EP2522711B1 - Verfahren zur Herstellung von Oleochemikalien mit vermindertem Gehalt an Nebenprodukten - Google Patents

Verfahren zur Herstellung von Oleochemikalien mit vermindertem Gehalt an Nebenprodukten Download PDF

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Publication number
EP2522711B1
EP2522711B1 EP11165985.0A EP11165985A EP2522711B1 EP 2522711 B1 EP2522711 B1 EP 2522711B1 EP 11165985 A EP11165985 A EP 11165985A EP 2522711 B1 EP2522711 B1 EP 2522711B1
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Prior art keywords
column
oil
fatty acids
distillate
oils
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English (en)
French (fr)
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EP2522711A1 (de
Inventor
Horst Josten
Ewelina Sobierska
Adrian Chan
Truc Tran Anh
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Cognis IP Management GmbH
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Cognis IP Management GmbH
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    • 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
    • C11B3/12—Refining fats or fatty oils by distillation
    • C11B3/14—Refining fats or fatty oils by distillation with the use of indifferent gases or vapours, e.g. steam
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols

Definitions

  • the present invention belongs to the area of oleochemicals and refers to an improved process for obtaining fatty acids, fatty acid alkyl esters and fatty alcohols with reduced content of ketones, aldehydes and phenols and their hydrogenation products.
  • EP 0127104 B1 discloses a process for making fatty acid esters of short-chain, aliphatic alcohols by catalytic transesterification of natural fats and/or oils containing free fatty acids (oil phase) with the corresponding alcohols, the oil phase is subjected to preliminary esterification with the alcohols in the presence of acidic esterification catalysts at temperatures no higher than 120 °C and under pressures of less than 5 bar and in the presence of a liquid entraining agent substantially immiscible with the oil phase, after which the reaction product is separated into an entraining agent phase containing the acidic catalyst and water of reaction and the treated oil phase.
  • the oil phase is then subjected to transesterification while the acidic catalyst-containing entraining agent phase is returned, after at least partial drying, to the preliminary esterification stage.
  • fats and/or oils with acid numbers of up to 60 can be processed in the preliminary esterification stage to give an oil phase having a low acid number.
  • EP 1092703 B1 (Cognis) teaches the preparation of fatty acid methyl esters having an acid number of less than 0.1 comprises subjecting a fatty acid glyceride, having an acid number of 5 to 20, with methanol in a ratio of 0.4 to 0.7 % w/v to a two stage esterification process comprising a first high-pressure and a second low-pressure esterification.
  • EP 1894913 A1 discloses a process for obtaining fatty acids, comprising: refining a soybean oil with an acid value of 3 and containing tocopherols, by steam stripping, obtaining a bottom fraction of de-acidified soybean oil, obtaining a distillate from the top of the column, which is thereafter separated into 2 distillates with scrubbers: a first distillate with tocopherols and sterols, and a second distillate with 98% by weight of fatty acids.
  • a first object of the present invention covers a process for obtaining fatty acids with reduced content of by-products, wherein
  • a second object of the present invention refers to a process for obtaining fatty acid alkyl esters with reduced content of by-products, wherein
  • a third object of the present invention is directed to a process for obtaining fatty alcohols with reduced content of by-products, wherein
  • the top fraction typically represents only 1, in particular about 0.5 % b.w. of the total mass of the distillation products (bottom product plus side streams) the amount of waste material compared to other processes is much smaller, what provides an additional economic advantage over the state of the art. Also, the first fatty acid distillate taken off as the side stream shows a seriously reduced content of by-products and thus represents also a valuable product, which can be combined with the bottom fraction of the de-acidified oils for transesterification or can be applied for other purposes.
  • the process according to the present invention can be applied to all kinds of vegetable oils, in particularly those oils showing an acid value typically of 1 to 20, but also higher.
  • suitable oils - without limitation - are palm oil, palm kernel oil, coconut oil, olive oil, sunflower oil, saflor oil, soy oil, line oil, rape oil, fish oil, lard oil, tallow and their mixtures.
  • the combined de-acidification and separation of impurities from crude fats or oils is preferably done under vacuum in a counter-current column with stripping steam as shown in Figure 1 (reference - outside the scope of the invention).
  • the crude oil is pre-heated by economizers (1, 2) and pre-heater (3) and fed to the top of the column (4).
  • economizers (1, 2) and pre-heater (3) While trickling down the column free fatty acids and other low boiling impurities like aldehydes, ketones and phenols are stripped from the oil with stripping steam, which is introduced at the column bottom.
  • the stripped off fatty acids and impurities are condensed from the stripping steam in two steps while the de-acidified oil is taken from the column as bottom product.
