巴西专利BR112013020106B1 Process for the production of refined oil having a reduced content of 3-MCPD ester and / or glycidyl

专利PDF首页>>巴西专利

专利附录

专利说明

权利要求

类似技术

同族专利

引用文献

法律状态

优先权

专利摘要:
A process for producing a refined oil having a reduced ester content of 3-mcpd and / or glycidyl ester the present invention relates to a refined oil composition having a reduced ester content of 3-mcpd and / or glycidyl ester and methods of preparing it.
公开号:BR112013020106B1
申请号:R112013020106-1
申请日:2012-02-09
公开日:2019-10-15
发明作者:Falk Brüse；Marcus Bernardus Kruidenberg
申请人:Cargill, Incorporated；
IPC主号:

专利说明:

[001] The present invention relates to new oil compositions for use in the preparation of beverages and / or foodstuffs and to the methods for their manufacture. In particular, the invention relates to refined oil compositions that have a very low ester content of 3-MCPD and / or glycidyl ester.
BACKGROUND OF THE INVENTION [002] Crude oils, as extracted from their original source, are not suitable for human consumption due to the presence of high levels of contaminants - such as fatty acids, phosphatides, soaps and pigments that can be toxic or can cause an undesirable color , an undesirable odor or an undesirable taste. Crude oils are therefore refined before use. The refining process typically consists of three main steps: degumming, clarification and deodorization. An oil obtained after the completion of the refining process (called a refined oil) is normally considered suitable for human consumption and can therefore be used in the production of numerous foods and beverages.
[003] Unfortunately, it has now been discovered that the refining process itself contributes to the introduction into the refined oil of high levels of esters of 3-monochloropropane-1,2-diol - fatty acid (3-MCPD esters ) and glycidyl esters - typically in an amount of about 10-25 ppm. 3-MCPD esters and glycidyl esters are produced as a result of exposing oils to high temperatures during processing, in particular during deodorization. Both glycidyl esters and 3-MCPD esters are associated with a possible
Petition 870190018319, of 02/22/2019, p. 8/39
2/26 carcinogenic effect. In particular, there is a risk that the 3-MCPD esters could be converted to free 3-MCPD in the body during digestion. It is known that free 3-MCPD, when present in the body in high concentrations, causes hyperplasia (increased cell count) in the renal tubes of animals which, in turn, can lead to the formation of tumors. A similar effect is seen with glycidyl esters that are converted to free glidicol in the body. Thus, groups of scientific experts from the EU (European Union), the World Health Organization and the Food and Agriculture Organization have determined a tolerable daily intake (TDI) of 2 micrograms of free 3-MCPD per kilogram of body weight for humans.
[004] Assuming that all 3-MCPD esters present in refined oils would be converted to free 3-MCPDs, it was calculated that a man consuming 100 g of vegetable margarine per day could exceed the above TDI by up to five times. Similarly, a baby being fed formula (which contains about 25% by weight of fat) could be overtaking TDI by up to 20 times.
[005] Thus, although there is still much uncertainty about the effect of 3-MCPD esters and glycidyl esters on the human body, numerous regulatory groups, including for example the German Federal Institute for Risk Assessment, have nevertheless recommended that efforts are made to lower the levels of 3-MCPD esters and glycidyl esters in refined oils. A joint effort has therefore been made, in the oil processing industry, to identify ways to reduce the levels of 3-MCPD ester and glycidyl ester in refined oils.
[006] To date, two main approaches have been suggested: the first involves the acquisition of crude oils that have very low levels of 3-MCPD precursors, meaning that the oil
Petition 870190018319, of 02/22/2019, p. 9/39
3/26 final refined will evidently have a lower ester level of 3-MCPD than standard refined oil. Unfortunately, this solution is expensive and unsustainable at high volumes due to a lack of available sources of low oil in 3-MCPD. Thus, the main method used in the industry to reduce the ester content of 3-MCPD has been the use of deodorization in order to reduce the conversion rate of 3-MCPD precursors to 3-MCPD esters. Unfortunately, even at the lowest possible temperatures (a minimum temperature being required to maintain food safety), 3-MCPD esters will be formed in quantities that exceed the maximum levels desired by the food industry. Certainly, this could be partially solved by combining low temperature deodorization with low crude oils in a 3-MCPD precursor but this solution still experiences the cost obstacles associated with acquiring such oils.
[007] Another suggestion to reduce the ester content of 3-MCPD is made in WO2010 / 036450 (Süd-Chemie). It is based on a modification in the refining process that uses very intensive clarification (with high amounts of clarifying clays). Unfortunately, this solution is prohibitively expensive for use on an industrial scale and is not effective enough: 3-MCPD ester levels are not sufficiently reduced and, in addition, the process results in high oil yield losses altogether.
[008] It has been observed that clarification can cause a reduction in ester levels of 3-MCPD (see WO2011 / 069028A1). However, clarification also increases the content of free fatty acid and negatively affects the taste. It therefore needs to be followed by an additional refining step, typically deodorizing, to make the oil suitable for consumption.
[009] So there is still a need in the industry for iden
Petition 870190018319, of 02/22/2019, p. 10/39
4/26 tify an efficient and effective method of producing refined oils with an acceptable taste and with very low levels of 3-MCPD ester and / or glycidyl ester. The present invention provides such a process.
SUMMARY OF THE INVENTION [0010] In accordance with a first aspect of the present invention, there is provided a process for the production of a refined oil that has a reduced ester content of 3-MCPD and / or glycidyl ester characterized by the fact that it comprises submit the oil to the following steps, in order: (a) a clarification step, (b) a deodorization step, (c) a final clarification step, and (d) a final deodorization step, the final deodorization (d) is carried out at a temperature at least 40 ° C lower than the temperature of the deodorization step (b), preferably at a temperature below 190 ° C.
[0011] According to another aspect of the present invention, a process is provided for the production of a refined oil that has a reduced ester content of 3-MCPD and / or glycidyl ester characterized by the fact that it comprises subjecting the oil to the following steps, in order: (a) a clarification step, (b) a deodorization step, and (c) a final clarification step, the final clarification step (c) being carried out at a temperature below 80 ° C, and preferably in an environment low in oxygen.
[0012] According to certain modalities, the above processes may additionally comprise an alkaline treatment step selected from an alkaline refining step and an alkaline interesterification step.
