EP0703960A1 - Fettenschleimungsverfahren und so erhaltenes fett - Google Patents
Fettenschleimungsverfahren und so erhaltenes fettInfo
- Publication number
- EP0703960A1 EP0703960A1 EP94916852A EP94916852A EP0703960A1 EP 0703960 A1 EP0703960 A1 EP 0703960A1 EP 94916852 A EP94916852 A EP 94916852A EP 94916852 A EP94916852 A EP 94916852A EP 0703960 A1 EP0703960 A1 EP 0703960A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fatty substance
- acids
- fatty
- emulsifier
- type
- 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.)
- Granted
Links
- 239000000126 substance Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims description 40
- 150000003904 phospholipids Chemical class 0.000 claims abstract description 34
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 23
- 239000007864 aqueous solution Substances 0.000 claims abstract description 20
- 239000008139 complexing agent Substances 0.000 claims abstract description 20
- 241001465754 Metazoa Species 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims description 32
- 150000007513 acids Chemical class 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 18
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 238000007670 refining Methods 0.000 claims description 11
- 125000000129 anionic group Chemical group 0.000 claims description 8
- 238000011065 in-situ storage Methods 0.000 claims description 8
- -1 phospho Chemical class 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 125000002091 cationic group Chemical group 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 6
- 235000021588 free fatty acids Nutrition 0.000 claims description 6
- 238000006386 neutralization reaction Methods 0.000 claims description 6
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical group [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 6
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 5
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 5
- 235000015165 citric acid Nutrition 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 235000011007 phosphoric acid Nutrition 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011975 tartaric acid Substances 0.000 claims description 5
- 235000002906 tartaric acid Nutrition 0.000 claims description 5
- 235000013311 vegetables Nutrition 0.000 claims description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 4
- 229940038773 trisodium citrate Drugs 0.000 claims description 4
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000008346 aqueous phase Substances 0.000 claims description 3
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 150000002632 lipids Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 2
- 239000003925 fat Substances 0.000 abstract description 11
- 239000010775 animal oil Substances 0.000 abstract 1
- 239000003599 detergent Substances 0.000 abstract 1
- 235000015112 vegetable and seed oil Nutrition 0.000 abstract 1
- 235000019871 vegetable fat Nutrition 0.000 abstract 1
- 239000008158 vegetable oil Substances 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 28
- 239000003921 oil Substances 0.000 description 23
- 235000019198 oils Nutrition 0.000 description 23
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 20
- 239000011574 phosphorus Substances 0.000 description 20
- 229910052698 phosphorus Inorganic materials 0.000 description 20
- 229910052742 iron Inorganic materials 0.000 description 13
- 150000001768 cations Chemical class 0.000 description 10
- 239000003549 soybean oil Substances 0.000 description 10
- 235000012424 soybean oil Nutrition 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000011777 magnesium Substances 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- 238000005119 centrifugation Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 5
- PORPENFLTBBHSG-MGBGTMOVSA-N 1,2-dihexadecanoyl-sn-glycerol-3-phosphate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP(O)(O)=O)OC(=O)CCCCCCCCCCCCCCC PORPENFLTBBHSG-MGBGTMOVSA-N 0.000 description 4
- JZNWSCPGTDBMEW-UHFFFAOYSA-N Glycerophosphorylethanolamin Natural products NCCOP(O)(=O)OCC(O)CO JZNWSCPGTDBMEW-UHFFFAOYSA-N 0.000 description 4
- 238000004061 bleaching Methods 0.000 description 4
- 238000010908 decantation Methods 0.000 description 4
- 150000008104 phosphatidylethanolamines Chemical class 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 230000008030 elimination Effects 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 240000002791 Brassica napus Species 0.000 description 2
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 241000243251 Hydra Species 0.000 description 2
- OYPRJOBELJOOCE-LZFNBGRKSA-N calcium-46 Chemical compound [46Ca] OYPRJOBELJOOCE-LZFNBGRKSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- QRXWMOHMRWLFEY-UHFFFAOYSA-N isoniazide Chemical compound NNC(=O)C1=CC=NC=C1 QRXWMOHMRWLFEY-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 235000014593 oils and fats Nutrition 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000012047 saturated solution Substances 0.000 description 2
