EP0429995B1 - Verfahren zur Hydrierung von Ölen - Google Patents

Verfahren zur Hydrierung von Ölen Download PDF

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Publication number
EP0429995B1
EP0429995B1 EP90121982A EP90121982A EP0429995B1 EP 0429995 B1 EP0429995 B1 EP 0429995B1 EP 90121982 A EP90121982 A EP 90121982A EP 90121982 A EP90121982 A EP 90121982A EP 0429995 B1 EP0429995 B1 EP 0429995B1
Authority
EP
European Patent Office
Prior art keywords
oil
hydrogenation
catalyst
oils
process according
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
EP90121982A
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English (en)
French (fr)
Other versions
EP0429995A3 (en
EP0429995A2 (de
Inventor
Joze Dr. Kobe
Andrej Smidovnik
Anton Stimac
Lidija Vidmar
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.)
Helios Oljarna Domzale d o o
Original Assignee
Helios Oljarna Domzale d o o
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Publication date
Application filed by Helios Oljarna Domzale d o o filed Critical Helios Oljarna Domzale d o o
Publication of EP0429995A2 publication Critical patent/EP0429995A2/de
Publication of EP0429995A3 publication Critical patent/EP0429995A3/en
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Publication of EP0429995B1 publication Critical patent/EP0429995B1/de
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Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • C11C3/12—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation

Definitions

  • the invention relates to the field of food technology and refers to a process for hydrogenating vegetable and animal oils or fats into products with unique melt profile by means of catalytic hydrogen transfer from an appropriate donor as well as to the products of said hydrogenation.
  • Textural characteristics of products which contain hydrogenated oils such as margarines, ice-creams, cakes etc., particularly "mouthmelt", result from solid content index (SCI) of hydrogenated oils.
  • SCI solid content index
  • the basic hydrogenation process means the conversion of liquid oils into semi-solid substances and partially hydrogenated oils.
  • Plastic fats are useful for preparing vegetable fats, margarine and special purpose fats. By means of hydrogenation there is also achieved increased stability and improvement of the basic colour.
  • Hydrogenation represents the double bond addition in fat in the presence of a metallic catalyst.
  • the purpose of the hydrogenation is the saturation of double bonds of fatty acids in fats.
  • the hydrogenation reaction is not simple since it is accompanied by the simultaneous double bond isomerization, which may be a positional or a geometrical one.
  • the position of the fatty acid in glycerol (1, 2 and 3) as well as the degree of unsaturation determine the physical properties of the molecule, especially the melting point of the fat, and thence influences on SCI.
  • the stepwise conversion of the most unsaturated fatty acid form proceeded to the saturated state, i.e. linolenic to linoleic, then to oleic, and finally to stearic.
  • a very narrow melting range or a controlled level of trans acids cannot be achieved by a common hydrogenation.
  • European Patent Application 0 246 366 A1 discloses a simplified one-step process with partly deactivated Ni catalyst at a temperature range from 160 to 250 °C and gauge pressure of hydrogen from 0 to 7.105 Pa.
  • the hydrogenation is carried on at a temperature fro 20 to 90 °C, usually at room temperature and at atmospheric pressure. However, better results are achieved at higher temperatures.
  • the batch process is carried out in an organic solvent or in an aqueous emulsion.
  • the continuous process is carried out in an organic solvent.
  • Oils containing unsaturated fatty acids with at least 12 carbon atoms are hydrogenated.
  • products having specific compositions which are the basis for producing margarine, creams, ice-creams etc., with improved edibility and appropriate melting properties as well as oxidation stability.
  • the oil acceptor (A) containing double bonds, the hydrogen donor (DHx) and the catalyst are in contact.
  • the hydrogen donor may be any organic compound having sufficiently low oxidation potential for carrying out the hydrogen transfer at relatively mild conditions.
  • the hydrogenation rate depends upon the nature of oil, the nature of hydrogen donor, the activity and the concentration of the catalyst as well as upon the velocity of the adsorption and desorption step of the unsaturated oil and the hydrogen donor on the catalyst.
  • the compositions and properties of hydrogenated products can vary with regard to the position of the double bonds to be hydrogenated and are due to the influence of the isomerization reactions, which accompany each hydrogenation step. They also largely depends on hydrogenation conditions.
  • Vegetable oils or mixture of vegetable oils, which are suitable for hydrogenation are e.g. soya oil, sunflower oil, safflower oil, maize oil, olive oil, bamboo oil, peanut oil, palm oil, rape oil, grape oil, coconut oil, pumpkin oil and castor oil.
  • cod-liver-oil or a mixture of cod-liver oil with vegetable oils may be used.
  • Suitable iodine values before hydrogenation range between 50 and 183 ; after hydrogenation they are reduced to 10 to 150.
  • regenerable catalysts such as 1 - 20% palladium on active carbon (Pd/C), Pd/C/FeCl3, Pd/C/Fe(III) hydroxide or oxide, 0.04 - 10% Pd/Al2O3, 5% Pt/C. 5% Pt/Al2O3, 5% rhodium on active carbon, Raney nickel, ruthenium black and platinum black.
  • the hydrogen donor must correspond to the catalyst, therefore formic acid and hypophosphorous acid as well as the salts thereof, such as triethylammonium formate, tri-n-butylammonium formate, sodium formate, potassium formate and ammonium formate as well as sodium hypophosphite are used.
  • solvents such as ethanol propan-2-ol, formic acid, acetic acid, acetone and ethyl acetate may be selected. Some solvents can also act as the hydrogen donor.
  • the reaction may be directed into products, which may be totally or only partly hydrogenated oils.
  • the reaction is especially suitable for obtaining partly hydrogenated oils. From soya oil, rape oil or some other vegetable oil, only within a few hours of hydrogenation, an oil containing less than 1 % linolenic acid is obtained.
  • cod-liver oils having high contents of poly-unsaturated ⁇ 3 acids (especially C18:3 ⁇ 3, C20:5 ⁇ 3 and C22:6 ⁇ 3), there are obtained fats with lower iodine values and adequate melting properties.
  • the continuous process is also very simple since neither mixing nor catalyst removal are necessary.
  • the catalyst may also be regenerated in a column and can be used for almost an unlimited period of time.
  • one disadvantage of the present process can be present, the solvent and the donor must be removed from the final product before its application.
  • weight amounts of oil, catalyst and hydrogen donor, dissolved in an organic solvent or water were agitated mechanically at about 900 rpm in a 150 ml flask which was immersed in a water bath at chosen temperature.
  • Iodine value was calculated from fatty acid composition.
  • a mixture of sunflower oil (2 ml) having an iodine value of 139.2, acetone (25 ml) and formic acid (2 ml) was eluted through a column filled with celite and with 100 mg of Pd/C.
  • the flow rate was 0.5 ml/min. After the removal of the solvent a hydrogenated product having an iodine value of 122.4 and with a fatty acid composition as given in the Table 2 was obtained.
  • Example 4 (batch hydrogenation in an aqueous emulsion)
  • the iodine value, the fatty acid composition and the trans content were determined by means of a gas chromatograph equipped with an ion trap detector.
  • IV (iodine value) 72 MP (melting point) 38°C SCI (solid content index) 10°C 63.4 15°C 60.2 20°C 53.0 25°C 40.8 30°C 24.7 35°C 10.8 TABLE 3 Change in fatty acid composition of soya oil during hydrogenation and the content of trans acids t(h) C 18:3 C 18:2 C 18:1 C 18:0 C 16:0 % trans* 0 7.5 51.7 23.4 5.4 10.5 1.5 1 4.7 48.6 30.7 5.5 10.5 3.7 3 1.9 40.7 41.2 5.6 10.6 8.5 9 - 22.0 60.5 7.0 10.5 15.1 24 - 7.0 75.1 8.4 10.5 33.0 33 - 1.4 77.3 10.8 10.5 33.1 * Positional and geometrical isomers of fatty acids expressed as percent of total fatty acids.