[0013] According to yet another aspect of the present invention, a refined oil, preferably a refined palm oil, is obtained according to one of the above processes. In particular, a refined oil is provided that has a combined ester content of
Petition 870190018319, of 02/22/2019, p. 11/39
5/26
3-MCPD + glycidyl ester less than 5 ppm and a flavor value, measured according to method C, of 8 or greater. A refined oil is also provided which has an undetectable glycidyl ester content. Beverages and / or foodstuffs comprising such refined oils are also part of the present invention.
DETAILED DESCRIPTION [0014] The present invention provides a process for the production of refined oils that have a reduced ester content of 3-MCPD and / or glycidyl ester.
[0015] Refined oils are oils that have experienced total refining and are suitable for use in their designated final application. In particular, they will be suitable for human consumption. Traditionally, refining has included at least one degumming step, a clarification step and a deodorizing step, although other refining steps can also be used. An unrefined oil (that is, an oil that has not undergone any refining steps) will be called a crude or virgin oil. Such crude oils could be obtainable by extraction with solvents (such as hexane) followed by evaporation of the solvent. A mixture of oil and solvent is called a micelle but, for simplicity, it will also be called crude oil. A partially refined oil is one that has undergone one or more refining steps but is not yet suitable for use in its final application. When the term oil is used alone, without a prefix, it can refer to an unrefined, partially refined and / or fully refined oil, its meaning becoming evident from the context.
Special Processing [0016] The present invention provides a process for the production of a refined oil that has a reduced ester content of 3-MCPD and / or glycidyl ester characterized by the fact that it comprises a step of
Petition 870190018319, of 02/22/2019, p. 12/39
6/26 clarification followed by a deodorization step and to comprise a mild final refining step, that is, a deodorization and / or final clarification step carried out under conditions that will limit the formation of undesirable substances.
[0017] According to a possible modality, the process will comprise subjecting an oil to the following steps, in order: (a) a clarification step, (b) a deodorization step, (c) a final clarification step, and ( d) a final deodorization step, the final deodorization step (d) being carried out at a temperature at least 40 ° C below the temperature of the deodorization step (b). When performed under these conditions, the final deodorization will be called a mild deodorization step. Preferably, the final deodorization will be carried out at a temperature of 190 ° C or less, more preferably at a temperature of 180 ° C or less, even more preferably at a temperature of 160 ° C or less, for example at a temperature in the range 140-160 ° C or 130-160 ° C.
[0018] According to another possible modality, the process will comprise subjecting an oil to the following steps, in order: (a) a clarification step, (b) a deodorization step, and (c) a final clarification step, being that the final clarification step (c) is carried out at a temperature below 80 ° C. When performed under such conditions, the final clarification step will be called a mild clarification step. Under these conditions, it was found that additional deodorization is not necessary. Preferably, the final clarification step will be carried out at a temperature of 70 ° C or less, for example at a temperature in the range of 50-70 ° C. Ideally, it will be performed in an oxygen-poor environment. An oxygen-poor environment will be understood as an environment or condition capable of significantly reducing the oil
Petition 870190018319, of 02/22/2019, p. 13/39
7/26 oxygen. Preferably, the oxygen-poor environment will be substantially devoid of oxygen. The final clarification step can, for example, be carried out in an inert gas (for example, under a nitrogen atmosphere) or in a fixed bed column (or similar structured filter systems). Although it should not be necessary, if a subsequent deodorization is used, it will be a final deodorization as described above (that is, preferably carried out at a temperature of 190 ° C or less).
Clarification [0019] Clarification is a process by which impurities are removed to improve the color and flavor of the oil. It is typically done before deodorizing. The nature of the clarification step will depend, at least in part, on the nature and quality of the oil being clarified. In general, a crude or partially refined oil will be mixed with a clarifying agent that combines with oxidation products (eg, peroxides), trace phosphatides, trace soaps, pigments and other compounds to allow their removal. The nature of the clarifying agent can be selected to match the nature of the crude or partially refined oil to give a desirable clarified oil. Clarifying agents in general include natural or activated clarifying clays, also called clarifying soils, activated carbon and various silicates. A knowledgeable person will be able to select a suitable clarifying agent from those that are commercially available based on the oil being refined and the desired end use of that oil.
[0020] The processes of the present invention will include at least two clarification steps. If the final clarification step is followed by a deodorization step, they can be the same or similar (for example with the same clarifying agents and carried out under the same conditions) - the final clarification step could still be
Petition 870190018319, of 02/22/2019, p. 14/39
8/26 more intense than the preceding one (s). Preferably, however, the final clarification step will be a mild clarification step, that is, less intensive than the preceding one (s). For example, the final clarification step can be performed with less clarifying agent (or less active clarifying agent), at lower temperatures and / or with a reduced retention time, or in clarifying equipment that will have less influence on the taste and the formation of free fatty acid (i.e., in an oxygen-poor environment as described above).
[0021] Thus, the process of the present invention will include a first clarification step followed by a first deodorization step and a final clarification step that may or may not be followed by a final deodorization step.
Deodorization [0022] Deodorization is a process by which free fatty acids (FFAs) and other volatile impurities are removed by treating (or extracting) a crude or partially refined oil with water vapor, nitrogen or other gases inert. The deodorization process and its many variations and manipulations are well known in the art and the deodorization step (s) of the present invention can be based on a single variation or multiple variations thereof.
[0023] For example, deodorizers can be selected from any of a wide variety of commercially available systems, including both multi-chamber deodorizers (such as those sold by Krupp in Hamburg, Germany; De Smet Group, SA in Brussels, Belgium; Gianazza Technology srl from Legnano, Italy; Alfa Laval AB from Lund, Sweden, or others) as well as multiple tray deodorizers (such as those sold by Krupp, DeSmet Group, SA, and Crown Ironworks of the States
