WO2011081119A1 - Method for controlling the production of chloropropanols and chloropropanol-forming substances in glyceride oils and fats - Google Patents

Method for controlling the production of chloropropanols and chloropropanol-forming substances in glyceride oils and fats Download PDF

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WO2011081119A1
WO2011081119A1 PCT/JP2010/073500 JP2010073500W WO2011081119A1 WO 2011081119 A1 WO2011081119 A1 WO 2011081119A1 JP 2010073500 W JP2010073500 W JP 2010073500W WO 2011081119 A1 WO2011081119 A1 WO 2011081119A1
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oil
fats
chloropropanols
glyceride
oils
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PCT/JP2010/073500
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French (fr)
Japanese (ja)
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雅充 栗山
晴康 木田
仁美 尾森
太 横溝
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不二製油株式会社
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Priority to JP2011547681A priority Critical patent/JPWO2011081119A1/en
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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
    • C11B3/006—Refining fats or fatty oils by extraction
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
    • A23D9/00—Other edible oils or fats, e.g. shortenings, cooking oils
    • A23D9/02—Other edible oils or fats, e.g. shortenings, cooking oils characterised by the production or working-up
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/58—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment

Definitions

  • the present invention relates to a method for inhibiting the production of chloropropanols and their forming substances in glyceride oils and fats.
  • Chloropropanol is a general term for substances in which chlorine is bonded to propanol, but 3-chloropropanediol, which is one of these substances, has conventionally been produced in small quantities as a by-product when mainly producing amino acid solutions such as soy sauce. In addition, it is said that it is formed by the presence of lipids and salt in the process of cooking food.
  • Non-Patent Document 1 Korean Patent Document 1
  • Non-Patent Document 2 glycidol fatty acid esters are present as forming substances in the process of producing chloropropanols in glyceride oils.
  • An object of the present invention is to provide a method for suppressing the production of chloropropanols such as 3-chloropropanediol and 3-chloropropanediol fatty acid ester and glycidol fatty acid ester which is a forming substance thereof in glyceride fats and oils.
  • chloropropanols such as 3-chloropropanediol and 3-chloropropanediol fatty acid ester and glycidol fatty acid ester which is a forming substance thereof in glyceride fats and oils.
  • the inventors of the present invention increase the chloropropanols and their forming substances in glyceride fats and oils through a process in which the fats and oils are heated, such as decolorization and deodorization, based on causative substances present in trace amounts in glyceride fats and oils.
  • oil raw materials or glyceride fats and oils before heat treatment were mixed with a solvent in the presence of water, and the solvent was removed after separating the fats and solvent fractions.
  • the present invention (1) purifies the oil obtained by mixing the oil raw material or glyceride fat before heating with a solvent in the presence of water, separating the aqueous phase from the fat / solvent phase, and then removing the solvent.
  • the heat treatment is a step in which the oil raw material or the glyceride fat is heated to 200 ° C. or higher (1).
  • the solvent is a nonpolar solvent.
  • chloropropanols such as 3-chloropropanediol and 3-chloropropanediol fatty acid ester and glycidol fatty acid ester which is a forming substance thereof in glyceride oils and fats.
  • oil raw material used in the present invention examples include oil seeds such as soybean, rapeseed, sesame, safflower, cottonseed, peanut, rice bran, corn germ, or olive or palm oil.
  • examples of the glyceride fats and oils include soybean oil, rapeseed oil, sesame oil, safflower oil, cottonseed oil, peanut oil, or rice oil, corn oil, olive oil, and palm oil unrefined fat And crude oil and fat obtained by filtering and centrifuging unpurified oil and fat.
  • the glyceride fat used in the present invention is other than vegetable oils such as soybean oil, rapeseed oil, safflower oil, corn oil, sunflower oil, cottonseed oil, rice oil, olive oil, palm oil, coconut oil, palm kernel oil, sesame oil.
  • vegetable oils such as soybean oil, rapeseed oil, safflower oil, corn oil, sunflower oil, cottonseed oil, rice oil, olive oil, palm oil, coconut oil, palm kernel oil, sesame oil.
  • animal fats such as beef tallow, pork tallow and fish oil.
  • the method of the present invention can be carried out in a step of obtaining crude palm oil from oil palm pulp or a step before refining the crude palm oil.
  • the method of the present invention is characterized in that it is applied to oily raw materials or glyceride oils before heat treatment. This is based on the knowledge that causative substances present in oily raw materials or glyceride fats and oils are heated to change into chloropropanols and their forming substances. Therefore, in the method of the present invention, it is necessary that the causative substance present in the oily raw material or glyceride fat has a heating history that does not change to chloropropanols and their forming substances.
