CA2833808A1 - A process for decreasing environmental pollutants in an oil or a fat, a volatile environmental pollutants decreasing working fluid, a health supplement, and an animal feed product - Google Patents

Abstract

The invention relates to a process for decreasing the amount of environmental pollutants in a mixture comprising a fat or an oil, being edible or for use in cosmetics, the fat or oil containing the environmental pollutants, which process comprises the steps of adding a volatile working fluid to the mixture, where the volatile working fluid comprises at least one of a fatty acid ester, a fatty acid amide, a free fatty acid and a hydro-carbon, and subjecting the mixture with the added volatile working fluid to at least one stripping processing step, in which an amount of environmental pollutant pre-sent in the fat or oil, being edible or for use in cosmetics, is separated from the mixture together with the volatile working fluid. The present invention also relates to a volatile environmental pollutants decreasing working fluid, for use in decreasing an amount of environmental pollutants present in a fat or oil, being edible or for use in cosmetics. In addition, the present invention relates to a health supplement, a pharmaceutical and an animal feed product prepared according to the process mentioned above.

Description

A PROCESS FOR DECREASING ENVIRONMENTAL POLLUTANTS IN
AN OIL OR A FAT, A VOLATILE ENVIRONMENTAL POLLUTANTS DE-CREASING WORKING FLUID, A HEALTH SUPPLEMENT, AND AN ANI-MAL FEED PRODUCT
TECHNICAL FIELD OF THE INVENTION
This invention relates to a process for decreasing the amount of environmental pollutants in a mixture corn-prising a fat or an oil, being edible or for use in cos-metics. The present invention also relates to a volatile environmental pollutants decreasing working fluid. In ad-dition, the present invention relates to a health supple-ment, a pharmaceutical, a cosmetic product and an animal feed product prepared according to the process mentioned above.
BACKGROUND OF THE INVENTION
DDT (2,2 bis-(p-chloropheny1)-1,1,1-trichloroethane) and its degradation products are today found almost eve-rywhere in the global environment. Numerous studies also report on the accumulation of often relatively high con-centrations of environmental pollutants like PCB, dioxins and brominated flame retardants, and pesticides like toxaphenes and DDT and its metabolites in the deposit of e.g. marine organisms. The hazard of these compounds for both humans and animals have caused a growing Concern about the content of toxic substances in food and food stuff. Consumption of dioxins above safe levels over a lifetime may result in an increased risk of cancer.
Food products that have no or reduced amounts of pollutants are gaining popularity as well as an increas-ing share of the market. Consequently, removal or reduc-tion of pollutants in food products have the potential to substantially increase marketability and value.
The commercially important polyunsaturated fatty ac-ids in marine oils, such as fish oil, are preferably EPA
(eicosapentaenoic acid, C20:5n-3) and DHA (docOsahex-aenoio acid, C22:6n-3). The full nomenclature of these acids according to the IUPAC system is: EPA all-cis-5,8,11,14,17-eicosapentaenoic acid, DHA all-cis-4,7,10,13,15,19-docosahexaenoic acid. For many purposes it is necessary that the marine oils should be refined in order to increase the content of EPA and/or DHA to suit-able levels, or to reduce the concentrations of, or even eliminate, certain other substances which occur naturally in the raw oil.
The fatty acids EPA and DHA are also proving in-creasingly valuable in the pharmaceutical and food sup-plement industries in particular. it is also very impor-tant for fish oils and other temperature sensitive oils (e.g. oils that contain long chain polyunsaturated fatty acids) to keep the temperature in some of the processes as low as possible.
The demand for marine oils of high quality is in-creasing. This issue forces the fish oil industry to con-sider use of alternative refining techniques for fish oils with inferior quality, i.e. oils with high amounts of free fatty acids that make the oils less useful for nutritional purposes and make traditional alkaline refin-ing more complicated and costly. If environmental pollut-ants can be successfully removed from such fish oils they are appropriate for use in the animal feed industry, e.g.
= in animal feed products.
From the literature it is known that molecular dis-tillation, or short path distillation as the technique alternatively may be named, can be used to remove the pesticides DDT and its metabolites from fish oil (K. Julshamn, L. Karlsen and O.R. Sraekkan, Removal of DDT and its metabolites from fish oils by molecular dis-tillation, Fiskeridirektoratets skrifter; Serie teknolo-giske undersekelser, Vol. 5 No.15 (1973)). A practical upper limit was 65% removal together with a loss of about 25% of vitamin A. In many industrial fish oil refining processes a removal of DDT up to 65% is not satisfactory.
Anthony P. Bimbo: Guidelines for characterization of food-grade fish oil. INFORM 9(5), 473-483 (1998), re-ported that vacuum stripping or thin-film distillation can be used to remove chlorinated hydrocarbons and free fatty acids from fats or oils. A disadvantage by using vacuum stripping to refine oils is that sufficient re-sults only can be achieved then the vacuum stripping process is carried out at a high temperature. Further, the high temperature gives rise to undesirable side reac-tions.
Jiri Cmolik og Jan Pokorny: Physical refining of edible oils, Eur. J. Lipid Sci. Technol. 102(7), 472-486 (2000) describes physical refining of edible oils and the use of molecular distillation for removal of undesirable substances in crude oils, preferably crude vegetable oils, respectively the use of steam stripping in order to remove free fatty acids from an oil composition. Physical refining is used to refine oils of good quality, i.e.
oils with small amounts of free fatty acids. However, physical refining is more complicated and costly for oils with inferior quality.
In WO 9524459 a process for treating an oil composi-tion containing saturated and unsaturated fatty acids in the form of triglycerides, in order to obtain a refined product with higher concentrations of the polyunsaturated fatty acids, is presented. This process also is intended to be used for removal of some environmental pollutants from an oil composition, wherein the process comprises the steps of; subjecting the oil composition to a trans-esterification reaction and thereafter subjecting the product obtained in the first step to one or more molecu-lar distillations. This technique has the severe limits-tion that it can only be used for fish oils that have been partially transesterified using a lipase catalyst that discriminates against omega-3 fatty acids. Obvi-ously, this technique can not be used for commercial fish oils.
In EP0632267 Al a method of measuring the content of polycyclic aromatic hydrocarbons(PAH) remaining it .lano-lin is presented. The European patent document also de-scribes a method of removing PAH remaining in wool grease or lanolin by a vacuum distillation of the grease or lanolin under specified conditions either directly or af-ter having been treated with a borate and, if necessary, obtaining various lanolin derivatives from the treated wool grease or lanolin. However, the technique described in said patent document requires very high temperatures (230 C) in order to achieve 90% reduction in PA H content.
Another interesting observation is that the removal of environmental pollutants from fats or oils is not a trivial matter. Several different techniques, some of which are mentioned above, to accomplish this task have been developed, but none of them is sufficiently effet-tive and gentle to the fat or oil. In addition, it is nowadays a problem for e.g. the marine oil industry that the amounts of pollutants in e.g. fish oil become in-creased.
SUMMARY OF THE INVENTION
One object of the present invention is to offer an effective process for decreasing the amount of environ-mental pollutants in a fat or an oil, being edible or for use in cosmetics.
According to a first aspect of the invention, this and other objects are achieved with a process for de-creasing the amount of environmental pollutants in a mix-ture comprising a fat or an oil, being edible or for use in cosmetics, the fat or oil containing the environmental pollutants, which process comprises the steps of adding a volatile working fluid to the mixture, where the volatile working fluid comprises at least one of a fatty acid es-ter, a fatty acid amide, a free fatty acid and a hydro-carbon, and subjecting the mixture with the added vola-tile working fluid to at least one stripping processing step, in which an amount of environmental pollutants pre-sent in the fat or oil, being edible or for use in cos-metics, is separated from the mixture together with the volatile working fluid. Herein, "an amount" is inter-preted to include decreasing of an amount up to 95-99% of some environmental pollutants, i.e. a substantial removal of specific pollutants and/or toxic components from a fat or oil composition.
The use of a volatile working fluid in a stripping process for decreasing an amount of environmental pollut-ants in a mixture comprising a fat or an oil, being edi-ble or for use in cosmetics, containing the environmental pollutants, and/or toxic components, has a number of ad-vantages.
An advantage of using a volatile working fluid in a process comprising at least one stripping processing step is that an amount of environmental pollutants in the mix-ture can more easily be stripped off together with the volatile working fluid, i.e. the environmental pollutants present in the fat or oil mixture is separated from the mixture together with the working fluid. Preferably this is possible as long as the volatile working fluid is es-sentially equally or less volatile than the environmental pollutants that is to be removed from the fat or oil mix-ture. The stripped pollutants (components) and most of the volatile working fluid will be found in the distil-late.
In addition, the use of a volatile working fluid comprising at least one of a fatty acid ester, a fatty acid amide, a free fatty acid and a hydrocarbon in at least one stripping process step results in that use of the inventive process decreases the amount of dioxins in a fish oil with more than 95%. By using the inventive process it is also possible to decrease the amount of chlorinated organic pesticides (or pollutants) in a mix-ture comprising a fat or an oil, being edible or for use in cosmetics, which pollutants are even less volatile than DDT, for instance dioxines, toxaphenes and/or PCB.
Separation of such heavy and undesirable components from the fat or oil mixture according to the invention, using mild conditions that do not decompose even very unsatu-rated oils, is surprising. Further, according to the pre-sent stripping process it is possible to decrease an ef-fective amount of PAH at much lower temperatures compared to the techniques known from the prior art.
Another advantage of adding a volatile working fluid to an oil or fat mixture prior to a stripping process is that removal of free fatty acids is facilitated, which will result in a higher quality of the oil product.
In addition, the Volatile working fluid according to the invention allows environmental pollutants or other toxic components to be stripped off by e.g. molecular distillation even from oils of lower quality, i.e. oil for feed purposes. Further, the process according to the invention can also be used for decreasing the amount of toxic compounds in a ricinus oil, preferably trace of ricinine (1,2-dihydro-4-methoxy-1-methyl-2-oxo-3-pyridinecarbonitrile). By using the process according to the invention the amount of ricinine may be decreased with at least 80-90 %, In a preferred embodiment of the present invention the volatile working fluid is an organic solvent or sol-vent mixture or a composition with a suitable volatility.
The volatile working fluid of the present invention is at least one of a fatty acid ester, a fatty acid amide, a free fatty acid, bio-diesel and a hydrocarbon, also in-cluding any combinations thereof.