Petition 870190018319, of 02/22/2019, p. 15/39
9/26
United).
[0024] If the process of the present invention includes two (or more) deodorization steps, a separate deodorizer will typically be used for each deodorization step. Each deodorizer can be of the same manufacture, of the same type, of the same configuration, etc. or they may be different - since, if more than one deodorization step is used, the final deodorization is a mild deodorization step. According to a possible configuration, however, multiple deodorisations can be carried out in a single deodorization device. According to this modality, an oil outlet would be provided in such a way that the oil leaves the deodorizer after the initial high temperature deodorization (meaning that the final deodorization will include at least one high temperature deodorization stage). It would then be clarified and reintroduced into the deodorizer through an inlet positioned in such a way that the oil would re-enter the deodorizer and be subjected to deodorization at a lower temperature (that is, deodorization at a temperature at least 40 ° C below the lower deodorization temperature) used during initial deodorization). This could be done, for example, in a multi-tray or multi-chamber deodorizer. In these deodorizers, heat exchangers are positioned in such a way that, for example, in the tray or in the top chamber, the oils are subjected to deodorization at 270 ° C. In the next tray or chamber, the deodorizing temperature will be 250 ° C, and so on, even in the bottom trays, where the deodorizing temperatures are 140 ° C or 120 ° C. Thus, the oil outlet could be positioned below a first set of trays / chambers in such a way that the oil leaves the deodorizer after deodorization at 200 ° C, for example. The oil inlet would then be positioned in such a way that the oil would be reintroduced into a tray / chamber in which
Petition 870190018319, of 02/22/2019, p. 16/39
10/26 deodorization is carried out at 190 ° C or lower. It would then be allowed to continue through the trays / chambers until the end / bottom of the deodorizer was reached.
[0025] Deodorization is typically carried out at high temperatures and reduced pressures to better volatilize FFAs and other impurities. The precise temperature and pressure can vary depending on the nature and quality of the oil being processed. The pressure, for example, will preferably not be greater than 1,333.2 Pa (10 mm Hg) but certain modalities may benefit from a pressure below or equal to 666.6 Pa (5 mm Hg), for example, 133, 3-533.3 Pa (1-4 mm Hg). The temperature in the deodorizer can be varied as desired to optimize the performance and quality of the deodorized oil. At higher temperatures, reactions that can degrade oil quality will occur more quickly. For example, at higher temperatures, cis-fatty acids can be converted to their less desirable trans form. Operating the deodorizer at lower temperatures can minimize the conversion from cis-to-trans, but in general it will take longer and will require more extraction medium or lower pressure to remove the required percentage of volatile impurities. Thus, deodorization is typically carried out at a temperature in the range of 200 to 280 ° C, with temperatures of around 220-270 ° C being useful for many oils (note: temperatures reflect the temperatures reached by the oils in the deodorizer at instead of, for example, that of water vapor used during the process).
[0026] According to one embodiment of the present invention, a first deodorization step will be carried out at a temperature within these typical ranges (that is, from 200 to 280 ° C, preferably from 220 to 270 ° C). For palm oil, the preferred temperature range for the first deodorization will be 240 to 270 ° C. If used, the
Petition 870190018319, of 02/22/2019, p. 17/39
11/26 final deodorization will be carried out at a temperature at least 40 ° C lower than the temperature of the first deodorization step. Preferably, the final deodorization step will be carried out at a temperature of 190 ° C or less, preferably at a temperature of 180 ° C or less, more preferably at a temperature of 160 ° C or less, for example, at a temperature in the range 140-160 ° C or 130-160 ° C.
[0027] Thus, the process of the present invention will include a first clarification step and a first deodorization step followed by a final clarification step and, optionally, a final deodorization step. It can also include one or more alkaline treatment steps.
Alkaline Treatment [0028] According to a preferred embodiment, the process of the present invention can also include one or more alkaline treatment steps. The term alkaline treatment as used herein is not to be understood as referring only to the traditional chemical refining process known as alkaline refining, but rather to any treatment of the oil with an alkali (that is, any process in which the oil raw or partially refined is to be contacted with an alkali), as will become evident below.
• Alkaline Refining [0029] According to a specific modality, the alkaline treatment will consist of an alkaline refining step that comprises: (a) mixing a crude or partially refined oil with an aqueous alkali solution to produce a partially oil mixture refined and sludge (soapstock); (b) separate the sludge (soapstock) (for example using a centrifuge or a sedimentation tank); and (c) washing the partially refined oil (preferably with water at a temperature in the range of 70-105 ° C). The partially refined oil,
Petition 870190018319, of 02/22/2019, p. 18/39
12/26 washed, it can then be released to the next refining step (note: in the case of micelle, alkaline refining will result in a washed, neutralized micelle, which will first have to undergo evaporation before the oil can be released to the refining step). [0030] Alkalis that can be used for alkaline refining will typically be strong alkalis like sodium hydroxide or sodium carbonate. Sodium hydroxide, for example, will preferably be used at a concentration of approximately 25%. This and other possible variations of the alkaline refining step will be evident to the person skilled in the art and therefore need not be described in detail here.
[0031] Without adhering to the theory, it is considered that this alkaline refining step will allow the 3-MCPD and / or glycidyl ester precursors to be removed from the crude or partially refined oil, thus reducing the total number of esters of 3-MCPD and / or glycidyl esters formed during further processing (for example, during deodorization). Thus, when used, this type of alkaline treatment step will preferably be carried out before the first deodorization step, more preferably before the first clarification step.
• Alkaline Interesterification [0032] According to another embodiment of the present invention, the alkaline treatment step can be an alkaline interesterification step, carried out by contacting a crude or partially refined oil with an alkaline interesterification catalyst.