  • the oil raw material or glyceride oils and fats before the heat treatment It is important to apply to.
  • the heat treatment means heating to a high temperature at which the causative substance present in the oily raw material or glyceride fat is changed to chloropropanols and its forming substance as described above.
  • a heat treatment such as a step in which fats and oils are heated to 200 ° C. or higher can be exemplified. Therefore, by performing the method of the present invention before the refining process in which the oil raw material or glyceride fat is heated to 200 ° C. or higher, the production of chloropropanols and its forming substances in the glyceride fat can be suppressed.
  • the method of the present invention is characterized in that the oily raw material and glyceride oil / fat before heat treatment are mixed with a solvent in the presence of water to separate the aqueous phase from the oil / fat / solvent phase.
  • Chloropropanols in glyceride oils and glycidol fatty acid esters which are the substances that form them, are thought to be produced when oils and fats are heated to a high temperature with water-soluble substances such as chloride salts remaining in the oils and fats. .
  • water-soluble substances such as chloride salts in oil raw materials or glyceride fats and oils migrate to the water phase, and water-soluble substances can be removed from the oil / fat and solvent phases. Become.
  • the solvent used for mixing in the presence of water it is preferable to use a highly hydrophobic nonpolar solvent such as hexane in order to improve separation of the aqueous phase and the oil / fat / solvent phase.
  • a highly hydrophobic nonpolar solvent such as hexane
  • the present invention can also be carried out by mixing with a solvent in the presence of moisture contained in the oil raw material in the step of extracting oil from the oil raw material.
  • the amount of water required is 0.1% by weight or more, preferably 50% by weight or more, more preferably 200% by weight, based on the glyceride oil. If it is too small, removal of water-soluble substances in glyceride oils and fats to the aqueous phase tends to be insufficient. Further, the amount of the necessary solvent is 10% by weight or more, preferably 50% by weight or more, more preferably 200% by weight with respect to the glyceride oil.
  • the glyceride fats and oils obtained by the method of the present invention are difficult to produce chloropropanols and their forming substances, and it is possible to obtain purified fats and oils with a low content of chloropropanols and their forming substances by decolorizing and deodorizing. it can.
  • the glyceride fats and oils obtained by the method of the present invention have a reduced content of 3-chloropropanediol and 3-chloropropanediol fatty acid esters that are chloropropanols, and glycidol fatty acid esters that form the chloropropanols.
  • the content of propanols and glycidol fatty acid esters which are substances forming the propanols is measured by the following method with reference to the following literature. (Determination of total 3-chloropropane-1,2-diol (3-MCPD) in editable oils by cleavage of MCPD esters with sodium method. Eur. J. Lipid Sci.
  • 0.1 g of fat / oil is dissolved in 1 ml of t-butyl methyl ether, 250 ⁇ l of 20 ⁇ g / ml internal standard substance (3-MCPD-d 5 ethyl acetate solution) is added, and NaOCH 3 solution (0.5 mol / l NaOCH 3 in MeOH) is added. Mix with 1 ml and let stand at room temperature for 10 minutes. Subsequently, 3 ml of hexane, 3 ml of NaCl solution (NaCl 200 g / water 1 l) and 0.1 ml of glacial acetic acid are added, and after stirring, the upper layer is removed.
  • the upper layer is subjected to GS-MS analysis.
  • GC-MS is quantified using molecular ion peaks m / z 196 (3-MCPD) and m / z 201 (3-MCPD-d 5 ).
  • the above method is adopted as a method for measuring 3-chloropropanediol fatty acid ester and glycidol fatty acid ester, which is a forming substance, in Germany (Deutsche Gesellchaft fur Fettsch: DGF). Hydrolyzes 3-chloropropanediol fatty acid ester and its forming substance glycidol fatty acid ester in fats and oils, all 3-chloropropanediol fatty acid ester and its forming substance glycidol fatty acid ester as 3-MCPD Measuring. “With this method, another compounds forming 3-MCPD under the conditions of the anomalous areal and detected three-MCPD esters”. (Ester-bound 3-chloropropane-1,2-diol (3-MCPD esters) and 3-MCPD forming subnets: DGF Standard Methods Section C-Fats / C-III 18 (09))
  • % in an example means a basis of weight.
  • Comparative Example 2 The RBD palm oil obtained in Comparative Example 1 was decolorized at 2% by weight of white clay at 110 ° C. and 20 Torr for 10 minutes, and further deodorized at 250 ° C. and 2 Torr for 90 minutes. The content of chloropropanols and the substances forming the purified palm oil was 4.7 ppm.