In another preferred embodiment the volatile working fluid comprises at least one fatty acid ester composed of C10-C22 fatty acids and Cl-C4 alcohols, or a combination of two or more fatty acid ester each composed of C10-C22 fatty acids and C1-C4 alcohols. Preferably, the volatile working fluid is at least one of amides composed of C10-C22 fatty acids and Cl-C4 amines, C10-C22 free fatty ac-ids, and hydrocarbons with a total number of carbon atoms from 10 to 40. Most preferably, the volatile working fluid is a mixture of fatty acids from marine oils, e.g.
fish body oil and/or fish liver oil, and/or ethyl or methyl esters of such marine fatty acids.
In another preferred embodiment of the process the volatile working fluid is constituted by free fatty acids comprised in the fat or oil, being edible or for use in cosmetics, containing the environmental pollutants, i.e.
the fat or oil itself contains free fatty acids. Here, the free fatty acids in the oil or fat acts as the vola-tile working fluid. Further, free fatty acids in an oil or fat also can contribute to an additive effect in a stripping process by partially acting as an internal working fluid (or by being an active part of the working fluid) in the process. Such oils or fats mentioned above could e.g. be silage oils or oils that have been stored or transported for a long period of time. This means that a volatile working fluid can be added to an oil or fat mixture prior to a stripping process and/or being com-prised in the fat or oil mixture containing the environ-mental pollutants or toxic components. In this way, the invention surprisingly is very efficient for purifying oils that normally are classified as oils of low quality.
In another preferred embodiment of the stripping process, the volatile working fluid is constituted by free fatty acids comprised in a mixture of at least a ma-rine oil, e.g. a fish oil, with a high content of free fatty acids (a low quality marine oil), wherein the free fatty acids in the oil mixture acts as a working fluid.
Further, it is hereby possible to decrease the amount of environmental pollutants and to reduce the amount of free fatty acids in the marine oil at the same time and in the same process.
In another preferred embodiment of the process, the fatty acid esters, fatty acid amides and free fatty acids are obtained from at least one of vegetable, microbial and animal fat or oil. The fatty acid esters mentioned above can e.g. be a by- product from distillation of an ethyl ester mixture prepared by ethylation of preferably a fish oil. In the process industry trade with intermedi-ates is increasing and opens up for an extra financial 'income.
In another preferred embodiment the volatile working fluid is obtained from at least one of animal fat or oil, wherein the animal fat or oil preferably is a marine oil e.g. a fish oil or an oil from other marine organism e.g.
sea mammals.
Further, in another preferred embodiment of the in-vention the fat or oil, being edible or for use in cos-metics, is obtained from at least one of vegetable, mi-crobial and animal fat or oil, or any combination thereof. Preferably, the fat or oil, being edible or for use in cosmetics, is a marine oil. Marine oils that have no or reduced amounts of environmental pollutants are gaining popularity as well as an increasing share of the market. Consequently, removal or reduction of pollutants in e.g. fish oils of high quality as well as fish oils with inferior quality have the potential to substantially increase marketability and value. Therefore, in a more preferred embodiment of the invention the marine oil is obtained from fish or sea mammals, containing at least saturated and unsaturated fatty acids in the form of triglycerides. It is important to note that the invention is not limited to procedures were the working fluid is prepared from the same origin as the oil that is being purified.
Additionally, the fat or oil, being edible or for use in cosmetics, may also be a ricinus oil for use in cosmetics or medicinal applications. It is also of com-mercial interest to decrease the amount of pollutants or toxic components in oil mixtures or blends comprising at least one microbial oil that e.g. will be used in food products or as food supplement (e.g. infant formula) preferable suitable for humans.
In another preferred embodiment of the invention the fat or oil, being edible or for use in cosmetics, is a tocopherol concentrate prepared from a condensate from at least one deodorization process of at least one vegetable oil, wherein the tocopherol concentrate containing at least one of PAH and volatile pollutants, or any combina-tion thereof. Commercially available tocopherol concen-trate contains about 65-90% tocopherol and it will be ap-parent for one skilled in the art that the stripping process according to the invention may be used to sepa-rate an amount of environmental pollutants from a toco-pherol concentrate.
In a preferred embodiment of the invention, the ra-tio of (volatile working fluid):(fat or oil, being edible or for use in cosmetics) is about 1:100 to 15:100. In a more preferred embodiment the ratio of (volatile working fluid) (fat or oil, being edible or for use in cosmetics) is about 3:100 to 8:100.
In a preferred embodiment of the invention, said stripping process step is carried out at temperatures in the interval of 120-270 C.
In a most preferred embodiment, the stripping proc-essing step is carried out at temperatures in the inter-val of 150-200 C. By adding a volatile working fluid to the fat or oil mixture at this temperatures the invention surprisingly shows that even termolabile polyunsaturated oils can be treated with good effect, without causing degradation of the quality of the oil.
In another preferred embodiment, the stripping proc-essing step is carried out at a pressure below 1 mbar.