[0033] Interesterification is used to change the acyl-glycerol profile of an oil (in particular by exchanging fatty acids between different triglycerides). Again, without sticking to the theory, it is considered that the alkaline interesterification step allows the removal of the 3-MCPD esters and / or glycidyl esters themselves from a treated oil. Of this
Petition 870190018319, of 02/22/2019, p. 19/39
13/26 mode, when used, the alkaline interesterification stage will preferably be performed after the first deodorization stage and, more preferably, before the final clarification stage.
[0034] Numerous alkaline interesterification catalysts are known in the art. These include, by way of example only, sodium alcoholates and potassium alcoholates such as sodium methoxide and / or sodium ethoxide; sodium stearate; sodium hydroxide and potassium hydroxide. Any of these can be used for the purposes of the present invention. According to a specific embodiment, sodium methoxide is used, preferably at levels of approximately 0.05 to 0.1%, by weight. Advantageously, the oil to be treated will be contacted with the alkaline interesterification catalyst under vacuum and at a temperature in the range of 80 to 120 ° C. The contact will preferably be maintained for 30 to 90 minutes. This will typically result in total oil interesterification although it should be noted that actual interesterification is not considered necessary to achieve reduced levels of 3-MCPD ester.
[0035] According to a specific embodiment, the process of the present invention can include multiple steps of alkaline treatment. for example, it can include an alkaline refining step before the first deodorization and an alkaline interesterification step subsequent to the first deodorization. Other possible permutations will be evident to a person skilled in the art.
[0036] Thus, by way of illustration, the possible modalities of the present invention include:
(I) subject an oil to (a) an alkaline refining step, (b) a clarification step, (c) a deodorization step, (d) a final clarification step, and (e) a mild deodorization step , Final.
(II) subjecting an oil to (a) a clarification step, (b)
Petition 870190018319, of 02/22/2019, p. 20/39
14/26 a deodorization step, (c) an alkaline interesterification step, (d) a final clarification step, and (e) a mild, final deodorization step.
(III) subjecting an oil to (a) an alkaline refining step, (b) a clarification step, (c) a deodorization step, (d) an alkaline interesterification step, (e) a final clarification step, and (f) a mild, final deodorization step.
(IV) subjecting an oil to (a) an alkaline refining step, (b) a clarification step, (c) a deodorization step, and (d) a mild, final clarification step.
(V) subjecting an oil to (a) a clarification step, (b) a deodorization step, (c) an alkaline interesterification step and (d) a mild, final clarification step.
(VI) subjecting an oil to (a) an alkaline refining step, (b) a clarification step, (c) a deodorization step, (d) an alkaline interesterification step and (e) a mild clarification step, Final.
Additional Steps [0037] In addition to the refining steps described above, the process of the present invention can include one or more additional treatment or refining steps. For example, crude or partially refined oil can be subjected to one or more degumming steps. Any of a variety of degumming processes known in the art can be used. Such a process (known as aqueous degumming) includes mixing water with the oil and separating the resulting mixture into an oily component and a component of oil-insoluble hydrated phosphatides, sometimes called wet gum or wet lecithin. Alternatively, the phosphatide content can be reduced (or further reduced) by other degumming processes, such as acid degumming (using, for example,
Petition 870190018319, of 02/22/2019, p. 21/39
15/26 citric acid or phosphoric acid), enzymatic degumming (eg ENZYMAX by Lurgi) or chemical degumming (eg, SUPERIUNI degumming by Unilever or TOP degumming by VandeMoortele / Dijkstra CS). If a degumming step is used, it will preferably precede the first clarification step.
[0038] The process can also optionally include one or more neutralization steps (before the first clarification), any type of dewaxing (at any stage in the process), fractionation (at any stage in the process).
[0039] The process of the invention can also include one or more steps of chemical or enzymatic modification, including for example hydrogenation and / or interesterification. Hydrogenation will preferably be carried out before either the first deodorization stage or the final clarification stage. Chemical interesterification will preferably be carried out after initial deodorization and before final deodorization, if used. If the oil being treated according to the present process has a relatively low FFA content, it can also be carried out before the initial deodorization. Enzymatic interesterification can be carried out at any stage in the process and will preferably be carried out with a lipase enzyme. Advantageously, it was found that when carried out after the initial deodorization step, enzymatic interesterification could be used as an alternative to the second clarification step, or it could be carried out at the same time, in the same process (for example, in a batch or in a fixed bed column).
[0040] The process may also include - or in fact be preceded or followed by - one or more mixing steps. It may be desirable, for example, to mix oils of different types or from multiple sources. For example, numerous crude or partially refined oils could be mixed before the first clarification step. Al
Petition 870190018319, of 02/22/2019, p. 22/39
16/26 ternatively, two or more refined oils could be mixed after the final refining step or partially refined oils could be mixed in an intermediate stage.
[0041] Many permutations and variations of the present process are possible. These will be evident to a knowledgeable person depending on the nature of the crude oil being used as a raw material and / or the type of refined oil being produced and its intended end use. The only restriction that will be imposed is that the oil should not be subjected to any treatment steps after the final refining step (ie, clarification and / or deodorization), which could significantly increase the levels of 3-MCPD esters and / or glycidyl ester in the oil beyond the target level.
Products [0042] Refined oils obtained by means of the above process are also part of the present invention. Specifically, a refined oil is provided which has a reduced ester content of 3-MCPD and / or glycidyl ester. Refined oils can be derived from crude or partially refined oils of any type, source or origin. They can be derived, for example, from one or more plant and / or animal sources and can include oils and / or fats from a single source or blends from two or more oils and / or fats from different sources or with different characteristics. They can be derived from standard oils or special quality oils such as 3-MCPD base oils, modified or unmodified oils and / or fats (ie, oils in their natural state or oils that have been subjected to chemical or enzymatic modification or fractionation) and etc. Preferably, they will be derived from vegetable oils or from blends of vegetable oils. Examples of suitable vegetable oils include: soybean oil, corn oil, cottonseed oil, palm oil, palm kernel oil, peanut oil, rapeseed oil,