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

Provided is a method for controlling the production of chloropropanols, such as 3-chloropropanediol and 3-chloropropanediol fatty acid esters, and chloropropanol-forming substances from glyceride oils and fats. The production of chloropropanols, such as 3-chloropropanediol and 3-chloropropanediol fatty acid esters, and chloropropanol-forming substances in oils and fats is controlled by mixing unheated edible oil starting materials or glyceride oils and fats in the presence of a solvent and water, separating the oil and fat and solvent fractions, removing the solvent, and purifying the resulting oil and fat.

Description

グリセリド油脂中のクロロプロパノール類及びその形成物質の生成を抑制する方法Method for inhibiting the formation of chloropropanols and their forming substances in glyceride oils and fats
本発明はグリセリド油脂中のクロロプロパノール類及びその形成物質の生成を抑制する方法に関する。 The present invention relates to a method for inhibiting the production of chloropropanols and their forming substances in glyceride oils and fats.
クロロプロパノールとは、プロパノールに塩素が結合した物質の総称であるが、これらの一種である、３－クロロプロパンジオールは、従来から、しょうゆなど主にアミノ酸液を製造する際、副産物として少量生成することが知られており、また食品を加熱調理する過程で、脂質と食塩の存在により生成するといわれている。 Chloropropanol is a general term for substances in which chlorine is bonded to propanol, but 3-chloropropanediol, which is one of these substances, has conventionally been produced in small quantities as a by-product when mainly producing amino acid solutions such as soy sauce. In addition, it is said that it is formed by the presence of lipids and salt in the process of cooking food.
最近、食用油脂中には、３－クロロプロパンジオールが脂肪酸と結合したエステル体で存在していることが明らかになった。（非特許文献１） Recently, it has been clarified that edible fats and oils contain 3-chloropropanediol in an ester form combined with a fatty acid. (Non-Patent Document 1)
さらに、最近、グリセリド油脂中にクロロプロパノール類が生成される過程において、グリシドール脂肪酸エステルがその形成物質として存在していることも報告されている。（非特許文献２） Furthermore, recently, it has been reported that glycidol fatty acid esters are present as forming substances in the process of producing chloropropanols in glyceride oils. (Non-Patent Document 2)
３－クロロプロパンジオール脂肪酸エステルについては、許容摂取量が定められている、というような規制は無いが、欧州においては、３－クロロプロパンジオール脂肪酸エステルに結合する脂肪酸が全て遊離して、３－クロロプロパンジオールになるとみなし、評価をする動きがあり、グリセリド油脂中の含量を低減する技術の開発が望ましい。 For 3-chloropropanediol fatty acid ester, there is no regulation that the allowable intake is set, but in Europe, all the fatty acids bound to 3-chloropropanediol fatty acid ester are released and 3-chloropropanediol fatty acid ester is released. Therefore, it is desirable to develop technology that reduces the content of glyceride oils and fats.
また、グリシドール脂肪酸エステルについても、毒性学的なデータはないが、クロロプロパノール類と同様、グリセリド油脂中の含量を低減する技術の開発が望ましい。 There is no toxicological data for glycidol fatty acid esters, but it is desirable to develop a technique for reducing the content in glyceride fats and oils, like chloropropanols.
本発明は、グリセリド油脂中のクロロプロパノール類である３－クロロプロパンジオールや３－クロロプロパンジオール脂肪酸エステル及びその形成物質であるグリシドール脂肪酸エステルなどの生成を抑制する方法を提供することを目的とする。 An object of the present invention is to provide a method for suppressing the production of chloropropanols such as 3-chloropropanediol and 3-chloropropanediol fatty acid ester and glycidol fatty acid ester which is a forming substance thereof in glyceride fats and oils.
本発明者らは、グリセリド油脂中のクロロプロパノール類及びその形成物質は、グリセリド油脂中に微量に存在する原因物質をもとに、脱色、脱臭といった油脂が加熱される工程を経ると、増加するという知見を得た。かかる知見から、上記課題に対し、鋭意研究を重ねた結果、加熱処理以前の油糧原料又はグリセリド油脂を水の存在下で溶媒と混合し、油脂・溶媒画分を分離後、溶媒を除去して得られた油脂を精製することで、グリセリド油脂中のクロロプロパノール類及びその形成物質であるグリシドール脂肪酸エステルなどの生成を抑制することができるという知見を見出し、本発明を完成させるに至った。 The inventors of the present invention increase the chloropropanols and their forming substances in glyceride fats and oils through a process in which the fats and oils are heated, such as decolorization and deodorization, based on causative substances present in trace amounts in glyceride fats and oils. I got the knowledge. Based on this knowledge, as a result of intensive research on the above problems, oil raw materials or glyceride fats and oils before heat treatment were mixed with a solvent in the presence of water, and the solvent was removed after separating the fats and solvent fractions. By refining the fats and oils obtained in this way, the inventors have found that the production of chloropropanols in glyceride fats and glycidol fatty acid esters which are the forming substances thereof can be suppressed, and have completed the present invention.