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical class [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 235000017060 Arachis glabrata Nutrition 0.000 description 1
- 244000105624 Arachis hypogaea Species 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000018262 Arachis monticola Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- QZKRHPLGUJDVAR-UHFFFAOYSA-K EDTA trisodium salt Chemical compound [Na+].[Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O QZKRHPLGUJDVAR-UHFFFAOYSA-K 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 241000219146 Gossypium Species 0.000 description 1
- 244000020551 Helianthus annuus Species 0.000 description 1
- 235000003222 Helianthus annuus Nutrition 0.000 description 1
- 229920000715 Mucilage Polymers 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- NEUSVAOJNUQRTM-UHFFFAOYSA-N cetylpyridinium Chemical compound CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 NEUSVAOJNUQRTM-UHFFFAOYSA-N 0.000 description 1
- 229960004830 cetylpyridinium Drugs 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229960000878 docusate sodium Drugs 0.000 description 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 1
- 229940043264 dodecyl sulfate Drugs 0.000 description 1
- VICYBMUVWHJEFT-UHFFFAOYSA-N dodecyltrimethylammonium ion Chemical compound CCCCCCCCCCCC[N+](C)(C)C VICYBMUVWHJEFT-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 150000002338 glycosides Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- IZWSFJTYBVKZNK-UHFFFAOYSA-N lauryl sulfobetaine Chemical compound CCCCCCCCCCCC[N+](C)(C)CCCS([O-])(=O)=O IZWSFJTYBVKZNK-UHFFFAOYSA-N 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229920002113 octoxynol Polymers 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- GLFDLEXFOHUASB-UHFFFAOYSA-N trimethyl(tetradecyl)azanium Chemical compound CCCCCCCCCCCCCC[N+](C)(C)C GLFDLEXFOHUASB-UHFFFAOYSA-N 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/006—Refining fats or fatty oils by extraction
-
- 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
- C11B3/001—Refining fats or fatty oils by a combination of two or more of the means hereafter
-
- 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
- C11B3/04—Refining fats or fatty oils by chemical reaction with acids
-
- 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
- C11B3/16—Refining fats or fatty oils by mechanical means
Definitions
- the present invention relates to a process for degumming a fatty substance, such as oil or fat, animal or vegetable, crude or delecithinate, as well as to the fatty substance thus obtained.
- a fatty substance such as oil or fat, animal or vegetable, crude or delecithinate
- All fatty substances contain a certain number of impurities, liposoluble substances entrained during the bursting of oil cells, which can make them unusable for consumption. Some of these impurities have a harmful influence on the taste, the odor, the appearance of the product, its conservation.
- the purpose of refining fatty substances is to eliminate free fatty acids, oxidation products, unpleasant flavors, dyes, toxic products (such as pesticides, glycosides) but also phospholipids and metals (such as iron, copper) present in trace amounts and generally linked to organic compounds.
- phospholipids and metals such as iron, copper
- the presence of phospholipids in crude oils leads to a certain number of drawbacks. In the presence of water, they hydrate and form deposits which decompose over time. Experience also shows that a refined oil poorly freed from its phospholipids acidifies, oxidizes and quickly takes an unpleasant taste.
- Phospholipids are often linked to heavy metals (such as calcium, magnesium, iron, copper), some of which have a harmful influence on the conservation of refined fatty substances since they are oxidation catalysts.
- Phospholipids are also thermally substances unstable which, when they decompose at high temperature, obscure the oil. Finally, since phospholipids are surfactants, their incomplete elimination from the start of refining leads to the formation of foams and emulsions with the consequence, abnormal losses of oil and deactivation of bleaching earths.
- fatty substances some contain little phospholipids (for example palm fat, lauric and animal fats); they can therefore be easily rid of these substances by dry degumming, that is to say by adding an acid to decompose them and an earth to fix them.
- these fatty substances can be refined by neutralizing distillation or physical refining.
- the oils obtained by pressure and / or by extraction using a solvent are very rich in phospholipids and are therefore generally refined chemically.
- This type of refining has several disadvantages; it generates, among other things, "soapstocks", mixtures of oil and soaps, which must be treated, which involves oil losses and additional costs.
