JP6991677B2 - Quantitative method of dialkyl ketone in fats and oils - Google Patents
Quantitative method of dialkyl ketone in fats and oils Download PDFInfo
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- 239000003921 oil Substances 0.000 title claims description 52
- 239000003925 fat Substances 0.000 title claims description 48
- 150000002576 ketones Chemical class 0.000 title claims description 11
- 238000004445 quantitative analysis Methods 0.000 title description 4
- 238000000034 method Methods 0.000 claims description 26
- 238000004808 supercritical fluid chromatography Methods 0.000 claims description 21
- 238000005809 transesterification reaction Methods 0.000 claims description 19
- 238000011002 quantification Methods 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- 235000019198 oils Nutrition 0.000 description 45
- 235000019197 fats Nutrition 0.000 description 42
- 239000000523 sample Substances 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000012071 phase Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 238000000605 extraction Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- -1 cyanopropyl group Chemical group 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000007127 saponification reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 235000019482 Palm oil Nutrition 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000002540 palm oil Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 description 3
- 235000019871 vegetable fat Nutrition 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000005526 G1 to G0 transition Effects 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000007717 exclusion Effects 0.000 description 2
- VCZMOZVQLARCOE-UHFFFAOYSA-N heptacosan-14-one Chemical compound CCCCCCCCCCCCCC(=O)CCCCCCCCCCCCC VCZMOZVQLARCOE-UHFFFAOYSA-N 0.000 description 2
- WTJKUFMLQFLJOT-UHFFFAOYSA-N heptadecan-9-one Chemical compound CCCCCCCCC(=O)CCCCCCCC WTJKUFMLQFLJOT-UHFFFAOYSA-N 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- YUPOCHDBBHTUBJ-UHFFFAOYSA-N nonadecan-10-one Chemical compound CCCCCCCCCC(=O)CCCCCCCCC YUPOCHDBBHTUBJ-UHFFFAOYSA-N 0.000 description 2
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000007781 pre-processing Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 240000002329 Inga feuillei Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- 239000000538 analytical sample Substances 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000000828 canola oil Substances 0.000 description 1
- 235000019519 canola oil Nutrition 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 238000002983 circular dichroism Methods 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical class OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000002009 diols Chemical group 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- DOACSXJVHDTDSG-UHFFFAOYSA-N henicosan-11-one Chemical compound CCCCCCCCCCC(=O)CCCCCCCCCC DOACSXJVHDTDSG-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000199 molecular distillation Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000006199 nebulizer Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 235000002378 plant sterols Nutrition 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
- C11C3/10—Ester interchange
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material 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)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Description
本発明は、油脂中のジアルキルケトンの定量方法に関する。 The present invention relates to a method for quantifying dialkyl ketones in fats and oils.
油脂（特に食用油）の改質方法としてエステル交換方法がある。触媒としてアルカリを用いるケミカルエステル交換方法では、改質された油脂の他、ジアルキルケトン（以下、「ＤＡＫｓ」ともいう）が副産物として生成する。ＤＡＫｓ量が多い場合、分子蒸留等により除去される。
また、ＤＡＫｓが低減された油脂の製造方法が知られている（特許文献１）。
There is a transesterification method as a method for reforming fats and oils (particularly edible oil). In the chemical transesterification method using an alkali as a catalyst, dialkyl ketones (hereinafter, also referred to as “DAKs”) are produced as by-products in addition to the modified fats and oils. If the amount of DAKs is large, it is removed by molecular distillation or the like.
Further, a method for producing fats and oils with reduced DAKs is known (Patent Document 1).
エステル交換反応条件の決定、エステル交換反応後のＤＡＫｓ除去の要否の判断や、ＤＡＫｓの新たな除去方法の開発にあたっては、油脂中のＤＡＫｓを正確に定量する必要がある。
しかし、ガスクロマトグラフィー（ＧＣ）へそのまま適用して定量分析を試みると、前記反応生成物中に含まれる植物ステロール類が、ＧＣにおいてＤＡＫｓと同様の挙動を示し、ＤＡＫｓの正確な定量を妨げることを本発明者らは初めて見いだした。そのため、ガスクロマトグラフィーを用いて、より高い精度の分析を行う場合、前処理が必要になり、煩雑な操作が必要であった。また、かなり低いＤＡＫｓ量の油脂を分析する場合、より高精度の分析が必要であった。
In determining the conditions of the transesterification reaction, determining the necessity of removing DAKs after the transesterification reaction, and developing a new method for removing DAKs, it is necessary to accurately quantify DAKs in fats and oils.