すなわち本発明は
（１）加熱処理以前の油糧原料又はグリセリド油脂を水の存在下で溶媒と混合し、水相と油脂・溶媒相を分離後、溶媒を除去して得られた油脂を精製することを特徴とする、グリセリド油脂中のクロロプロパノール類及びその形成物質の生成を抑制する方法
（２）該加熱処理が油糧原料又はグリセリド油脂が２００℃以上に加熱される工程である（１）記載の方法
（３）溶媒が非極性溶媒である（１）の方法
である。 That is, the present invention (1) purifies the oil obtained by mixing the oil raw material or glyceride fat before heating with a solvent in the presence of water, separating the aqueous phase from the fat / solvent phase, and then removing the solvent. (2) The heat treatment is a step in which the oil raw material or the glyceride fat is heated to 200 ° C. or higher (1). (3) The method according to (1), wherein the solvent is a nonpolar solvent.
本発明の方法により、グリセリド油脂中のクロロプロパノール類である３－クロロプロパンジオールや３－クロロプロパンジオール脂肪酸エステル及びその形成物質であるグリシドール脂肪酸エステルなどの生成を抑制することができる。 According to the method of the present invention, it is possible to suppress the production of chloropropanols such as 3-chloropropanediol and 3-chloropropanediol fatty acid ester and glycidol fatty acid ester which is a forming substance thereof in glyceride oils and fats.
以下に、本発明を詳細に説明する。 The present invention is described in detail below.
本発明に用いられる油糧原料としては、大豆、菜種、ごま、サフラワー、綿実、落花生などの油糧種子や、米糠、トウモロコシの胚芽、あるいはオリーブやパーム（アブラヤシ）の果肉などの油糧原料が挙げられる、またグリセリド油脂としては、前記油糧原料から得られる大豆油、菜種油、ごま油、サフラワー油、綿実油、落花生油、あるいは米油、コーン油、またはオリーブ油、パーム油の未精製油脂や、未精製油脂をろ過、遠心分離した粗精製油脂などが挙げられる。 Examples of the oil raw material used in the present invention include oil seeds such as soybean, rapeseed, sesame, safflower, cottonseed, peanut, rice bran, corn germ, or olive or palm oil. Examples of the glyceride fats and oils include soybean oil, rapeseed oil, sesame oil, safflower oil, cottonseed oil, peanut oil, or rice oil, corn oil, olive oil, and palm oil unrefined fat And crude oil and fat obtained by filtering and centrifuging unpurified oil and fat.
また、本発明に用いられるグリセリド油脂は、大豆油、菜種油、サフラワー油、コーン油、ひまわり油、綿実油、米油、オリーブオイル、パーム油、ヤシ油、パーム核油、ゴマ油といった植物性油脂以外にも、牛脂、豚脂、魚油などの動物性油脂にも適用することができる。 The glyceride fat used in the present invention is other than vegetable oils such as soybean oil, rapeseed oil, safflower oil, corn oil, sunflower oil, cottonseed oil, rice oil, olive oil, palm oil, coconut oil, palm kernel oil, sesame oil. In addition, it can be applied to animal fats such as beef tallow, pork tallow and fish oil.
本発明の方法は、これら油糧原料やグリセリド油脂の中でも、アブラヤシの果肉から粗パーム油を得る工程や、粗パーム油を精製する前の工程で行うことができる。 Among these oil raw materials and glyceride fats and oils, the method of the present invention can be carried out in a step of obtaining crude palm oil from oil palm pulp or a step before refining the crude palm oil.
本発明の方法は、加熱処理以前の油糧原料又はグリセリド油脂に適用することを特徴とする。
これは油糧原料又はグリセリド油脂中に存在する原因物質が加熱されることにより、クロロプロパノール類及びその形成物質へ変化すると考えられる知見に基づく。
従って、本発明の方法においては、油糧原料又はグリセリド油脂中に存在する原因物質が、クロロプロパノール類及びその形成物質に変化しない程度の加熱履歴であることが必要である。
また、加熱処理を経て、生成してしまったクロロプロパノール類及びその形成物質のグリセリド油脂中からの除去は困難であることから、本発明の方法においては、加熱処理以前の油糧原料又はグリセリド油脂に適用することが重要である。 The method of the present invention is characterized in that it is applied to oily raw materials or glyceride oils before heat treatment.
