WO2016139921A1 - Process for producing edible oil-and-fat - Google Patents

Abstract

Provided is a method capable of producing edible oil-and-fat capable of sufficiently removing soap contained in oil-and-fat after transesterification using a small amount of filter aid or without using any filter aid such as clay, and having excellent oxidation stability and more flavor than conventional oil-and-fat obtained using a large amount of filter aid. The amount of used filter aid that requires waste processing is furthermore considerably reduced and the yield of oil-and-fat is increased. Animal and plant oil-and-fat is subjected to transesterification using an alkaline substance, and the resulting oil-and-fat is brought into contact with a specific amount of neutral water, yielding a liquid containing a first water layer and a first oil layer. The first water layer is removed from the liquid and an aqueous solution of an acidic substance is mixed with the first oil layer so that the usage amount of the acidic substance satisfies specific conditions, yielding a liquid composed of a second water layer and a second oil layer. The second water layer is removed from the liquid, and the second oil layer is subjected to a deodorizing step, yielding a transesterified oil.

Description

食用油脂の製造方法Method for producing edible fats and oils

　本発明は、エステル交換により得られる食用油脂の製造方法に関する。 The present invention relates to a method for producing edible fats and oils obtained by transesterification.

　触媒を用いた油脂の化学エステル交換プロセスは、「油脂の加熱→脱水→触媒投入→水洗→静置→水相及び乳化相除去→真空脱水」の順序で進行する。触媒投入によって、触媒であるアルカリ性物質と油脂が反応することで、化学エステル交換反応が進行すると共に、副生物のセッケン（脂肪酸のアルカリ金属塩）が生成する。これまで、前記セッケンを除去するために、化学エステル交換反応後の油脂に対して「水洗→静置→水相及び乳化相除去」との工程を実施していたが、セッケンを完全に除去することが出来ず、一部が油脂中に残っていた。 The chemical transesterification process of fats and oils using a catalyst proceeds in the order of “heating of fats and oils → dehydration → catalyst input → water washing → still standing → removal of water phase and emulsion phase → vacuum dehydration” When the catalyst is charged, the alkaline substance, which is a catalyst, reacts with fats and oils, whereby a chemical transesterification reaction proceeds and a by-product soap (alkali metal salt of fatty acid) is generated. Until now, in order to remove the soap, the oil and fat after the chemical transesterification reaction has been subjected to a process of “water washing → stationary → water phase and emulsified phase removal”, but the soap is completely removed. It was not possible, and a part was left in fats and oils.

　そのため、セッケンを完全に除去するためには、前記水洗後の油脂に対して、白土等の濾過助剤による処理を施す必要があった。しかし、通常の方法で白土処理を行った場合、セッケン除去には多量の白土が必要となり、白土の臭いが油脂に移行して油脂の風味に悪影響を及ぼしたり、白土に油脂が付着して歩留りが悪くなったり、廃棄処理が必要な使用済みの白土が発生するという問題があった。また、白土の臭いを除去する為に高温脱臭すると、多くの好ましい風味成分が飛んでしまい、油脂の酸化安定性も悪くなるという問題もあった。 Therefore, in order to completely remove the soap, it was necessary to perform a treatment with a filter aid such as white clay on the oil and fat after washing with water. However, when clay is treated by the usual method, a large amount of clay is required to remove soap, and the odor of clay migrates to fats and oils and has a negative effect on the flavor of fats and oils. There is a problem that the used white clay that needs to be disposed of becomes worse. In addition, when high temperature deodorization is performed to remove the odor of white clay, there are problems that many preferred flavor components fly away and the oxidation stability of fats and oils also deteriorates.

　水洗以外の方法で、白土処理前に予めセッケン量を低減する方法として、特許文献１では、例えば化学エステル交換反応を実施した後に、副生したセッケンを無機酸ないしは有機酸を添加することにより酸分解し、脱色脱臭を実施する方法が開示されている。しかし、化学エステル交換反応を実施した直後、油層中でセッケンを酸分解するためには、過剰量の酸を添加して、ホモミキサーのような強力な撹拌力を有する機器を使用する必要があった。また、生成したセッケンが全て脂肪酸に変化し、生じた油層中の多量の脂肪酸を除去するためには６０～９０分間という比較的長時間の脱臭が必要となり、油脂の酸化安定性が悪化し、良好な風味が損なわれるという問題があった。 As a method of reducing the amount of soap in advance before the clay treatment by a method other than water washing, in Patent Document 1, for example, after carrying out a chemical transesterification reaction, by-product soap is added by adding an inorganic acid or an organic acid. A method for decomposing and carrying out decolorization and deodorization is disclosed. However, immediately after the chemical transesterification reaction, in order to acidolyze soap in the oil layer, it is necessary to add an excessive amount of acid and use a device having a strong stirring force such as a homomixer. It was. In addition, all the generated soap is converted into fatty acids, and in order to remove a large amount of fatty acids in the oil layer, it is necessary to deodorize for a relatively long time of 60 to 90 minutes, and the oxidation stability of fats and oils deteriorates. There was a problem that good flavor was impaired.