5 In another preferred embodiment, the stripping proc-essing step is at least one of a thin-film evaporation process, a molecular distillation or a short-path distil-lation, or any combination thereof. If at least one stripping process step is a thin-film evaporation the 10 process is also carried out at mixture flow rates in the range of 10-300 kg/h*m2, preferably 40-150 kg/h-m2. By us-ing a stripping process, e.g. a distillation method, for decreasing the amount of environmental pollutants in a fat or oil mixture comprising a volatile working fluid it is possible to carry out the stripping processes at lower temperatures, which spare the oil and is at the same time favourable to the end oil product.
In a preferred embodiment of the invention, the volatile working fluid is stripped off together with the environmental pollutants by at least one short-path dis-tillation or molecular distillation step. This is possi-ble as long as the volatile working fluid is essentially equally or less volatile than the environmental pollut-ants that are to be separated from the fat or oil mix-ture.
In another preferred embodiment of the invention, the process allows the environmental pollutants to flash off most effective at process conditions of low tempera-tures and preferable high mixture flow rates. Further, this embodiment offers similar advantages as described above by using the volatile working fluid.
In a preferred embodiment according to the invention the stripping process is carried out by a molecular dis-tillation in the following intervals; mixture flow rates in the interval of 10-300 kg/h-m2, temperatures in the interval of 120-270 *C and a pressure below 1 mbar.

In a most preferred embodiment of the invention the molecular distillation is carried out at temperatures in the interval of 150-20e and at a pressure below 0,05 mbar.
In a further preferred process of the present inven-tion, said process is a thin-film process that is carried out at 40-150 kg/tom2 or at flow rates in the range of 400-1200 kg/h at a heated thin film area of 11 m2; 36-109 kgRom2. Please note, that the present invention can also be carried out in one or more subsequent stripping processing steps.
In another preferred embodiment of the present in-vention, for use in decreasing an amount of environmental pollutants and/or toxic components, Such as dioxins and/or PCB, present in a fat or oil, being edible or for use in cosmetics, the working fluid is comprising at least one of a fatty acid ester, a fatty acid amide, a free fatty acid and a hydrocarbon with essentially equally or less volatility compared to the environmental pollutants that are to be separated from the fat or oil mixture, or any combination thereof.
Preferably, the Volatile environmental pollutants decreasing working fluid is generated as a fractionation product. Additionally, the volatile environmental pollut-ants decreasing working fluid is a by-product, such as a distillation fraction, from a regular process for produc-tion of ethyl and/or methyl ester concentrates. This by-product according to the invention can be used in a new process for decreasing the amount of environmental poi-lutants in a fat or an oil. More preferably, the volatile environmental pollutants decreasing working fluid, for use in decreasing an amount of environmental and/or toxic components, present in a fat or oil, can be a by-product (a distillate fraction) from a regular process for pro-duction of ethyl ester concentrates, wherein a mixture comprising an edible or a non-edible fat or oil, prefera-bly a fish oil, is subjected to an ethylating process and preferably a two-step molecular distillation. In the two-step molecular distillation process a mixture consisting of many fatty acids on ethyl ester form is separated from each other in; a volatile (light fraction), a heavy (re-siduum fraction) and a product fraction. The volatile fraction from the first distillation is distilled once more and the volatile fraction from the second distilla-tion process is then at least composed of the volatile working fluid, preferably a fatty acid ethyl ester frac-tion. This fraction consists of at least one of C14 and C16 fatty acids and at least one of the C18 fatty acids from the fat or oil, and is therefore also compatible with the edible or non-edible oil. The fraction can be redistilled one or more times if that is deemed to be su-itable. This prepared working fluid can then be used as a working fluid in a new process for decreasing the amount of environmental pollutants in a fat or an oil, wherein the edible or non-edible fats or oils and the oil or fat, being edible or for use in cosmetics, are of the same or different types.
In another embodiment of the invention a volatile working fluid may be produced by subjecting fats or oils from an available source, for instance fats or oils ob-tained from at least one of animal, microbial or vegeta-ble origin, to an inter-esterification process, in which process the triglycerides in the fats or oils are con-verted into esters of aliphatic alcohols. Additionally, a bio-diesel and/or a mineral oil can be used as a volatile working fluid. In the case when the volatile working fluid is a biodiesel, it can be produced by a process, which is in common use for production of engine fuels (biodiesel), and therefore also known by a man skilled in the art, which process comprises mixing the fat or oil with a suitable amount of aliphatic alcohol, adding a suitable catalyst and heating the mixture for a period of time. Similar esters of aliphatic alcohols may also be produced by a high-temperature catalytic direct esterifi-cation process reacting a free fatty acid mixture with the appropriate aliphatic alcohol. The fatty acid ester S mixture produced in this manner may be used as a volatile working fluid as it is, but normally the conversion to esters of aliphatic alcohols is not complete, the conver-sion process preferably leaving some un-reacted non-volatile glycerides in the mixture. Additionally, some fats or oils may also contain certain amounts of non-volatile, non-glyceride components (e.g. polymers). Such non-volatile components will preferably be transferred to, and mixed with the final product, which product is low in environmental pollutants, when the fatty acid es-ter mixture is used as working fluid. A working fluid produced in this manner should therefore be subjected to a distillation, preferably a molecular and/or short path distillation, in at least one step, which distillation process generates a distillate more suitable to be used as a new volatile working fluid.
In another preferred embodiment of the invention the volatile working fluid comprises at least one of an ester and/or an amide composed of shorter fatty acids and longer alcohols or amines, or any combination thereof.
In a preferred embodiment of the invention, the volatile environmental pollutants decreasing working fluid, for use in decreasing an amount of environmental pollutants present in a fat or oil, being edible or for use in cosmetics, is preferably a fatty acid ester (e.g.
fatty acid ethyl ester or fatty acid methyl ester), a fatty acid amide or free fatty acids obtained from at least one of vegetable, microbial and animal origin, or any combination thereof. Preferably, said animal origin is fish or sea mammals, i.e. that the volatile fat or oil environmental pollutants decreasing working fluid is ob-tained from marine oils, e.g. from fish or from sea mam-mals. Further, in a preferred embodiment of the volatile environmental pollutants decreasing working fluid, said fat or oil is edible for humans and/or animals or for use in cosmetics.
In another embodiment of the invention, a volatile environmental decreasing working fluid according to the present invention, is used in a process for decreasing an amount of environmental pollutants, in a mixture compris-ing a fat or oil, being edible or for use in cosmetics, preferably a marine oil, containing the unwanted compo-nents, in which process the volatile working fluid is added to the mixture and then the mixture is subjected to at least one stripping processing step, preferably a thin-film evaporation process, a molecular distillation or a short-path distillation, or any combination thereof, and in which process an amount of toxic components pre-sent in the fat or oil, being edible or for, use in cos-metics, is separated from the mixture together with the volatile working fluid.
In another preferred embodiment a health supplement, a pharmaceutical and/or an animal feed product containing at least fat or oil (end) products, e.g. oil ingredient of fish feed, with a decreased amount of environmental pollutants or toxic components, prepared according to at least one of the previously mentioned processes is dis-closed. For the pharmaceutical and food supplement indus-tries, marine oils have to be processed in order to in-crease the content of EPA and/or DHA to suitable levels and the removal or reduction of different kinds of poi-lutants have the potential to substantially increase mar-ketability and value. Therefore, the present invention also discloses a health supplement and a pharmaceutical respectively, containing at least a marine oil, such as fish oil, which marine oil is prepared according to the previously mentioned process, in order to decrease the amount of environmental pollutants in the marine oil.