Petition 870190018319, of 02/22/2019, p. 23/39
17/26 saffron, sunflower oil, sesame seed oil, rice bran oil, coconut oil, canola oil and any fractions or derivatives thereof. According to a particularly preferred embodiment, the refined oils of the present invention will be derived from palm oil.
[0043] Different oils contain different levels of 3-MCPD ester precursors and glycidyl esters and therefore produce different levels of 3-MCPD esters and glycidyl esters after processing. The refined oils of the present invention will have a reduced ester content of 3-MCPD and / or glycidyl ester, the reduced term referring to an ester content of 3-MCPD and / or glycidyl ester which is less than that of a corresponding oil obtained by standard refining (ie, degumming, clarification and standard deodorization). Preferably, the refined oils will have a combined ester content of 3-MCPD and glycidyl ester which is at least 50% lower than that of the corresponding oil obtained by standard refining. More preferably, the combined content of 3-MCPD ester and glycidyl ester will be at least 60% lower, more preferably at least 70% lower, more preferably at least 80% lower, more preferably at least 90% lower .
[0044] Considering palm oil as an example, when refined by standard physical refining (degumming, clarification, deodorization), it has a combined content of 3-MCPD ester and 15 to 25 ppm glycidyl ester. By way of comparison, a refined palm oil of the invention (or obtainable according to the process of the invention) will have a combined content of esters of 3-MCPD and glycidyl esters (M + G) preferably not more than 5 ppm not greater than 3 ppm, more preferably not greater than 2 ppm, more preferably not greater than 1 ppm, more preferably not greater than 0.5 ppm. According to certain modalities
Petition 870190018319, of 02/22/2019, p. 24/39
Specific 18/26, will have a combined M + G content of 2.5 to 5 ppm. Alternatively, it can have a combined M + G content of 1 to 3 ppm. Alternatively, it can have a combined M + G content of 1 to 2.5 ppm. Alternatively, they can have a combined M + G content of 0.3 to 1.7 ppm. Alternatively, it can have a combined M + G content of 0.5 to 1 ppm.
[0045] Unless otherwise specified, the combined content of 3-MCPD esters and glycidyl esters will be determined using method A (DGF Standard Methods Section C (Fats) C-III 18 (09) Option A. The ester content of 3-MCPD alone can be determined by method B (DGF Standard Methods Section C (Fats) C-III 18 (09) Option B). The glycidyl ester content can therefore be calculated as the result of method A minus the result of method B.
[0046] Advantageously, the process of the present invention will be able to produce oils with detectable levels of glycidyl esters. Undetectable means that any glycidyl esters that are measured will be within the error range of the test method. For example, refined oil may have a glycidyl ester content of 0.05 ppm or less, more preferably 0.01 ppm or less.
[0047] Refined oils also preferably have an FFA content of less than 0.1%, more preferably less than 0.05% by weight - to avoid disgusting or unpleasant odor and / or taste. In fact, the refined oils of the present invention will ideally have a flavor value, measured according to method C, of 8 or greater, preferably 9 or greater.
Drinks and Foodstuffs [0048] The refined oils of the present invention can be packaged and sold as such (i.e., as low oils in 3-MCPD / low in glycidyl ester) or can be further mixed with one or more other oils or other oily compositions and / or with a
Petition 870190018319, of 02/22/2019, p. 25/39
19/26 or more other ingredients, including, if desired, with one or more additives. If the refined oils of the invention are mixed with one or more other oils, they will preferably be deodorized oils and, even more preferably, refined oils obtainable according to the process of the invention.
[0049] These refined oils and blends of refined oils can be used for any desired purpose, for example, in the food and beverage industry. Thus, according to a specific embodiment, the present invention provides a food and / or drink composition comprising a refined oil or a blend of refined oils as described above.
[0050] The refined oils of the invention can, for example, be used in bakery products (for example, cakes, breads, raw doughs, sweets and savory products in general made with wheat flour, soft doughs, etc.), culinary (for example, broths), frozen products (for example, pizzas, chips, etc.) or dairy products (for example, cheese products, yoghurts, ice cream, etc.), in fat-based products (such as margarine or frying oils), in baby formulas, nutritional supplements and so on, just like any other oil or other blend of oils. The refined oils of the present invention will be particularly suitable for use in baby formula and / or other products for baby nutrition. Preferably, they will be used in baby nutrition products to replace other oils and / or other fats.
Methods and Examples
Method C:
[0051] The taste of refined oils and fats is an important criterion for judging the quality of the oil; mainly oxidation products that are recognized during tasting.
• Tasting area
Petition 870190018319, of 02/22/2019, p. 26/39
20/26 [0052] The tasting test area must be located in a clean and neutral environment.
• Sample withdrawal [0053] Each batch of refined oils / fats should be evaluated for flavor. A representative sample of a tank must be taken to taste the oil. The sample must be removed in accordance with the applicable local instruction. To take a representative sample, washing may be necessary. If oils are stored before testing, they need to be stored properly (that is, not at high temperatures).
• Sample / Materials Preparation
Used utensils for tasting Waste cups
White background Drinking water at 38 ° C
Microwave / oven clean glasses [0054] When sampling bottles that are dirty both on the outside and on the inside; pour the oil / grease into a glass beaker to avoid strange flavors from the dirty bottle. Before the tasting can begin, the samples must be at specific temperatures: vegetable oils are tasted at room temperature; fats are tasted at a temperature of ± 50 ° C (or 10 ° C above the melting point). Fats can be heated in an oven or microwave to reach this temperature.
• Odor and Flavor Testing Methods [0055] 1 or 2 tasting panel members (who are trained and qualified to taste oils) must test the taste of each batch of refined oils / fat. They need to first clean their mouths with water (moderately hot at about 38 ° C) and evaluate the oil / fat (swirling the oil / fat before sniffing). 10 ml of the oil / fat are then added in the mouth and
Petition 870190018319, of 02/22/2019, p. 27/39
21/26 carefully rolled throughout the mouth (at least for 10 s, without swallowing). The oil / fat is then spit into a waste glass and any aftertaste is observed. If other samples need to be tested, testers need to wash their mouths with hot water (about 38 ° C) between each sample.