- the total phospholipid content of these crude oils, expressed in the form of phosphorus, can be easily lowered from 800 ppm to 150-200 ppm by an aqueous degumming or delecithination.
- the oil is stirred in the presence of water at 80 ° C., causing hydration and flocculation of the phospholipids.
- the 150-200 ppm of remaining phosphorus mainly represent non-hydratable phospholipids, which are complexes of phosphatidic acid and phosphatidyl ethanolamine associated with bivalent ions (such as calcium, iron, magnesium).
- bivalent ions such as calcium, iron, magnesium.
- One of the essential aims of the present invention consists in remedying the aforementioned drawbacks of existing methods, and in providing for an industrial process. trially and economically valid, making it possible to obtain fatty substances such as oils or fats, animal or vegetable, crude or delecithineum, perfectly degummed to allow their physical refining, in particular for virtually eliminating the phospholipids they contain, and more particularly the non-hydratable phospholipids, when they contain them, and to reduce their iron content.
- the degumming process of the invention consists in mixing the fatty substance to be treated with a reactive aqueous solution of a complexing agent chosen from the group comprising citric acid, phosphoric acid, oxalic acid, tartaric acid, acids of the aminocarboxylic type, acids of the polyhydroxycarboxylic type, polycarboxylic acids, the salts of these acids and mixtures of two or more of these substances and of an emulsifier of the anionic, cationic type , zwitterionic, nonionic or generated in situ by partial neutralization of the free fatty acids present in the fatty substance, said solution making it possible to extract the phospholipids contained in said fatty substance, said mixture being produced by adding the aqueous solution at once complexing agent and emulsifier to the fatty substance or vice versa and subjecting the whole to intense agitation the speed of which is between 500 and 15,000 rpm so to form a fine emulsion.
- a complexing agent chosen from the group comprising citric
- the above-mentioned stirring speed is between 1200 and 10,000 revolutions / minute.
- the above-mentioned mixture is carried out at a temperature of 20 to 100 ° C., advantageously from 60 to 90 ° C.
- the complexing agent is trisodium citrate or is an acid of the aminocarboxylic type, such as ethylenediaminetetraacetic acid or the disodium or trisodium salt of the latter and the emulsifier is of the anionic type and consists of sodium lauryl sulfate, of the nonionic type and consists of one or more monoglycerides or is generated in situ and is sodium and / or potassium carboxylate.
- the degumming process consists in dispersing the fatty substance in the form of fine droplets in a reactive aqueous solution of a complexing agent chosen from the group comprising citric acid, phosphoric acid, oxalic acid, tartaric acid, acids of the aminocarboxylic type, acids of the polyhydroxycarboxylic type, polycarboxylic acids, the salts of these acids and mixtures of two or more of these substances and d an emulsifier of the anionic, cationic, zwitterionic, nonionic type, or generated in situ by partial neutralization of the free fatty acids present in the fatty substance, said solution making it possible to extract the phospholipids contained in said fatty substance.
- a complexing agent chosen from the group comprising citric acid, phosphoric acid, oxalic acid, tartaric acid, acids of the aminocarboxylic type, acids of the polyhydroxycarboxylic type, polycarboxylic acids, the salts of these acids and mixtures of two or more of these
- the subject of the invention is also the degummed oils and fats, obtained according to the process described above.
- the present invention proposes to erase fatty substances, such as oils or fats, animal or vegetable, crude or delecithinates, by bringing the fatty substance to be treated into contact with a reactive aqueous solution of '' a complexing agent and an emulsifier allowing hydra ⁇ ter not only hydratable phospholipids but especially and in particular non-hydra ⁇ table phospholipids, if this contains them.
- non-hydratable phospholipids such as phosphatidic acid and phosphatidyl ethanolamine associated with bivalent and trivalent metals (Ca ++ , Mg ++ , Fe ++ or Fe +++ ) is a difficult reaction.
- phosphatidic acid and phosphatidyl ethanolamine associated with monovalent metals (Na + , K + ) or even an H + cation are easily hydrated and eliminated from the fatty substance.
