EP2594625B2 - Verfahren zur steuerung des pegels von 3-chloro-1,2-propandiol oder estern davon in ölen und fetten - Google Patents

Verfahren zur steuerung des pegels von 3-chloro-1,2-propandiol oder estern davon in ölen und fetten Download PDF

Info

Publication number
EP2594625B2
EP2594625B2 EP11806292.6A EP11806292A EP2594625B2 EP 2594625 B2 EP2594625 B2 EP 2594625B2 EP 11806292 A EP11806292 A EP 11806292A EP 2594625 B2 EP2594625 B2 EP 2594625B2
Authority
EP
European Patent Office
Prior art keywords
oil
amount
stirring
minutes
refined
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP11806292.6A
Other languages
English (en)
French (fr)
Other versions
EP2594625A4 (de
EP2594625A1 (de
EP2594625B1 (de
Inventor
Yuanrong Jiang
Wei Luo
Yong Wang
Yeting Liu
Lee Kee Gui
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wilmar Shanghai Biotechnology Research and Development Center Co Ltd
Original Assignee
Wilmar Shanghai Biotechnology Research and Development Center Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=45468931&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP2594625(B2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Wilmar Shanghai Biotechnology Research and Development Center Co Ltd filed Critical Wilmar Shanghai Biotechnology Research and Development Center Co Ltd
Publication of EP2594625A1 publication Critical patent/EP2594625A1/de
Publication of EP2594625A4 publication Critical patent/EP2594625A4/de
Application granted granted Critical
Publication of EP2594625B1 publication Critical patent/EP2594625B1/de
Publication of EP2594625B2 publication Critical patent/EP2594625B2/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/02—Refining fats or fatty oils by chemical reaction
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils

Definitions

  • the present invention relates to a method for processing edible oils and fats.
  • the present invention relates to a modified method for processing edible oils and fats, i.e., a method for controlling the amount of 3-chloro-1,2-propanediol or ester thereof (3-MCPD/3-MCPD FE) during the refinement of oils and fats.
  • Crude oil generally refers to the oils and fats extracted from plant or animal through leaching or pressing process while containing certain inedible or industrial impurities.
  • the main component of crude oil is a mixture of triglyceride fatty acids, which generally known as neutral oil.
  • crude oil further comprises non-glyceride substances (collectively called as impurities).
  • the impurities can roughly be classified by their types, properties and states into three categories, i.e., mechanical impurities, fat-soluble impurities and water-soluble impurities.
  • Refining oil and fat generally refers to the refinement of crude oil. Impurities in crude oil not only affect the edibleness and safe storage of the oils and fats, but also make intensive processing difficult. Meanwhile, rather than removing all of the impurities, refining is aimed at the removal of the impurities that are deleterious to edibleness, storage and industrial production, etc., including gossypol, proteins, phospholipids, slimes, water and the like, while keeping the beneficial "impurities” such as tocopherol, etc. Therefore, the purpose of refining oils and fats is to remove undesirable and deleterious impurities from the oils and fats for the producing of oil products that satisfy certain quality standard(s) based on various requirements and applications.
  • 3-MCPD is a carcinogenic contaminant commonly acknowledged worldwide, which is mainly produced during the processing of food product.
  • the refining process of oils and fats greatly increases the content of 3-MCPD; the presence of which in oils and fats is primarily in the forms of alcohol and ester, with ester as the dominant form.
  • the amount of it varies among different oils.
  • Chemical & Veterinary Test Agency (CVUA, Germany) classifies the amount of 3-MCPD in the common plant oils and fats into the following three levels:
  • the refined palm oil contains 4-30 mg/kg of 3-MCPD, the highest level in all of the oils.
  • TDI tolerable daily intake
  • the present invention is to provide a method for effectively controlling 3-MCPD and 3-MCPD FE during refining oils and fats without undue increasing of the factorial production cost.
  • the methods of the subject invention can be used in industrial production of food, thereby achieving an industrial production.
  • Another purpose of the subject invention is to provide an optimized process and refined oils and fats of high quality produced by the optimized process.
  • the amount of water used in step (E1) is in the range of 0.5-30 wt%, such as 0.5-20 wt%, 0.5-10 wt%, 2-20 wt%, or the like, of the bleached oil.
  • the mixing in step (E1) is performed at a temperature of not higher than 100°C, such as not higher than 95°C.
  • the mixing step is performed at temperature in the range of 60-100°C, preferably 70-95°C, and best 80-95°C.
  • the degumming step includes a process of mixing the crude oil, degumming medium and water, etc.
  • the degumming medium may be selected from the group consisting of citric acid solution, phosphoric acid solution and degummase. If a degummase is used, the reaction system is generally held at 50-80°C, with pH 5-6 for 2-4 hours. In industrial production, citric acid buffer (NaOH) may be used to adjust the pH to 5-6.
  • the degumming medium is used in an amount of no less than 0.05 wt% of the crude oil.
  • the water is used in an amount of no less than 0.5 wt% of the crude oil.
  • the concentration of acid in the degumming medium is no less than 5 wt% based on the total weight of the solution.
  • the degumming medium is not higher than 2 wt% of the crude oil.
  • the amount of water used in each degumming step is not higher than 30 wt% of the oil, such as in the range of 0.5-20 wt%, 0.5-10 wt%, 5-25 wt%. Said amount of water does not include the water in the degumming medium.
  • the concentration of acid is not higher than 80 wt%, such as in the range of 5-65 wt%, 10-60 wt% or 20-50 wt%. Degumming with water only may be difficult to reduce the amount of phospholipid in the oils and fats (unable to remove non-hydratable phospholipids via the conversion to hydratable phospholipid).
  • the bleaching medium used in the bleaching step (D) may be selected from the group consisting of natural clay, activated clay, activated carbon, attapulgite clay, etc., preferably the low-acidity clay activated by sulfuric acid (having a pH close to neutral).
  • the bleaching step (D) comprises:
  • the amount of water used in step (E1) is equal to or larger than 0.5 wt% of the bleached oil from step (D), generally within 30 wt%, such as 0.5-20 wt%, 0.5-10 wt%, and 5-25 wt%.
  • the mixing is carried out at 60-120°C, generally not higher than 100°C (such as 95°C). For example, the mixing is performed at 70-95°C or 80-95°C.
  • the method further comprises, after the deodorizing step, a step (E) of further contacting the deodorized refined oil with water, wherein step (E) comprises (E1) mixing with water and/or (E2) transesterification step; and a step (F) of drying the resultant water-containing oil phase.
  • step (E1) may be performed as mentioned above.
  • the present invention also provides a method for refining oils and fats comprising the following steps:
  • the method for refining oils and fats further comprises, between step (A) and step (D), an alkali refining step (B) in which an alkali solution is added to neutralize the oil phase from step (A-1), a soap-removing step (C) in which hot water is added to the oil phase from step (B) to remove soap stock, and an isolating and drying step (C-1) in which the water phase is removed and the oil phase from step (C) is dried.
  • Step (E1) and the degumming step are as described above.
  • the degumming medium is used in an amount of no less than 0.05 wt% of the crude oil.
  • the water is used in an amount of no less than 0.5 wt% of the crude oil.
  • the concentration of acid is not less than 5 wt% based on the total weight of the solution.
  • the degumming medium is not higher than 2 wt% of the crude oil.
  • the amount of water used in each degumming step is not higher than 30 wt% of the oil, such as in the range of 0.5-20 wt%, 0.5-10 wt%, 5-25 wt%. Said amount of water does not include the water in the degumming medium.
  • the concentration of acid generally is not higher than 80 wt%, such as in the range of 5-65 wt%, 10-60 wt% or 20-50 wt%.
  • the degumming step (D) includes:
  • the amount of water used in step (E1) is equal to or larger than 0.5 wt% of the bleached oil from step (D), generally within 30 wt%, such as 0.5-20 wt%, 0.5-10 wt%, and 5-25 wt%.
  • the mixing is carried out at 60-120°C, generally not higher than 100°C (such as 95°C). For example, the mixing is performed at 70-95°C or 80-95°C.
  • the crude oil or the bleached oil used in the present invention may be oils and fats extracted from plant oil material or animal through leaching or pressing processes, including but not limited to vegetable oils and fats and animal oils and fats, such as soybean oil, rapeseed oil, sunflower oil, coconut oil, peanut oil, safflower oil, cottonseed oil, rice bran oil, corn oil, olive oil, hydrogenated oils and fats, palm oil, etc., or mixtures thereof.
  • vegetable oils and fats and animal oils and fats such as soybean oil, rapeseed oil, sunflower oil, coconut oil, peanut oil, safflower oil, cottonseed oil, rice bran oil, corn oil, olive oil, hydrogenated oils and fats, palm oil, etc., or mixtures thereof.