  • the column internals can either be structured or dumped packing or trays depending on the solids or gum content of the crude oil.
  • coconut oil or palm kernel oil structured packing is preferred due to low pressure drop.
  • oils with higher solids/gum content umbrella bubble cap trays are preferred due to lower pressure drop than for other tray types.
  • the height of the packing can be about 3 to about 8, preferably about 4 to about 6 m.
  • the number of trays should be about 6 to about 18, preferably about 8 to about 14.
  • Partial condensation of the fatty acid vapours is typically performed by a partial condenser ("dephlegmator") or more preferably by a direct condensation in a packing (5) with recirculation loop and external plate cooler (6).
  • An additional feature of the invention is to install an additional packing (8) above the feed and run the column with a small reflux - about 1 to about 10 % of the distillate - of the first distillate in order to reduce the amount of glycerides in the fatty acid distillate.
  • an additional reboiler (9) is required to provide the heat of vaporization for the reflux stream.
  • the de-acidification column should be operated at a vacuum of about 2 to about 20, preferably about 5 to about 10 mbar.
  • the crude oil feed should be heated to about 225 to about 280, preferably about 245 to about 260 °C.
  • the stripping steam rate should be adjusted to about 1 to about 5 % w/w, while it is preferred to adjust the rate to about 1 to about 2 % w/w of the crude oil feed rate.
  • the resulting acid values of the de-acidified oils and fats are typically between about 0.02 and about 1 and preferably between about 0.1 and about 0.5, the resulting water content between about 0.01 and about 0.1, preferably between about 0.01 to about 0.03 %.
  • the second condensate can either be discarded as waste or be used as a low fatty acid quality for technical applications.
  • the first distillate of the de-acidification column contains mainly - which means about 50 to about 99 % b.w. - fatty acids, the rest being glycerides.
  • This stream can either directly be routed to high pressure transesterification or esterified and subsequently routed to a low or high pressure transesterification together with the bottom product from the column.
  • an alternative procedure is to replace the partial condensation shown in Figure 1 by a fractionation in a packed section in the top of the column (5) with refluxing and fractionating at least a part of the second quality fatty acid as shown in Figure 2 . Doing this the split of the low-boilers between the fatty acid qualities can substantially be improved.
  • reaction mixture leaving the transesterification step is then hydrogenated and the resulting fatty alcohol mixture is improved in quality compared to the processing of unrefined oils without the described de-acidification procedure.
  • These processes represent major operations in technical industry and are well known for one skilled in the art so that additional explanations are not necessary.
  • EP 0332971 B1 (Henkel) referring to the transesterification of fatty acid lower alkyl esters and DE 4321837 A1 (Henkel) disclosing the hydrogenation of methyl esters to fatty alcohols which is conducted in two fixed-bed reactors.
  • Raw coconut oil with an acid value of 12 had the following content of low-boiling impurities: Impurity Content [ppm] C 7 Ketone 29 C 9 Ketone 71 C 11 Ketone 581 C 13 Ketone 19 Phenol 214
  • the oil was pre-heated to 260 °C via a pre-heater and pumped at a flow rate of 200 kg/hr to the top of a column with an internal diameter of 130 mm packed with 4.6 m of a structured packing with a specific surface of 350 m 2 /m 3 .
  • the column was run at a top pressure of 10 mbar. Stripping steam was introduced into the bottom of the column at a flow rate of 2.0 kg/h.
  • the condenser of the column was adjusted to 80 °C, a second condenser to 40 °C.
  • the de-acidified oil had an acid value of 0.14, ketone and phenol contents were reduced to below detection limit.
  • a fatty acid stream of 10.6 kg/h was condensed having an acid value of 182.4 and a glyceride content of 16 %.
  • Contents of low-boiling impurities were: Impurity Content [ppm] C 7 Ketone 17 C 9 Ketone 70 C 11 Ketone 1,971 C 13 Ketone 343 Phenol 240
  • Raw coconut oil with an acid value of 9.5 had the following content of low-boiling impurities: Impurity Content [ppm] C 7 Ketone 33 C 9 Ketone 73 C 11 Ketone 570 C 13 Ketone 14 Phenol 237
  • the oil was pre-heated to 245 °C via a pre-heater and feeded at a flow rate of 200 kg/h to the third packing of a column as shown in Figure 2 with an internal diameter of 130 mm equipped with three sections of a structured packing with a specific surface of 500 m 2 /m 3 , each of the packages having a height of 1.25 m.
  • the column was run at a top pressure of 10 mbar. Stripping steam was introduced into the bottom of the column at a flow rate of 2.0 kg/h.
  • the condenser of the column was adjusted to 40 °C.
  • the condensed second quality fatty acid was split into 0.2 kg, which were taken as top-cut and 14.7 kg reflux, which were fed back to the column top.
  • the second fatty acid quality had an acid value of 288 and a glyceride content of 0.1 %.
  • Contents of low-boiling impurities were: Impurity Content [ppm] C 7 Ketone 35.5 C 9 Ketone 498 C 11 Ketone 33,270 C 13 Ketone 3,330 Phenol 893