- the oil or fat to be degummed and the aqueous solution of complexing agent and emulsifier are mixed by adding the aqueous solution to the oil or fat at once or vice versa and subjecting the whole to intense agitation, the speed of which is between 500 and 15,000 revolutions / minute and advantageously between 1,200 and 10,000 revolutions / minute, for a duration generally of 10 seconds to 5 minutes.
- this intense mixture is in fact to disperse the aqueous phase containing the reactants brought into contact (complexing agent and emulsifier) intensively in the oil or the fat so as to form a fine emulsion.
- the mixture of fatty substances / aqueous solution of the reactants brought into contact is generally carried out at a temperature of the order of 20 to 100 ° C., but a temperature between 60 and 90 ° C. is advantageously used.
- the aqueous phase thus formed is added or not with a sodium chloride solution whose concentration varies between 0.1 and 10% and is then separated by decantation or centrifugation so as to obtain an essential degummed fatty substance. ment free of phospholipids.
- the degummed fatty substance is then either dried and then treated with bleaching earth or treated directly without drying.
- the total content of phospholipids, expressed in the form of phosphorus, after degumming is much less than 10 ppm. Furthermore, a content of less than 0.2 ppm of iron is obtained, a value required for good conservation of the oil (AJ Dijkstra, B. Cleenetechnik FST 317-322, 1992).
- the complexing agents have a much higher affinity constant for the bivalent cations than for the monovalent cations; therefore, they preferentially displace and complex the cations Ca ++ , Mg ++ , Fe ++ , Fe +++ .
- the phosphatidic acid and the phosphatidyl ethanolamine thus released are therefore easily hydrated in sodium form.
- This complexing reaction of bivalent or trivalent cations (Mg, Ca, Fe) by the complexing agent requires the prior dissociation of the bivalent phospholipid cation cation complex.
- a complexing agent chosen from the group comprising citric acid, phosphoric acid, oxalic acid, tartaric acid, acids of the aminocarboxylic type, acids of the polyhydroxycarboxylic type, polycarboxylic acids, the salts of these acids and mixtures of two or more of these substances and of an emulsifier of the anionic, cationic, zwitterionic, nonionic type or generated in situ by partial neutralization of the acids free fats present in the fatty substance and, as has just been specified, the use of intense agitation and a temperature preferably of at least 60 ° C., advantageously from 60 to 90 ° C.
- Examples of preferred complexing agents used in the context of the present invention are trisodium citrate or acids of the aminocarboxylic type, such as ethylenediaminetetraacetic acid or the disodium and trisodium salts thereof.
- the complexing agent will be used at least in stoichiometric amount relative to the amount of non-hydratable phospholipids or total cations (g, Ca, Fe) present in the fatty substance to be treated.
- the emulsifier for its part, is of the anionic, cationic, zwitterionic or nonionic type.
- L 1 anionic emulsifier such as sodium lauryl sulfate is particularly suitable.
- the emulsifier can also be generated in situ by partial neutralization of the free fatty acids present in the fatty substance.
- Emulsifiers produced in this way are, for example, sodium and potassium carboxylates.
- non-ionic emulsifiers non-limiting examples will be mentioned monoglycerides and their mixtures.
- the amount of water in the aqueous solution-fatty substance mixture can vary between 0.1% and 99% by weight depending on the separation conditions used. As already specified above, the reaction normally takes place between 10 seconds and 5 minutes but can be shortened or take longer if one of the parameters is modified, for example the quantity of water used, the temperature of reaction, the type of reagents brought into contact.
- the degumming of soybean oils as well as those of rapeseed, cotton, peanut, sunflower, corn has been successfully achieved using the process of the invention.
- the process of the invention is particularly suitable for degumming fatty substances containing phospholi ⁇ pides essentially formed from non-hydratable phospholipids, but it is also suitable for degumming. fatty substances poor in non-hydratable phospholipids so as to better eliminate certain gums or mucilages.
- the degumming is carried out batchwise or continuously, followed by separation by decantation or centrifugation. Washing with water, after degumming the fatty substance, is beneficial but absolutely not necessary.