  • the refined oil obtained from the method of the present invention comprises less than 0.5 ppm of 3-MCPD and 3-MCPD FE, based on the total weight of the refined oil.
  • a step (E) of rinsing the bleached oil is performed between the bleaching step (D) and the deodorizing step (G), wherein the step (E) is referring to a rinsing step (E1) by mixing with water.
  • the oil from the deodorizing step may be subjected to freezing crystallization processing.
  • the oil to be bleached may be subjected to freezing crystallization processing.
  • the freezing crystallization processing can be performed with the methods well known in the art.
  • the freezing crystallization processing can be performed according to the methods described in Examples 14 and 15 herein.
  • the amount of 3-MCPD or 3-MCPD FE in the refined oil may be advantageously reduced during the refinement of oils and fats if water is incorporated into the oil phase, specifically prior to the deodorizing step, and then isolating the water phase, followed by drying the oil phase before the deodorizing processing.
  • the degumming step is a step of degumming through acidifying and rinsing, which could effectively reduce the amount of the substances such as phospholipids, thereby further reducing the amount of 3-MCPD or 3-MCPD FE in the refined oil.
  • alkali refining step or neutralizing step
  • soap-removing step are optional.
  • the present inventors find that the alkali refining step and the subsequent soap-removing step may contribute to reducing the amounts of phosphorous substances and the precursors of 3-MCPD or 3-MCPD FE, such as chlorine ions, thereby further reducing the amount of 3-MCPD or 3-MCPD FE in the refined oil.
  • the inventors point out that, effectively controlling the amount of the phosphorus-containing substances, such as phospholipid, during the refining process may advantageously reduce the amount of 3-MCPD or 3-MCPD FE in the refined oil.
  • lower amount of the phosphorus-containing substances in the oils and fats before the deodorizing step is in favor of reducing the amount of 3-MCPD or 3-MCPD FE.
  • the amount of 3-MCPD or 3-MCPD FE may be reduced to a distinguish level, such as lower than 0.5 ppm.
  • the bleached oil used in the present invention may be oils and fats extracted from plant or animal through leaching or pressing processes and having been subjected to refining and bleaching, including but not limited to vegetable oils and fats and animal oils and fats, such as soybean oil, rapeseed oil, sunflower oil, coconut oil, peanut oil, safflower oil, cottonseed oil, rice bran oil, corn oil, olive oil, hydrogenated oils and fats, palm oil, etc., or mixtures thereof.
  • vegetable oils and fats and animal oils and fats such as soybean oil, rapeseed oil, sunflower oil, coconut oil, peanut oil, safflower oil, cottonseed oil, rice bran oil, corn oil, olive oil, hydrogenated oils and fats, palm oil, etc., or mixtures thereof.
  • steps (a) and (b) are duplicated for 1 or 2 or more times.
  • a step (c) may be performed by introducing nitrogen gas or vapor as deodorizing medium under a vacuum degree of not higher than 25 mBarA at a suitable temperature to carry out the deodorization for 45-90 minutes.
  • the vacuum may be released at a temperature below 50°C and the refined oil after deodorization could be obtained through filtration.
  • the present invention also provides a method according to claim 1for producing refined oils and fats, comprising the following steps:
  • the amount of phosphorus (PHOS) in the bleached oil obtained in step (D) is less than 3 ppm, best 1 ppm or less.
  • step (A) of the above method is repeated for 2 or 3 times.
  • steps (A) to (G) of the above method are repeated for 2 or 3 times.
  • the method for refining oils comprises the following steps:
  • the amount of phosphorus (PHOS) in the bleached oil obtained in step (6) is less than 3 ppm, more preferably 1 ppm or less.
  • step (1) of the above method is repeated for 2 or 3 times.
  • steps (1) to (9) of the above method is repeated for 2 or 3 times.
  • the alkali solution in step (3) may be any alkali solution, preferably selected from the group consisting of NaOH solution and KOH solution.
  • the alkali solution has a concentration of not higher than 35 wt%.
  • the hot water used in step (4) may have a temperature of 50°C or higher.
  • the degumming medium used in the degumming step is a citric acid solution with the concentration of the acid not less than 5 wt% based on the total weight of the solution.
  • the degumming medium is no less than 0.05 wt% of the crude oil and water is no less than 0.5 wt% of the crude oil.
  • the bleaching step may be carried out with conventional bleaching methods in the art.
  • the bleaching agent may contain but is not limited to natural clay, activated clay, activated carbon, attapulgite clay, etc., preferably the clay activated by sulfuric acid.
  • a further rinsing step is carried out after the deodorizing step (9), and then the oil is dried to ensure that the final refined oil is water-free.
  • steps including rinsing following by water isolating and oil phase drying are identical to steps (7) and (8) in the method of the present invention.
  • a step of transesterification (including rinsing) with drying may be incorporated into any stage of the process.
  • the step of transesterification with drying may be a conventional method in the art, such as, but is not limited to mixing the oil and fat with sodium methoxide, terminating the reaction with citric acid solution, rinsing the mixture to a neutral pH, obtaining the oil phase by centrifugation, and drying the oil at an elevated temperature under vacuum.
  • the "crude oil” refers to oils and fats extracted from plant or animal through leaching or pressing processes, including but not limited to vegetable oils and fats and animal oils and fats, such as soybean oil, rapeseed oil, sunflower oil, coconut oil, peanut oil, safflower oil, cottonseed oil, rice bran oil, corn oil, olive oil, hydrogenated oil and fat, palm oil, etc., or mixtures thereof.
  • the amount of 3-MCPD in the crude oil is 0.3 ppm or more based on the total weight of the crude oil.
  • crude palm oil with not higher than 3 wt% of free fatty acids is preferred.
  • refined oil refers to the oils and fats comprising less than 1 ppm of 3-MCPD, based on the total weight of the refined oil.
  • the refined oil obtained from the method of the present invention comprises less than 0.5 ppm of 3-MCPD and/or 3-MCPD FE, based on the total weight of the refined oil.
  • a method for improving the quality of a refined oil and fat including the steps of degumming through acidifying, alkali refining, rinsing and drying, wherein the method further comprises, in the following order, the steps of freezing crystallizing, bleaching and deodorizing.
  • several days such as after 5 days or more, 10 days or more, 20 days or more, or 30 days or more after rinsing and drying, the oil and fat are subjected to freezing crystallization, re-bleaching and re-deodorizing.
  • 5-40 days such as 10-30 days, after rinsing and drying, the oil and fat are subjected to freezing crystallization, re-bleaching and re-deodorizing.
  • the present invention also incorporates a method for transporting the oil and fat, including the steps of degumming through acidifying, alkali refining, rinsing and drying, wherein the oil and fat obtained after rinsing and drying are transported under normal temperature or with refrigeration.
  • the rinsed and dried oil and fat are subjected to freezing crystallization, re-bleaching and re-deodorizing treatments.
  • the above steps such as degumming through acidifying, alkali refining, rinsing and drying, bleaching, and deodorizing, may be performed according to the methods described herein.
  • the freezing-crystallization may be performed, for instance, according to the methods described in Examples 14 and 15 of the present invention.