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In another embodiment of the invention the pharma-ceutical and/or health supplement is preferably intended for treating cardiovascular diseases (CVD) and inflamma-tory diseases, but they also have positive effects on 5 other CVD risk factors such as the plasma lipid profile, hypertension and vascular inflammation. In more preferred embodiment of the invention the pharmaceutical and/or health supplement comprises at least one of EPA/DHA ethyl esters and is intended for a range of potential therapeu-18 tic applications including; treatment of hypertriglyreri-daemia, secondary prevention of myocardial infarction, prevention of atherosclerosis, treatment of hypertension and/or kidney disease and to improve children's learning ability.
15 Further, the present invention also disclose a ma-rine oil product, prepared according to at least one of the previously mentioned processes. Preferably, the ma-rine oil product is based on fish oil or a fish oil com-position.
In addition, there is a demand for marine oils of high quality, This issue forces the fish oil industry to consider alternative refining techniques. Further, by us-ing one of the processes according to the invention it is now possible to simultaneously decrease the amount of en-vironmental pollutants and/or to decrease the amount of free fatty acids in e.g. marine oils with inferior qual-ity With a good result. Such oils are appropriate to be used in e.g. animal feed products. If the oil or fat is constituted by high amounts of free fatty acids, said free fatty acids may act as the volatile working fluid in the stripping process.
In another preferred embodiment of the invention, an animal feed product, containing at least a marine oil, which marine oil is prepared according to one of the processes presented before, in order to decrease the amount of environmental pollutants and/or the amount of free fatty acids in the marine oil. Preferably the animal feed product is a fish feed product.
For companies producing tocopherol preparations it is of commercial interest to refine their tocopherol con-centrate from environmental pollutants, especially PAH's (polycyclic aromatic hydrocarbons). Tocopherol is pro-duced from condensate from deodorization of soy and/or palm oil. Vegetable oils are deodorized preferably in the same way as fish oils, but at higher temperatures in or-der to distil off the tocopherols. Therefore, the conden-sate from the mentioned process also contains, except components causing bad taste and odour of the oil, high amounts of tocopherol. Further, this condensate is raw material in all tocopherol preparations that are so-called natural preparations.
In another preferred embodiment of the invention a tocopherol concentrate product, based on a tocopherol concentrate prepared from a condensate from a deodoriza-tion process of at least one vegetable fat or oil, such as palm oil or soy oil, which concentrate contains at least one of PAR and volatile pollutants, is prepared ac-cording to the stripping process of the present inven-tion, in order to decrease the amount of environmental pollutants in the tocopherol concentrate. The process for decreasing the amount of environmental pollutants and/or PAH's in a tocopherol concentrate, comprises the steps of adding a volatile working fluid to a tocopherol concen-trate and subjecting the concentrate, with the added volatile working fluid, to a stripping processing step, in which preferably PAH's are separated from the concen-trate with the volatile working fluid. The volatile work-ing fluid may be at least one of the working fluids men-tioned before, or any combinations thereof, and said stripping process step is carried out at process condi-tions mentioned before. In a embodiment of the invention said stripping process step is carried out at a tempera-ture in the interval of 120-180 C and at a pressure be-low 1 mbar. The ratio of (volatile working fluid):(toco-pherol concentrate) is preferably about 4:100 to 8:100.
For the cosmetic industry it is of commercial inter-est to refine ricinus oil from trace of toxic components.
It is valuable for this industry to market cosmetic prod-ucts, such as lipstick, that are essentially free from toxic components, such as ricinine. Ricinus oil is a vegetable oil produced from the seeds of Ricinus communis L., Euphorbiaceae. The oil is a triglyceride of fatty ac-ids, with ricinoleic acid (d-12-hydroxyoleic acid) as the.
major fatty acid (approximately 87%). Due to the hydroxyl group of ricinoleic acid, ricinus oil can not be refined in traditional ways, i.e. by alkali refining. Thus, traces of toxic components may not be easily removed.
Ricinine is a toxic nitrilpyridinone that might be pre-sent in the oil in trace amounts. Herein, the invention also disclose a cosmetic product, based on ricinus oil, which ricinus oil is prepared according to at least one of the processes mentioned before, in order to decrease the amount of toxic components in the ricinus oil.
In another preferred eMbodiment of the invention the fat or oil is a ricinus oil, for use in cosmetics or me-dicinal applications, and the pollutants that are to be separated according to the process of the invention are toxic compounds, such as nitrilpyridinones.
In a preferred embodiment, the process for decreas-ing the amount of toxic compounds in a ricinus oil, pref-erably trace of ricinine, comprises the steps of adding a volatile working fluid to a ricinus oil mixture and sub-jecting the mixture, with the added volatile working fluid, to a stripping processing step, in which prefera-bly traces of ricinine (from the ricinus oil) is sepa-rated from the mixture with the volatile working fluid.
The volatile working fluid may be at least one of the working fluids mentioned before, or any combinations thereof. In a more preferred process in order to decrease an amount of toxic compounds in a ricinus oil, the strip-ping processing step is at least one of a molecular dis-tillation process, a thin-film evaporation process or a short-path distillation or any combination thereof, car-ried out at temperatures in the interval of 120-220 C, at a pressure below 0,1mbar. In the case of a thin-film evaporation process the process is carried out at a mix-ture flow rate in the interval of 10-300 kg/h*m2.
In a most preferred embodiment of the invention, the ricinus oil mixture was distilled at a temperature about 170 C, a pressure around 0,001 mbar respectively a mix-ture flow rate about 150 kg/h.m2. Up to 95% of the amount of ricinine present in the start oil may be removed with the stripping process according to the invention.
DEFINITIONS
As used herein the term environmental pollutants preferably means toxic components and/or pesticides like polychlorinated biphenyls (PCB), DDT and its metabolites, organic compounds found in the sea environment and iden-tified as potentially harmful and/or toxic; Polychlori-nated triphenyls (PCTs), dibenzo-dioxins (PCDDs), and dibenzo-furans (PCDFs), Chlorophenols and hexachloro-cyclohexanes (HCHs), toxaphenes, dioxins, brominated flame retardants, polyaromatic hydrocarbons (PH), or-ganic tin-compounds (e.g. tributyltin, triphenyltin) and organic mercury-compounds (e.g. Methyl-Mercury).
As used herein the term oil and fat means fatty ac-ids in at least one of the triglyceride and phospholipid forms Generally, if the start material in the stripping process is a marine oil, the oil may be any of raw or partially treated oil from fish or other marine sources and which contains fatty acids, including polyunsaturated fatty acids, in the form of triglycerides. Typically, each triglyoeride molecule in such a marine oil will con-, tam, more or less randomly, different fatty acid ester moieties, be the saturated, monounsaturated or polyun-saturated, or lOng chain or short chain. Further, exam-ples of vegetable oils or fats are corn oil, palm oil, rapeseed oil, soybean oil, sunflower oil and olive oil.
Further, the fat or oil may be pre-processed in one or several steps before constituting the start material in the stripping process as described above. An example of such a pre-processing step is a deodorization process. It shall also be noted that the fat or oil may be edible in one or several such pre-processing steps and/or in the processing steps according to the invention.
As used herein the term edible means edible for hu-mans and/or animals. Additionally, as used herein the term "for use in cosmetics" means an oil or a fat that can be used in products that contributes to enhance hu-mans appearance and/or health, e.g. cosmetic and/or beauty care products.
As used herein the term working fluid is interpreted to include a solvent, a solvent mixture, a composition and a fraction, e.g. a fraction from a distillation proc-ess, that has a suitable volatility, comprising at least one of esters composed of C10-C22 fatty acids and C1-C4 alcohols, amides composed of C10-C22 fatty acids and Cl-C4 amines, C10-C22 free fatty acids, mineral oil, hydro-carbons and bio-diesel.
As used herein the term essentially equally or less volatile is interpreted to include that the volatile working fluids having a suitable volatility in relation to the volatility of the environmental pollutants that is to be stripped off from a fat or oil mixture. Further, commonly this is the case when the volatility of the working fluid is the same or lower than the volatility of the environmental pollutants. However, the term essen-equally or less volatile is also intended to in-clude the case when the volatile working fluid is some-what more volatile than the environmental pollutant.
Further, as used herein the term stripping is inter-preted to include a general method for removing, separat-5 ing, forcing or flashing off gaseous compounds from a liquid stream. In addition, the term "stripping process-ing step"' preferable herein is related to a method/pro-cess for decreasing the amount of environmental pollut-ants in an oil or fat by one or more distilling or die-10 tillation processes, e.g. short path distillations, thin-film distillations (thin-film stripping or thin-film (steam) stripping), falling-film distillations and mo-lecular distillations, and evaporation processes.
As used herein the term "oils with a low quality"
15 preferably means that the oil contains high amounts of free fatty acids, that makes them less useful for nutri-tional purposes and that traditional alkaline refining in such oils is complicated and costly. Additionally, as used herein, the term mineral oil is interpreted to in-20 clude mineral oil products such as e.g. fractions from distillation processes and white spirit. As used herein hydrocarbons is interpreted to include organic compounds, that are relatively large molecules composed mainly of carbon and hydrogen. They can also include nuclei of ni-trogen, phosphorus, sulphur, and chlorine, among others.
As used herein bio-diesel means a commercial product (or products under development) used as an environment friendly alternative to fuel for cars comprising e.g.
methyl esters from preferable vegetable or animal oils.
As used herein the term marine oils includes oil from fish, shellfish (crustaceans) and sea mammals. Mon limiting examples of fish oils are e.g. Menhaden oil, Cod Liver oil, Herring oil, Capelin oil, Sardine oil, An-chovy oil and Salmon oil. The fish oils mentioned above may be recovered from fish organs, e.g. cod liver oil, as well as from the meat of the fish or from the whole fish.