- the fatty substance such as oil
- This technique described in Belgian patent n ° 595.219 uses a column equipped with a jacket and a distribution system in which the fatty substance or the oil is injected continuously in an extremely divided form. An infinite number of oil droplets are thus formed which slowly rise against the current in the aqueous solution. These oil droplets after coalescence at the top of the column are continuously separated by decantation or centrifugation.
- the reaction can be carried out in a counter-current extractor or in a pulsed column for liquid / liquid extraction.
- the emulsion thus obtained is broken by adding 10 ml of a saturated solution of sodium chloride or centrifuged directly at 5,000 rpm.
- the phosphorus content determined by the calorimetric phosphorus determination method is 6 ppm.
- the cation content determined by atomic absorption according to the IUPAC 2.631 method is given in ppm.
- 300 g of delecithinated soybean oil are heated to 75 ° C in a beaker.
- 900 ml of an aqueous solution composed of 5 millimolar di- or trisodium ethylenediaminetetraacetate salt and 1.7 millimolar sodium lauryl sulfate are also heated to 75 ° C.
- the aqueous solution is added all at once to the oil.
- the emulsion thus obtained is broken by adding 400 ml of a saturated sodium chloride solution or centrifuged directly at 5,000 rpm.
- the phosphorus content determined by the colorimetric phosphorus determination method is 6 ppm.
- the cation content determined by atomic absorption according to the IUPAC 2.63-1 method is given in ppm.
- the aqueous solution is added all at once to the oil.
- the ulsion thus obtained is broken by adding 10 ml of a saturated solution of sodium chloride or centrifuged directly at 5,000 rpm.
- the phosphorus content determined by the colorimetric phosphorus determination method (AOCS ca 12-55) and the cation content determined by atomic absorption according to the IUPAC 2.631 method is given below.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Microbiology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Fats And Perfumes (AREA)
- Edible Oils And Fats (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Detergent Compositions (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SI9430150T SI0703960T1 (en) | 1993-06-18 | 1994-06-16 | Method of degumming a fatty substance and fatty body so obtained |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BE9300627A BE1007151A3 (fr) | 1993-06-18 | 1993-06-18 | Procede de degommage d'un corps gras et corps gras ainsi obtenu. |
BE9300627 | 1993-06-18 | ||
PCT/BE1994/000041 WO1995000609A1 (fr) | 1993-06-18 | 1994-06-16 | Procede de degommage d'un corps gras et corps gras ainsi obtenu |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0703960A1 true EP0703960A1 (de) | 1996-04-03 |
EP0703960B1 EP0703960B1 (de) | 1998-04-08 |
Family
ID=3887117
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP94916852A Expired - Lifetime EP0703960B1 (de) | 1993-06-18 | 1994-06-16 | Fettenschleimungsverfahren und so erhaltenes fett |
Country Status (18)
Country | Link |
---|---|
US (1) | US6015915A (de) |
EP (1) | EP0703960B1 (de) |
JP (1) | JPH09501453A (de) |
CN (1) | CN1054395C (de) |
AT (1) | ATE164880T1 (de) |
AU (1) | AU675544B2 (de) |
BE (1) | BE1007151A3 (de) |
BG (1) | BG62212B1 (de) |
CA (1) | CA2164840C (de) |
DE (1) | DE69409520T2 (de) |
DK (1) | DK0703960T3 (de) |
ES (1) | ES2116596T3 (de) |
HU (1) | HU220380B (de) |
NZ (1) | NZ266746A (de) |
RU (1) | RU2122013C1 (de) |
SG (1) | SG45243A1 (de) |
UA (1) | UA61872C2 (de) |
WO (1) | WO1995000609A1 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104277913A (zh) * | 2014-10-20 | 2015-01-14 | 河南工业大学 | 一种芝麻油中凝絮物脱除方法 |
Families Citing this family (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2296004A1 (fr) * | 1997-07-09 | 1999-01-21 | Etienne Defense | Procede d'elimination des metaux des corps gras et des gommes associes a ces metaux |