However, when a quantitative analysis is attempted by applying it to gas chromatography (GC) as it is, the plant sterols contained in the reaction product behave in the same manner as DAKs in GC, which hinders accurate quantification of DAKs. The present inventors have found for the first time. Therefore, when performing analysis with higher accuracy using gas chromatography, pretreatment is required and complicated operations are required. In addition, when analyzing fats and oils with a considerably low amount of DAKs, more accurate analysis was required.
本発明者らは、上記課題を解決するために鋭意検討した結果、油脂を超臨界流体クロマトグラフィーで定量することで、ＤＡＫｓを高精度で定量できることを見いだし、本発明を完成させるに至った。すなわち、本発明は下記に関するものである。
〔１〕油脂を超臨界流体クロマトグラフィーで定量する工程、を含むことを特徴とする、油脂中のジアルキルケトンの定量方法。
〔２〕超臨界流体クロマトグラフィーで定量する工程に供される油脂が、アルカリ触媒を用いた油脂のエステル交換反応生成物である、前記〔１〕に記載の定量方法。
〔３〕エステル交換反応により油脂を製造する方法であって、 前記エステル交換反応後の油脂中のジアルキルケトンを、前記〔１〕又は〔２〕に記載の方法に従い定量する工程を含み、定量する工程後の精製条件及び／又はブレンド条件を、定量されたジアルキルケトン量に基づいて決定する、ことを特徴とする製造方法。
As a result of diligent studies to solve the above problems, the present inventors have found that DAKs can be quantified with high accuracy by quantifying fats and oils by supercritical fluid chromatography, and have completed the present invention. That is, the present invention relates to the following.
[1] A method for quantifying dialkyl ketones in fats and oils, which comprises a step of quantifying fats and oils by supercritical fluid chromatography.
[2] The quantification method according to the above [1], wherein the fat or oil used in the step of quantification by supercritical fluid chromatography is a transesterification reaction product of the fat or oil using an alkali catalyst.
[3] A method for producing a fat or oil by a transesterification reaction, which comprises a step of quantifying the dialkyl ketone in the fat or oil after the transesterification reaction according to the method according to the above [1] or [2]. A production method comprising determining post-step purification conditions and / or blending conditions based on a quantified amount of dialkyl ketone.
後述の実施例で示されるように、本発明の方法によると、油脂（特に、油脂のエステル交換反応生成物）中のＤＡＫｓを正確に定量することができる。 As shown in Examples described later, according to the method of the present invention, DAKs in fats and oils (particularly, transesterification reaction products of fats and oils) can be accurately quantified.
「油脂」は特に限定されないが、例えば植物性油脂や動物性油脂が挙げられるが、植物性油脂が好ましい。
植物性油脂としては、キャノーラ油や、パーム油等やこれらのエステル交換油が挙げられ、エステル交換油が好ましい。
また、油脂としては食用油脂が好ましい。
The "fat and oil" is not particularly limited, and examples thereof include vegetable fats and oils and animal fats and oils, but vegetable fats and oils are preferable.
Examples of vegetable oils and fats include canola oil, palm oil and the like, and transesterified oils thereof, and transesterified oil is preferable.
Further, as the fat and oil, edible fat and oil are preferable.
本実施の形態は、特に限定されるものではないが、「アルカリ触媒を用いた油脂のエステル交換反応生成物」である油脂に対して好適に用いることができる。
「アルカリ触媒を用いた油脂のエステル交換反応」は、油脂製造分野で用いられているものを特に制限なく用いることができる。
アルカリ触媒としては、例えば水酸化ナトリウム、水酸化カリウム、炭酸ナトリウムや炭酸カリウム等が挙げられる。
エステル交換反応の条件は、油脂のエステル交換反応で一般的に用いられているものを特に制限なく採用することができる。
The present embodiment is not particularly limited, but can be suitably used for fats and oils that are "transesterification reaction products of fats and oils using an alkali catalyst".
As the "transesterification reaction of fats and oils using an alkali catalyst", those used in the field of fats and oils production can be used without particular limitation.