  • the unit of the percent weight in volume is well known in the art. For example, it means the weight of a solute in 100 ml of a solution.
  • the quantity of 3-MCPD is determined by an indirect measuring approach which means several pre-treatments before GC-MS measurement (gas chromatography-mass spectroscopy).
  • Test example 1 the relationship between the amount of phospholipid and the amount of 3-MCPD in the refined oil and fat
  • Table 1 The quality of a crude oil is shown in Table 1.
  • Table 1 The conventional chemical and physical indexes of a crude palm oil (about 3% FFA) Sample Acid value mg KOH/g peroxide value mmol/kg Amount of phosphorus mg/kg Color R/Y,1" Iodine value gI/100g Amount of 3-MCPD ppm Crude palm oil 6.05 0.20 10.54 20.3/30 52.63 0.52
  • Example 1 Dry degumming (without rinsing and drying)-a control example
  • This example indicates that the formation of 3-MCPD in the bleached oil obtained from the conventional dry degumming method has substantially been enhanced upon the deodorizing step.
  • Example 2 Degumming through acidifying and rinsing with a combination of physical refining (not in scope of claim 1)
  • This example illustrates that the step of degumming through acidifying and rinsing may suppress the formation of 3-MCPD during deodorizing step.
  • Example 3 Dry degumming with a combination of rinsing the bleached oil (not in scope of claim 1)
  • Example 4 Degumming through acidifying and rinsing with a combination of rinsing the bleached oil (not in scope of claim 1)
  • This example displays that degumming through acidifying and rinsing along with rinsing and drying the bleached oil may effectively control the formation of 3-MCPD in the deodorizing step.
  • Example 5 Secondary refining (Multiple refining) (not in scope of claim 1)
  • Test example 1 The crude oil used in Test example 1 was employed.
  • Test example 1 The crude oil used in Test example 1 was employed.
  • Pure water was prepared using reverse osmosis (R/O) membrane.
  • Example 7 Degumming through acidifying and rinsing + transesterification (not in scope of claim 1)
  • Test example 1 The crude oil used in Test example 1 was employed.
  • Pure water was prepared using reverse osmosis (R/O) membrane.
  • Example 8 Rinsing the refined oil (not in scope of claim 1)
  • Pure water was prepared using reverse osmosis (R/O) membrane.
  • Example 9 Degumming through acidifying and rinsing + alkali refining + rinsing (not in scope of claim 1)
  • the amount of 3-MCPD in the final refined product could be effectively controlled by rounds of degumming through acidifying and rinsing, alkali refining, using activated clay with weak acidity and the subsequent rinsing.
  • Example 10 Dry degumming + rinsing + bleaching (not in scope of claim 1)
  • Test example 1 The crude oil of Test example 1 was used.
  • Example 11 Bleaching + deodorizing VS bleaching + rinsing + deodorizing (not in scope of claim 1)
  • the feed material was the material used in Test example 1.
  • Example 12 crude oil ⁇ (rinsing) ⁇ deodorizing (not in scope of claim 1)
  • the feed material used was the same as in Test example 1.
  • Example 14 Freezing fractionation after deodorization (not in scope of claim 1)
  • the processes were as follows: 1. Degumming through acidifying and rinsing: adding citric acid solution (50% mass concentration), in an amount of 0.1 wt% of the oil, and deionized water, in an amount of 10 wt% of the oil, into the oil, stirring at 80°C for 30 minutes, centrifuging at 4500 rpm for 15 minutes, and collecting the light phase, i.e., the oil; repeating this step twice and the resultant light phase proceeding to the next refining step; 2.
  • Rinsing stirring the oil with deionized water in an amount of 20 wt% of the oil at 90°C for 10 minutes, wherein the deionized water needs to be pre-heated to 85°C; 4. Drying: stirring at 90°C for 1 hour under vacuum; 5.
  • Bleaching adding Taiko Supreme 1B in an amount of 1 wt% of the oil into the dried oil at 95°C, stirring for 30 minutes under vacuum, obtaining the bleached oil by suction filtration while the processed oil was hot; 6.
  • Deodorizing introducing nitrogen gas (as a stirring and deodorizing medium) into the bleached oil under a vacuum degree of about 3-20 mBarA, maintaining at 240°C for 1 hour and then removing the heating jacket, releasing the vacuum at 50°C or below and then stopping the introduction of nitrogen gas, obtaining the refined oil by filtration; 7.
  • Freezing crystallization placing the refined oil into a crystallizer and freezing crystallized according to the following: Temperature (°C) Time for cooling (min) Time of constant temperature (min) Duration (min) 65 / / 240 65 / 60 60 50 60 / 60 40 60 / 60 30 60 60 15 120 300 420 15 / 300 300
  • the solid fat has a lowest amount of 3-MCPD and thus provides a higher safety.
  • Example 15 Freezing fractionation before bleaching (not in scope of claim 1)
  • the processes were as follows: 1. Degumming through acidifying and rinsing: adding citric acid solution (50 wt%), in an amount of 0.1 wt% of the oil, and deionized water in an amount of 10 wt% of the oil into the oil, stirring at 80°C for 30 minutes, centrifuging at 4500 rpm for 15 minutes, and collecting the oil-containing light phase; repeating this step twice and the light phase proceeding to the next refining step; 2.
  • Rinsing stirring the oil with deionized water in an amount of 20 wt% of the oil at 90°C for 10 minutes, wherein the deionized water needs to be pre-heated to 85°C; 4. Drying: stirring at 90°C for 1 hour under vacuum; 5.
  • Freezing crystallization placing the neutralized oil into a crystallizer and being freezing crystallized according to the following: Temperature (°C) Time for cooling (min) Time of constant temperature (min) Duration (min) 65 / / 240 65 / 60 60 50 60 / 60 40 60 / 60 30 60 60 15 120 300 420 15 / 300 300 Upon the completion of the above freezing crystallization, liquid oil and solid fat were obtained by pressure filtering through a plate-and-frame filter. 6. Bleaching: adding 1 wt% of Taiko Supreme 1B into the resultant liquid oil and solid fat, respectively, stirring for 30 minutes at 110°C under vacuum, obtaining the bleached oils by suction filtration while the oils were hot; 7.
  • Deodorizing introducing nitrogen gas (as a stirring and deodorizing medium) into the bleached oils under a vacuum degree of 1-20 mBarA, maintaining at 240°C for 1 hour and then removing the heating jacket, releasing the vacuum at 50°C or below and then stopping the introduction of nitrogen gas, obtaining the refined oils by filtration;
  • palm oil is separated into liquid oil and solid fat to ease applications with different requirements.
  • the freezing crystallization is generally performed after the deodorizing step, as described in Example 14.
  • the resultant liquid oil and solid fat will comprise lower amount of 3-MPCD and have favorable acid value and flavor. Palm oil is mainly produced outside China.
  • the refined oil and fat could still be processed by the freezing crystallization, bleaching and deodorizing even after 30 days of transportation for the purpose of acquiring excellent product qualities in various aspects. Therefore, the above process could solve the problem about poor quality of the refined palm oil obtained from the refining process as a result of the quality deterioration during long term transportation.
  • Example 16 Clay with strong acidity as the bleaching medium (not in scope of claim 1)
  • this example indicated that using clay with a near neutral pH may control the amount of 3-MCPD in the refined oil and fat more effectively.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Microbiology (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fats And Perfumes (AREA)
  • Edible Oils And Fats (AREA)

