Preferably, ethanol is used. In the processing of higher melting waxes, it may also be necessary to use a higher boiling alcohol. Here, for example, Offer propanol.
- the process is suitable for the treatment of all waxes whose sources may possibly come into contact with pesticides or pesticides.
- the process exploits the insolubility of waxes in short chain alcohols such as methanol, ethanol, propanol and its isomers, butanol and its isomers.
- the method in one embodiment can proceed as follows:
- the wax to be purified is melted, mixed with alcohol at a ratio of wax to alcohol of 20% to 80%, for example, and extracted for a certain time (20 minutes-60 minutes), for example with stirring.
- the mixture is then cooled with stirring to about 8 ° C, so that the wax precipitates quantitatively. It is advantageous that it is stirred constantly, so that a pumpable wax-alcohol slurry is obtained.
- This is then filtered off in a suitable device (filter press, clarifying centrifuge).
- the recovered alcohol is recycled and fed to the rectification.
- the filter residue is melted a second time and extracted a second time with fresh alcohol in the ratio 20% wax and 80% alcohol. It will take about 20-60 min. cooled again with stirring to about 8 ° C and then filtered off.
- the filter residue is distilled alcohol-free (eg vacuum distillation) and can as wax the corresponding Applications are supplied.
- the alcohol fractions are combined and can be rectified and used again next time.
- waxes such as e.g. Beeswax, carnauba wax.
- Fluvalinate can be considered as a lead substance, i. This substance is usually always present when a pesticide wax is loaded.
- beeswax was prepared by the process according to the invention as follows: 50 g of beeswax were melted in a conical flask with reflux condenser and, after melting, 200 ml of ethanol were added. It was then 20 min. at 75-80 ° C further stirred. Thereafter, the reflux condenser was degraded and replaced with a KPG stirrer and cooled with vigorous stirring. To complete the crystallization, the wax-alcohol slurry was placed in the refrigerator at 4-8 ° C for about 60 minutes. Subsequently, the wax was separated from the ethanol via a suction filter. The wax was subjected to a second extraction as described under the above conditions. After separating wax and ethanol, the residual ethanol was evaporated or distilled off in vacuo.
- the process shows a good to very good removal of the various pesticides, in particular, the extension of the extraction time to 45 min. (compared to Example 1) has provided for an even better removal of the tau-fluvalinate.
- the process thus shows a good to very good removal of the various pesticides even with higher melting waxes.
- the starting material was contaminated with the following pesticides: DDE, o, p- 0.056 ppm DDE, p, p'- 0.024 ppm DDT (total) 0.10 ppm DDT, o, p'- 0.078 ppm Dicofol, p, p- 0.45 ppm S421 0.11 ppm Tau-fluvalinate 4.0 ppm coumaphos 1.2 ppm
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fats And Perfumes (AREA)
Description
Die Erfindung bezieht sich auf ein Verfahren zur Verringerung von Schädlingsbekämpfungsmittel in tierischen und pflanzlichen Wachsen.The invention relates to a method for reducing pesticides in animal and vegetable waxes.
Typische tierische Wachse sind z.B. Bienenwachs oder Wollwachs; unter den pflanzlichen Wachsen finden sich z.B. Zuckerrohrwachs, Reiswachs, Carnaubawachs oder Candelillawachs, um nur einige Beispiele zu nennen.Typical animal waxes are e.g. Beeswax or wool wax; among the vegetable waxes can be found e.g. Sugarcane wax, rice wax, carnauba wax or candelilla wax, just to name a few.
Wachse finden sich in einer Vielzahl von unterschiedlichen Produkten. Insbesondere bei pharmazeutischen Produkten ist es erforderlich und bei kosmetischen Produkten zumindest erwünscht, dass die dort verarbeiteten Wachse die in der Pharmakopöe festgelegten Kriterien erfüllen, d.h. möglichst keine schädlichen Fremdstoffe enthalten.Waxes are found in a variety of different products. In the case of pharmaceutical products in particular, it is necessary and, in the case of cosmetic products, at least desirable that the waxes processed there satisfy the criteria defined in the Pharmacopoeia, i. contain as possible no harmful foreign substances.