Examples of the alkaline catalyst include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like.
As the conditions of the transesterification reaction, those generally used in the transesterification reaction of fats and oils can be adopted without particular limitation.
＜油脂中のジアルキルケトンの定量方法＞
本実施の形態の油脂中のジアルキルケトンの定量方法は、超臨界流体クロマトグラフィーで定量する工程、を含む。
ここで、「超臨界流体クロマトグラフィー」とは、ＳＦＣとも呼ばれるカラムクロマトグラフィーの一種であり、移動相に超臨界流体を用いるものをいう。超臨界流体クロマトグラフィーでは、低粘度で拡散性が高いという特性を有する亜臨界流体や超臨界流体を移動相として用いることで、移動相に液体を用いる液体クロマトグラフィー（ＨＰＬＣ）に比べ、分解能や検出能を向上することができる。
超臨界流体クロマトグラフィーの「移動相」としては、特に限定されるものではないが、例えば、液化状態、亜臨界状態、又は、超臨界状態の二酸化炭素を用いることができる。移動相としては、これらを単独で用いることもできるが、これに加えて、有機溶媒（モディファイヤー）を併用することが好ましい。モディファイヤーの濃度を変えることで、油脂中のＤＡＫｓの溶出力や保持の強さを調整することができるからである。モディファイヤーとしては、特に限定されるものではないが、メタノール、エタノール、イソプロパノール、アセトニトリル、ジクロロメタン等の有機溶媒を用いることができる。
超臨界流体クロマトグラフィーの「固定相」としては、液体クロマトグラフィーに用いられる固定相を使用することができる。一例として、超臨界流体クロマトグラフィーの「固定相」としては、逆相カラムや順相カラム、イオン交換樹脂カラム、サイズ排除カラム等を用いることができる。ここで、逆相カラムとしては、例えば、シリカゲル又はポリメタクリレート等の高分子を含む基材に、オクタデシル基、オクチル基、ブチル基、フェニル基、シアノプロピル基等を結合したものが挙げられる。順相カラムとしては、例えば、シリカゲルやシリカゲルを含む基材にアミノプロピル基、シアノプロピル基、ジオール基、カルバモイル基等を結合したものが挙げられる。ＤＡＫｓの検出量を向上する観点から、逆相カラムを用いることが好ましい。イオン交換樹脂カラムとしては、陽イオン交換樹脂および陰イオン交換樹脂が用いられるが、例えば、高分子を含む基材に、第４級アンモニウム基やジエチルアミノエチル基等を結合したものが挙げられる。サイズ排除カラムとしては、例えば、シリカゲルを含む基材に、プロピルジオール基を結合させたものが挙げられる。
超臨界流体クロマトグラフィーの「検出器」としては、特に限定されるものではないが、例えば、紫外／可視吸光度検出器、ダイオードアレイ検出器、質量分析計、円二色性検出器等を用いることができる。
超臨界流体クロマトグラフィーの条件は、油脂の抽出に用いられているものを特に制限なく採用することができる。
<Method for quantifying dialkyl ketones in fats and oils>
The method for quantifying dialkyl ketones in fats and oils according to the present embodiment includes a step of quantifying by supercritical fluid chromatography.
Here, "supercritical fluid chromatography" is a kind of column chromatography also called SFC, and refers to one using a supercritical fluid as a mobile phase. In supercritical fluid chromatography, subcritical fluids and supercritical fluids, which have the characteristics of low viscosity and high diffusivity, are used as mobile phases, resulting in higher resolution and higher resolution than liquid chromatography (HPLC), which uses a liquid as the mobile phase. The detectability can be improved.
The "mobile phase" of supercritical fluid chromatography is not particularly limited, and for example, carbon dioxide in a liquefied state, a subcritical state, or a supercritical state can be used. As the mobile phase, these can be used alone, but in addition to this, it is preferable to use an organic solvent (modifier) in combination. This is because the elution output and retention strength of DAKs in fats and oils can be adjusted by changing the concentration of the modifier. The modifier is not particularly limited, but an organic solvent such as methanol, ethanol, isopropanol, acetonitrile, or dichloromethane can be used.