This is based on the knowledge that causative substances present in oily raw materials or glyceride fats and oils are heated to change into chloropropanols and their forming substances.
Therefore, in the method of the present invention, it is necessary that the causative substance present in the oily raw material or glyceride fat has a heating history that does not change to chloropropanols and their forming substances.
In addition, since it is difficult to remove chloropropanols and the substances formed from the glycerides and oils formed through heat treatment from the glyceride oils and fats, in the method of the present invention, the oil raw material or glyceride oils and fats before the heat treatment It is important to apply to.
本発明における、加熱処理とは、上記のように、油糧原料又はグリセリド油脂中に存在する原因物質が、クロロプロパノール類及びその形成物質に変化する高い温度への加熱を意味し、例えば油脂の脱臭工程において、油脂が２００℃以上に加熱される工程などの加熱処理を挙げることができる。
従って、油糧原料又はグリセリド油脂が２００℃以上に加熱される精製工程前に、本発明の方法を行うことにより、グリセリド油脂中のクロロプロパノール類及びその形成物質の生成を抑制することができる。 In the present invention, the heat treatment means heating to a high temperature at which the causative substance present in the oily raw material or glyceride fat is changed to chloropropanols and its forming substance as described above. In the deodorizing step, a heat treatment such as a step in which fats and oils are heated to 200 ° C. or higher can be exemplified.
Therefore, by performing the method of the present invention before the refining process in which the oil raw material or glyceride fat is heated to 200 ° C. or higher, the production of chloropropanols and its forming substances in the glyceride fat can be suppressed.
さらに本発明の方法は、加熱処理以前の油糧原料やグリセリド油脂を水の存在下で溶媒と混合し、水相と油脂・溶媒相を分離することを特徴する。グリセリド油脂中のクロロプロパノール類及びその形成物質であるグリシドール脂肪酸エステルなどは、塩化物塩などの水溶性物質が油脂中に残存した状態で、油脂が高い温度に加熱されることにより生成すると考えられる。従って、水の存在下で溶媒と混合することにより、油糧原料又はグリセリド油脂中の塩化物塩などの水溶性物質が水相に移行し、油脂・溶媒相から水溶性物質の除去が可能となる。 Furthermore, the method of the present invention is characterized in that the oily raw material and glyceride oil / fat before heat treatment are mixed with a solvent in the presence of water to separate the aqueous phase from the oil / fat / solvent phase. Chloropropanols in glyceride oils and glycidol fatty acid esters, which are the substances that form them, are thought to be produced when oils and fats are heated to a high temperature with water-soluble substances such as chloride salts remaining in the oils and fats. . Therefore, by mixing with a solvent in the presence of water, water-soluble substances such as chloride salts in oil raw materials or glyceride fats and oils migrate to the water phase, and water-soluble substances can be removed from the oil / fat and solvent phases. Become.
本発明において、水の存在下で混合に用いる溶媒としては、水相と油脂・溶媒相の分離を良くさせるため、ヘキサンなどの疎水性の強い非極性溶媒を用いることが好ましい。 In the present invention, as the solvent used for mixing in the presence of water, it is preferable to use a highly hydrophobic nonpolar solvent such as hexane in order to improve separation of the aqueous phase and the oil / fat / solvent phase.
本発明は、油糧原料から搾油する工程で、油糧原料に含まれる水分の存在下で溶媒と混合することによっても行うことができる。 The present invention can also be carried out by mixing with a solvent in the presence of moisture contained in the oil raw material in the step of extracting oil from the oil raw material.
本発明の方法において、水の存在下で溶媒と混合する際、必要な水の量は、グリセリド油脂に対し、０．１重量％以上、好ましくは５０重量％以上、より好ましくは２００重量％であり、少なすぎると、グリセリド油脂中の水溶性物質の水相への除去が不十分になりやすい。
又、必要な溶媒の量は、グリセリド油脂に対し、１０重量％以上、好ましくは５０重量％以上、より好ましくは２００重量％である。 In the method of the present invention, when mixing with a solvent in the presence of water, the amount of water required is 0.1% by weight or more, preferably 50% by weight or more, more preferably 200% by weight, based on the glyceride oil. If it is too small, removal of water-soluble substances in glyceride oils and fats to the aqueous phase tends to be insufficient.
Further, the amount of the necessary solvent is 10% by weight or more, preferably 50% by weight or more, more preferably 200% by weight with respect to the glyceride oil.
また本発明の方法により得られたグリセリド油脂は、クロロプロパノール類及びその形成物質が生成されにくく、脱色、脱臭を行うことで、クロロプロパノール類及びその形成物質の含量の少ない精製油脂を得ることができる。 Moreover, the glyceride fats and oils obtained by the method of the present invention are difficult to produce chloropropanols and their forming substances, and it is possible to obtain purified fats and oils with a low content of chloropropanols and their forming substances by decolorizing and deodorizing. it can.