DE10257215B4 (de) * | 2002-12-07 | 2005-12-22 | Lurgi Ag | Verfahren zur Verbesserung der Langzeitstabilität von Biodiesel |
BRPI0707414A2 (pt) * | 2006-03-31 | 2011-05-03 | Archer Daniels Midland Co | óleos vegetais de cor clara e métodos relacionados |
JP5378001B2 (ja) | 2009-02-17 | 2013-12-25 | 花王株式会社 | 脂肪酸アルキルエステルの精製方法 |
GB0904787D0 (en) | 2009-03-20 | 2009-05-06 | Desmet Ballestra Engineering Sa | Improved enzymatic oil recuperation process |
DE102010048367A1 (de) | 2010-10-13 | 2012-04-19 | Süd-Chemie AG | Verfahren zur Entfernung von Phosphor-haltigen Verbindungen aus Triglycerid-haltigen Zusammensetzungen |
GB201019639D0 (en) * | 2010-11-19 | 2010-12-29 | Loders Croklaan Bv | Method |
DE102010055969A1 (de) | 2010-12-23 | 2012-06-28 | Süd-Chemie AG | Verfahren zur Aufreinigung von organischen Flüssigkeiten |
ES2641363T3 (es) | 2013-04-15 | 2017-11-08 | Alfa Laval Corporate Ab | Desacidificación de grasas y aceites |
US9340749B1 (en) | 2015-05-06 | 2016-05-17 | Arisdyne Systems, Inc. | Method for degumming triglyceride oils |
BR112017023635B1 (pt) * | 2015-05-06 | 2021-11-30 | Archer-Daniels-Midland Company | Método para degomar um óleo de triglicerídeo |
CN105062670A (zh) * | 2015-08-21 | 2015-11-18 | 崇州市白头甘泉工业油脂厂 | 一种油脂的精炼方法 |
WO2017066027A1 (en) | 2015-10-14 | 2017-04-20 | Arisdyne Systems, Inc. | Method for reducing neutral oil losses during neutralization step |
CN107011991B (zh) * | 2017-04-12 | 2021-04-13 | 西北大学 | 一种油脂的阳离子树脂脱磷方法 |
CN106987312B (zh) * | 2017-04-12 | 2021-04-13 | 西北大学 | 一种油脂同时脱磷脱酸的方法 |
WO2018217270A1 (en) | 2017-05-24 | 2018-11-29 | Arisdyne Systems, Inc. | Oil degumming systems |
WO2019157334A1 (en) | 2018-02-09 | 2019-08-15 | Poet Research, Inc. | Methods of refining a grain oil composition to make one or more grain oil products, and related systems |
CA3103242C (en) | 2018-06-11 | 2023-08-29 | Poet Research, Inc. | Methods of refining a grain oil composition feedstock, and related systems, compositions and uses |
EP4417676A2 (de) * | 2020-07-31 | 2024-08-21 | REG Synthetic Fuels, LLC | Verfahren zur vorbehandlung eines biokraftstoff-rohmaterials |
WO2022032011A1 (en) | 2020-08-06 | 2022-02-10 | Poet Research, Inc. | Endogenous lipase for metal reduction in distillers corn oil |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR518593A (fr) * | 1917-06-29 | 1921-05-27 | Elektro Osmose Ag | Procédé d'épuration des graisses et huiles |
GB687843A (en) * | 1948-03-17 | 1953-02-25 | Frederick Charles Bersworth | Methods of treating and processing animal and vegetable oils |
FR1388567A (fr) * | 1964-04-17 | 1965-02-05 | Procédé de raffinage des graisses et des huiles | |
SU897841A1 (ru) * | 1980-02-18 | 1982-01-15 | Всесоюзный Научно-Исследовательский Институт Жиров | Способ рафинации масел и жиров |
SU1244170A1 (ru) * | 1984-02-20 | 1986-07-15 | Всесоюзный Научно-Исследовательский Институт Жиров | Способ рафинации масел и жиров |
US4866044A (en) * | 1985-07-09 | 1989-09-12 | Takeda Chemical Industries, Ltd. | Solubilized composition of poorly-soluble pharmaceutical product |
JPS6227665A (ja) * | 1985-07-29 | 1987-02-05 | Seitai Kinou Riyou Kagakuhin Shinseizou Gijutsu Kenkyu Kumiai | 脂質測定法 |
BR8703598A (pt) * | 1987-07-13 | 1989-01-24 | Brasil Pesquisa Agropec | Processo de degomagem de oleos brutos de soja com alto conteudo de fosfatidios nao-hidrataveis |
FR2633936B1 (fr) * | 1988-07-05 | 1991-04-12 | Sanofi Sa | Procede d'extraction du cholesterol contenu dans une matiere grasse d'origine animale |
BE1003488A3 (fr) * | 1989-03-14 | 1992-04-07 | Corman N Sa | Procede de reduction de la teneur en cholesterol et en acides gras libres de la matiere grasse d'origine animale et matiere grasse ainsi obtenue. |
EP0407037B1 (de) * | 1989-06-12 | 1994-09-21 | Merck & Co. Inc. | Verfahren zur Entfernung von bakteriellen Endotoxinen aus gram-negativen Polysacchariden |
US4968518A (en) * | 1989-08-14 | 1990-11-06 | Klenz, Inc. | Process for the treatment of frying and/or cooking oil |