As the "stationary phase" of supercritical fluid chromatography, the stationary phase used for liquid chromatography can be used. As an example, as the "fixed phase" of supercritical fluid chromatography, a reverse phase column, a normal phase column, an ion exchange resin column, a size exclusion column and the like can be used. Here, examples of the reverse phase column include those in which an octadecyl group, an octyl group, a butyl group, a phenyl group, a cyanopropyl group and the like are bonded to a substrate containing a polymer such as silica gel or polymethacrylate. Examples of the normal phase column include those in which an aminopropyl group, a cyanopropyl group, a diol group, a carbamoyl group and the like are bonded to a base material containing silica gel or silica gel. From the viewpoint of improving the detection amount of DAKs, it is preferable to use a reverse phase column. As the ion exchange resin column, a cation exchange resin and an anion exchange resin are used, and examples thereof include those in which a quaternary ammonium group, a diethylaminoethyl group, or the like is bonded to a substrate containing a polymer. Examples of the size exclusion column include those in which a propyldiol group is bonded to a substrate containing silica gel.
The "detector" for supercritical fluid chromatography is not particularly limited, but for example, an ultraviolet / visible absorbance detector, a diode array detector, a mass analyzer, a circular dichroism detector, or the like may be used. Can be done.
As the conditions of supercritical fluid chromatography, those used for the extraction of fats and oils can be adopted without particular limitation.
超臨界流体クロマトグラフィーに先立ち、油脂をけん化工程、及び／又は、抽出工程（例えば、液相抽出、及び／又は、固相抽出）等の前処理に付すると、ＤＡＫｓの定量性をより高めることができるので好ましい。
前処理の各条件は、油脂の抽出に用いられているものを特に制限なく採用することができる。
例えば、けん化工程としては、特にこれに限定されるものではないが、アルカリ性の水溶液、あるいはアルカリ性のアルコール溶液を用いることができ、例えば、水酸化ナトリウム、水酸化カリウム等のアルコール溶液を用いることが好ましい。アルコール溶液は、メタノール、エタノール、プロパノール、ブタノール等を用いることができ、水を含むこともできる。けん化温度は、３０～１２０℃が好ましく、７０～１００℃がより好ましい。
また、液相抽出としては、特にこれに限定されるものではないが、水に溶解しにくい有機溶媒、例えば、エーテル、ヘキサン、ヘプタン、オクタン、石油エーテル、ベンゼン、トルエン、キシレン、ジクロロメタン等を用いて、有機溶媒に可溶な成分を抽出することができる。その後、抽出された成分を濃縮することができるように、沸点が１００℃以下の有機溶媒が好ましい。
さらに、液相抽出後に、有機相のアルカリを除去するために、水洗を行うことが好ましい。
さらにまた、液相抽出後及び／又は水洗後に、ＤＡＫｓの濃度を高めるために、濃縮することが好ましい。濃縮方法としては、特に限定するものではないが、無水硫酸ナトリウム、塩化カルシウム、モレキュラーシーブ等の乾燥剤で乾燥させた後、有機溶媒を蒸留することが挙げられる。
一方、固相抽出としては、特にこれに限定されるものではないが、担体として、アミノプロピル基、及び、シリカゲル又はグラファイトカーボン等を使用し、溶媒として、ヘキサンやクロロホルム等を使用することができる。
Prior to supercritical fluid chromatography, fats and oils are subjected to pretreatment such as a saponification step and / or an extraction step (for example, liquid phase extraction and / or solid phase extraction) to further enhance the quantitativeness of DAKs. It is preferable because it can be used.
As each condition of the pretreatment, those used for the extraction of fats and oils can be adopted without particular limitation.
For example, the saponification step is not particularly limited to this, but an alkaline aqueous solution or an alkaline alcohol solution can be used, and for example, an alcohol solution such as sodium hydroxide or potassium hydroxide can be used. preferable. As the alcohol solution, methanol, ethanol, propanol, butanol and the like can be used, and water can also be contained. The saponification temperature is preferably 30 to 120 ° C, more preferably 70 to 100 ° C.
The liquid phase extraction is not particularly limited to this, but an organic solvent that is difficult to dissolve in water, for example, ether, hexane, heptane, octane, petroleum ether, benzene, toluene, xylene, dichloromethane or the like is used. Therefore, a component soluble in an organic solvent can be extracted. Then, an organic solvent having a boiling point of 100 ° C. or lower is preferable so that the extracted components can be concentrated.