[0056] The following needs to be taken into account: fats must not harden inside the mouth, nor be too hot because this influences the taste; to release the aromas in oil / fats, it is necessary to alternately draw a little air through the mouth and circulate with the tongue; the taste test must be carried out no earlier than half an hour after smoking, drinking coffee or eating. In general, the first sample will not score well. This is because the person who tastes it has to overcome the aversion to adding oil / fat in the mouth. Therefore, it is recommended that the taste of the first sample be tested again after 3 or 4 oils / fats tested.
• Evaluation [0057] The oil is evaluated using a rating scale to judge the quality. This rating scale is based on the scales mentioned in AOCS Cg 2-83, and ranges from 1 to 10 - with 8 or higher being considered good, that is, which has a mild flavor.
Punctuation Intensity level 10 Zero 9 Trace 8 Weak 7 Tenuous 6 Mild 5 Moderate 4 Need 3 Strong 2 Very strong
Petition 870190018319, of 02/22/2019, p. 28/39
22/26
1 Extreme
[0058] Mild is defined as an (a) oil / fat that has no strange taste, which negatively influences the flavor and aroma of the oil. It does not mean that the oil has no taste and aroma.
Example 1 (reference) [0059] Crude palm oil with 5.52% FFA was alkaline refined (on an industrial scale) using 5.4% sodium hydroxide solution (20%). Neutralization was carried out by mixing and centrifugation at 105 ° C. The washing after separation is done with 10% water under the same conditions. Clarification with 1% Taiko classic G was carried out for 37 min at 98 ° C. Deodorization was carried out for 50 min at 240 ° C and 400 Pa (4 mbar) using 2% water spray.
[0060] From these, standard production samples were taken, showing on average: 0.65 ppm 3-MCPD, and 2.13 ppm 3-MCPD + glycidol (ie 0.99 ppm glycidol).
[0061] After 2 clarification of this oil with 0.5% clarifying clay (Taiko classic L) for 30 min at 100 ° C, the product showed 0.65 ppm of 3-MCPD and 0.66 ppm of 3- MCPD + glycidol. The taste, however, had a strong strange taste suggesting a significant increase in FFA levels. Further physical refining under standard conditions was therefore carried out and resulted, on average, in 3.43 ppm 3-MCPD and 10.02 ppm 3-MCPD + glycidol (meaning 4.42 ppm glycidol).
Example 2 (soft deodorization end) [0062] An alkali - refined palm oil obtained according to the above description (2 without clarification and deodorizing) was reclarificado clarifier with 0.5% clay (Izegem BC) and deodorized at temperatures 183.7 ° C, 188.1 ° C and 196.3 ° C, respectively. The oils obtained were analyzed and the results are shown below:
Petition 870190018319, of 02/22/2019, p. 29/39
23/26
Deodorizing Temp. 3-MCPD (ppm) 3-MCPD + glycid ol (ppm) Glycidol (ppm) 196.3 ° C 0.73 0.85 0.080 188.1 ° C 0.67 0.71 0.027 183.7 ° C 0.67 0.68 0.007
[0063] As can be seen from these results, the final smooth refining step results in oils with very low levels of 3-MCPD ester and glycidol-ester. In fact, at deodorizing temperatures below 190 ° C, the glycidyl ester levels are effectively undetectable.
Example 3 (flavor analysis) [0064] In a pilot system for clarification and deodorization, 25 kg of physically refined palm oil (RBD standard palm oil) was re-refined with 0.5% Taiko classic G at 100 ° Ç. The product was filtered and then deodorized at temperatures between 120 and 220 ° C. At each setpoint, the temperature was maintained for 30 min, a tasting sample was taken and the temperature was then increased to the next setpoint. The taste analysis (according to method C) is shown in the table below, demonstrating that, from 140 ° C onwards, all samples were as good in taste as the standard RBD palm oil and that, even at 120 ° C, the samples still taste very smooth, very good.
Sample: Flavor RBD palm oil 9 RBD palm oil re-refined 4 RBD re-refined and redesodorized @ 120 ° C 8 RBD reclarified and redesodorized @ 140 ° C 9 RBD reclarified and redesodorized @ 160 ° C 9 RBD reclarified and redesodorized @ 180 ° C 9 RBD reclarified and redesodorized @ 200 ° C 9
Petition 870190018319, of 02/22/2019, p. 30/39
24/26
Sample: Flavor RBD reclarified and redesodorized @ 220 ° C 9
zxample 4 [0065] In a pilot system for clarification and deodorization, 25 kg of palm oil (RDB) physically refined were reclarified with 0.5% Taiko classic G at 100 ° C. The product was filtered and deodorized at 140 ° C. The flavor and 3-MCPD and glycidol data are shown in the table below, demonstrating that, at 140 ° C, the taste was again as good as that of the RBD palm oil being tested, and that the 3-MCPD values / glycidol did not increase again after additional deodorization.
Sample: Flavor 3-MCPD +glycidol 3-MCPD RBD palm oil 8 21.29 2.86 RBD palm oil re-refined 4 2.78 2.77 RBD reclarified and redesodorized@ 140 ° C for 60 min 8 2.77 2.59 Example 5 (final smooth clarification)
[0066] Reclarification of 150 ml of RBD palm oil was performed using 0.2% Taiko classic G. Clarification was performed for 30 min at 70 ° C, 85 ° C and 100 ° C under vacuum. All filling and filtration steps were performed under atmospheric conditions. The table below shows the 3-MCPD content data and flavor analysis. The advantage of the lower temperature in clarification in relation to the flavor could be demonstrated.
Reclarification temperature [° C] Flavor 3-MCPD + glycidol[pm] 3-MCPD[pm] 100 ° C 4 2.36 n.m. 85 ° C 6 3.22 n.m.
Petition 870190018319, of 02/22/2019, p. 31/39
25/26
70 ° C 7 5.26 n.m. Standard RBD 9 9.44 2.40
(n.m. = not measured)
Example 6 (clarification in a low oxygen environment) [0067] Reclarification of 150 ml of RBD palm oil was performed using 0.2% Taiko classic G. Clarification was performed for 1 h at 70 ° C and 85 ° C, under vacuum. All stages of filling and filtration were carried out under a nitrogen atmosphere. The table below shows the 3-MCPD content data and flavor analysis. Under nitrogen, the results for flavor were significantly better. Even in prolonged clarification time, clarification did not lower the flavor rating compared to the RBD palm oil being tested, although glycidol removal was complete.
Temperature[° C] Flavor 3-MCPD + glycidol [pm] 3-MCPD[pm] 85 8 3.63 n.m. 70 8 3.97 n.m. RBD 7 16.7 3.54 Example 7
[0068] On an industrial scale, 28 mt of RBD palm oil (deodorized at 270 ° C) were chemically interesterified using 0.1% sodium methoxide as an interesterification catalyst. After reaction for 1 h at 95 ° C, the catalyst was neutralized with water and removed by washing. After clarification with 0.5% BC at 100 ° C and deodorization at 235 ° C, the product was reclarified and deodorized at 220 ° C.
Sample 3-MCPD[pm] 3-MCPD + glycidol [pm] Gicidol[pm] RBD palm oil 3.22 41.6 25.71
Petition 870190018319, of 02/22/2019, p. 32/39
26/26
After chemical interesterification and clarifying 1 0.47 1.28 0.54 After deodorization at 235 ° C 0.63 2.84 1.48 After reclarification 0.66 0.67 0.01 After deodorization at 220 ° C 0.64 1.13 0.33
Petition 870190018319, of 02/22/2019, p. 33/39

