EP0189049B2 - Stabilisierung von Palmkernfettsäuremethylestern für deren Verarbeitung zu farbneutralen Reaktionsfolgeprodukten - Google Patents

Stabilisierung von Palmkernfettsäuremethylestern für deren Verarbeitung zu farbneutralen Reaktionsfolgeprodukten Download PDF

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Publication number
EP0189049B2
EP0189049B2 EP86100134A EP86100134A EP0189049B2 EP 0189049 B2 EP0189049 B2 EP 0189049B2 EP 86100134 A EP86100134 A EP 86100134A EP 86100134 A EP86100134 A EP 86100134A EP 0189049 B2 EP0189049 B2 EP 0189049B2
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EP
European Patent Office
Prior art keywords
palm kernel
fatty acid
acid methyl
kernel oil
reaction products
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.)
Expired - Lifetime
Application number
EP86100134A
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German (de)
English (en)
French (fr)
Other versions
EP0189049B1 (de
EP0189049A1 (de
Inventor
Alfred Dr. Struve
Richard Schuh
Horst Dr. Baumann
Hartwig Dr. Schütt
Harald Wallis
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.)
Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication date
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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
    • C11B5/00—Preserving by using additives, e.g. anti-oxidants
    • C11B5/0021—Preserving by using additives, e.g. anti-oxidants containing oxygen
    • C11B5/0035—Phenols; Their halogenated and aminated derivates, their salts, their esters with carboxylic acids