Further, after the liquid phase extraction, it is preferable to perform washing with water in order to remove the alkali of the organic phase.
Furthermore, after liquid phase extraction and / or after washing with water, it is preferable to concentrate in order to increase the concentration of DAKs. The concentration method is not particularly limited, and examples thereof include drying with a desiccant such as anhydrous sodium sulfate, calcium chloride, and molecular sieve, and then distilling an organic solvent.
On the other hand, the solid-phase extraction is not particularly limited to this, but an aminopropyl group, silica gel, graphite carbon or the like can be used as the carrier, and hexane, chloroform or the like can be used as the solvent. ..
本実施の形態では、油脂中に含まれる多種のジアルキルケトン（Dialkylketones: ＤＡＫｓ）を定量することができる。
ＤＡＫｓとしては、一般式（１）：Ｒ１Ｃ（Ｏ）Ｒ２（式中、Ｒ１及びＲ２は独立してＣ１～Ｃ２４のアルキル基である）で表される化合物が挙げられる。具体例としては、9-ヘプタデカノン（一般式（１）中、Ｒ１及びＲ２がＣ８のアルキル基である化合物）、10-ノナデカノン、11-ヘンエイコサノン、14-ヘプタコサノン、16-ヘントリアコンタノンや、18-ペンタトリアコンタノン等が挙げられるが、他のＤＡＫｓも定量可能である。
In this embodiment, various dialkylketones (DAKs) contained in fats and oils can be quantified.
Examples of DAKs include compounds represented by the general formula (1): R 1 C (O) R 2 (in the formula, R 1 and R 2 are independently alkyl groups of C 1 to C 24 ). .. Specific examples include 9-heptadecanone (a compound in which R1 and R2 are alkyl groups of C8 in the general formula (1)), 10-nonadecanone, 11-heneicosanone, 14-heptacosanone, and 16-hentoria-contanone. , 18-Pentatoria Contanone, etc., but other DAKs can also be quantified.
＜エステル交換反応により油脂を製造する方法＞
本発明のエステル交換反応により油脂を製造する方法において、エステル交換反応後の油脂中のジアルキルケトンを、前記＜油脂中のジアルキルケトンの定量方法＞に記載の方法に従い定量する工程を含み、定量する工程後の精製条件を、定量されたジアルキルケトン量に基づいて決定する。
本発明において、定量する工程は、エステル交換後であればよく、精製工程の前、あるいは精製工程の途中でもよい。エステル交換油の精製工程は、アルカリ触媒の酸性物質との中和あるいは水洗、脱酸、脱色、脱臭、分別等の一つ以上が行われるが、いずれの前後、あるいは工程中でもよい。
<Method of producing fats and oils by transesterification reaction>
In the method for producing fats and oils by the transesterification reaction of the present invention, a step of quantifying the dialkylketone in the fats and oils after the transesterification reaction according to the method described in the above <Method for quantifying dialkylketone in fats and oils> is included and quantified. Post-step purification conditions are determined based on the quantified amount of dialkylketone.
In the present invention, the quantification step may be performed after transesterification, before the purification step, or during the purification step. The process of refining the transesterified oil may be one or more such as neutralization of the alkaline catalyst with an acidic substance, washing with water, deoxidation, decolorization, deodorization, separation, etc., but it may be before, after, or during the process.
例えば、ＤＡＫｓ量が多い場合、酸性の液で洗浄する工程を追加で行うことで、ＤＡＫｓ量を低減することができる。酸性の液で洗浄する場合、その後、水洗、脱臭することが好ましい。また、短工程蒸留等の高真空化での蒸留工程を追加で行うことで、ＤＡＫｓを除去することができる。ＤＡＫｓ量が少ない（あるいは存在しない）場合、これらの工程を行わないことを選択することができる。 For example, when the amount of DAKs is large, the amount of DAKs can be reduced by additionally performing a step of washing with an acidic liquid. When washing with an acidic liquid, it is preferable to wash with water and then deodorize. In addition, DAKs can be removed by additionally performing a distillation step with high vacuum such as short-step distillation. If the amount of DAKs is small (or non-existent), you can choose not to perform these steps.