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

Claims (11)

  1. Verfahren zur Herstellung von Fettsäuren mit verringertem Gehalt an Nebenprodukten, wobei
    (a) unraffinierte Fette oder Öle Dampfstrippen in einer Gegenstromkolonne unterzogen werden, um:
    (i) eine Bodenfraktion von entsäuerten Fetten oder Ölen,
    (ii) ein erstes Destillat, das hauptsächlich aus Fettsäuren und Glyceriden besteht, und
    (iii) ein zweites Destillat, das Fettsäuren und im Wesentlichen alle unerwünschten Ketone, Aldehyde und Phenole enthält,
    zu erzeugen; und
    (b) die Bodenfraktion (i), die die entsäuerten Fette oder Öle enthält, und das erste Destillat (ii), das Fettsäuren und Glyceride enthält, kombiniert werden,
    wobei Öle oder Fette, die Reinigung unterzogen werden, ausgewählt sind aus der Gruppe bestehend aus Palmöl, Palmkernöl, Kokosnussöl, Olivenöl, Sonnenblumenöl, Distelöl, Sojaöl, Leinöl, Rapsöl, Fischöl, Specköl, Talg und deren Gemischen,
    wobei das erste Destillat, das hauptsächlich aus Fettsäuren und Glyceriden besteht, als Nebenstrom entnommen wird,
    wobei das zweite Destillat, das Fettsäuren und im Wesentlichen alle unerwünschten Ketone, Aldehyde und Phenole umfasst, an dem Kopf der Kolonne entnommen wird,
    wobei ein Strom von Fettsäuren an der Seite der Kolonne entnommen wird, um den Strom von freien Fettsäuren einer fraktionierten Kondensation zu unterwerfen, um ein erstes Destillat von Fettsäuren aus den Kolonnendämpfen zu gewinnen,
    wobei das erste Destillat der Entsäuerungskolonne hauptsächlich - was etwa 50 bis etwa 99 Gew.-% bedeutet - Fettsäuren enthält, wobei der Rest Glyceride sind,
    und
    dieser Strom entweder direkt einer Hochdruck-Umersterung zugeführt werden kann oder verestert und anschließend einer Nieder- oder Hochdruck-Umesterung zusammen mit dem Bodenprodukt aus der Kolonne zugeführt werden kann,
    wobei wenigstens ein Teil des zweiten Destillats refluxiert in einem Packungsabschnitt in dem Kopf der Kolonne fraktioniert wird.
  2. Verfahren gemäß Anspruch 1 zur Herstellung von Fettsäurealkylestern mit verringertem Gehalt an Nebenprodukten, dadurch gekennzeichnet, dass
    (c) die so erhaltenen kombinierten Fraktionen Umesterung mit niedrigen C1-C4-Alkoholen unterzogen werden.
  3. Verfahren gemäß Anspruch 2 zur Herstellung von Fettalkoholen mit verringertem Gehalt an Nebenprodukten, dadurch gekennzeichnet, dass
    (d) die so erhaltenen Umesterungsprodukte Hydrierung unterzogen werden.
  4. Verfahren gemäß einem der vorstehenden Ansprüche 1 bis 3, dadurch gekennzeichnet, dass Öle oder Fette, die einen Säurewert von 1 bis 20 aufweisen, Reinigung unterzogen werden.
  5. Verfahren gemäß einem der vorstehenden Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die Gegenstromkolonne Packungen enthält.
  6. Verfahren gemäß einem der vorstehenden Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die rohen Öle oder Fette dem Kopf der Kolonne zugeführt werden, während der Strippstrom im Gegenstrom geführt wird.
  7. Verfahren gemäß einem der vorstehenden Ansprüche 1 bis 6, dadurch gekennzeichnet, dass die Kolonne Packungen über der Zuführung enthält.
  8. Verfahren gemäß einem der vorstehenden Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die Kolonne mit einem kleinen Rückfluss des ersten Destillats geführt wird.
  9. Verfahren gemäß einem der vorstehenden Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die Kolonne bei einem Unterdruck von 2 bis 20 mbar betrieben wird.
  10. Verfahren gemäß einem der vorstehenden Ansprüche 1 bis 9, dadurch gekennzeichnet, dass die Kolonne bei Temperaturen von 225 bis 280 °C betrieben wird.
  11. Verfahren gemäß einem der vorstehenden Ansprüche 1 bis 10, dadurch gekennzeichnet, dass die Kondensatoren bei Temperaturen von 70 bis 100 °C betrieben werden.
EP11165985.0A 2011-05-13 2011-05-13 Verfahren zur Herstellung von Oleochemikalien mit vermindertem Gehalt an Nebenprodukten Active EP2522711B1 (de)