权利要求:
Claims (4)
[1]
1. Process for the production of a refined oil that has a reduced ester content of 3-MCPD and / or glycidyl-ester characterized by the fact of understanding to subject the oil to the following steps, in order: (a) a clarification step , (b) a deodorization step, (c) a final clarification step with activated clarifying clay, and (d) a final deodorization step, the final deodorization step (d) being carried out at a temperature of at least 40 ° C below the temperature of the deodorization step (b) and the final deodorization step (d) is carried out at a temperature of 190 ° C or less.
[2]
2. Process according to claim 1, characterized by the fact that the final deodorization step (d) is carried out at a temperature below 80 ° C.
[3]
3. Process according to claim 1, characterized in that it additionally comprises one or more alkaline treatment steps.
[4]
4. Process according to claim 1, characterized by the fact that it produces a refined palm oil with a combined ester content of 3-MCPD + glycidyl-ester not more than 5 ppm, preferably not more than 3 ppm, more preferably no more than 2 ppm.

类似技术:

公开号 | 公开日 | 专利标题

BR112013020106B1|2019-10-15|Process for the production of refined oil having a reduced content of 3-MCPD ester and / or glycidyl ester

JP6134399B2|2017-05-24|Method for producing gamma-oryzanol-containing fat / oil

AU2018273218A1|2019-12-19|Oils without unwanted contaminants

JPWO2009028483A1|2010-12-02|Oil composition

JP2017029044A|2017-02-09|Edible oil/fat

JP5416519B2|2014-02-12|Method for producing refined fats and oils

KR20090094397A|2009-09-04|Oil-and-fat composition, and food or beverage containing the oil-and-fat composition

CN110708961A|2020-01-17|Stability of oil by short path evaporation

BR112020015549A2|2021-02-02|process for preparing purified liquid vegetable oil, deodorized liquid vegetable oil, food product, and use of an adsorbent

DK2435545T3|2017-08-21|OIL FORMATIONS

同族专利:

公开号 | 公开日

CA2825534A1|2012-08-16|

EP3056558A1|2016-08-17|

EP3385360B1|2021-03-31|

RU2599643C2|2016-10-10|

AU2012216164B2|2016-01-07|

EP3388502B1|2021-03-31|

US20130323394A1|2013-12-05|

HUE054538T2|2021-09-28|

EP3385360A1|2018-10-10|

PL3385360T3|2021-09-06|

HUE054537T2|2021-09-28|

EP3056558B1|2019-04-24|

US20190082710A1|2019-03-21|

CN106867658A|2017-06-20|

BR112013020106A2|2017-06-13|

MX2013008558A|2013-08-21|

DK3385360T3|2021-05-31|

CA2825534C|2019-01-15|

DK3056558T3|2019-05-20|

MX344568B|2016-12-20|

AU2012216164A1|2013-07-18|

ES2728007T3|2019-10-21|

EP3388502A1|2018-10-17|

UA112766C2|2016-10-25|

ES2683348T3|2018-09-26|

EP3398450A1|2018-11-07|

US20170042174A1|2017-02-16|

RU2013141411A|2015-03-20|

EP2672834A1|2013-12-18|

EP2672834B1|2018-07-18|

WO2012107230A1|2012-08-16|

DK2672834T3|2018-08-20|

ES2872957T3|2021-11-03|

ES2872956T3|2021-11-03|

DK3388502T3|2021-05-31|

MY177791A|2020-09-23|

CN103369972A|2013-10-23|

PL3388502T3|2021-09-27|

引用文献:

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

DE879137C|1950-10-12|1953-06-11|Metallgesellschaft Ag|Process for cleaning vegetable or animal oils or fats|

US4089880A|1975-03-13|1978-05-16|Sullivan Systems Inc.|Proces for refining fatty oils|

US5434278A|1989-09-20|1995-07-18|Nabisco, Inc.|Synthesis of acetoglyceride fats|

EP1178103A1|2000-08-02|2002-02-06|Dsm N.V.|Purifying crude pufa oils|

EP1417288B1|2001-07-23|2018-08-29|Cargill, Incorporated|Method and apparatus for processing vegetable oils|

EP1505145B1|2003-08-06|2006-06-28|De Smet Engineering N.V.|Method and apparatus for vacuum stripping|

US20080003329A1|2006-06-30|2008-01-03|Ricardo Rueda|Enriched infant formulas|

FR2934385B1|2008-07-25|2011-09-16|Continental Automotive France|INTERFACE SYSTEM FOR SEIZING A SUITE OF CHARACTERS|

US8344681B2|2008-09-29|2013-01-01|Francesco Servidone|Apparatus and method for minimizing undesirable stepper motor rotor motions|

DE102008060059A1|2008-12-02|2010-06-10|Süd-Chemie AG|Method for reducing the 3-MCPD content in refined vegetable oils|