また、複数のエステル交換油をブレンドする場合、ＤＡＫｓ量が多いロットと少ないロットを組わせて、一定の規格内のＤＡＫｓ量に抑えることができる。特に、複数のＤＡＫｓ量が異なる油脂の製品タンクを有している場合、精製前、あるいは精製途中でＤＡＫｓを測定すれば、精製油のＤＡＫｓ量が予測でき、適切な製品タンクに精製後に導入でき、各製品タンクのＤＡＫｓ量を抑えることができるので好ましい。 Further, when a plurality of transesterified oils are blended, a lot having a large amount of DAKs and a lot having a small amount of DAKs can be combined to keep the amount of DAKs within a certain standard. In particular, if you have multiple product tanks of oils and fats with different amounts of DAKS, you can predict the amount of DAKS of refined oil by measuring DAKs before or during refining, and you can introduce it into an appropriate product tank after refining. , It is preferable because the amount of DAKs in each product tank can be suppressed.
以下、実施例により本発明を更に詳細に説明するが、本発明はこれに限定されるものではない。 Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.
[実施例１]：油脂中のＤＡＫｓの定量分析（１）
（サンプル調製）
所定量のＤＡＫｓを含むように予め調製した油脂サンプルを用いて、本実施の形態の定量方法を評価した。具体的には、ＤＡＫｓを含まないパーム油（日清オイリオグループ株式会社製）へ各種ＤＡＫｓ標準試薬を表１の配合量となるように添加して調製したサンプル１～６を使用した。
[Example 1]: Quantitative analysis of DAKs in fats and oils (1)
(Sample preparation)
The quantification method of the present embodiment was evaluated using a fat sample prepared in advance so as to contain a predetermined amount of DAKs. Specifically, Samples 1 to 6 prepared by adding various DAKs standard reagents to palm oil (manufactured by Nisshin Oillio Group Co., Ltd.) containing no DAKs so as to have the blending amounts shown in Table 1 were used.
超臨界流体クロマトグラフィー装置に供する前に、各サンプルを、下記の前処理に付して分析用試料を作成した。
（前処理）
サンプル１００ｍｇとクロロホルム１ｍＬとをメスフラスコに加え、さらにアセトンを加えて全体で１０ｍＬの試料を調整し、各分析試料とした。
Each sample was subjected to the following pretreatment to prepare a sample for analysis before being subjected to a supercritical fluid chromatography apparatus.
(Preprocessing)
100 mg of the sample and 1 mL of chloroform were added to the measuring flask, and acetone was further added to prepare a total of 10 mL of the sample, which was used as each analysis sample.
（超臨界流体クロマトグラフィー操作）
各分析試料を、下記条件下での超臨界流体クロマトグラフィー装置へ供した。
(Supercritical fluid chromatography operation)
Each analytical sample was subjected to a supercritical fluid chromatography apparatus under the following conditions.
（超臨界流体クロマトグラフィー条件）
超臨界流体クロマトグラフィー装置：Ｎｅｘｅｒａ ＵＣ （島津製作所社製）
カラム：島津製作所製Ｓｈｉｍ－ｐａｃｋ ＵＣ－ＲＰ 長さ１５ｍｍ×内径２１ｍｍ 粒子径３μｍ（オクタデシル基および極性官能基）
移動相：超臨界流体ＣＯ２ （流量：０．３６ｍＬ／ｍｉｎ）
モディファイヤー：メタノール（流量：０，０４ｍＬ／ｍｉｎ）、及び、０．１％ギ酸アンモニウムを含むメタノール（流量：０．１ｍＬ／ｍｉｎ）
検出器：ＬＣ－ＭＳ／ＭＳ
注入量：５μＬ
標準物質：ジアルキルケトン試薬のクロロホルム溶液（配合量：５０ｐｐｍ（質量基準））
(Supercritical fluid chromatography conditions)
Supercritical fluid chromatography device: Nexus UC (manufactured by Shimadzu Corporation)
Column: Shimadzu Shima-pack UC-RP Length 15 mm x Inner diameter 21 mm Particle diameter 3 μm (octadecyl group and polar functional group)
Mobile phase: Supercritical fluid CO 2 (Flow rate: 0.36 mL / min)
Modifier: Methanol (flow rate: 0.04 mL / min) and methanol containing 0.1% ammonium formate (flow rate: 0.1 mL / min).