Definitions

  • coconut oil and palm kernel oil are important natural raw materials for the production of fat chemical secondary products on an industrial scale.
  • the chemical preparation of this natural starting material is generally preceded by the conversion of the triglyceride obtained to the corresponding fatty acid esters with lower monofunctional alcohols, in particular to the corresponding methyl esters.
  • the methyl ester or the fatty acid methyl ester mixture can be obtained by transesterifying the triglyceride directly with methanol or via the triglyceride cleavage to fatty acid and glycerol and subsequent esterification of the fatty acids or fatty acid mixtures to give the alkyl esters.
  • a comparison of the quality - determined in particular in terms of storage behavior, oxidation stability and stabilization options and in particular with regard to the influence on the color values of subsequent reaction products from these stored feedstocks - shows that coconut oil or the reaction products obtained from coconut oil behave much better than palm kernel oil and its reaction follow-up products. Coconut oil is much more stable to oxidation than palm kernel oil. The same applies to the methyl esters or methyl ester mixtures produced therefrom. The reason for this can only partially be the slightly increased iodine numbers of palm kernel oil compared to the iodine numbers of coconut oil. Both fat raw materials contain natural antioxidants, essentially in the form of ⁇ -tocotrienol.
  • coconut oil contains significantly more antioxidant than palm kernel oil (3 ppm), compare H. Behringer et al. in Fette, Seifen Anstrichstoff 78 (1976) pp. 228-231.
  • coconut oil and coconut fatty acid methyl ester are usually stable against autoxidation for months at room temperature, this is not the case for palm kernel oil and palm kernel fatty acid methyl ester.
  • the applicant was able to demonstrate that palm kernel oil and palm kernel fatty acid methyl ester take up oxygen significantly faster than coconut oil and cocofatty acid methyl ester.
  • Corresponding studies have already shown that palm kernel oil itself has a 10- to 25-fold greater oxygen uptake than coconut oil.
  • the induction time of the palm kernel oils, after which a strong oxygen uptake occurs is around 80 ° C 10 to 20 hours, while in comparative studies with coconut oil after oxygen measuring times of 50 or 90 hours, no oxygen absorption can be determined.
  • the invention is based on the object of eliminating the undesirable instability of palm kernel oil or the reaction products obtained therefrom.
  • the obvious idea to compensate for the deficiency of palm kernel oil in natural antioxidants by the addition of known antioxidants led to the surprising finding that satisfactory reaction products cannot easily be obtained with this concept.
  • Important figures for the usability of a fat raw material on a natural basis are color number values, which are measured on soap solution - obtained by alkaline saponification of the corresponding fatty acid methyl esters or fatty acid methyl ester mixtures - or on fatty acid diethanolamides - obtained by amidating cleavage of the fatty acid methyl ester starting materials. These color numbers are decisive parameters for the usability of both the oils originally used and the methyl esters made from them.
  • the object of the invention in the narrower sense is accordingly the stabilization of palm kernel fatty acid methyl esters against harmful influences during storage in the presence of air in such a way that reaction products of such color neutrality can be obtained in the subsequent reaction of the stored oleochemical starting materials that no undesirable color deteriorations have to be accepted.
  • color neutrality here and in the following description of the invention means a color stability within the scope of the individual reaction stages, which approximately corresponds to the color stability of coconut oil of normal quality and its secondary products known and accepted in practice.
  • the invention thus aims to make the palm kernel fatty acid methyl esters obtainable from palm kernel oil comparable in practical handling and processing to the corresponding materials based on coconut oil.
  • the invention accordingly relates to the use of di-3,5-tert-butyl-4-hydroxytoluene in amounts of 10-100 ppm as the exclusive stabilizing agent in palm kernel fatty acid methyl esters of the C12-C18 fatty acid range for their processing into color-neutral reaction products.
  • Said palm kernel fatty acid methyl esters of different provenance can be stabilized by adding small amounts of BHT according to the invention to standard-compliant starting materials. It is advisable to add the stabilizing additives used according to the invention to the fatty acid methyl ester or fatty acid methyl ester mixture immediately after production - or to clean an insufficient fatty acid methyl ester mixture by preferably multiple distillation and to stabilize the distillate immediately.
  • the required color neutrality is not obtained in the reaction secondary products of the palm kernel fatty acid methyl ester.
  • the use of 2-tert-butylhydroquinone or the use of butylated hydroxyanisole and the use of propyl gallic acid do not show the stabilization effect aimed for according to the invention.
  • High color number values are obtained for the saponification products and for the diethanolamides both in the case of the tert-butylhydroquinone derivative and in the case of the propyl gallate.
  • the use of the butylated hydroxyanisol initially leads to undesirably high saponification color numbers with higher additions, for example in amounts above 500 ppm, but after prolonged storage, undesirably high diethanol amide color numbers are also obtained.
  • BHT can deliver satisfactory results in the sense of the task according to the invention even in amounts of 10 to 100 ppm and in particular in the range of about 20 to 50 ppm.
  • complexing agents for metal ions for example citric acid, ascorbic acid or ascorbic acid fatty alcohol ester, in particular ascorbic acid palmitate.
  • the palm kernel fatty acid methyl esters to be stabilized according to the invention are obtained by known processes either by fat cleavage of the palm kernel oil and subsequent esterification of the fatty acid mixture obtained with methanol or by direct transesterification of the palm kernel oil with methanol.
  • the palm kernel fatty acid alkyl esters intended for chemical processing contain only fatty acids with 12 to 18 carbon atoms as the acid component. From this point of view, the so-called leading fatty acids with 6 to 10 carbon atoms are separated from the mixtures of the free fatty acids by fractional distillation in the direct esterification. If the palm kernel fatty acid alkyl esters are obtained by transesterification, the undesired esters of C6-C12 fatty acids are removed from the ester mixture by distillation after the transesterification.
  • the invention accordingly relates in a particular embodiment to palm kernel fatty acid methyl ester mixtures of the C12-C18 fatty acid range, prepared by esterification of palm kernel fatty acids having 12 to 18 carbon atoms with methanol or by transesterification of palm kernel oil with methanol and isolation of the C12-C18 fatty acid ester cut, exclusively as a stabilizing agent added di-3,5-tert-butyl-4-hydroxytoluene in amounts of 10 to 100 ppm for the production of color-neutral reaction products.
  • the POZ was determined using the Wheeler method - see DGF standard methods C-VI 6a (84),ticianliche Verlagsgesellschaft mbH, Stuttgart (1950-1984) reacted a sample of the ester in a mixture of chloroform and glacial acetic acid with potassium iodide in the cold and the iodine formed by the peroxide present was determined titrimetrically using starch solution as an indicator using starch solution.
  • a consumption of sodium thiosulfate standard solution (ml)
  • N normality of the standard sodium thiosulfate solution
  • E weight of the sample (g)
  • the COZ was also determined using a DGF standard method. See loc. cit. CV 18 (58).
  • a sample of the ester is heated to reflux with a 0.5 N aqueous alcoholic hydroxylamine chlorohydrate solution for a long time.
  • the released hydrogen chloride in the cooled mixture is then titrated with 0.5 N alcoholic sodium hydroxide solution using a pyridine / bromophenol blue indicator.
  • VFZ 10 g of fatty acid ester are heated to reflux with 100 ml of methanolic 1N potassium hydroxide solution for 1 hour.
  • the VFZ of the cooled sample are measured using a 5 1/4 '' cuvette in a Lovibond tintometer. For good quality esters the values red ⁇ 1.0 and yellow ⁇ 5 should be observed.
  • palm kernel oil was split with water at 220 ° C. After washing out the glycerol, the C6 ⁇ 10 fatty acids were largely distilled off from the fatty acid mixture obtained, so that a mixture consisting essentially of C12 ⁇ 18 fatty acids receded.
  • the C12 ⁇ 18 palm kernel fatty acid mixture obtained was reacted in an autoclave with methanol in a weight ratio of 1: 1 at 220 ° C. under autogenous pressure over the course of 2 hours. Methanol and water of reaction were distilled off from the resulting mixture. By repeated reaction with excess methanol and distillation, a C12 ⁇ 18 palm kernel fatty acid methyl ester mixture was obtained, which had the following characteristics: acid number 0.3; Saponification number approx. 238; Iodine number 18.
  • Example 2 a C12 ⁇ 18 palm kernel fatty acid methyl ester prepared by the above method was stabilized with 10 ppm BHT.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (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)
  • Fats And Perfumes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Cosmetics (AREA)
EP86100134A 1985-01-14 1986-01-07 Stabilisierung von Palmkernfettsäuremethylestern für deren Verarbeitung zu farbneutralen Reaktionsfolgeprodukten Expired - Lifetime EP0189049B2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3500938 1985-01-14
DE19853500938 DE3500938A1 (de) 1985-01-14 1985-01-14 Stabilisierung von palmkernoel und palmkernfettsaeurealkylestern fuer deren verarbeitung zu farbneutralen reaktionsfolgeprodukten