Claims (1)

  1. Verfahren zur Raffinierung von Öl und Fett, das die folgenden Schritte umfasst:
    (A) Entschleimen;
    (D) Bleichen der Ölphase aus Schritt (A);
    (E) Inkontaktbringen des gebleichten Öls aus Schritt (D) mit Wasser, das Folgendes umfasst:
    (E1) Mischen mit Wasser;
    (F) Isolieren der Wasserphase, Trocknen der Ölphase aus Schritt (E); und
    (G) Desodorieren der Ölphase aus Schritt (F),
    wobei das Verfahren weiter zwischen Schritt (A) und Schritt (D) Folgendes umfasst:
    einen Alkaliraffinierungsschritt (B) des Zugebens einer alkalischen Lösung, um die Ölphase aus Schritt (A) zu neutralisieren;
    einen Seifenentfernungsschritt (C) des Zugebens von heißem Wasser in die Ölphase aus Schritt (B), um Seifenstock zu entfernen, und
    einen Isolierungs- und Trocknungsschritt (C-1) des Entfernens der Wasserphase und Trocknens der Ölphase aus Schritt (C);
    und wobei der Phosphor des gebleichten Öls und Fetts weniger als 3 ppm, am besten weniger als 1 ppm beträgt,
    wobei der Bleichungsschritt (D) Folgendes umfasst:
    (i) Erhitzen der Ölphase aus Schritt (C-1) auf 80-90 °C unter Vakuum;
    (ii) Zugeben eines Bleichmediums;
    (iii) weiteres Erhitzen bis zu 100-110 °C und Rühren unter Vakuum für mindestens 10 Minuten; und
    (iv) Entfernen des Bleichmediums durch Filtration.
EP11806292.6A 2010-07-16 2011-07-13 Verfahren zur steuerung des pegels von 3-chloro-1,2-propandiol oder estern davon in ölen und fetten Active EP2594625B2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201010228009.XA CN102334563B (zh) 2010-07-16 2010-07-16 控制油脂中3-氯-1,2-丙二醇或其酯含量的方法
PCT/CN2011/077096 WO2012006950A1 (zh) 2010-07-16 2011-07-13 控制油脂中3-氯-1，2-丙二醇或其酯含量的方法