Detector: LC-MS / MS
Injection volume: 5 μL
Standard substance: Chloroform solution of dialkyl ketone reagent (blending amount: 50 ppm (mass standard))
（質量分析条件）
質量分析装置：液体クロマトグラフ質量分析計ＬＣＭＳ－８０５０（島津製作所製）
イオン化モード：ＥＳＩ
インターフェース温度：４００℃
ヒーティングガス流量：１２Ｌ／ｍｉｎ
ネブライザーガス流量：２．５Ｌ／ｍｉｎ
Ｄｅｓｏｌｖａｔｉｏｎガス温度：２５０℃
ヒートブロック温度：４００℃
ドライインガス流量：５Ｌ／ｍｉｎ
(Mass spectrometry conditions)
Mass spectrometer: Liquid chromatograph mass spectrometer LCMS-8050 (manufactured by Shimadzu Corporation)
Ionization mode: ESI
Interface temperature: 400 ° C
Heating gas flow rate: 12 L / min
Nebulizer gas flow rate: 2.5 L / min
Desolution gas temperature: 250 ° C
Heat block temperature: 400 ° C
Dry ingas flow rate: 5 L / min
各サンプルのピークと標準サンプルのピークとを比較することで、ＤＡＫｓ量を算出した。結果を表２に示す。表２の回収率は、定量方法に供する前のサンプル中のＤＡＫｓ量（質量基準）を１００％とした場合の値である。 The amount of DAKs was calculated by comparing the peak of each sample with the peak of the standard sample. The results are shown in Table 2. The recovery rate in Table 2 is a value when the amount of DAKs (based on mass) in the sample before being subjected to the quantification method is 100%.
前記の定量方法では、定量前のサンプル中のＤＡＫｓ量に対して１００～１０８％という高い回収率でＤＡＫｓが検出された。
分析誤差（本実施例において、１００％±１０％）を考慮すると、この結果は、本実施例の方法によって油脂中のＤＡＫｓを正確に定量できることを示すものである。
In the above quantification method, DAKs were detected with a high recovery rate of 100 to 108% with respect to the amount of DAKs in the sample before quantification.
Considering the analysis error (100% ± 10% in this example), this result shows that the method of this example can accurately quantify DAKs in fats and oils.
[実施例２]：油脂中のＤＡＫｓの定量分析（２）
（サンプル調製）
所定量のＤＡＫｓを含むように予め調製した油脂サンプルを用いて、本実施の定量方法を評価した。具体的には、ＤＡＫｓを含まないパーム油（日清オイリオグループ株式会社製）へ各種ＤＡＫｓ標準試薬を表３の配合量となるように添加して調製したサンプル６～１０を使用した。
[Example 2]: Quantitative analysis of DAKs in fats and oils (2)
(Sample preparation)
The quantification method of this practice was evaluated using a fat sample prepared in advance so as to contain a predetermined amount of DAKs. Specifically, Samples 6 to 10 prepared by adding various DAKs standard reagents to palm oil (manufactured by Nisshin Oillio Group Co., Ltd.) containing no DAKs so as to have the blending amounts shown in Table 3 were used.
超臨界流体クロマトグラフィー装置に供する前に、各サンプルを、下記の前処理に付して分析用試料を作成した。
（前処理）
サンプル１００ｍｇと１Ｎ 水酸化カリウム／エタノール１０ｍＬとを試験管に加え、８０℃で４０分還流させて、けん化分解を行った。その後、室温（２０℃）まで降温し、飽和クエン酸水溶液２．５ｍＬと水１．０ｍＬを加え中和した。次いで、ヘキサン５ｍＬを加え、振とうして、上層を分析試料とした。
超臨界流体クロマトグラフィー操作は前述の実施例１と同様である。
各サンプルのピークと標準サンプルのピークとを比較することで、ＤＡＫｓ量を算出した。結果を表４に示す。表４の回収率は、定量方法に供する前のサンプル中のＤＡＫｓ量（質量基準）を１００％とした場合の値である。
Each sample was subjected to the following pretreatment to prepare a sample for analysis before being subjected to a supercritical fluid chromatography apparatus.