Publications (3)

Publication Number Publication Date
EP0189049A1 EP0189049A1 (de) 1986-07-30
EP0189049B1 EP0189049B1 (de) 1990-08-01
EP0189049B2 true EP0189049B2 (de) 1993-12-15

Family

ID=6259752

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86100134A Expired - Lifetime EP0189049B2 (de) 1985-01-14 1986-01-07 Stabilisierung von Palmkernfettsäuremethylestern für deren Verarbeitung zu farbneutralen Reaktionsfolgeprodukten

Country Status (6)

Country Link
EP (1) EP0189049B2 (OSRAM)
JP (1) JPH0753874B2 (OSRAM)
BR (1) BR8600103A (OSRAM)
DE (2) DE3500938A1 (OSRAM)
GB (1) GB2169611B (OSRAM)
MY (1) MY102435A (OSRAM)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IE980887A1 (en) * 1998-10-27 2000-05-03 Diarmaid Joseph Long Anti-oxidant formulations
DE102005015474A1 (de) 2005-04-04 2006-10-05 Degussa Ag Verfahren zur Erhöhung der Oxidationsstabilität von Biodiesel
WO2009108747A1 (en) * 2008-02-27 2009-09-03 Wayne State University The effect of natural and synthetic antioxidants on the oxidative stability of biodiesel
US20120233912A1 (en) 2011-03-18 2012-09-20 Otkrytoe Aktsionernoe Obschestvo "Sterlitamaxky Neftekhimichesky Zavod" Antioxidant additive composition, a solution thereof, and a method for improving the storage stability of biodiesel fuel (variants)
CN104024355A (zh) * 2011-11-16 2014-09-03 泰克尼克斯工业有限公司 沥青稀释剂
RU2476585C1 (ru) 2012-03-07 2013-02-27 Открытое Акционерное Общество "Стерлитамакский Нефтехимический Завод" Композиция антиокислительной присадки, ее раствор и способ повышения стабильности биодизельного топлива при хранении (варианты)
AU2022233124A1 (en) 2021-03-08 2023-09-21 Technix EnviroCutter IP Limited Bitumen cutback compositions and methods of use thereof

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB754388A (en) * 1954-04-02 1956-08-08 Alfred William Brickman Improvements in the inhibition of oxidation of fats or fatty oils
JPS5373206A (en) * 1976-12-10 1978-06-29 Riken Vitamin Co Ltd Antioxidant composition for fat and oil
JPS5554400A (en) * 1978-10-17 1980-04-21 Nisshin Oil Mills Ltd Manufacture of high antiioxidability fat and oil
JPS5944344B2 (ja) * 1978-11-17 1984-10-29 田辺製薬株式会社 抗酸化剤
JPS6042495A (ja) * 1983-08-17 1985-03-06 日清製油株式会社 油脂脱臭留出物のメチルエステル化法

Also Published As

Publication number Publication date
GB2169611A (en) 1986-07-16
DE3500938C2 (OSRAM) 1993-06-24
EP0189049B1 (de) 1990-08-01
GB8600027D0 (en) 1986-02-12
GB2169611B (en) 1989-09-13
DE3673027D1 (de) 1990-09-06
BR8600103A (pt) 1986-09-23
MY102435A (en) 1992-06-30
DE3500938A1 (de) 1986-07-17
JPS61163999A (ja) 1986-07-24
EP0189049A1 (de) 1986-07-30
JPH0753874B2 (ja) 1995-06-07

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