EP0269904B1 - Verfahren zum Raffinieren von Fett - Google Patents

Verfahren zum Raffinieren von Fett Download PDF

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Publication number
EP0269904B1
EP0269904B1 EP87116353A EP87116353A EP0269904B1 EP 0269904 B1 EP0269904 B1 EP 0269904B1 EP 87116353 A EP87116353 A EP 87116353A EP 87116353 A EP87116353 A EP 87116353A EP 0269904 B1 EP0269904 B1 EP 0269904B1
Authority
EP
European Patent Office
Prior art keywords
mixture
free fatty
solvent
liquid
fatty acid
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
Application number
EP87116353A
Other languages
English (en)
French (fr)
Other versions
EP0269904A3 (en
EP0269904A2 (de
Inventor
Wataru C/O Asahi Denka Kogyo K.K. Matsumoto
Eiji C/O Asahi Denka Kogyo K.K. Nakai
Kazuaki C/O Asahi Denka Kogyo K.K. Suzuki
Susumu C/O Asahi Denka Kogyo K.K. Satoh
Shouji C/O Asahi Denka Kogyo K.K. Maruzeni
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.)
Adeka Corp
Original Assignee
Asahi Denka Kogyo KK
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
Priority claimed from JP26839486A external-priority patent/JPS63122794A/ja
Priority claimed from JP26839386A external-priority patent/JPS63122793A/ja
Application filed by Asahi Denka Kogyo KK filed Critical Asahi Denka Kogyo KK
Priority to AT87116353T priority Critical patent/ATE69464T1/de
Publication of EP0269904A2 publication Critical patent/EP0269904A2/de
Publication of EP0269904A3 publication Critical patent/EP0269904A3/en
Application granted granted Critical
Publication of EP0269904B1 publication Critical patent/EP0269904B1/de
Expired 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
    • 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