Ein wesentliches Problem in Bezug auf die Wachsreinheit stellt der Einsatz von Schädlingsbekämpfungsmitteln wie Pflanzenschutzmitteln oder Insektiziden dar. In sensiblen Produkten wird daher zumeist pflanzliches bzw. tierisches Wachs verwendet, das aus Gegenden stammt, in denen keine Schädlingsbekämpfungsmittel eingesetzt werden.A key problem in wax purity is the use of pesticides such as pesticides or insecticides. Sensitive products are therefore mostly made from vegetable or animal wax originating from areas where no pesticides are used.
Diese Strategie ist aber zunehmend schwieriger umzusetzen. Insbesondere der weltweite Vormarsch unterschiedlicher Schädlinge, wie z.B. der für das Bienensterben mitverantwortlichen Varroa-Milbe, macht einen flächendeckenden Einsatz von Schädlingsbekämpfungsmitteln erforderlich, der auch vor bislang unberührten Gebieten nicht halt macht oder halt machen wird. Man muss daher damit leben, dass in Zukunft zunehmend nur noch begrenzt pflanzliche oder tierische Wachse zur Verfügung stehen, die den Anforderungen der Pharmakopöe genügen.However, this strategy is increasingly difficult to implement. In particular, the worldwide advance of various pests, such as those for bee mortality co-responsible Varroa mite, requires a nationwide use of pesticides, which will not stop at previously untouched areas or stop. One must therefore live with the fact that in the future there will be increasingly limited vegetable or animal waxes available that meet the requirements of the pharmacopoeia.
Zukünftig wird es also zunehmend erforderlich sein, die zur Verfügung stehenden belasteten Wachse so aufzubereiten, dass sie den Reinheitsanforderungen entsprechen.In the future, it will be increasingly necessary to prepare the available contaminated waxes so that they meet the purity requirements.
Aufgabe der Erfindung ist es, ein Verfahren zu schaffen, mit dem sich der Anteil an unerwünschten schädlichen Substanzen, insbesondere Schädlingsbekämpfungsmitteln, in Wachs schonend verringern lässt.The object of the invention is to provide a method with which the proportion of undesirable harmful substances, in particular pesticides, can be gently reduced in wax.
Gelöst wird diese Aufgabe mit einem Verfahren, das die Merkmale des Anspruches 1 aufweist.This object is achieved by a method having the features of claim 1.
Erfindungsgemäß ist vorgesehen, dass das aufzureinigende Wachs gelöst und dann mit einem polaren Lösungsmittel vermischt wird, wobei das polare Lösungsmittel Alkohol ist, und das Wachs im Verhältnis von 20% zu 80% Alkohol mit dem Alkohol vermischt wird. das auf eine Temperatur oberhalb der Schmelztemperatur des Wachses erwärmt ist. Das Gemisch wird für einen definierten Zeitraum auf dieser Temperatur gehalten. Der Zeitraum sollte ausreichend sein, um dem Lösungsmittel eine möglichst quantitative Extraktion von in dem Wachs enthaltenen in polaren Lösungsmitteln löslichen Stoffen zu ermöglichen. Um den Grad der Extraktion zu verbessern, kann insbesondere vorgesehen sein, dass das Gemisch agitiert, z.B. geschüttelt oder sonstwie bewegt wird.According to the invention it is provided that the wax to be purified is dissolved and then mixed with a polar solvent, wherein the polar solvent is alcohol, and the wax is mixed with the alcohol in the ratio of 20% to 80% alcohol. which is heated to a temperature above the melting temperature of the wax. The mixture is kept at this temperature for a defined period of time. The period of time should be sufficient to allow the solvent to extract as quantitatively as possible from that contained in the wax polar solvents soluble substances. In order to improve the degree of extraction, it may be provided, in particular, that the mixture agitates, for example shaken or otherwise agitated.
Anschließend lässt man dann das Gemisch soweit abkühlen bis sich das Wachs wieder verfestigt hat und entfernt dann das flüssige polare Lösungsmittel.Then allowed to cool then the mixture until the wax has solidified again and then removes the liquid polar solvent.
Ähnliche Verfahren sind bekannt, mit denen Duftstoffe aus z.B. Bienenwachs extrahiert werden. Diese reichern sich in dem polaren Lösungsmittel, in der Regel Ethanol, an und können daraus in Form eines in der Parfümindustrie eingesetzten sogenannten Absolues isoliert werden.Similar methods are known with which fragrances are extracted from eg beeswax. These accumulate in the polar solvent, usually ethanol, and can be isolated from it in the form of a so-called absolute used in the perfume industry.