本発明の方法によって得られたグリセリド油脂は、クロロプロパノール類である３－クロロプロパンジオールや３－クロロプロパンジオール脂肪酸エステル及びその形成物質であるグリシドール脂肪酸エステルの含量が低減されるが、本発明において、クロロプロパノール類及びその形成物質であるグリシドール脂肪酸エステルの含量は以下の文献を参考に次のような方法で測定している。
（Ｄｅｔｅｒｍｉｎａｔｉｏｎ　ｏｆ　ｔｏｔａｌ　３－ｃｈｌｏｒｏｐｒｏｐａｎｅ－１，２－ｄｉｏｌ　（３－ＭＣＰＤ）　ｉｎ　ｅｄｉｂｌｅ　ｏｉｌｓ　ｂｙ　ｃｌｅａｖａｇｅ　ｏｆ　ＭＣＰＤ　ｅｓｔｅｒｓ　ｗｉｔｈ　ｓｏｄｉｕｍ　ｍｅｔｈｏｘｉｄｅ．　Ｅｕｒ．　Ｊ．　Ｌｉｐｉｄ　Ｓｃｉ．　Ｔｅｃｈｎｏｌ．　２００８，　１１０，：１８３－１８６） The glyceride fats and oils obtained by the method of the present invention have a reduced content of 3-chloropropanediol and 3-chloropropanediol fatty acid esters that are chloropropanols, and glycidol fatty acid esters that form the chloropropanols. The content of propanols and glycidol fatty acid esters which are substances forming the propanols is measured by the following method with reference to the following literature.
(Determination of total 3-chloropropane-1,2-diol (3-MCPD) in editable oils by cleavage of MCPD esters with sodium method. Eur. J. Lipid Sci.
まず、油脂　０．１ｇをｔ‐ブチルメチルエーテル　１ｍｌに溶かし、２０μｇ／ｍｌ内部標準物質（３－ＭＣＰＤ－ｄ５　酢酸エチル溶液）２５０μｌを加え、ＮａＯＣＨ３　溶液（０．５ｍｏｌ／ｌＮａＯＣＨ３　ｉｎ　ＭｅＯＨ）１ｍｌと混和後、室温で１０分静置する。
続いて、ヘキサン　３ｍｌ、ＮａＣｌ　溶液（ＮａＣｌ　２００ｇ／水　１ｌ）３ｍｌ、氷酢酸　０．１ｍｌを添加し、攪拌後、上層を除去する。
さらに、ヘキサン　３ｍｌを添加、攪拌後、上層を除去する。
そして、フェニルボロン酸溶液（フェニルボロン酸１ｇをアセトン：水＝１９：１　４ｍｌに溶解）を添加、攪拌後、８０℃、２０分放置し、室温に放冷後、ヘキサン　２ｍｌを添加、攪拌し、上層をＧＳ－ＭＳ分析に供する。
なお、ＧＣ－ＭＳについては、分子イオンピークｍ／ｚ　１９６（３－ＭＣＰＤ）、ｍ／ｚ　２０１（３－ＭＣＰＤ－ｄ５）を用いて定量する。 First, 0.1 g of fat / oil is dissolved in 1 ml of t-butyl methyl ether, 250 μl of 20 μg / ml internal standard substance (3-MCPD-d 5 ethyl acetate solution) is added, and NaOCH 3 solution (0.5 mol / l NaOCH 3 in MeOH) is added. Mix with 1 ml and let stand at room temperature for 10 minutes.
Subsequently, 3 ml of hexane, 3 ml of NaCl solution (NaCl 200 g / water 1 l) and 0.1 ml of glacial acetic acid are added, and after stirring, the upper layer is removed.
Furthermore, 3 ml of hexane is added, and after stirring, the upper layer is removed.
Then, a phenylboronic acid solution (1 g of phenylboronic acid was dissolved in acetone: water = 19: 1, 4 ml) was added and stirred, then left at 80 ° C. for 20 minutes, allowed to cool to room temperature, and then 2 ml of hexane was added and stirred. The upper layer is subjected to GS-MS analysis.
GC-MS is quantified using molecular ion peaks m / z 196 (3-MCPD) and m / z 201 (3-MCPD-d 5 ).