Definitions

  • This invention relates to a process for refining a fat. More particularly, it relates to a process for removing and separating partial glyceride(s) and/or free fatty acid(s) from an oleaginous mixture comprising a fat and the partial glyceride(s) and/or free fatty acid(s).
  • a product obtained by, for example, transesterifying a fat with the use of lipase contains DG at a high concentration.
  • Solvent fractionation of fats using acetone is known e.g. from GB-A-1.539.032, and FR-A-911.371. These documents do not, however, mention liquid-liquid extraction.
  • Known methods for separating an oleaginous mixture comprising fatty acids and triglycerides as main components, e.g., a fat having an extremely high acid value or a product obtained by transesterifying fatty acids with glycerides, into fatty acids and triglycerides on an industrial scale include alkali deacidification and steam distillation.
  • alkali deacidification can be applied to an oleaginous mixture of a relatively low fatty acid content, it can not be applied to those having a high fatty acid content since considerable amounts of the acids are incorporated in the foots formed thereby to bring about a significant loss in the yield of the acids.
  • the fatty acids and partial glycerides contained in the oleaginous mixture reside within a still for a prolonged period of time and thus suffer from thermal changes in the triglyceride composition. Therefore it is impossible to obtain a preferable triglyceride composition thereby.
  • the rate of thermal decomposition is doubled for each 10°C rise in temperature and the decomposition rate is proportional to the residence time in a distillation process in general (cf. Chem. Rev., 54 . 51 (1944)).
  • fatty acids may be removed by adsorbing the same by column chromatography.
  • this method is available in a laboratory, the high cost thereof makes it inavailable at present on an industrial scale.
  • Japanese Patent Publication No. 40000/1986 teaches that free fatty acids can be distilled off during removal of partial glycerides by molecular distillation.
  • the molecular distillation in the above case is carried out using a falling film type molecular still and the acid value of the starting fat is 10 at the highest. It is impossible to appropriately treat an oleaginous mixture of a high acid value containing free fatty acids at a high concentration by the method as described in Japanese Patent Publication No. 40000/1986.
  • Free fatty acids may be removed from an oleaginous mixture by liquid/liquid extraction with the use of a solvent.
  • the liquid/liquid extraction in particular furfural extraction, which is known as a method for purifying a liquid mixture which can be hardly separated by distillation, has been employed for deacidifying or deodorizing cod-liver oil. Recently, however, liquid/liquid extraction has been scarcely applied to oleaginous products, since it is difficult to handle an extraction solvent. In liquid/liquid extraction, furfural and propane are frequently employed.
  • the acetone to be used in the present invention may be either absolute or aqueous one. Since acetone containing a large amount of water would lower the solubility of a fat and thus sometimes cause liquid/liquid separation, it is desirable that acetone contains 2% or below, preferably 0.5% or below, of moisture.
  • the solvent i.e., acetone
  • acetone may be used in an amount of one to ten parts (by weight; the same will apply hereinbelow), preferably three to six parts, per part of the oleaginous mixture.
  • the oleaginous mixture to be refined by the process of the present invention comprises 2% or more of partial glyceride(s).
  • the content of partial glyceride(s) of 5 to 6% or more would deteriorate the physical properties of triglyceride(s), in particular, a hard butter.
  • the content of the partial glyceride(s) less than 2% hardly affects the properties of the triglyceride(s).
  • partial glyceride(s) can be efficiently separated from an oleaginous mixture comprising 5% or more of the same.
  • the oleaginous mixture to be refined by the acetone solvent fractionation step may comprise 20% or less of free fatty acid(s).
  • the content of tree fatty acid(s) exceeds 20%, it is difficult to concentrate most of the free fatty acid(s) in the liquid phase.
  • the solvent-fractionation with acetone as effected in the process of the present invention includes the following three steps: dissolving an oleaginous mixture in acetone and cooling the obtained solution to thereby precipitate crystals: separating the liquid phase from the solid phase, i.e., the crystals, and washing the latter; and finally removing the solvent from each phase.
  • 0.2 to 2.0%, based on the oleaginous mixture, of crystalline seeds, which have been preliminarily obtained by supercooling a fat, are added to the solution at a temperature higher than the crystallizing temperature by 1 to 8°C, while slowly cooling the solution, thus accelerating the crystallization and giving crystals which can be readily separated.
  • the crystalline seeds may be prepared from any fat so long as it is insoluble in the solvent under the above conditions.
  • the oleaginous mixture to be refined has an acid value as high as 50 or above, it is desirable to pretreat it for removing free fatty acid(s) therefrom to thereby lower the acid value thereof to 40 or below, preferably 25 or below, prior to the solvent-fractionation as mentioned above.
  • solvent to be used in the above liquid/liquid extraction examples include furfural, n-propyl alcohol, propionitrile, hexane, acetone, methanol and ethanol.
  • solvents may be used alone. Alternately, a mixture thereof or an aqueous solvent may be employed.
  • the liquid/liquid extraction may be carried out with the use of an extractor such as a mixer-settler extractor, a spray tower, a packed column, a perforated-plate extractor or a baffle tower, a rotary extractor, a rotary disc tower, a Scheibel column or a pulsed extraction column.