Überraschend wurde nun von der Anmelderin festgestellt, dass sich mit dem erfindungsgemäßen Verfahren auch die üblichen in dem Wachs angereicherten Schädlingsbekämpfungsmittel wie z.B. Fluvalinate, Brompropylate, DDT oder Dicofol, um nur einige Beispiele zu nennen, entfernen lassen. Dies war insbesondere deswegen überraschend, weil nicht zu erwarten war, dass die in der Regel fettlöslichen Schädlingsbekämpfungsmittel mit polaren Lösungsmitteln aus dem Wachs extrahiert werden können.Surprisingly, it has now been found by the Applicant that with the method according to the invention the usual pesticides enriched in the wax, such as e.g. Fluvalinate, Bromopropylate, DDT or Dicofol, just to name a few. This was surprising in particular because it was not to be expected that the usually fat-soluble pesticides could be extracted from the wax with polar solvents.
Im Rahmen der Erfindung einsetzbare polare Lösungsmittel sind insbesondere Alkohole. Bevorzugt wird Ethanol eingesetzt. Bei der Aufbereitung höher schmelzender Wachse kann es allerdings auch erforderlich sein, einen ebenfalls höher siedenden Alkohol einzusetzen. Hier würde sich z.B. Propanol anbieten.Polar solvents which can be used in the context of the invention are, in particular, alcohols. Preferably, ethanol is used. In the processing of higher melting waxes, it may also be necessary to use a higher boiling alcohol. Here, for example, Offer propanol.
Wie oben bereits angesprochen, eignet sich das Verfahren zur Aufbereitung aller Wachse, deren Quellen möglicherweise in Kontakt mit Pflanzenschutzmitteln oder Schädlingsbekämpfungsmitteln kommen können.As already mentioned above, the process is suitable for the treatment of all waxes whose sources may possibly come into contact with pesticides or pesticides.
Das Verfahren nutzt die Unlöslichkeit von Wachsen in kurzkettigen Alkoholen wie Methanol, Ethanol, Propanol und seine Isomere, Butanol und seine Isomere aus.The process exploits the insolubility of waxes in short chain alcohols such as methanol, ethanol, propanol and its isomers, butanol and its isomers.
Grundsätzlich kann das Verfahren in einer Ausgestaltung wie folgt ablaufen:
Das aufzureinigende Wachs wird geschmolzen, mit Alkohol versetzt im Verhältnis Wachs zu Alkohol von 20% zu 80% z.B. und eine gewisse Zeit (20 min. - 60min.) extrahiert, z.B. unter Rühren. Anschließend wird unter Rühren auf ca. 8°C abgekühlt, damit das Wachs quantitativ ausfällt. Es ist vorteilhaft, dass dabei konstant gerührt wird, damit eine pumpfähige Wachs-Alkoholaufschlämmung erhalten wird. Diese wird dann in einer geeigneten Vorrichtung (Filterpresse, Klärzentrifuge) abfiltriert. Dabei wird der gewonnene Alkohol wieder verwertet und der Rektifikation zugeführt. Der Filterrückstand wird ein zweites Mal aufgeschmolzen und wird ein zweites Mal mit frischem Alkohol im Verhältnis 20% Wachs und 80% Alkohol extrahiert. Es wird nach ca. 20-60 min. wieder unter Rühren auf ca. 8°C gekühlt und anschließend abfiltriert. Der Filterrückstand wird alkoholfrei destilliert (z.B. Vakuumdestillation) und kann als Wachs den entsprechenden Anwendungen zugeführt werden. Die Alkoholfraktionen werden vereinigt und können rektifiziert werden und können damit beim nächsten Mal wieder verwendet werden.In principle, the method in one embodiment can proceed as follows:
The wax to be purified is melted, mixed with alcohol at a ratio of wax to alcohol of 20% to 80%, for example, and extracted for a certain time (20 minutes-60 minutes), for example with stirring. The mixture is then cooled with stirring to about 8 ° C, so that the wax precipitates quantitatively. It is advantageous that it is stirred constantly, so that a pumpable wax-alcohol slurry is obtained. This is then filtered off in a suitable device (filter press, clarifying centrifuge). The recovered alcohol is recycled and fed to the rectification. The filter residue is melted a second time and extracted a second time with fresh alcohol in the ratio 20% wax and 80% alcohol. It will take about 20-60 min. cooled again with stirring to about 8 ° C and then filtered off. The filter residue is distilled alcohol-free (eg vacuum distillation) and can as wax the corresponding Applications are supplied. The alcohol fractions are combined and can be rectified and used again next time.