Publications (4)

Publication Number Publication Date
EP2594625A1 EP2594625A1 (de) 2013-05-22
EP2594625A4 EP2594625A4 (de) 2014-09-10
EP2594625B1 EP2594625B1 (de) 2016-11-16
EP2594625B2 true EP2594625B2 (de) 2019-12-04

Family

ID=45468931

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11806292.6A Active EP2594625B2 (de) 2010-07-16 2011-07-13 Verfahren zur steuerung des pegels von 3-chloro-1,2-propandiol oder estern davon in ölen und fetten

Country Status (5)

Country Link
EP (1) EP2594625B2 (de)
CN (1) CN102334563B (de)
ES (1) ES2613987T5 (de)
MY (1) MY161245A (de)
WO (1) WO2012006950A1 (de)

Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MY160521A (en) 2010-09-03 2017-03-15 Stepan Specialty Products Llc Elimination of organohalo and oxirane species in carboxylic acid ester streams
GB201019639D0 (en) 2010-11-19 2010-12-29 Loders Croklaan Bv Method
DK2672834T4 (da) 2011-02-10 2022-11-28 Cargill Inc Fremgangsmåde til fremstilling af en raffineret olie
CN102504950B (zh) * 2011-11-08 2013-06-05 安徽绿健生物科技有限公司 一种茶籽油的脱色方法
JP2013199581A (ja) * 2012-03-26 2013-10-03 Fuji Oil Co Ltd クロロプロパノール類の含有量が低減された精製パーム油（ｒｂｄｐｏ）の製造方法
WO2014012548A1 (en) 2012-07-18 2014-01-23 Aarhuskarlshamn Ab Reduction of mcpd-compounds in refined plant oil for food
CN103525548B (zh) * 2013-11-06 2014-10-01 江南大学 一种用于降低植物油中氯源及3-氯-1,2-丙二醇酯前体物质含量的脱胶方法
CN104698113A (zh) * 2013-12-06 2015-06-10 上海良友（集团）有限公司 一种食用油脂中的3-氯丙二醇脂肪酸酯和环氧甘油脂肪酸酯的检测方法
CN104694250B (zh) * 2013-12-10 2020-02-04 丰益(上海)生物技术研发中心有限公司 一种降低油脂中3-mcpd酯和/或缩水甘油酯的方法
HUE039998T2 (hu) 2014-05-16 2019-02-28 Sime Darby Malaysia Berhad Eljárás nyers pálmagyümölcs-olaj termék finomítására
CN105767227A (zh) * 2014-12-26 2016-07-20 丰益(上海)生物技术研发中心有限公司 一种能降低氯丙醇酯的油脂组合物
CN104531349A (zh) * 2015-01-23 2015-04-22 上海交通大学 一种降低油脂加工中3-氯-1,2-丙二醇酯的方法
CN106916630B (zh) * 2015-12-25 2021-05-18 丰益(上海)生物技术研发中心有限公司 一种控制油脂危害物产生的方法
CN105802731B (zh) * 2016-06-03 2019-11-01 上海交通大学 一种除去3-氯丙二醇酯的方法
CN108239573A (zh) * 2016-12-27 2018-07-03 中粮集团有限公司 油脂及其制备方法
MY193401A (en) * 2017-08-04 2022-10-11 Sime Darby Plantation Intellectual Property Sdn Bhd Process for producing a refined palm fruit oil having a reduced 3-mcpd content
CZ2017491A3 (cs) * 2017-08-25 2018-10-17 Vysoká škola chemicko-technologická v Praze Způsob odstranění acylderivátů monochlorpropandiolu a glycidolu z plně ztužených tuků určených pro potravinářské účely
JP2021516712A (ja) 2018-03-14 2021-07-08 ソシエテ・デ・プロデュイ・ネスレ・エス・アー トリアシルグリセリド油の精製
CN113242901A (zh) * 2018-12-19 2021-08-10 雀巢产品有限公司 防止三酰基甘油酯油中mcpde的形成
CN110358624A (zh) * 2019-07-09 2019-10-22 南海油脂工业(赤湾)有限公司 一种降低油脂中3-氯丙二醇酯的方法
CN113122377B (zh) * 2019-12-30 2024-05-28 丰益(上海)生物技术研发中心有限公司 一种在油脂精炼加工过程中脱除塑化剂的方法
CN113122387A (zh) * 2019-12-30 2021-07-16 丰益(上海)生物技术研发中心有限公司 油脂脱色及塑化剂脱除方法
CN113122382B (zh) * 2019-12-31 2024-02-20 丰益(上海)生物技术研发中心有限公司 一种低污染物含量的油脂的制备方法
CN111349513B (zh) * 2020-03-12 2023-03-17 青岛天祥食品集团有限公司 用于控制食用油中3-mcpd酯和缩水甘油酯生成的加工工艺
CN112592761A (zh) * 2020-09-30 2021-04-02 天津南侨食品有限公司 用于降低牛油中3-氯丙醇酯含量的控制方法
CN113755240A (zh) * 2021-09-17 2021-12-07 中粮农业产业管理服务有限公司 一种棕榈油中三氯丙醇酯和缩水甘油酯脱除方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB855349A (en) † 1956-12-21 1960-11-30 Unilever Ltd Improvements in or relating to confectioners' hard butter
GB989540A (en) † 1960-12-02 1965-04-22 Proctor & Gamble Ltd Interesterification process for fatty glycerides
GB990034A (en) † 1961-03-22 1965-04-22 Henkel & Cie Gmbh Production of fats by interesterification of natural triglycerides
WO2010069028A1 (en) † 2008-12-18 2010-06-24 Assessa Indústria Comércio E Exportação Ltda Process for manufacturing perfumes and colognes and for purifying and polishing alcohol
EP2311930A1 (de) † 2008-07-31 2011-04-20 Mizusawa Industrial Chemicals Ltd. Verfahren zur reinigung von umgeestertem öl