  • an extractor such as a mixer-settler extractor, a spray tower, a packed column, a perforated-plate extractor or a baffle tower, a rotary extractor, a rotary disc tower, a Scheibel column or a pulsed extraction column.
  • the mixing ratio of the oleaginous mixture to the extraction solvent may be arbitrarily altered.
  • the extraction temperature which significantly affects the extraction efficiency, is preferably within a range of 10 to 50°C.
  • the partial glyceride(s) and/or free fatty acid(s) including DG are concentrated in the solvent phase, i.e., the liquid phase, and thus can be readily separated from the triglyceride(s) constituting the crystalline phase, i.e., the solid phase, by using acetone as a solvent.
  • the process for refining a fat of the present invention is particularly effective in refining a fat having a concentration of partial glyceride(s) elevated by hydrolysis, or a product having a high acid value which is obtained by transesterifying a fat with lipase (EC: 3.1.1.3), which is a hydrolase for fats and oils, as a catalyst.
  • free fatty acid(s) and triglyceride(s) can be separated from an oleaginous mixture, which comprises free fatty acid(s) at a high concentration and thus has a high acid value, while minimizing the recovery loss and without causing any change in the triglyceride composition.
  • Example 1 and 2 each refer to a pretreatment step for removing most of free fatty acids from an oleaginous mixture comprising free fatty acids at a high concentration by liquid/liquid extraction.
  • Example 3 refers to a process for removing partial glycerides and the residual free fatty acids from the oleaginous mixture, from which some portion of the free fatty acids has been removed in the above pretreatment, by solvent-fractionation with the use of acetone.
  • the reaction product was subjected to liquid/liquid extraction to thereby remove the free fatty acids therefrom.
  • the extraction solvent methanol was employed at a ratio to the reaction product of 1 : 4. The extraction was carried out at 45°C. Thus the free fatty acids were concentrated in the methanol phase. The two phases were separated with the use of a separatory funnel and the solvent was distilled off from both the oily and methanol phases. The yield of the oily phase, i.e., an oleaginous mixture was 60% and the acid value thereof was lowered to 7.5. The recovery yield of the triglycerides was 89%.
  • Example 1 The reaction product used in Example 1 was deodorized in a conventional manner by steam distillation to thereby remove the free fatty acids therefrom.
  • the distillation residue thus obtained had an acid value of 15, was significantly colored and showed a largely altered triglyceride composition.
  • Example 1 The procedure of Example 1 was followed except that 15% aqueous ethanol was employed as the extraction solvent. Thus the free fatty acids were removed.
  • the yield of the oily phase, i.e., an oleaginous mixture was 58.8% and the acid value thereof was lowered to 12.5.
  • the recovery yield of the triglycerides was 96%.
  • Example 2 One part of the oleaginous mixture as obtained in Example 1, from which same portion of the free fatty acids had been removed to give a composition of 4% of free fatty acids, 6.8% of diglycerides and 89.2% of triglycerides, was completely dissolved in three parts of acetone containing 0.15% of moisture at 40°C to give a micelle mixture.
  • This micelle mixture was cooled under stirring while adding crystalline seeds, which had been preliminarily prepared by supercooling 0.005 part of the micelle mixture, thereto at 22°C (seeding). Subsequently the mixture was slowly cooled to 18°C to thereby precipitate crystals. After further cooling, the mixture was maintained at 2°C for one hour and then filtered. The crystalline phase thus obtained was washed to prepare a high-melting fraction.
  • the solvent phase i.e., the liquid phase as obtained above was completely dissolved in five parts of acetone containing 0.15% of moisture at 40°C to give a micelle mixture.
  • This micelle mixture was cooled under stirring while adding crystalline seeds, which had been preliminarily prepared by dissolving 0.005 part of the micelle mixture in 0.05 part of acetone and precipitating crystals at 10°C, thereto at 18°C. Then the mixture was further cooled slowly to 2°C under stirring. After maintaining at 2°C for one hour, the mixture was filtered. The crystalline phase thus obtained was washed to prepare a medium-melting fraction.
  • the solvent was distilled off from the solvent (liquid) phase in a conventional manner to prepare a low-melting fraction.
  • Table 1 shows the yield and analytical data of each fraction thus obtained.
  • the content of each of the partial glycerides and free fatty acids was determined by TLC/FID method with the use of Iatroscan TH-10 (mfd. by Iatron).
  • Table 2 shows the analytical data on the composition of the fatty acids at the 2-position of the triglycerides of each fraction as well as those in the total triglycerides of the combined fractions.
  • the free fatty acids and partial glycerides present in the oleaginous mixture used in Example 3 were removed therefrom by molecular distillation.
  • the distillation was carried out at a temperature of 250°C and a degree of vacuum of 5 x 10 ⁇ 3 Torr.
  • the triglyceride composition of the mixture was significantly altered (cf. Table 2). This result suggests that transesterification might occur at the high temperature.
  • Table 1 Yield (%) Composition(%) Partial glyceride Free fatty acid Triglyceride Starting material - 6.8 4.0 89.2 High-melting fraction 11.0 1.3 0.5 98.2 Medium-melting fraction 41.0 0.4 0.1 99.5 Low-melting fraction 48.0 13.5 8.2 78.3
  • Table 2 Composition of fatty acids at 2-position of triglycerides Starting material Ex. *1 *2 *3 *4 Comp. Ex.