Besonders angesprochen im Rahmen der Erfindung sind Wachse wie z.B. Bienenwachs, Carnaubawachs.Particularly addressed within the scope of the invention are waxes such as e.g. Beeswax, carnauba wax.
Im Folgenden soll die Erfindung anhand einiger Beispiele näher erläutert werden.In the following, the invention will be explained in more detail with reference to some examples.
Aus einer Charge Bienenwachs wurden circa 20g Probematerial genommen und darin nach gängigen Methoden der Gehalt an Fluvalinat bestimmt. Fluvalinat kann als Leitsubstanz betrachtet werden, d.h. diese Substanz ist bei Belastung eines Wachses mit Schädlingsbekämpfungsmitteln in der Regel immer präsent.From a batch of beeswax about 20g of sample material were taken and determined therein by conventional methods, the content of fluvalinate. Fluvalinate can be considered as a lead substance, i. This substance is usually always present when a pesticide wax is loaded.
Das Ergebnis betrug 3,2mg/kg und liegt damit deutlich über dem in der Pharmakopöe vorgeschriebenen Grenzwert von 0,05mg/kg.The result was 3.2mg / kg, well above the Pharmacopoeia limit of 0.05mg / kg.
Aus derselben Charge wurde Bienenwachs nach dem erfindungsgemäßen Verfahren wie folgt aufbereitet:
Es wurden 50g Bienenwachs in einem Erlenmeierkolben mit Rückflusskühler geschmolzen und nach dem Aufschmelzen mit 200ml Ethanol versetzt. Es wurde anschließend 20 min. bei 75-80°C weitergerührt. Danach wurde der Rückflusskühler abgebaut und durch einen KPG-Rührer ersetzt und es wurde unter kräftigem Rühren abgekühlt. Zur Vervollständigung der Kristallisation wurde die Wachs-AlkoholAufschlämmung für ca. 60 min in den Kühlschrank bei 4-8 °C gestellt. Anschließend wurde über eine Filternutsche das Wachs vom Ethanol angetrennt. Das Wachs wurde wie unter den obigen Bedingungen beschrieben einer zweiten Extraktion unterworfen. Nach dem Trennen von Wachs und Ethanol wurde der Restethanol abgedampft oder im Vakuum abdestilliert.From the same batch beeswax was prepared by the process according to the invention as follows:
50 g of beeswax were melted in a conical flask with reflux condenser and, after melting, 200 ml of ethanol were added. It was then 20 min. at 75-80 ° C further stirred. Thereafter, the reflux condenser was degraded and replaced with a KPG stirrer and cooled with vigorous stirring. To complete the crystallization, the wax-alcohol slurry was placed in the refrigerator at 4-8 ° C for about 60 minutes. Subsequently, the wax was separated from the ethanol via a suction filter. The wax was subjected to a second extraction as described under the above conditions. After separating wax and ethanol, the residual ethanol was evaporated or distilled off in vacuo.
Es wurde dann wiederum der Gehalt an Fluvalinat bestimmt, der nun 0,6 mg/kg betrug. Das aufbereitete Wachs war damit deutlich geringer belastet als das nicht behandelte Ausgangsmaterial. Der Wert liegt zwar nach wie vor über dem Grenzwert. Allerdings handelte es sich hier nur um ein Experiment mit dem grundsätzlich die Eignung des Verfahrens zur Entfernung von Fluvalinat und gezeigt werden sollte.In turn, the content of fluvalinate was determined, which was now 0.6 mg / kg. The processed wax was thus significantly less stressed than the untreated starting material. The value is still above the limit. Indeed this was just an experiment that basically demonstrated the suitability of the process for the removal of fluvalinate.
In weiteren Beispielen wird gezeigt, dass sich mit dem erfindungsgemäßen Verfahren noch höhere Reinheitsgrade erreichen lassen.In further examples, it is shown that even higher degrees of purity can be achieved with the method according to the invention.