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EP11165985.0A EP2522711B1 (de) 2011-05-13 2011-05-13 Verfahren zur Herstellung von Oleochemikalien mit vermindertem Gehalt an Nebenprodukten

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EP11165985.0A EP2522711B1 (de) 2011-05-13 2011-05-13 Verfahren zur Herstellung von Oleochemikalien mit vermindertem Gehalt an Nebenprodukten

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EP2522711B1 true EP2522711B1 (de) 2018-12-05

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Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015164106A1 (en) * 2014-04-24 2015-10-29 The Procter & Gamble Company Method for converting odor containing fatty acids to deodorized glycerides

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8314496D0 (en) * 1983-05-25 1983-06-29 Unilever Plc Treating triglyceride oil
DE3319590A1 (de) 1983-05-30 1984-12-06 Henkel KGaA, 4000 Düsseldorf Verfahren zur herstellung von fettsaeureestern kurzkettiger aliphatischer alkohole aus freie fettsaeuren enthaltenden fetten und/oder oelen
DE3808427A1 (de) 1988-03-14 1989-09-28 Henkel Kgaa Verfahren zur kontinuierlichen umesterung von fettsaeure-niedrigalkyl-estern
DE4321837A1 (de) 1993-07-01 1995-01-12 Henkel Kgaa Herstellung von Fettalkoholen durch Hydrieren von Fettderivaten, insbesondere Fettsäuremethylester
DE19810440C1 (de) * 1998-03-11 1999-09-23 Dhw Deutsche Hydrierwerke Gmbh Verfahren zur Herstellung von ungesättigten Fettalkoholen aus Lauricölen
DE19949718A1 (de) 1999-10-14 2001-04-19 Cognis Deutschland Gmbh Verfahren zur Herstellung von Fettsäuremethylestern
CA2360986A1 (en) * 2001-11-01 2003-05-01 Nicole Cadoret Method for fractionating grease trap waste and uses of fractions therefrom
EP1894913A1 (de) * 2006-08-21 2008-03-05 Desmet Ballestra Oleo s.p.a. Herstellung von Fettsäureestern und niederen Alkoholen
ES2391466T3 (es) * 2006-10-11 2012-11-27 Cognis Ip Management Gmbh Procedimiento para la hidrogenación parcial de ésteres de ácidos grasos

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