As used herein the term health supplement is inter-preted to include food and food supplement to animals and/or humans, fortification of food, dietary supplement, functional (and medical) food and nutrient supplement.
As used herein the term "treating" means both treat-ment having a curving or alleviating purpose and treat-ment having a preventive purpose. The treatment can be made either acutely or chronically. Herein the term ani-mal feed product means food or food supplement specially to animals e.g. fish, fowls, pigs and furred (fur-bearing) animal.
As used herein the term fish feed product also in-cludes a fish larvae feed product.
As used herein the term microbial oils also includes "single cell oils" and blends, or mixtures, containing unmodified microbial oils. Microbial oils and single cell oils are those oils naturally produced by microorganisms during their lifespan.
Further, a fat or an oil, being edible or for use in cosmetics, according to the invention can also be a blend of e.g. microbial oils, fish oils, vegetable oils, or any combination thereof.
As used herein the term free fatty acids means fatty acids in free acid form. The free fatty acids is opera-tive as a volatile working fluid and/or included in the fat or oil, being edible or for use in cosmetics.
As used herein the term "together with", means that the volatile working fluid will be stripped off together with, combined with, or adhering the pollutants, namely that the pollutants will accompany the working fluid.
As used herein the term acid value of a fat or an oil means the amount of free acids presented in a fat or an oil equal to the number of milligrams of potassium hy-droxide needed to neutralize one gram of the oil, i.e.
that the term serves as an index of the efficiency of re-= =

fining. This means that a high acid value is characteris-tic for low quality oil or fat products.
While the invention has. been described in detail and with reference to specific embodiments thereof, it will be apparent for one skilled in the art that various =
changes and modifications, i.e. other combinations of temperatures, pressures, and flow rates during the'strip-.
ping process can be made therein without departing from.
the spirit and scope thereof. =
BRIEF DESCRIPTION OF THE DRAWINGS
The advantages and details of the present invention will become apparent from the following description when 'T
taken in conjugation with the accompanying drawings,'in which;
FIG I is a schematic flow chart of one embodiment .
illustrating a method for decreasing the. amount of envi-.
ronmental pollutants in a fat or an oil, being edible or for use in cosmetics, by adding a volatile working fluid prior to a molecular distillation. .
FIG 2 shows the concentrations of different environ-mental pollutants in a fish oil mixture before and after =
stripping according to the present disclosure. =
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
A number of preferred embodiments of the process for . =
decreasing the amount of environMental pollutants in a ' mixture comprising a volatile working fluid and.a fat or.
=
an oil, being edible or for use in cosmetics, containing.
environmental pollutants will be disclosed below. .
A first embodiment of a process for decreasing the amount of environmental pollutants in a fat or an oil, -being edible or for use in cosmetics, by adding.a vola-tile working fluid prior to. a molecular distillation is presented in figure I. The starting fat or oil, being 22a edible or for use in cosmetics, in the first embodiment of the invention is a fish oil whether freshly refined, reverted or mixtures thereof characterized by a level of environmental pollutants. The exact amount of environ-.

mental pollutants varies depending upon such factors as fish species, seasonality, geographical catch location and the like.
As used herein the term molecular distillation is a distillation process performed at high vacuum and pref-erably low temperature (above 120 C). Herein, the conden-sation and evaporation surfaces are within a short dis-tance from each other, so as to cause the least damage to the oil composition. This technique is also called short path distillation, and commercial equipment is readily available.
The molecular distillation plant (1) illustrated in figure 1, comprises a mixer (2), a pre-heater (3), a de-gasser (4), a distillation unit (5) and a vacuum pump (6). In accordance to this embodiment, a volatile working fluid comprising an ethyl ester fraction (6% relative to the oil) is added to a fish oil mixture and blended in a mixer (2). The oil mixture is then optionally passed through a means (3) for controlling the oil feed rate (herein about 400 kg/h), such as an ordinary throttling valve. The fish oil mixture is then preheated with a heating means (3) such as a plate heat exchanger to pro-vide a preheated fish oil mixture. The mixture is then passed through a degassing step (4) and admitted into the molecular path distance evaporator (5), a tube (7) in-cluding the condensation (B) and evaporation (9) surface.
The stripping process is carried out at a pressure be-tween 0,1 and 0,001 mbar and at a temperature of about 200 *1:. The fish oil mixture to be concentrated is picked up as it enters the tube (7a) by rotating blades. The blades extend nearly to the bottom of the tube and mounted so that there is a clearance of about 1,3 mm be-tween their tips and the inner surface of the tube. In addition, the blades are driven by an external motor. The fish oil mixture is thrown against the tube wall and is immediately spread into a thin film and is forced quickly down the evaporation surface. The film flows down by gravity and becomes concentrated as it falls. Heated walls and high vacuum strips off the volatile working fluid together with the environmental pollutants, i.e.
the more volatile components (distillate) is derived to the closely positioned internal condenser (8), the less volatile components (residue) continues down the cylin-der. The resulting fraction, the stripped fish oil mix-ture containing at least the fatty acids EPA and DEA is separated and exit through an individual discharge outlet (10).
In a second embodiment a falling film evaporator is used. In falling film evaporators liquid and vapours flow downwards in parallel flow. The liquid to be concen-trated, herein the fish oil mixture, is preheated to boiling temperature. The oil mixture enters the heating tubes via a distribution device in the head of the evapo-rator, flows downward at boiling temperature, And is par-tially evaporated. This gravity-induced downward movement is increasingly augmented by the co-current vapour flow.
Falling film evaporators can be operated with low tem-perature differences between the heating media and the boiling liquid, and they also have short product contact times, typically just a few seconds per pass.
In a third embodiment of the invention the process is carried out by a short path distillation, which in-cludes the use of a short path evaporator that integrates the features and advantages of thin film or wiped film evaporators but adds internal condensing for applica-tions. Short path evaporators are widely used in fine and specialty chemicals for thermal separation of intermedi-ates, concentration of high value products, and molecular distillation under fine vacuum conditions. Their key fea-tures make them uniquely suitable for gentle evaporation and concentration of heat sensitive products at low pres-sures and temperatures.