特開昭５１－６１５１０号公報JP-A-51-61510

　本発明の目的は、白土等の濾過助剤の使用量が少ない、或いは全く使用しなくても、エステル交換反応後の油脂中に含まれているセッケンを十分に除去でき、濾過助剤を多量に使用して得られた従来の油脂よりも風味が豊かで、酸化安定性に優れた食用油脂を製造できる方法を提供することである。さらには、食用油脂の製造において、廃棄物処理が必要な使用済みの濾過助剤の量を大幅に減らし、油脂の歩留りを上昇させることも目的とする。 The object of the present invention is to sufficiently remove soap contained in fats and oils after the transesterification reaction even when the amount of filter aid such as clay is small or not used at all. It is to provide a method capable of producing an edible fat and oil that has a richer flavor than conventional fats and oils obtained by using it and has excellent oxidation stability. Furthermore, in the production of edible fats and oils, it is also an object to greatly reduce the amount of used filter aid that requires waste disposal and increase the yield of fats and oils.

　本発明者らは上記課題を解決するために鋭意研究を重ねた結果、動植物油脂をアルカリ性物質によりエステル交換反応させた後、前記油脂と中性水とを特定量接触させてから、水層を除去した後、特定量の酸性物質の水溶液を油層に混合し、水層を除去してから脱臭することにより、多量の濾過助剤を使用しなくても、エステル交換反応後の油脂中に含まれているセッケンを十分に除去でき、多量の濾過助剤を用いた処理を行って得られた油脂よりも風味が豊かで酸化安定性に優れた油脂を得ることができ、さらには、使用済みの濾過助剤の量を大幅に減らせ、油脂の歩留りが上昇することを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors conducted a transesterification reaction of animal and vegetable oils and fats with an alkaline substance, and then contacted the oils and fats with neutral water for a specific amount, and then the aqueous layer was formed. After removal, a specific amount of an aqueous solution of acidic substances is mixed in the oil layer, and the water layer is removed before deodorization, so that it is contained in the fat after transesterification without using a large amount of filter aid. Can be removed sufficiently, it is possible to obtain fats and oils that are richer in flavor and superior in oxidation stability than those obtained by processing with a large amount of filter aid. It was found that the amount of the filter aid was greatly reduced, and the yield of fats and oils was increased, and the present invention was completed.

　即ち、本発明の第一は、動植物油脂を、アルカリ性物質を用いたエステル交換反応に付する第一工程、
　前記エステル交換反応後に得られた油脂と、前記動植物油脂１００重量部に対して１０～２００重量部の中性水とを接触させて、第一水層及び第一油層を含む液を得る第二工程、
　第二工程で得た液から第一水層を除去する第三工程、
　酸性物質の使用量が下記式１を満足するように当該酸性物質の水溶液を、第三工程で得られた第一油層に混合して、第二水層と第二油層からなる液を得る第四工程、
　第四工程で得た液から第二水相を除去する第五工程、及び
　第五工程で得られた第二油層を脱臭工程に付して、エステル交換油を得る第六工程
を含む、食用油脂の製造方法に関する。
Ａ×α＝ｎ×Ｂ　　（式１）
（Ａ：第一油層中のセッケン濃度（ｐｐｍ）／（３.０４４×１０^８）により算出される第一油層１ｇ当たりのセッケン総ｍｏｌ数、ｎ：前記酸性物質の価数、Ｂ：第一油層１ｇ当たりに混合する前記酸性物質のｍｏｌ数、α：０．７～５）
　好ましくは、酸性物質が有機酸である。 That is, the first of the present invention is a first step in which animal and vegetable fats and oils are subjected to a transesterification reaction using an alkaline substance,
A second oil is obtained by bringing the oil and fat obtained after the transesterification reaction into contact with 10 to 200 parts by weight of neutral water with respect to 100 parts by weight of the animal and vegetable oils and fats to obtain a liquid containing a first aqueous layer and a first oil layer. Process,
A third step of removing the first aqueous layer from the liquid obtained in the second step;
The aqueous solution of the acidic substance is mixed with the first oil layer obtained in the third step so that the amount of the acidic substance used satisfies the following formula 1 to obtain a liquid composed of the second aqueous layer and the second oil layer. Four steps,
Including a fifth step of removing the second aqueous phase from the liquid obtained in the fourth step, and a sixth step of obtaining a transesterified oil by subjecting the second oil layer obtained in the fifth step to a deodorization step. It is related with the manufacturing method of fats and oils.
A × α = n × B (Formula 1)
(A: soap concentration in the first oil layer (ppm) / (3.044 × 10 ⁸ ) calculated by total mol number of soap per 1 g of the first oil layer, n: valence of the acidic substance, B: first Mol number of the acidic substance to be mixed per 1 g of oil layer, α: 0.7 to 5)
Preferably, the acidic substance is an organic acid.