IN2012DN00608A|2009-07-21|2015-05-22|Nestec Sa|

SG177707A1|2009-07-21|2012-02-28|Nestec Sa|A deodorized edible oil or fat with low levels of bound mcpd and process of making using an inert gas|

JP5700503B2|2009-09-07|2015-04-15|日清オイリオグループ株式会社|Glyceride composition and method for producing the glyceride composition|

WO2011040539A1|2009-09-30|2011-04-07|不二製油株式会社|Method for reducing chloropropanols and formative substance thereof, glycidol fatty acid esters, in glyceride oils|

US20120238770A1|2009-12-04|2012-09-20|Archer Daniels Midland Company|Glycidyl ester reduction in oil|

JP5717351B2|2010-03-17|2015-05-13|花王株式会社|Method for producing refined fats and oils|

CN102334563B|2010-07-16|2015-03-25|丰益生物技术研发中心有限公司|Method for controlling content of 3-chloro-1,2-propanediol or ester thereof in oil|

GB201019639D0|2010-11-19|2010-12-29|Loders Croklaan Bv|Method|

US20130323394A1|2011-02-10|2013-12-05|Cargill, Incorporated|Oil compositions|

JP5216942B1|2011-07-29|2013-06-19|日清オイリオグループ株式会社|Purified glyceride composition and method for producing the purified glyceride composition|

EP3321348B1|2017-08-23|2019-12-18|Bunge Loders Croklaan B.V.|Process for refining vegetable oil with suppression of unwanted impurities|JP5717351B2|2010-03-17|2015-05-13|花王株式会社|Method for producing refined fats and oils|

US20130323394A1|2011-02-10|2013-12-05|Cargill, Incorporated|Oil compositions|

WO2014012548A1|2012-07-18|2014-01-23|Aarhuskarlshamn Ab|Reduction of mcpd-compounds in refined plant oil for food|

JP5399544B1|2012-08-31|2014-01-29|日清オイリオグループ株式会社|Method for producing refined fats and oils|

US9534182B1|2012-12-18|2017-01-03|LiquiTech, LLC|Method of producing industrial corn base oil from a fermentation byproduct of a corn ethanol production process|

WO2015057139A1|2013-10-14|2015-04-23|Aak Ab|Mitigation of 2-mcpd, 3-mcpd, esters therof and glycidyl esters in vegetable oil|

EP3068854B1|2013-11-14|2020-07-29|Cargill, Incorporated|Removal of unwanted propanol components|

CN104694250B|2013-12-10|2020-02-04|丰益生物技术研发中心有限公司|Method for reducing 3-MCPD ester and/or glycidyl ester in grease|

CN104705422B|2013-12-16|2020-10-30|丰益生物技术研发中心有限公司|Method for preparing grease by enzyme method|

PL3154374T3|2014-05-16|2018-12-31|Sime Darby Malaysia Berhad|Process of refining a crude palm fruit oil product|

CN105767227A|2014-12-26|2016-07-20|丰益生物技术研发中心有限公司|Fat composition capable of reducing chloropropanol ester|

JP6779789B2|2015-01-16|2020-11-04|太陽油脂株式会社|Oil and fat composition for use in formula milk powder for childcare|

EP3098293A1|2015-05-27|2016-11-30|Evonik Degussa GmbH|A process for removing metal from a metal-containing glyceride oil comprising a basic quaternary ammonium salt treatment|

EP3098292A1|2015-05-27|2016-11-30|Evonik Degussa GmbH|A process for refining glyceride oil comprising a basic quaternary ammonium salt treatment|

GB2538758A|2015-05-27|2016-11-30|Green Lizard Tech Ltd|Process for removing chloropropanols and/or glycidol|

EP3630929A1|2017-05-24|2020-04-08|Cargill, Incorporated|Oils without unwanted contaminants|

EP3424346A1|2017-07-03|2019-01-09|Alfa Laval Corporate AB|Reduction of the content of glycidyl esters in edible oils|

WO2019027315A2|2017-08-04|2019-02-07|Sime Darby Plantation Intellectual Property Sdn Bhd|Process for producing a refined palm fruit oil having a reduced 3-mcpd content|

EP3321348B1|2017-08-23|2019-12-18|Bunge Loders Croklaan B.V.|Process for refining vegetable oil with suppression of unwanted impurities|

US10516824B2|2017-09-11|2019-12-24|Samsung Electronics Co., Ltd.|Apparatus and method for processing image received through a plurality of cameras|

US11149229B2|2018-02-21|2021-10-19|Cargill, Incorporated|Oil processing|

BR112021009237A2|2018-12-19|2021-08-10|Société des Produits Nestlé S.A.|prevention of mcpde formation in triacylglyceride oils|

WO2019175258A1|2018-03-14|2019-09-19|Societe Des Produits Nestle S.A.|Mechanical purification of triacylglyceride oils|

US20210363460A1|2018-05-07|2021-11-25|Arisdyne Systems, Inc.|Method for Refined Palm Oil Production with Reduced 3-MCPD Formation|

EP3942005A1|2019-03-22|2022-01-26|Cargill, Incorporated|Oil processing|

EP3739027A1|2019-05-14|2020-11-18|Clariant International Ltd|Method for reducing the 3-mcpd content in refined vegetable oils|

WO2021048271A1|2019-09-13|2021-03-18|Société des Produits Nestlé S.A.|Prevention of mcpd formation in triacylglyceride oils|

法律状态:
2018-02-14| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

2018-03-27| B15K| Others concerning applications: alteration of classification|Ipc: A23D 9/04 (2006.01), A23L 2/52 (2006.01), A23L 5/2 |

2018-12-04| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

2019-09-03| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

2019-10-15| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 09/02/2012, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 09/02/2012, OBSERVADAS AS CONDICOES LEGAIS |

优先权:

申请号 | 申请日 | 专利标题

EP11001076.6|2011-02-10|

EP11001076|2011-02-10|

PCT/EP2012/000593|WO2012107230A1|2011-02-10|2012-02-09|Oil compositions|

[返回顶部]