It should be understood that many modifications of the above embodiments of the invention are possible within the scope of the invention such as the latter is defined in the appended claims.

EXAMPLES
The invention will now be illustrated by means of the following non-limiting examples. These examples are set forth merely for illustrative purposes and many other 10 variations of the process may be used. The examples below summarizes some results from different purification of fish oils by molecular distillation.
Equipment and conditions for laboratory experiments 15 In example 1-3 below decachlorobiphenyl, 0.60 mg/kg, was added to a fish oil composition as a pollutant model substance. The high chlorine content in decachlorobi-phenyl ensures that this compound is less volatile than environmental pollutants like PCB, DDT and its metabo-20 lites, toxaphenes, dioxins and brominated flame retar-dants.
Unless otherwise stated, in all the examples the pressure was 0,001 mbar. However, as this is the lower limit of the pressure indicator, the real pressure will 25 vary. That is the reason for somewhat varying results from one example to the next. When the distillation equipment is running under stable conditions, no signifi-cant variations are expected. However, this points out that constant pressure is not a very strong condition for carrying out the present invention.
EXAMPLE I: The effect of adding a working fluid A fish oil composition containing fatty acids on triglyceride form and decachlorobiphenyl (0,60 mg/kg), with or without a working fluid, herein an ethyl ester, 8% relative to fish oil, (the ratio of (volatile working fluid) (fish oil) is about 8:100) was distilled by a laboratory scale molecular distillation at a rate of 600 ml/h and a temperature of 180 'C. The used ethyl ester mixture was a by-product (distillate fraction) from pro-S duction of EPA and DHA ethyl ester concentrates.
Decachlorobiphenyl Decachlorobiphenyl (mg/kg) (% of start value) Without WF 0.43 72 With WF ,0.022 3.7 * WF = working fluid Table 1: The effect of adding a volatile working fluid The results in table 1 show that addition of a vola-tile working fluid to a fish oil composition has a sur-prisingly and dramatic effect on the removal of de-cachlorobiphenyl. Here, more than 95% of the amount of decachlorobiphenyl has been removed ("stripped" off) from the fish oil mixture by molecular distillation.
EXAMPLE 2: The effect of different flow rates.
A fish oil composition containing fatty acids in triglyceride form and decachlorobiphenyl (0,60 mg/kg) was added a working fluid in the form of a ethyl ester frac-tion in the same way as in example 1. The oil mixture was then stripped by a molecular distillation carried out at different flow rates, but at the same temperature (180 'C).
,Flow rate (ml/h) Decachlorobiphenyl (mg/k9) 400 0.02 600 0.05 1000 0.20 1 Table 2: The effect of different flow rates The results given in the table above show that decachlorobiphenyl (and other volatile pollutants) will be flashed off (reduced) more successfully at lower flow rates. However, the results of optimising the flow rates are less important compared to the effect of adding a working fluid, such as a solvent, solvent mixture or a fraction containing an ethyl ester.
EXAMPLE 3: The effect of different temperatures Here, an ethyl ester fraction was added to a fish oil composition containing decachlorobiphenyl (0,60 mg/kg) in the same way as in example 1. The oil mixture was then stripped by molecular distillation at different temperatures.
Temperature ( C) Decachlorobiphenyl (mg/kg) .
180 0.11 200 0.04 Table 3: The effect of different temperatures Table 3 illustrates that an increased temperature gives an improved removal of pollutants, when a volatile working fluid has been added to the oil mixture prior to a molecular distillation. Further, it is important to know that polyunsaturated fatty acids in fish oil are thermo-labile compounds and an increase in temperature is only applicable within strict limits.
For a person skilled in the art it is obvious that the same effect as described in example 1-3 will be achieved according to the invention by using other vola-tile working fluids, as long as the working fluids are essentially equally or less volatile than the environ-mental pollutants that is to be separated from the oil or fat mixture.

EXAMPLE 4: Sardine oil - Industrial full scale process This example shows an industrial scale process for decreasing the amount of pollutants in a fish oil mix-ture, which process comprises a step of adding a volatile working fluid to the fish oil mixture prior to a molecu-lar distillation. 63.9 tons of a sardine oil containing different environmental pollutants was added a volatile working fluid in the form of a fatty acid ethyl ester mixture (ethyl ester of fish oil (8%)) before subjecting it to a molecular distillation process. The molecular distillation process was then carried out at a tempera-ture of 200 it, a pressure of 0,04 mbar and a mixture flow rate of 300 l/h with a heated surface of 3 m2.
After treatment, 61.0 tons of purified product were collected. The results in table 4 show the content of vi-tamin A(trans-retinol), cholesterol, toxaphenes and diox-ins in the sardine oil before and after stripping respec-tively.
Before stripping After stripping Vitamin A 15.3 mg/g 13.0 mg/g Cholesterol 3.6 mg/g 1.31 mg/g Toxaphenes 0.3 mg/g <0.1 mg/g Dioxins 4.1 pg/g 0.34 pg/g Table 4: Toxaphenes and dioxins in a sardine oil before and after stripping The results confirm that adding a working fluid to an oil before stripping is effective in reducing the amounts of volatile pollutants at the same time as the concentration of vitamin A, a valuable component in many fish oils, is not seriously affected. This means that this purification method can be used for products that contains vitamin A, e.g. cod liver oil.
In some cases a certain cholesterol level can be of value for some applications of fish oils e.g. for fish feed, especially feed for fish larvae. In these applica-tions it is important to perform a preferential removal only of pollutants.
EXAMPLE 5: Fish oil mixture - Industrial full scale proc-ess This example also shows an industrial full scale process for decreasing the amount of pollutants in a fish oil, which process comprises the steps of adding a vola-tile working fluid to the fish oil mixture and subjecting the mixture, with the added volatile working fluid, to a molecular distillation processing step, in which environ-mental pollutants present in the fish oil is separated from the mixture with the volatile working fluid.
30 tons of a fish oil mixture containing different environmental pollutants (see fig 2) was added a volatile working fluid in the form of an fatty acid ethyl ester mixture (ethyl ester of fish oil (6%)) before subjecting it to a molecular distillation process. The molecular distillation process was then carried out at a tempera-ture of 200 C, a pressure of 0,005 mbar and a mixture flow rate of 400 kg oil/h with a heated surface of 11 m2.
After treatment, 29,5 tons of purified product were col-lected. The results are shown in Figure 2. The results confirms that the content of environmental pollutants in the fish oil mixture was strongly reduced after the stripping process according to the invention. For in-stance, the content of PCB in the fish oil mixture was reduced with about 98%, the content of PCDD was reduced with approximately 80%, the content of PCDF with about 95% and the amount of hexachlorocyclohexane respectively TE-PCB was almost negligible after stripping. For a per-son skilled in the art it is obvious that the same effect may be achieved according to the invention by using a volatile working fluid for decreasing an amount of pol-lutants in some other fat or oil compositions.