Hier sollte gezeigt werden, dass und wie sich verschiedene Pestizidtypen mit dem erfindungsgemäßen Verfahren entfernen lassen. Dazu wurde ein unbelastetes Bienenwachs mit folgenden Pestiziden in den jeweiligen Konzentrationen versehen:
- Lindan: 0,36 ppm
- a-HCH: 0,32 ppm
- 2,4'- DDT: 0,36 ppm
- Coumaphos: 2,00 ppm
- Brompropylat: 2,16 ppm
- tau-Fluvalinat: 2,16 ppm
- Lindane: 0.36 ppm
- a-HCH: 0.32 ppm
- 2,4'-DDT: 0.36 ppm
- Coumaphos: 2.00 ppm
- Bromopropylate: 2.16 ppm
- tau-fluvalinate: 2.16 ppm
Es wurden 50g derart dotiertes Bienenwachs in einem Erlenmeierkolben mit Rückflusskühler geschmolzen und nach dem Aufschmelzen mit 200ml Ethanol versetzt. Es wurde anschließend 45 min bei 75-80°C weitergerührt. Danach wurde der Rückflusskühler abgebaut und durch einen KPG-Rührer ersetzt und es wurde unter kräftigem Rühren abgekühlt. Zur Vervollständigung der Kristallisation wurde die Wachs-Alkohol-Aufschlämmung für ca. 60 min. in den Kühlschrank bei 4-8 °C gestellt. Anschließend wird über eine Filternutsche das Wachs vom Ethanol angetrennt. Das Wachs wurde wie unter den obigen Bedingungen beschrieben einer zweiten Extraktion unterworfen. Nach dem Trennen von Wachs und Ethanol wurde der Restethanol abgedampft oder im Vakuum abdestilliert.50 g of beeswax doped in this way were melted in an Erlenmeyer flask with reflux condenser and, after melting, 200 ml of ethanol were added. It was then further stirred at 75-80 ° C for 45 min. Thereafter, the reflux condenser was degraded and replaced with a KPG stirrer and cooled with vigorous stirring. To complete the crystallization, the wax-alcohol slurry was dried for about 60 minutes. placed in the refrigerator at 4-8 ° C. Subsequently, the wax is separated from the ethanol via a suction filter. The wax was subjected to a second extraction as described under the above conditions. After separating wax and ethanol, the residual ethanol was evaporated or distilled off in vacuo.
Die anschließende Pestizidanalyse zeigte folgendes Ergebnis:
- Lindan: 0,01 ppm
- a-HCH: 0,01 ppm
- 2,4'- DDT: < 0,01 ppm
- Coumaphos: < 0,03 ppm
- Brompropylat: < 0,1 ppm
- tau-Fluvalinat: < 0,1 ppm
- Lindane: 0.01 ppm
- a-HCH: 0.01 ppm
- 2,4'-DDT: <0.01 ppm
- Coumaphos: <0.03 ppm
- Bromopropylate: <0.1 ppm
- tau-fluvalinate: <0.1 ppm
Das Verfahren zeigt also eine gute bis sehr gute Entfernung der verschiedenen Pestizide, wobei insbesondere die Verlängerung der Extraktionszeit auf 45 min. (gegenüber dem Beispiel 1) für eine noch bessere Entfernung des tau-Fluvalinats gesorgt hat.Thus, the process shows a good to very good removal of the various pesticides, in particular, the extension of the extraction time to 45 min. (compared to Example 1) has provided for an even better removal of the tau-fluvalinate.
Hier soll gezeigt werden, dass das Verfahren auch für höher schmelzende Wachse anwendbar ist.Here it should be shown that the method is also applicable to higher melting waxes.