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  • Chemical & Material Sciences (AREA)
  • General 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)
  • Fats And Perfumes (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Claims (6)

  1. Verfahren zur Hydrierung von Pflanzen- oder Tierölen oder -fetten mit Jodzahlen von 50 bis 183 mit einem Wasserstoffdonator in Anwesenheit eines Katalysators, dadurch gekennzeichnet, daß
    der Katalysator aus der Gruppe bestehend aus Palladium auf Aktivkohle, Pd/C/FeCl₃, Pd/C/Fe(III)-Hydroxid oder -Oxid, Pd(Al₂O₃), Pt/C, Pt/Al₂O₃, Rhodium auf Aktivkohle, Raney-Nickel, Rutheniummohr und Platinmohr ausgewählt wird und der Wasserstoffdonator aus der Gruppe bestehend aus Ameisensäure oder hypophosphoriger Säure oder deren Salzen, wie Triäthylammonium, Tri-n-butylammonimum, Natriumhypophosphit augewählt wird, und der Ausgangsstoff gegebenenfalls in einem Lösungsmittel hydriert wird und die Jodzahlen des Ausgangsstoffs zu Zahlen von 10 bis 150 reduziert werden.
  2. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß Ptlanzenöle oder Tierfette oder deren Gemische, zusammengesetzt aus wenigstens 12 Kolhenstoffatomen in der Kette enthaltenden Fettsäuren, verwendet werden.
  3. Verfahren gemäß Ansprüchen 1 und 2, dadurch gekennzeichnet, daß die Pflanzenöle Sojaöl, Sonnenblumenöl, Kürbiskernöl, Safranöl, Maisöl, Olivenöl, Bambusöl, Erdnussöl, Palmenöl, Rapsöl, Traubenöl, Kokosöl und Rizinusöl sind.
  4. Verfahren gemäß Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß Lebertran oder eine Mischung von Lebertran mit Pflanzenölen hydriert wird.
  5. Verfahren gemäß Ansprüchen 1 bis 4, dadurch gekennzeichnet, daß 0,03 bis 1,5% von Katalysator hinsichtlich (bezieht) auf die Eingangsgewicht der Ölen verwendet wird.
  6. Verfahren gemäß Ansprüchen 1 bis 4, dadurch gekennzeichnet, daß die Hydrierung beim Luftdruck im Temperaturbereich von 20 bis 90°C verlauft.
EP90121982A 1989-11-20 1990-11-16 Verfahren zur Hydrierung von Ölen Expired - Lifetime EP0429995B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
YU2204/89 1989-11-20
YU220489A YU46273B (sh) 1989-11-20 1989-11-20 Postopek za hidrogeniranje olj

Publications (3)

Publication Number Publication Date
EP0429995A2 EP0429995A2 (de) 1991-06-05
EP0429995A3 EP0429995A3 (en) 1991-12-11
EP0429995B1 true EP0429995B1 (de) 1996-02-28

Family

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EP90121982A Expired - Lifetime EP0429995B1 (de) 1989-11-20 1990-11-16 Verfahren zur Hydrierung von Ölen

Country Status (4)

Country Link
EP (1) EP0429995B1 (de)
DE (1) DE69025553T2 (de)
SI (1) SI8912204A8 (de)
YU (1) YU46273B (de)

Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6645261B2 (en) 2000-03-06 2003-11-11 Cargill, Inc. Triacylglycerol-based alternative to paraffin wax
US7128766B2 (en) 2001-09-25 2006-10-31 Cargill, Incorporated Triacylglycerol based wax compositions
US7820841B2 (en) 2003-07-31 2010-10-26 Cargill, Incorporated Low trans-fatty acid fat compositions; low-temperature hydrogenation, e.g., of edible oils
US7585990B2 (en) 2003-07-31 2009-09-08 Cargill, Incorporated Low trans-fatty acid fat compositions; low-temperature hydrogenation, e.g., of edible oils
AU2006205023C1 (en) 2005-01-10 2012-05-24 Elevance Renewable Sciences, Inc. Candle and candle wax containing metathesis and metathesis-like products
US8888908B2 (en) 2006-03-07 2014-11-18 Elevance Renewable Sciences, Inc. Colorant compositions comprising metathesized unsaturated polyol esters
KR101660420B1 (ko) 2006-03-07 2016-09-27 엘레반스 리뉴어블 사이언시즈, 인코포레이티드 메타세시스된 불포화 폴리올 에스테르를 포함하는 조성물
WO2008008420A1 (en) 2006-07-12 2008-01-17 Elevance Renewable Sciences, Inc. Hot melt adhesive compositions comprising metathesized unsaturated polyol ester wax
US8067610B2 (en) 2006-07-13 2011-11-29 Yann Schrodi Synthesis of terminal alkenes from internal alkenes and ethylene via olefin metathesis
US8501973B2 (en) 2006-10-13 2013-08-06 Elevance Renewable Sciences, Inc. Synthesis of terminal alkenes from internal alkenes via olefin metathesis
EP2074079B1 (de) 2006-10-13 2011-08-10 Elevance Renewable Sciences, Inc. Metatheseverfahren mit hydrierung, und damit in zusammenhang stehende zusammensetzungen
WO2008048520A2 (en) 2006-10-13 2008-04-24 Elevance Renewable Sciences, Inc. Methods of making organic compounds by metathesis and hydrocyanation
WO2008140468A2 (en) 2006-10-13 2008-11-20 Elevance Renewable Sciences, Inc. METHODS OF MAKING α, ω -DICARBOXYLIC ACID ALKENE DERIVATIVES BY METATHESIS
US9051519B2 (en) 2009-10-12 2015-06-09 Elevance Renewable Sciences, Inc. Diene-selective hydrogenation of metathesis derived olefins and unsaturated esters
US8704019B2 (en) 2010-12-13 2014-04-22 Exxonmobil Research And Engineering Company Catalyst recovery in hydrothermal treatment of biomass
US8487148B2 (en) 2010-12-13 2013-07-16 Exxonmobil Research And Engineering Company Hydrothermal treatment of biomass with heterogeneous catalyst
US8704020B2 (en) 2010-12-13 2014-04-22 Exxonmobil Research And Engineering Company Catalytic hydrothermal treatment of biomass
US8624070B2 (en) 2010-12-13 2014-01-07 Exxonmobil Research And Engineering Company Phosphorus recovery from hydrothermal treatment of biomass
CA2861848A1 (en) 2012-01-10 2013-06-28 Monika Mujkic Renewable fatty acid waxes and methods of making
AU2013277107B2 (en) 2012-06-20 2018-03-08 Wilmar Trading Pte Ltd Natural oil metathesis compositions
CN110564513A (zh) * 2019-10-21 2019-12-13 黑龙江精益检测有限公司 一种在超声无需添加氢气条件下氢化大豆油脂的方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5774042A (en) * 1980-10-27 1982-05-10 Asahi Denka Kogyo Kk Preparation of hard butter
JPS5984992A (ja) * 1982-11-04 1984-05-16 第一クロ−ダケミカルズ株式会社 油脂の精製方法

Non-Patent Citations (1)

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Title
Lehrbuch der Lebensmittelchemie, H.-D. Belitz, W. Grosch; Springer Verlag, 2.Auflage, 1985, p.145 *

Also Published As

Publication number Publication date
SI8912204A8 (en) 1997-08-31
EP0429995A3 (en) 1991-12-11
EP0429995A2 (de) 1991-06-05
DE69025553D1 (de) 1996-04-04
YU220489A (en) 1991-08-31
YU46273B (sh) 1993-05-28
DE69025553T2 (de) 1996-09-26

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