EXAMPLE 6: Salmon oil In this example oil from fresh by-products from At-lantic salmon was processed according to the invention.
5 The process according to the invention comprises the steps of adding a volatile working fluid to the oil mix-ture and further subjecting the mixture, with the added volatile working fluid, to a molecular distillation proc-essing step. 8% working fluid (the ratio of (volatile 10 working fluid):(salmon oil) is here about 8:100) was added to the oil and the distillation process was per-formed at a pressure of 1x103 mbar, at a temperature of 180 C and at a mixture flow rate of 600 ml/hour.
Samples of the oil mixture was analysed before and 15 after distillation respectively, regarding the amount of brominated flame retardants, PCBs and some chlorinated pesticides, see the tables 5 and 6 below.
Brominated flame Before treatment 'After distillation retardants,jig/kg [EDE 28 0.3 < 0.2 IBDE 47 5.3 < 0.2 IBDE 66 0.4 < 0.2 IBDE 71 ,< 0.2 < 0.2 IBM 75 < 0.2 < 0.2 1BDE 77 < 0.2 < 0.2 BDE 85 <0.2 <0.2 FIDE 99 ,1.2 < 0.2 soE 100 1.0 < 0.2 BDE 119 < 0.2 < 0.2 iBDE 138 < 0.2 < 0.2 IBDE 153 < 0.2 < 0.2 IBDE 154 0.5 < 0.2 IBDE 183 < 0.2 < 0.2 1BDE 190 !< 0.2 < 0.2 Me-TBBP-A 0.2 < 0.2 HBCD 1.1 <1.2 20 Table 5 (above): Brominated flame retardants, #gikg, before and after a distillation process 1BefoPCB and chlorin-re treatment After distillation ated pesticides, (n/kg) CB 28 <3 <3 , CB 52 5 <3 r ICB 101 11 <7 CB 118 <9 <9 CB 105 <3 <3 CB 138 13 <7 ICB 156 <3 <3 .
'CB 180 4.8 _< 4 , Dieldrin 22 < 4 iEndrin < 3 < 3 HCB 12 <1 , a-HCH 3.8 < 1 y-HCH 5.3 < 1 0-HCH< J r < 6 P-HEPO < 2 <3 .
p,p'-DDE 38 < 3 p,p'-DDD 15 < 3 p,p'-DDT nd = not detected < 8 Table 6: PCB and chlorinated pesticides, pg/kg, before and after dis-tillation It is observed that the invention removes almost all of the analysed environmental pollutants to a level below the analytical detection limit.
Additionally, for a person skilled in the art it will be obvious that the same procedure could be used for other marine oils, for example cod liver oil or fish oil intended to be used as a component of feed for farmed fish. Nowadays, commercial fish feed contains high amounts of pollutant's and it is therefore of large inter-est to decrease the amounts of toxic components in the current marine oil before the oil is added to the feed.

EXAMPLE 7; Removal of PARS
In this example benzo[alpyrene (8.36 gg/kg oil) was added to a fish oil composition, that already had been treated according to the invention, in order to remove environmental pollutants. The fish oil composition con-taining the added benzo(a]pyrene was processed in a simi-lar way and with the same distillation equipment as de-scribed in example 1. A volatile working fluid in the =
form of a fatty acid ethyl ester mixture, 8 % working fluid relative to the fish oil, was added to the fish oil composition, before subjecting the composition to a mo-lecular distillation process. The molecular distillation process was carried out at a temperature of 160 C, a pressure of 110-3 mbar, and a mixture flow rate of 600 ml oil/h. The concentration of benzo[a]pyrene was analysed before processing and after processing, see table 7.
Before processing After processing Benzo[a3pyrene 7,9 0,77 (fig/kg) Table 7: The amount of benzotalpyrene before and after processing The results given in the table above show that benzo[a]pyrene will be flashed off successfully according to the invention. In this example the concentration of benzo[a]pyrene was reduced with about 90%.
This confirms that adding a volatile working fluid to a fat or an oil composition, at least containing poly-cyclic aromatic hydrocarbons (PAH's), before a stripping process according to the itvention is effective in sepa-rating an amount of PMI's from the start fat or oil com-position together with the volatile working fluid.

A working fluid consisting of ethyl esters of fish oil (8%) was added to an oil produced from farmed salmon.

A distillation process was carried out under the same conditions as in example 1 and a distillate fraction of 8.3% was collected. The acid value of the residual oil was reduced from 0.4 mgKOH/g before distillation to 0.1 mgKOH/g after distillation and the oil was analysed for contaminants before and after processing.
CB- CB- CB- CB- CB- CB- CB- CB- CB-Before <3 5 11 <9 16 <3 13 <3 4.8 After <3 <3 <7 <9 <7 <3 <7 <3 <4 Table 8: Salmon oil. Content of Indicator-PCBs (/kg) before and after prooesaning Die1 Endr HCB a- -y- 'b- 'b- pp_Dipp_D pp_D
drin in HCH HCH HCH HEPO DE DD DT
Before 22 <3 12 3.8 5.3 <6 '<3 38 15 <8 After ;
<4 <3 <1 1<1 <1 <6 j<3 <3 <3 <8 Table 9: Salmon oil. Content of organochlorine pesticides (Ae/kg) before and after processing The results show that adding a volatile working fluid prior to a stripping (distillation) process is ef-fective in decreasing the amount of organo-chlorine pes-ticides in a fish oil composition. In addition, the vola-tile working fluid also facilitates removal of free fatty acids in the oil. Therein the acid value was decreased with 75%, i.e. from 0,4 to 0,1. It is hereby possibly to decrease the amount of environmental pollutants and to reduce the amount of free fatty acids in an oil or a fat at the same time and in the same process.
EXAMPLE 9: Removal of free fatty acids A fish oil purchased for production of fish feed was distilled by a molecular distillation process under the same conditions as given in example 1 and the start oil had an acid value of 6.8 mgKOH/g. After removal of a die-tillate corresponding to 4.3% by weight, the acid value of the residual oil was reduced to 0.2 mgKOH/g and the amount of environmental pollutants in the start oil was decreased.
In an identical distillation procedure, an oil with an acid value of 20.5 mgKOH/g was distilled. After re-moval of a distillate of 10.6 the acid value was re-duced to about 1.0 mgKOHig and the amount of environ- -mental pollutants in the start oil were decreased.
Due to the fact that the stripping process in exam-ple 8 also facilitates removal of free fatty acids in the oil and that the free fatty acids are volatile it can be expected that even oils with a low quality, i.e. a high content of free fatty acids, can be treated successfully according to the invention. An example of oils with low quality is silage oils or oils that have been stored or transported for a long period of time. Fish oils with low quality may be used for production of fish feed.
This example therefore shows that a stripping proc-ess for decreasing the amount of environmental pollutants in a mixture comprising at least a fat or an oil with a high content of free fatty acids (a low quality oil or fat) is effective since the free fatty acids in the oil or fat act as a working fluid. Further, the free fatty acids in the oil or fat also contributes to an additive effect in the stripping process by partially acting as an internal working fluid (or by being an active part of the working fluid) in the stripping process.
A person known in the art will also realise that the same stripping effect can be obtained by adding a vola-tile working fluid containing a similar volume of suit-able free fatty acids to an oil or fat containing envi-ronmental pollutants in order to decrease the amount of environmental pollutants in the fat or oil.