Dazu wurde ein unbelastetes Sonnenblumenwachs mit folgenden Pestiziden in den jeweiligen Konzentrationen versehen:
- Lindan: 0,85 ppm
- a-HCH: 0,46 ppm
- 2,4'- DDT: 0,50 ppm
- Coumaphos: 3,00 ppm
- Brompropylat: 3,50 ppm
- tau-Fluvalinat: 3,10 ppm
- Lindane: 0.85 ppm
- a-HCH: 0.46 ppm
- 2,4'-DDT: 0.50 ppm
- Coumaphos: 3.00 ppm
- Bromopropylate: 3.50 ppm
- tau-fluvalinate: 3.10 ppm
Es wurden 50g derart dotiertes Sonnenblumenwachs in einem Erlenmeierkolben mit Rückflusskühler geschmolzen und nach dem Aufschmelzen mit 200 ml Ethanol versetzt. Es wurde anschließend 45 min bei 75-80°C weitergerührt. Danach wurde der Rückflusskühler abgebaut und durch einen KPG-Rührer ersetzt und es wurde unter kräftigem Rühren abgekühlt. Zur Vervollständigung der Kristallisation wurde die Wachs-Alkohol-Aufschlämmung für ca. 60 min. in den Kühlschrank bei 4-8 °C gestellt. Anschließend wurde über eine Filternutsche das Wachs vom Ethanol angetrennt. Das Wachs wurde wie unter den obigen Bedingungen beschrieben einer zweiten Extraktion unterworfen. Nach dem Trennen von Wachs und Ethanol wurde der Restethanol abgedampft oder im Vakuum abdestilliert.50 g of sunflower wax doped in this way were melted in an Erlenmeyer flask with reflux condenser and 200 ml of ethanol were added after melting. It was then further stirred at 75-80 ° C for 45 min. Thereafter, the reflux condenser was degraded and replaced with a KPG stirrer and cooled with vigorous stirring. To complete the crystallization, the wax-alcohol slurry was dried for about 60 minutes. placed in the refrigerator at 4-8 ° C. Subsequently, the wax was separated from the ethanol via a suction filter. The wax was subjected to a second extraction as described under the above conditions. After separating wax and ethanol, the residual ethanol was evaporated or distilled off in vacuo.
Die anschließende Pestizidanalyse zeigte folgendes Ergebnis:
- Lindan: 0,07 ppm
- a-HCH: 0,04 ppm
- 2,4'- DDT: < 0,01 ppm
- Coumaphos: < 0,03 ppm
- Brompropylat: 0,2 ppm
- tau-Fluvalinat: 0,2 ppm
- Lindane: 0.07 ppm
- a-HCH: 0.04 ppm
- 2,4'-DDT: <0.01 ppm
- Coumaphos: <0.03 ppm
- Bromopropylate: 0.2 ppm
- tau-fluvalinate: 0.2 ppm
Das Verfahren zeigt also auch bei höher schmelzenden Wachsen eine gute bis sehr gute Entfernung der verschiedenen Pestizide.The process thus shows a good to very good removal of the various pesticides even with higher melting waxes.
Dazu wurden 50 g gesprühtes Bienenwachs mit einer Teilchengröße von ca. 300µm mit 250 g Ethanol versetzt und es wurde eine Temperatur von 40°C eingestellt. Anschließend wurde bei dieser Temperatur 45 min. gerührt. Nach dem Abfiltrieren wurde der Filterrückstand erneut mit 250 g Ethanol versetzt und es wurde wieder eine Temperatur von 40°C eingestellt. Anschließend wurde bei dieser Temperatur 45 min. gerührt. Nach dem Abfiltrieren wurde der Rückstand bei 80-90°C vom restlichen Ethanol befreit.For this purpose, 50 g of sprayed beeswax having a particle size of about 300 .mu.m were admixed with 250 g of ethanol and a temperature of 40.degree. C. was set. Subsequently, at this temperature for 45 min. touched. After filtration, the filter residue was added again with 250 g of ethanol and it was again set to a temperature of 40 ° C. Subsequently, at this temperature for 45 min. touched. After filtration, the residue was freed from the remaining ethanol at 80-90 ° C.
Mit folgenden Pestiziden war das Ausgangsmaterial belastet:
Nach der Extraktion wurden folgende Werte ermittelt:
Die Kaltextraktion mit Ethanol zeigt bei allen Pestiziden eine deutliche Reduktion, die teilweise sogar bis unter die Nachweisgrenze geht.The cold extraction with ethanol shows a significant reduction in all pesticides, which in some cases even goes below the detection limit.
Claims (11)
- Method for reducing the amount of pesticides in animal and plant waxes, in which the wax, in liquid state, is mixed for a defined period of time with a polar solvent that has been heated to a temperature above the melting temperature of the wax, and the mixture is then cooled appropriately such that the wax solidifies while the solvent remains liquid, and the solvent is then removed, whereby the polar solvent is alcohol and the wax is mixed with the alcohol at a ratio of 20% wax to 80% alcohol.
- Method according to claim 1, characterised in that the solvent is alcohol, in particular ethanol or propanol or isomers thereof.
- Method according to any one of the claims 1 or 2, characterised in that the wax to be treated is beeswax, rice wax or carnauba wax.
- Method according to any one of the claims 1 to 3, whereby the mixture is being cooled to approximately 8°C while stirring after the mixing.
