EP0189049B2 - Stabilisation des esters méthyliques des acides gras de l'huile de palmiste pour leur transformation en produits réactionnels de couleur neutre - Google Patents

Stabilisation des esters méthyliques des acides gras de l'huile de palmiste pour leur transformation en produits réactionnels de couleur neutre Download PDF

Info

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
Authority
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
Other languages
German (de)
English (en)
Other versions
EP0189049A1 (fr
EP0189049B1 (fr
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
Original Assignee
Henkel AG and Co KGaA
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=6259752&utm_source=***_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0189049(B2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0189049A1 publication Critical patent/EP0189049A1/fr
Publication of EP0189049B1 publication Critical patent/EP0189049B1/fr
Application granted granted Critical
Publication of EP0189049B2 publication Critical patent/EP0189049B2/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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
    • 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.

Landscapes

  • 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)

Claims (3)

  1. Utilisation du 3,5-diterbutyl-4-hydroxytoluène en quantités allant de 10 à 100 ppm comme agent exclusif de stabilisation dans les esters méthyliques d'acides gras de palmiste de la zone des acides gras en C₁₂ à C₁₈ en vue de leur transformation en produits réactionnels de coloration neutre.
  2. Mode d'exécution selon la revendication 1, caractérisé en ce que comme produit à stabiliser, des esters méthyliques d'acides gras de palmiste se présentent, qui ont été obtenus par transestérification de l'huile de palmiste avec le méthanol.
  3. Mélange d'esters méthyliques d'acides gras de palmiste, de la zone des acides gras en C₁₂ à C₁₈, obtenus par estérification d'acides gras de palmiste, ayant de 12 à 18 atomes de carbone, avec du méthanol ou par transestérification d'huile de palmiste avec du méthanol et isolement de la coupe d'esters d'acides gras en C₁₂-C₁₈ contenant exclusivement comme agent de stabilisation du 3,5-diterbutyl-4-hydroxytoluène ajouté en quantités allant de 10 à 100 ppm, pour l'obtention de produits réactionnels de coloration neutre.
EP86100134A 1985-01-14 1986-01-07 Stabilisation des esters méthyliques des acides gras de l'huile de palmiste pour leur transformation en produits réactionnels de couleur neutre Expired - Lifetime EP0189049B2 (fr)

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 (fr) 1986-07-30
EP0189049B1 EP0189049B1 (fr) 1990-08-01
EP0189049B2 true EP0189049B2 (fr) 1993-12-15

Family

ID=6259752

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86100134A Expired - Lifetime EP0189049B2 (fr) 1985-01-14 1986-01-07 Stabilisation des esters méthyliques des acides gras de l'huile de palmiste pour leur transformation en produits réactionnels de couleur neutre

Country Status (6)

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

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
US8657890B2 (en) * 2008-02-27 2014-02-25 Wayne State University 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)
WO2022191718A1 (fr) 2021-03-08 2022-09-15 Technix EnviroCutter IP Limited Compositions de réduction de bitume et leurs procédés d'utilisation

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

Similar Documents

Publication Publication Date Title
DE3446795C2 (de) Verfahren zur Herstellung einer Fettsäuremischung mit einer hohen Konzentration an Eicosapentaensäure
EP1135996B1 (fr) Utilisation de triglycérides synthétiques à base d'acide linoléique conjugué comme stabilisant de couleur dans les produits alimentaires
EP0007058A1 (fr) Procédé et composition pour la détermination du glycérol
DE3107318A1 (de) Verfahren zur herstellung hochwertiger fettsaeureester
EP0189049B2 (fr) Stabilisation des esters méthyliques des acides gras de l'huile de palmiste pour leur transformation en produits réactionnels de couleur neutre
DE4318673A1 (de) Keimhemmungsmittel für Kartoffeln
DE69323003T2 (de) Antioxydierende Zusammensetzungen
DE1114319B (de) Formmasse aus Polyolefinen und einer Stabilisatormischung
EP0339382B1 (fr) Procédé pour désodoriser des mélanges d'esters d'acides gras
DE2147327C3 (de) Verfahren zur Gewinnung von gereinigtem, nicht-acylierbarem Phosphatid
DE2425215C3 (de) Verfahren zum Schützen von organischen Stoffen mit Hilfe eines bakteriostatischen Mittels
DE843285C (de) Lichtschutzmittel
Vidic et al. Eine gaschromatographische Bestimmung quaternärer Ammoniumverbindungen
DE857118C (de) Verfahren zur Verhinderung der Selbstoxydation von Fetten und OElen
Husain et al. Cyclopropenoid fatty acids of Sida grewioides and Hibiscus caesius (Malvaceae) seed oils
DE837800C (de) Stabilisieren von Speiseoelen und -fetten
DE673535C (de) Verfahren zur Stabilisierung von Celluloseestern organischer Saeuren
DE557516C (de) Verfahren zur Herstellung von sauerstoffaktivem Aceton
AT309695B (de) Verfahren zur Herstellung eines antibakteriellen Toiletteseifenstückes
DE921696C (de) Verfahren zur Herstellung von Injektionspraeparaten aus Testosteronestern mit besonders stark ausgepraegter protrahierter androgener Wirkung
DE889819C (de) Verfahren zur Verhinderung der Selbstoxydation von Fetten und OElen
DE2340914C2 (de) Verfahren zur Herstellung haltbarer 2,2-Dimethyl-4-oxymethyl-1,3-dioxolanhaltiger Drogenextrakte aus proazulenhaltigen Drogen
DE750180C (de) Verfahren zur Herstellung von Schaedlingsbekaempfungsmitteln
DE2928903A1 (de) Antibakterielle seife
DE1089165B (de) Gegen die Einwirkung von Hitze, Licht und Sauerstoff stabilisierte Formmasse aus Hoch- oder Niederdruckpolyolefinen

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

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE FR IT LI NL SE

17P Request for examination filed

Effective date: 19861220

17Q First examination report despatched

Effective date: 19880331

RBV Designated contracting states (corrected)

Designated state(s): DE FR IT NL

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR IT NL

REF Corresponds to:

Ref document number: 3673027

Country of ref document: DE

Date of ref document: 19900906

ET Fr: translation filed
ITF It: translation for a ep patent filed

Owner name: STUDIO JAUMANN

ITTA It: last paid annual fee
PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

26 Opposition filed

Opponent name: UNILEVER PLC

Effective date: 19910427

NLR1 Nl: opposition has been filed with the epo

Opponent name: UNILEVER PLC

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 PLC

Effective date: 19910427

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

27A Patent maintained in amended form

Effective date: 19931215

AK Designated contracting states

Kind code of ref document: B2

Designated state(s): DE FR IT NL

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

Ref country code: NL

Payment date: 19940131

Year of fee payment: 9

NLR2 Nl: decision of opposition
ITF It: translation for a ep patent filed

Owner name: STUDIO JAUMANN

NLR3 Nl: receipt of modified translations in the netherlands language after an opposition procedure
ET3 Fr: translation filed ** decision concerning opposition
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19950801

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19950801

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

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

Ref country code: DE

Payment date: 20041231

Year of fee payment: 20

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;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050107

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

Ref country code: FR

Payment date: 20050110

Year of fee payment: 20