EXAMPLE 10: Removal of toxic components from a ricinus oil This example shows a process for decreasing the amount of toxic compounds in a ricinus oil (castor oil, 5 oil from the seeds of Ricinus communis L. Euphorbiaceae), which process comprises the steps of adding a volatile working fluid to a ricinus oil mixture and subjecting the mixture, with the added volatile working fluid, to a mo-lecular distillation processing step, in which traces of 10 ricinine from the ricinus oil is separated from the mix-ture with the volatile working fluid.
Firstly, 8% of a working fluid, (the ratio of (vola-tile working fluid): (ricinus oil) is here about 8:100) a distilled fraction of ethyl esters from a fish oil, was 15 added to a ricinus oil prior to a distillation processing step. Secondly, the ricinus oil mixture was distilled in a molecular distillation process at a temperature of 170 C, at a pressure of 10-3 mbar and at a mixture flow of 500 ml/min. The concentration of toxic compounds were 20 analysed before and after treatment. This analysis showed that the concentration of ricinine was substantially re-duced compared to the concentration in the starting ricinus oil. This shows that it is possible to reduce traces of toxic components in a ricinus oil according to 25 the invention, as long as the used volatile working fluid is essentially equally or less volatile than the compo-nents that is to be separated from the ricinus oil. Fur-ther, ricinus oil is used in both medicinal and cosmetic applications and the reduction of the existing trace 1ev-30 els of ricinin has commercial value.

Claims (31)

1. A process for decreasing the amount of environ-mental pollutants in a mixture comprising a fat or an oil, being edible or for use in cosmetics, the fat or oil containing the environmental pollutants, characterized in that the process comprises the steps of;
-adding a volatile working fluid to the mixture, where the volatile working fluid comprises at least one of a fatty acid ester, a fatty acid amide, a free fatty acid and a hydrocarbon, and -subjecting the mixture with the added volatile working fluid to at least one stripping processing step, in which an amount of environmental pollutant present in the fat or oil, being edible or for use in cosmetics, is sepa-rated from the mixture together with the volatile working fluid.

2. A process according to claim 1, wherein the vola-tile working fluid is essentially equally or less vola-tile than the environmental pollutants that are to be separated from the fat or oil mixture.

3. A process according to claim 1, wherein the vola-tile working fluid is constituted by free fatty acids comprised in the fat or oil, being edible or for use in cosmetics, containing the environmental pollutants.

4. A process according to claim 1, wherein the at least one of a fatty acid ester, a fatty acid amide and a free fatty acid is obtained from at least one of vegeta-ble, microbial and animal fat or oil.

5. A process according to claim 4, wherein the ani-mal fat or oil is a fish oil and/or an oil obtained from sea mammals.

6. A process according to claim 1, wherein the vola-tile working fluid comprises at least one fatty acid es-ter composed of C10-C22 fatty acids and C1-C4 alcohols, or a combination of two or more fatty acid ester each composed of C10-C22 fatty acids and C1-C4 alcohols.

7. A process according to claim 1, wherein the fat or oil, being edible or for use in cosmetics, is obtained from at least one of vegetable, microbial and animal fat or oil, or any combination thereof.

8. A process according to claim 7, wherein the fat or oil, being edible or for use in cosmetics, is a marine oil.

9. A process according to claim 8, wherein the ma-rine oil is obtained from fish or sea mammals, containing at least saturated and unsaturated fatty acids in the form of triglycerides.

10. A process according to claim 7, wherein the fat or oil is a ricinus oil for use in cosmetics or medicinal applications.

11. A process according to claim 7, wherein the fat or oil is a tocopherol concentrate prepared from a con-densate from at least one deodorization process of at least one vegetable oil, wherein the tocopherol concen-trate containing at least one of PAH and volatile pollut-ants, or any combination thereof.

12. A process according to claim 1, wherein the ra-tio of (volatile working fluid):(fat or oil, being edible or for use in cosmetics) is about 1:100 to 15:100.

13. A process according to claim 12, wherein the ra-tio of (volatile working fluid):(fat or oil, being edible or for use in cosmetics) is about 3:100 to 8100.

14. A process according to claim 1, wherein said stripping processing step is carried out at temperatures in the interval of 120-270 °C.

15. A process according to claim 1, wherein said stripping processing step is carried out at temperatures in the interval of 150-200 °C.

16. A process according to claim 1, wherein said stripping processing step is carried out at a pressure below 1 mbar.

17. A process according to claim 1, wherein the at least one stripping processing step is one of a thin-film evaporation process, a molecular distillation or a short-path distillation or any combination thereof.

18. A process according to claim 17, wherein the at least one thin-film evaporation process is carried out at a mixture flow rate in the interval of 10-300 kg/h-m2.

19. A volatile environmental pollutants decreasing working fluid, for use in decreasing an amount of envi-ronmental pollutants present in a fat or oil, being edi-ble or for use in cosmetics, the working fluid comprising at least one of a fatty acid ester, a fatty acid amide, a free fatty acid and a hydrocarbon, or any combination thereof.

20. A volatile environmental pollutants decreasing working fluid according to claim 19, wherein said at least one of a fatty acid ester, a fatty acid amide, a free fatty acid is obtained from at least one of vegeta-ble, microbial and animal origin, or any combination thereof.

21. A volatile tat or oil environmental pollutants decreasing working fluid according to claim 20, wherein the animal origin is fish or sea mammals.

22. Use of a volatile environmental decreasing work-ing fluid according to claim 19, in a process for de-creasing an amount of environmental pollutants, such as toxic component, in a mixture comprising a fat or oil, being edible or for use in cosmetics, preferably a marine oil, containing the toxic components, in which process the volatile working fluid is added to the mixture and then the mixture is subjected to at least one stripping processing step, preferably a thin-film evaporation proc-ess, a molecular distillation or a short-path distilla-tion, or any combination thereof, and in which process an amount of toxic components present in the fat or oil, be-ing edible or for use in cosmetics, is separated from the mixture together with the volatile working fluid.

23. A volatile environmental pollutants decreasing working fluid, wherein the volatile working fluid is a by-product, such as a distillate fraction, from a regular process for production of ethyl and/or methyl ester concentrates.

24. A health supplement, containing at least a ma-rine oil, which marine oil is prepared according to the process presented in claim 1, in order to decrease the amount of environmental pollutants in the marine oil.

25. A pharmaceutical, containing at least a fish oil, which fish oil is prepared according to the process presented in claim 1, in order to decrease the amount of environmental pollutants in the fish oil.

26. An animal feed product, containing at least a marine oil, which marine oil is prepared according to the process presented in claim 1, in order to decrease the amount of environmental pollutants respectively the amount of free fatty acids in the marine oil.

27. An animal feed product according to claim 26, wherein the feed product is a fish feed product.

28. A cosmetic product, based on ricinus oil, which ricinus oil is prepared according to the process pre-sented in claim 1, in order to decrease the amount of en-vironmental pollutants in the ricinus oil.

29. A marine oil product, prepared according to the process presented in claim 1.

30. A marine oil product according to claim 29, wherein the marine oil product is a fish oil product or a fish oil composition.

31. A tocopherol concentrate product, based on a to-copherol concentrate prepared from a condensate from a deodorization process of at least one vegetable fat or oil, such as palm oil or soy oil, which concentrate con-taining at least one of PAH and volatile pollutants and is prepared according to the process presented in claim 1, in order to decrease the amount of PAH and volatile pollutants in the tocopherol concentrate.