なお、上記方法は、ドイツ（Ｄｅｕｔｓｃｈｅ　Ｇｅｓｅｌｌｓｃｈａｆｔ　ｆｕｒ　Ｆｅｔｔｗｉｓｓｅｎｓｃｈａｆｔ：ＤＧＦ）の、３－クロロプロパンジオール脂肪酸エステル及びその形成物質であるグリシドール脂肪酸エステルの測定方法として採用されているものであるが、この方法では、グリセリド油脂中の３－クロロプロパンジオール脂肪酸エステル及びその形成物質であるグリシドール脂肪酸エステルを加水分解し、グリセリド油脂中に存在する３－クロロプロパンジオール脂肪酸エステル及びその形成物質であるグリシドール脂肪酸エステルを全て３－ＭＣＰＤとして測定している。
「Ｗｉｔｈ　ｔｈｉｓ　ｍｅｔｈｏｄ，　ｏｔｈｅｒ　ｃｏｍｐｏｕｎｄｓ　ｆｏｒｍｉｎｇ　３－ＭＣＰＤ　ｕｎｄｅｒ　ｔｈｅ　ｃｏｎｄｉｔｉｏｎｓ　ｏｆ　ａｎａｌｙｓｉｓ　ａｒｅ　ａｌｓｏ　ｄｅｔｅｃｔｅｄ．　Ｔｈｅ　ｍｏｓｔ　ｉｍｐｏｒｔａｎｔ　３－ＭＣＰＤ　ｅｓｔｅｒｓ　ｆｏｒｍｉｎｇ　ｃｏｍｐｏｕｎｄｓ　ｉｓ　ｇｌｙｃｉｄｏｌ　（ｏｘｉｒａｎｅ－２－ｍｅｔｈａｎｏｌ）．」
（Ｅｓｔｅｒ－ｂｏｕｎｄ　３－ｃｈｌｏｒｏｐｒｏｐａｎｅ－１，２－ｄｉｏｌ（３－ＭＣＰＤ　ｅｓｔｅｒｓ）　ａｎｄ　３－ＭＣＰＤ　ｆｏｒｍｉｎｇ　ｓｕｂｓｔａｎｃｅｓ：ＤＧＦ　Ｓｔａｎｄａｒｄ　Ｍｅｔｈｏｄｓ　Ｓｅｃｔｉｏｎ　Ｃ－Ｆａｔｓ／Ｃ－ＩＩＩ　１８（０９）） The above method is adopted as a method for measuring 3-chloropropanediol fatty acid ester and glycidol fatty acid ester, which is a forming substance, in Germany (Deutsche Gesellchaft fur Fettwissenschaft: DGF). Hydrolyzes 3-chloropropanediol fatty acid ester and its forming substance glycidol fatty acid ester in fats and oils, all 3-chloropropanediol fatty acid ester and its forming substance glycidol fatty acid ester as 3-MCPD Measuring.
“With this method, another compounds forming 3-MCPD under the conditions of the anomalous areal and detected three-MCPD esters”.
(Ester-bound 3-chloropropane-1,2-diol (3-MCPD esters) and 3-MCPD forming subnets: DGF Standard Methods Section C-Fats / C-III 18 (09))
以下、実施例を示し、本発明をさらに具体的に説明する。なお、例中の％は重量基準を意味する。 Hereinafter, the present invention will be described more specifically with reference to examples. In addition,% in an example means a basis of weight.
２００℃以上に加熱される工程を経ていない粗パーム油（酸価＝７．８）１ｋｇとヘキサン２ｋｇと水２ｋｇを混和し、分離させる。油脂・溶媒相からヘキサンを留去し、油脂を得た。得られた油脂を脱ガム処理した後、白土１重量％、１１０℃、２０Ｔｏｒｒで１０分間脱色し、さらに２５０℃、２Ｔｏｒｒで９０分間脱臭処理を行った。得られたＲＢＤパーム油（ＩＶ：５２．２、上昇融点：３６．５℃）のクロロプロパノール類及びその形成物質の含量は１．８ｐｐｍであった。 1 kg of crude palm oil (acid value = 7.8), 2 kg of hexane, and 2 kg of water that have not been heated to 200 ° C. or higher are mixed and separated. Hexane was distilled off from the oil / fat / solvent phase to obtain an oil / fat. The obtained fat was degummed, decolorized at 1% by weight of white clay, 110 ° C., 20 Torr for 10 minutes, and further deodorized at 250 ° C., 2 Torr for 90 minutes. The obtained RBD palm oil (IV: 52.2, ascending melting point: 36.5 ° C.) had a content of chloropropanols and its forming substances of 1.8 ppm.