- Use of a polar solvent for reducing the amount of pesticides in wax, in which the wax, in liquid state, is mixed for a defined period of time with the polar solvent that has been heated to a temperature above the melting temperature of the wax, and the mixture is then cooled appropriately such that the wax solidifies while the solvent remains liquid, and the solvent is then removed.
- Use according to claim 5, whereby the pesticide is a fat-soluble pesticide.
- Use according to any one of the claims 5 to 6, whereby the pesticide is fluvalinate, bromopropylate, DDT or dicofol.
- Use according to claim 7, whereby the pesticide is a fluvalinate.
- Use according to any one of the claims 5 to 8, whereby the wax to be treated is beeswax, rice wax or carnauba wax.
- Use according to claim 9, whereby the wax to be treated is beeswax.
- Use according to any one of the claims 5 to 10, whereby the solvent is alcohol, preferably ethanol or propanol or isomers thereof.
Applications Claiming Priority (1)
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DE102014005404.7A DE102014005404A1 (en) | 2014-04-14 | 2014-04-14 | Process for the preparation of animal and vegetable waxes |
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EP2933322B1 true EP2933322B1 (en) | 2018-11-07 |
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EP15000877.9A Active EP2933322B1 (en) | 2014-04-14 | 2015-03-25 | Method for the treatment of animal and vegetable waxes |
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DE (1) | DE102014005404A1 (en) |
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ES2834658A1 (en) * | 2019-12-18 | 2021-06-18 | Univ Almeria | Beeswax Contaminant Removal Procedure (Machine-translation by Google Translate, not legally binding) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH06200289A (en) * | 1992-12-28 | 1994-07-19 | Nippon Petrochem Co Ltd | Method for purifying natural crude wax |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
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US1194014A (en) * | 1916-08-08 | Methob oe beeiming wool-gbease | ||
US2456661A (en) * | 1947-11-05 | 1948-12-21 | Johnson & Son Inc S C | Cane wax production |
GB675001A (en) * | 1949-04-05 | 1952-07-02 | Christian Missions Foundation | Improved sisal wax and method of producing the same |
GB1510421A (en) * | 1976-02-05 | 1978-05-10 | Woolcombers Ltd | Lanolin and more particularly to a process for the production of lanolin rendered hypoallergenic |
JPH02284996A (en) * | 1989-04-26 | 1990-11-22 | Kurooda Japan Kk | Purification of lanolin |
JPH06200287A (en) * | 1992-12-28 | 1994-07-19 | Nippon Petrochem Co Ltd | Method for purifying natural crude wax |
JPH0711286A (en) * | 1993-06-25 | 1995-01-13 | Nisshin Oil Mills Ltd:The | Method for purifying carnauba wax |
JPH0711285A (en) * | 1993-06-25 | 1995-01-13 | Nisshin Oil Mills Ltd:The | Method for purifying vegetable wax |
JPH0711284A (en) * | 1993-06-25 | 1995-01-13 | Nisshin Oil Mills Ltd:The | Method for extracting sugar cane wax composition |
AUPO605097A0 (en) * | 1997-04-07 | 1997-05-01 | James Cook University Of North Queensland | Food grade wax and process for preparing same |
-
2014
- 2014-04-14 DE DE102014005404.7A patent/DE102014005404A1/en not_active Withdrawn
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2015
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Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06200289A (en) * | 1992-12-28 | 1994-07-19 | Nippon Petrochem Co Ltd | Method for purifying natural crude wax |
Non-Patent Citations (3)
Title |
---|
"Purification of natural crude wax,ensuring effective removal of undesiredingredients", WPI/DERWENT, 19 July 1994 (1994-07-19), XP002962011 * |
E KORTA ET AL: "Determination of amitraz and other acaricide residues in beeswax", ANALYTICA CHIMICA ACTA, vol. 475, no. 1-2, 1 January 2003 (2003-01-01), AMSTERDAM, NL, pages 97 - 103, XP055351394, ISSN: 0003-2670, DOI: 10.1016/S0003-2670(02)01221-7 * |
M FERNANDEZ ET AL: "Analytical Methods for Pesticide Residue Determination in Bee Products", JOURNAL OF FOOD PROTECTION, 25 March 2002 (2002-03-25), pages 1502 - 1511, XP055351162, Retrieved from the Internet <URL:http://jfoodprotection.org/doi/pdf/10.4315/0362-028X-65.9.1502> [retrieved on 20170302] * |
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