SU1717621A1 (ru) * | 1990-01-30 | 1992-03-07 | Ташкентский Политехнический Институт Им.А.Р.Бируни | Способ рафинации серосодержащих растительных масел в мисцелле |
-
1993
- 1993-06-18 BE BE9300627A patent/BE1007151A3/fr not_active IP Right Cessation
-
1994
- 1994-06-16 CN CN94192792A patent/CN1054395C/zh not_active Expired - Fee Related
- 1994-06-16 DK DK94916852T patent/DK0703960T3/da active
- 1994-06-16 RU RU96101059A patent/RU2122013C1/ru not_active IP Right Cessation
- 1994-06-16 JP JP7502258A patent/JPH09501453A/ja active Pending
- 1994-06-16 DE DE69409520T patent/DE69409520T2/de not_active Expired - Fee Related
- 1994-06-16 HU HU9503629A patent/HU220380B/hu not_active IP Right Cessation
- 1994-06-16 SG SG1996001891A patent/SG45243A1/en unknown
- 1994-06-16 AT AT94916852T patent/ATE164880T1/de not_active IP Right Cessation
- 1994-06-16 ES ES94916852T patent/ES2116596T3/es not_active Expired - Lifetime
- 1994-06-16 WO PCT/BE1994/000041 patent/WO1995000609A1/fr active IP Right Grant
- 1994-06-16 EP EP94916852A patent/EP0703960B1/de not_active Expired - Lifetime
- 1994-06-16 NZ NZ266746A patent/NZ266746A/en unknown
- 1994-06-16 UA UA96010218A patent/UA61872C2/uk unknown
- 1994-06-16 US US08/564,182 patent/US6015915A/en not_active Expired - Fee Related
- 1994-06-16 AU AU68392/94A patent/AU675544B2/en not_active Ceased
- 1994-06-16 CA CA002164840A patent/CA2164840C/fr not_active Expired - Fee Related
-
1996
- 1996-01-11 BG BG100280A patent/BG62212B1/bg unknown
Non-Patent Citations (1)
Title |
---|
See references of WO9500609A1 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104277913A (zh) * | 2014-10-20 | 2015-01-14 | 河南工业大学 | 一种芝麻油中凝絮物脱除方法 |
Also Published As
Publication number | Publication date |
---|---|
CA2164840A1 (fr) | 1995-01-05 |
NZ266746A (en) | 1996-08-27 |
HUT75502A (en) | 1997-05-28 |
HU220380B (hu) | 2002-01-28 |
SG45243A1 (en) | 1998-01-16 |
WO1995000609A1 (fr) | 1995-01-05 |
DE69409520D1 (de) | 1998-05-14 |
HU9503629D0 (en) | 1996-02-28 |
DK0703960T3 (da) | 1999-01-18 |
CN1054395C (zh) | 2000-07-12 |
UA61872C2 (en) | 2003-12-15 |
BG62212B1 (bg) | 1999-05-31 |
AU675544B2 (en) | 1997-02-06 |
AU6839294A (en) | 1995-01-17 |
US6015915A (en) | 2000-01-18 |
CN1127564A (zh) | 1996-07-24 |
ES2116596T3 (es) | 1998-07-16 |
RU2122013C1 (ru) | 1998-11-20 |
JPH09501453A (ja) | 1997-02-10 |
BG100280A (bg) | 1996-07-31 |
EP0703960B1 (de) | 1998-04-08 |
DE69409520T2 (de) | 1998-10-29 |
CA2164840C (fr) | 2005-06-14 |
ATE164880T1 (de) | 1998-04-15 |
BE1007151A3 (fr) | 1995-04-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0703960B1 (de) | Fettenschleimungsverfahren und so erhaltenes fett | |
EP1131392B1 (de) | Verbessertes verfahren zur raffienierung von pflanzlichen öl | |
US6844458B2 (en) | Vegetable oil refining | |
CA2049720C (en) | Degumming process for plant oils | |
WO1999002630A1 (fr) | Procede d'elimination des metaux des corps gras et des gommes associes a ces metaux | |
RU2242505C2 (ru) | Способ удаления свободных жирных кислот из жиров и масел биологического происхождения или их паровых дистиллятов (варианты) | |
JPS5949278B2 (ja) | トリグリセリド油の脱ガム方法 | |
US6426423B1 (en) | Methods for treating phosphatide-containing mixtures | |
Choukri et al. | Improved oil treatment conditions for soft degumming | |
JPH05117685A (ja) | トリグリセリド油からの連続的脱ガム方法 | |
Forster et al. | Physical refining | |
IT9020317A1 (it) | Procedimento di deodorazione di olii e grassi | |
FR2459828A1 (fr) | Procede pour raffiner des huiles et des graisses animales ou vegetales | |
US6441209B1 (en) | Method for treating organic acid-treated phosphatides | |
JP3949901B2 (ja) | リン含有分の低い米ぬか油の製造方法 | |
GB2144143A (en) | Refining of palm oils | |
MXPA01005035A (en) | Improved method for refining vegetable oil | |
EP0058712A1 (de) | Verfahren zum reinigen von roh- oder teilweise gereinigten pflanzlichen, tierischen oder meerestriglyceriden ölen |
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: 19951222 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LI LU MC NL PT SE |
|
AX | Request for extension of the european patent |