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2003250528A1 (en) * 2002-05-30 2003-12-19 Council Of Scientific And Industrial Research Process for the pre-treatment of vegetable oils for physical refining
CN100531583C (zh) * 2006-05-23 2009-08-26 大连兴龙垦有机粮油有限公司 低热量食用油脂生产方法
CN101168501B (zh) * 2007-07-11 2010-04-07 南京工业大学 一种从隐甲藻中提取并精制富含dha脂肪酸的工艺
MY157449A (en) * 2008-03-17 2016-06-15 Lipid Nutrition Bv Process for refining a triglyceride oil
CN101305974B (zh) * 2008-07-11 2010-04-14 广东新大地生物科技股份有限公司 化妆品用的山茶油制备方法
DE102008060059A1 (de) 2008-12-02 2010-06-10 Süd-Chemie AG Verfahren zur Reduzierung des 3-MCPD-Gehalts in raffinierten Pflanzenölen
CN101455242B (zh) * 2008-12-26 2011-05-04 河南华泰粮油机械工程有限公司 米糠一级油精炼的生产方法
EP2586854A1 (de) 2009-06-30 2013-05-01 Sime Darby Malaysia Berhad Verfahren zur Beseitung unerwünschter Propanolbestandteile aus unbenutztem Triglyzeridöl
MX2012000945A (es) 2009-07-21 2012-02-28 Nestec Sa Un aceite o grasa comestible desodorizada con niveles bajos de mcpd ligado y proceso de elaboracion mediante purificacion de carboximetil celulosa y/o resina.
SG177707A1 (en) 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
CN101665742A (zh) * 2009-09-29 2010-03-10 陈军 一种大叶种茶籽油的制备工艺
BR112012013162A2 (pt) 2009-12-04 2015-09-15 Archer Daniels Midlan Company método para a remoção de ésteres glicidílicos de óleo, método para a remoção de ésteres glicidílicos de óleo branqueado, composição e método para converter ésteres glicidílicos em monoacilgliceróis

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB855349A (en) † 1956-12-21 1960-11-30 Unilever Ltd Improvements in or relating to confectioners' hard butter
GB989540A (en) † 1960-12-02 1965-04-22 Proctor & Gamble Ltd Interesterification process for fatty glycerides
GB990034A (en) † 1961-03-22 1965-04-22 Henkel & Cie Gmbh Production of fats by interesterification of natural triglycerides
EP2311930A1 (de) † 2008-07-31 2011-04-20 Mizusawa Industrial Chemicals Ltd. Verfahren zur reinigung von umgeestertem öl
WO2010069028A1 (en) † 2008-12-18 2010-06-24 Assessa Indústria Comércio E Exportação Ltda Process for manufacturing perfumes and colognes and for purifying and polishing alcohol

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
"3-MCPD Esters in Food Products", ILSI EUROPE, February 2009 (2009-02-01), XP055403507 †
BERTRAND MATTHAUS: "Möglichkeiten der Minimierung von 3-MCPD-Fettsäureestern und verwandten Susbtanzen in Pflanzenölen", PRESENTATION, 20100125, XP055399320 †
D R TAYLOR: "Bailey's Industrial Oil and Fat Products, 6th Edition", part chapter 7 2005, article "Bleaching", pages: 285 - 339 †
DAN ANDERSON: "bailey's industrial oil and fat products,", article "A Primer on Oils Processing Technologies", pages: 1 - 29, XP055403496 †
RICHARD D O'BRIEN: "Fats and Oils", 1 January 2009, article "Formulating and processing for Applications", pages: 73-110, 122 - 132, XP055403493 †