(Preprocessing)
100 mg of a sample and 10 mL of 1N potassium hydroxide / ethanol were added to a test tube and refluxed at 80 ° C. for 40 minutes for saponification decomposition. Then, the temperature was lowered to room temperature (20 ° C.), and 2.5 mL of saturated citric acid aqueous solution and 1.0 mL of water were added for neutralization. Then, 5 mL of hexane was added and shaken to use the upper layer as an analysis sample.
The supercritical fluid chromatography operation is the same as in Example 1 described above.
The amount of DAKs was calculated by comparing the peak of each sample with the peak of the standard sample. The results are shown in Table 4. The recovery rate in Table 4 is a value when the amount of DAKs (based on mass) in the sample before being subjected to the quantification method is 100%.
前記の定量方法では、定量前のサンプル中のＤＡＫｓ量に対して９９～１０７％という高い回収率でＤＡＫｓが検出された。
分析誤差（本実施例において、１００％±１０％）を考慮すると、この結果は本実施例の方法によって油脂中のＤＡＫｓを正確に定量できることを示すものである。
In the above quantification method, DAKs were detected with a high recovery rate of 99 to 107% with respect to the amount of DAKs in the sample before quantification.
Considering the analysis error (100% ± 10% in this example), this result shows that DAKs in fats and oils can be accurately quantified by the method of this example.
本発明は、油脂分野で利用することができる。 The present invention can be used in the field of fats and oils.
Claims (2)
前記エステル交換反応後の油脂中のジアルキルケトンを、超臨界流体クロマトグラフィーで定量する工程を含み、
定量する工程後の精製条件及び／又はブレンド条件を、定量されたジアルキルケトン量に基づいて決定する、ことを特徴とする製造方法。 It is a method of producing fats and oils by transesterification reaction.
The step of quantifying the dialkyl ketone in the fat and oil after the transesterification reaction by supercritical fluid chromatography is included.
A production method comprising determining the purification conditions and / or blending conditions after the quantification step based on the quantified amount of dialkyl ketone.
Priority Applications (2)
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| JP2018044702A JP6991677B2 (en) | 2018-03-12 | 2018-03-12 | Quantitative method of dialkyl ketone in fats and oils |
| PCT/JP2019/009221 WO2019176750A1 (en) | 2018-03-12 | 2019-03-08 | Method for quantifying dialkyl ketones in oil and fat |
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| JP2018044702A JP6991677B2 (en) | 2018-03-12 | 2018-03-12 | Quantitative method of dialkyl ketone in fats and oils |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013250186A (en) | 2012-06-01 | 2013-12-12 | Fuji Oil Co Ltd | Method for separating or measuring 3-mono chloropropane-1,2-diol fatty acid esters in edible oil and fat using supercritical fluid chromatography |
| JP2014002082A (en) | 2012-06-20 | 2014-01-09 | Chikuno Shokuhin Kogyo Kk | Quantitative method of volatile organic compound |
| JP2016538879A (en) | 2013-10-28 | 2016-12-15 | トータリー ナチュラル ソリューションズ リミテッド | Fractionation method, flavor products and beer products |
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- 2018-03-12 JP JP2018044702A patent/JP6991677B2/en active Active
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013250186A (en) | 2012-06-01 | 2013-12-12 | Fuji Oil Co Ltd | Method for separating or measuring 3-mono chloropropane-1,2-diol fatty acid esters in edible oil and fat using supercritical fluid chromatography |
| JP2014002082A (en) | 2012-06-20 | 2014-01-09 | Chikuno Shokuhin Kogyo Kk | Quantitative method of volatile organic compound |
| JP2016538879A (en) | 2013-10-28 | 2016-12-15 | トータリー ナチュラル ソリューションズ リミテッド | Fractionation method, flavor products and beer products |
Non-Patent Citations (2)
| Title |
|---|
| A. Cert et al.，Chromatographic analysis of minor constituents in vegetable oils，Journal of Chromatography A,，2000年，881，131-148 |
| Katsuhito Horia et al.，High-throughput and sensitive analysis of 3-monochloropropane-1,2-diol fatty acid esters in edible oils by supercritical fluid chromatography/tandem massspectrometry，Journal of Chromatography A，2012年，1250，99-104 |
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| JP2019158536A (en) | 2019-09-19 |
| WO2019176750A1 (en) | 2019-09-19 |
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