Free format text: SI PAYMENT 951220 |
|
RAX | Requested extension states of the european patent have changed |
Free format text: SI PAYMENT 951220 |
|
17Q | First examination report despatched |
Effective date: 19960402 |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LI LU MC NL PT SE |
|
AX | Request for extension of the european patent |
Free format text: SI PAYMENT 951220 |
|
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: 19980408 |
|
REF | Corresponds to: |
Ref document number: 164880 Country of ref document: AT Date of ref document: 19980415 Kind code of ref document: T |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REF | Corresponds to: |
Ref document number: 69409520 Country of ref document: DE Date of ref document: 19980514 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: NV Representative=s name: PATENTANWALTSBUERO FELDMANN AG |
|
ITF | It: translation for a ep patent filed | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 19980708 |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 19980618 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2116596 Country of ref document: ES Kind code of ref document: T3 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: 79753 |
|
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 NON-PAYMENT OF DUE FEES Effective date: 19981231 |
|
REG | Reference to a national code |
Ref country code: DK Ref legal event code: T3 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
EUG | Se: european patent has lapsed | ||
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IE Payment date: 20030523 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20030526 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 20030613 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 20030925 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20040614 Year of fee payment: 11 |
|
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: 20040616 Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040616 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: LU Payment date: 20040616 Year of fee payment: 11 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040617 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20040617 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DK Payment date: 20040618 Year of fee payment: 11 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040630 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040630 |
|
REG | Reference to a national code |
Ref country code: SI Ref legal event code: IF |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
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: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050616 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050630 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20040617 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20060101 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20060228 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20060101 |
|
REG | Reference to a national code |
Ref country code: DK Ref legal event code: EBP |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20060228 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20060509 Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20060609 Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20060614 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: 20060616 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: 20060630 Year of fee payment: 13 |
|
BERE | Be: lapsed |
Owner name: S.A. FRACTIONNEMENT *TIRTIAUX Effective date: 20070630 |
|
EUG | Se: european patent has lapsed | ||
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20070616 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070630 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20080101 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070616 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070617 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070616 |