２００℃以上に加熱される工程を経ていない粗パーム油（酸価＝７．８）１ｋｇとヘキサン２ｋｇと水２ｋｇを混和し、分離させる。油脂・溶媒相からヘキサンを留去し、油脂を得た。得られた油脂を脱ガム処理した後、白土１重量％、１１０℃、２０Ｔｏｒｒで１０分間脱色し、さらに２２０℃、２Ｔｏｒｒで９０分間脱臭処理を行った。得られたＲＢＤパーム油（ＩＶ：５２．２、上昇融点：３６．５℃）のクロロプロパノール類及びその形成物質の含量は１．１ｐｐｍであった。 1 kg of crude palm oil (acid value = 7.8), 2 kg of hexane, and 2 kg of water that have not been heated to 200 ° C. or higher are mixed and separated. Hexane was distilled off from the oil / fat / solvent phase to obtain an oil / fat. The obtained fat was degummed, decolorized at 1% by weight of white clay, 110 ° C. and 20 Torr for 10 minutes, and further deodorized at 220 ° C. and 2 Torr for 90 minutes. The obtained RBD palm oil (IV: 52.2, ascending melting point: 36.5 ° C.) had a content of chloropropanols and its forming substances of 1.1 ppm.
（比較例１）
２００℃以上に加熱される工程を経ていない粗パーム油（酸価＝７．８）を脱ガム処理した原料パーム油に、白土１重量％、１１０℃、２０Ｔｏｒｒで１０分間脱色し、さらに２５０℃、２Ｔｏｒｒで９０分間脱臭処理を行った。得られたＲＢＤパーム油（ＩＶ：５２．２、上昇融点：３６．５℃）のクロロプロパノール類及びその形成物質の含量は７．４ｐｐｍであった。 (Comparative Example 1)
Raw material palm oil that has been degummed with crude palm oil that has not been heated to 200 ° C. or higher (acid value = 7.8) is decolorized at 1 wt% white clay, 110 ° C., 20 Torr for 10 minutes, and further 250 ° C. Deodorizing treatment was performed for 90 minutes at 2 Torr. The obtained RBD palm oil (IV: 52.2, ascending melting point: 36.5 ° C.) had a content of chloropropanols and substances forming the same of 7.4 ppm.
（比較例２）
比較例１で得られたＲＢＤパーム油を白土２重量％、１１０℃、２０Ｔｏｒｒで１０分間脱色し、さらに２５０℃、２Ｔｏｒｒで９０分間脱臭処理を行った。得られた精製パーム油のクロロプロパノール類及びその形成物質の含量は４．７ｐｐｍであった。 (Comparative Example 2)
The RBD palm oil obtained in Comparative Example 1 was decolorized at 2% by weight of white clay at 110 ° C. and 20 Torr for 10 minutes, and further deodorized at 250 ° C. and 2 Torr for 90 minutes. The content of chloropropanols and the substances forming the purified palm oil was 4.7 ppm.
（比較例３）
比較例１で得られたＲＢＤパーム油１ｋｇとヘキサン２ｋｇと水２ｋｇを混和し、分離させる。油脂・溶媒相からヘキサンを留去し、油脂を得た。得られた油脂を、白土２重量％、１１０℃、２０Ｔｏｒｒで１０分間脱色し、さらに２５０℃、２Ｔｏｒｒで９０分間脱臭処理を行った。得られた精製パーム油のクロロプロパノール類及びその形成物質の含量は４．６ｐｐｍであった。 (Comparative Example 3)
1 kg of RBD palm oil obtained in Comparative Example 1, 2 kg of hexane and 2 kg of water are mixed and separated. Hexane was distilled off from the oil / fat / solvent phase to obtain an oil / fat. The obtained fat was decolorized at 2% by weight of white clay, 110 ° C., 20 Torr for 10 minutes, and further deodorized at 250 ° C., 2 Torr for 90 minutes. The content of chloropropanols and the substances forming the purified palm oil was 4.6 ppm.

Claims (3)

  1. 加熱処理以前の油糧原料又はグリセリド油脂を水の存在下で溶媒と混合し、水相と油脂・溶媒相を分離後、溶媒を除去して得られた油脂を精製することを特徴とする、グリセリド油脂中のクロロプロパノール類及びその形成物質の生成を抑制する方法。 Oily raw material or glyceride oil / fat before heat treatment is mixed with a solvent in the presence of water, and after separating the aqueous phase and the oil / fat / solvent phase, the oil / fat obtained by removing the solvent is purified, A method for suppressing the production of chloropropanols and their forming substances in glyceride fats.
  2. 該加熱処理が油糧原料又はグリセリド油脂が２００℃以上に加熱される工程である請求項１記載の方法。 The method according to claim 1, wherein the heat treatment is a step in which the oil raw material or glyceride fat is heated to 200 ° C. or higher.
  3. 溶媒が非極性溶媒である請求項１記載の方法。 The method of claim 1, wherein the solvent is a nonpolar solvent.
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