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Microbiology (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)

Claims (1)

  1. Ein Verfahren zum Raffinieren von Fett, das umfaßt

    Entfernen von freier bzw. freien Fettsäure(n) aus einer öligen Mischung, enthaltend partielle(s) Glycerid(e) und/oder freie Fettsäure(n), durch Flüssig-Flüssigextraktion und dann Entfernen des bzw. der partiellen Glyceride und/oder der restlichen freien Fettsäure(n) aus der öligen Mischung durch Lösungsmittelfraktionierung unter Verwendung von Aceton in einer Menge von 1 bis 10 Gewichtsteilen der öligen Mischung und unter Zusatz von Impfkristallen,

    dadurch gekennzeichnet,

    daß eine ölige Mischung mit einem Säurewert von 50 oder darüber verwendet wird, und daß der Säurewert der öligen Mischung auf 25 oder weniger eingestellt wird durch die Flüssig-Flüssigextraktion vor der Lösungsmittelfraktionierung.
EP87116353A 1986-11-11 1987-11-05 Verfahren zum Raffinieren von Fett Expired EP0269904B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87116353T ATE69464T1 (de) 1986-11-11 1987-11-05 Verfahren zum raffinieren von fett.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP26839486A JPS63122794A (ja) 1986-11-11 1986-11-11 トリグリセリドの精製方法
JP268393/86 1986-11-11
JP268394/86 1986-11-11
JP26839386A JPS63122793A (ja) 1986-11-11 1986-11-11 油脂の精製方法

Publications (3)

Publication Number Publication Date
EP0269904A2 EP0269904A2 (de) 1988-06-08
EP0269904A3 EP0269904A3 (en) 1988-07-06
EP0269904B1 true EP0269904B1 (de) 1991-11-13

Family

ID=26548292

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87116353A Expired EP0269904B1 (de) 1986-11-11 1987-11-05 Verfahren zum Raffinieren von Fett

Country Status (6)

Country Link
EP (1) EP0269904B1 (de)
AT (1) ATE69464T1 (de)
DE (1) DE3774540D1 (de)
ES (1) ES2026884T3 (de)
GR (1) GR3003124T3 (de)
SG (1) SG127192G (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PT95218A (pt) * 1989-09-08 1991-05-22 Siegfried Peter Processo para a preparacao de monogliceridos puros, digliceridos puros e/ou trigliceridos puros
US5104587A (en) * 1990-05-16 1992-04-14 The Procter & Gamble Company Countercurrent liquid/liquid extraction to fractionate complex mixtures containing medium and long chain fatty acid triglycerides

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR911371A (fr) * 1945-06-09 1946-07-05 Raffinage des huiles et corps gras végétaux et séparation de leurs constituants
US2664431A (en) * 1948-10-02 1953-12-29 Kellogg M W Co Method for stabilizing soybean oil refined by solvent treatment
GB1539032A (en) * 1976-03-23 1979-01-24 Boc International Ltd Treatment of tall oil
JPS5815598A (ja) * 1981-07-21 1983-01-28 日本油脂株式会社 高度不飽和脂肪酸の濃縮分離方法
JPS5915492A (ja) * 1982-07-19 1984-01-26 日本油脂株式会社 高度不飽和脂肪酸の濃縮分離方法

Also Published As

Publication number Publication date
SG127192G (en) 1993-03-12
ES2026884T3 (es) 1992-05-16
ATE69464T1 (de) 1991-11-15
DE3774540D1 (de) 1991-12-19
EP0269904A3 (en) 1988-07-06
EP0269904A2 (de) 1988-06-08
GR3003124T3 (en) 1993-02-17

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