Also Published As

Publication number Publication date
EP2594625A4 (de) 2014-09-10
CN102334563A (zh) 2012-02-01
WO2012006950A1 (zh) 2012-01-19
EP2594625A1 (de) 2013-05-22
ES2613987T5 (es) 2020-08-07
EP2594625B1 (de) 2016-11-16
CN102334563B (zh) 2015-03-25
MY161245A (en) 2017-04-14
ES2613987T3 (es) 2017-05-29

Similar Documents

Publication Publication Date Title
EP2594625B2 (de) Verfahren zur steuerung des pegels von 3-chloro-1,2-propandiol oder estern davon in ölen und fetten
EP0689578B1 (de) Entfernung von phospholipiden aus glyceridoelen
EP2449071B1 (de) Verfahren zur herstellung von palmölfraktionen praktisch frei von 3-monochlorpropandiolfettsäureestern
US7081542B2 (en) Chemical process for the production of 1,3-diglyceride oils
US11427781B2 (en) Products produced from distillers corn oil
JP5955119B2 (ja) 食用油脂の製造方法
WO2011009841A1 (en) A deodorized edible oil or fat with low levels of bound mcpd and process of making by carboxymethyl cellulose and/or resin purification
CN111349515B (zh) 一种零反的绿色精准适度加工油脂组合物及其制备方法
US5248799A (en) Process for refining glyceride oil
TW201408767A (zh) 精製油脂的製造方法
US20230227749A1 (en) Method for Refined Palm Oil Production with Reduced 3-MCPD Formation
CN111187660B (zh) 一种从磷虾中提取高品质磷虾油的方法
EP0077528B1 (de) Raffiniertes geniessbares Öl und Verfahren zur Herstellung desselben
CN114144506A (zh) 精制油脂的制造方法
TWI556744B (zh) Manufacture of grease
EP0116408A2 (de) Raffinieren von Triglycerid-Ölen in Anwesenheit von Alkalimetall-Borhydriden
EP2592133B1 (de) Enzymatische Entgummierung
US4609500A (en) Refining of oil and product thereof
JP2003529617A (ja) 植物原料油を安定化する方法
US4981620A (en) In-line dewaxing of edible vegetable oils
JP2014000012A (ja) 食用油脂の製造方法
JP6857017B2 (ja) 油脂組成物
CN113122382B (zh) 一种低污染物含量的油脂的制备方法
CN113122377B (zh) 一种在油脂精炼加工过程中脱除塑化剂的方法
CN111040873A (zh) 一种鱼油加工精制过滤工艺

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20130129

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
TPAC Observations filed by third parties

Free format text: ORIGINAL CODE: EPIDOSNTIPA

A4 Supplementary search report drawn up and despatched

Effective date: 20140807

RIC1 Information provided on ipc code assigned before grant

Ipc: C11B 3/00 20060101AFI20140801BHEP

Ipc: C11B 3/02 20060101ALI20140801BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20160603

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 845930

Country of ref document: AT

Kind code of ref document: T

Effective date: 20161215

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602011032541

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161116

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 845930

Country of ref document: AT

Kind code of ref document: T

Effective date: 20161116

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170217

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161116

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170216

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161116

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2613987

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20170529

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161116

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161116

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161116

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161116

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170316

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161116

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 7

REG Reference to a national code

Ref country code: DE

Ref legal event code: R026

Ref document number: 602011032541

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161116

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161116

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161116

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161116

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161116

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170216

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161116

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161116

26 Opposition filed

Opponent name: CARGILL, INCORPORATED

Effective date: 20170726

26 Opposition filed

Opponent name: UNILEVER N.V. / UNILEVER PLC

Effective date: 20170811

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161116

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20170713

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170713

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170731

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170731

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170713

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170713

R26 Opposition filed (corrected)

Opponent name: CARGILL, INCORPORATED

Effective date: 20170726

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170713

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

R26 Opposition filed (corrected)

Opponent name: UNILEVER N.V. / UNILEVER PLC

Effective date: 20170811

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO

APBM Appeal reference recorded

Free format text: ORIGINAL CODE: EPIDOSNREFNO

APBP Date of receipt of notice of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA2O

APBU Appeal procedure closed

Free format text: ORIGINAL CODE: EPIDOSNNOA9O

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161116

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20110713

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20161116

PUAH Patent maintained in amended form

Free format text: ORIGINAL CODE: 0009272

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT MAINTAINED AS AMENDED

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161116

27A Patent maintained in amended form

Effective date: 20191204

AK Designated contracting states

Kind code of ref document: B2

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: DE

Ref legal event code: R102

Ref document number: 602011032541

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161116

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161116

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170316

REG Reference to a national code

Ref country code: ES

Ref legal event code: DC2A

Ref document number: 2613987

Country of ref document: ES

Kind code of ref document: T5

Effective date: 20200807

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20230626

Year of fee payment: 13

Ref country code: FR

Payment date: 20230622

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20230627

Year of fee payment: 13

Ref country code: ES

Payment date: 20230809

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20230627

Year of fee payment: 13