　好ましくは、第四工程において、第一油層に酸性物質の水溶液を添加して混合物を得、当該混合物を、第一油層が融解している温度以上の温度に保ちながら撹拌し、次いで、５～８０分間静置して全水滴のうち９０重量％以上が沈降した後、第五工程を実施する。 Preferably, in the fourth step, an aqueous solution of an acidic substance is added to the first oil layer to obtain a mixture, and the mixture is stirred while maintaining a temperature equal to or higher than the temperature at which the first oil layer is melted, and then 5 to After standing for 80 minutes and 90% by weight or more of all water droplets have settled, the fifth step is performed.

　好ましくは、第五工程後の第二油層１００重量部に対して０．１～１．０重量部の濾過助剤を添加して濾過助剤による処理を行い、次いで、濾過助剤を第二油層から除去した後、第六工程を実施する。 Preferably, 0.1 to 1.0 part by weight of a filter aid is added to 100 parts by weight of the second oil layer after the fifth step, and the treatment with the filter aid is performed. After removing from the oil layer, the sixth step is performed.

　好ましくは、第六工程における脱臭温度が１８０～２３０℃である。 Preferably, the deodorization temperature in the sixth step is 180 to 230 ° C.

　好ましくは、第六工程における脱臭時間が２０～５０分である。 Preferably, the deodorization time in the sixth step is 20 to 50 minutes.

　第二工程において、第一水層及び第一油層を含む液を得る際に乳化層が生じた場合には、
　第三工程において、第二工程で得られた液から第一水層及び乳化層を除去することが好ましい。 In the second step, when an emulsified layer is produced when obtaining a liquid containing the first aqueous layer and the first oil layer,
In the third step, it is preferable to remove the first aqueous layer and the emulsified layer from the liquid obtained in the second step.

　本発明に従えば、白土等の濾過助剤の使用量が少ない、或いは全く使用しなくても、エステル交換反応後の油脂中に含まれているセッケンを十分に除去でき、濾過助剤を多量に使用して得られた従来の油脂よりも風味が豊かで、酸化安定性に優れた食用油脂を製造できる方法を提供することができる。さらには、廃棄物処理が必要な使用済みの濾過助剤の量を大幅に減らし、油脂の歩留りを上昇させることができる。 According to the present invention, even if the amount of filter aid such as white clay is small or not used at all, soap contained in the oil and fat after the transesterification reaction can be sufficiently removed, and a large amount of filter aid is obtained. It is possible to provide a method capable of producing an edible oil and fat having a richer flavor than that of the conventional oil and fat obtained by using the oil and having excellent oxidation stability. Furthermore, the amount of used filter aid that requires waste disposal can be greatly reduced, and the yield of fats and oils can be increased.

　以下、本発明につき、さらに詳細に説明する。本発明の食用油脂の製造方法は、以下の通りである。まず、アルカリ性物質を触媒として動植物油脂をエステル交換反応させた後、得られた油脂と中性水とを特定量接触させてから、水層、及び、水層と油層の間に乳化層が生じた場合には乳化層を除去した後、特定量の酸性物質の水溶液を油層に混合し、水層、及び、水層と油層の間に乳化層が生じた場合には乳化層を除去してから脱臭することを特徴とする。 Hereinafter, the present invention will be described in more detail. The manufacturing method of the edible fat of the present invention is as follows. First, after subjecting animal and vegetable fats and oils to transesterification using an alkaline substance as a catalyst, the resulting fats and fats are brought into contact with a specific amount of water, and then an aqueous layer and an emulsified layer are formed between the water layer and the oil layer. In this case, after removing the emulsified layer, an aqueous solution of a specific amount of acidic substance is mixed with the oil layer, and when an emulsified layer is formed between the water layer and the water layer, the emulsified layer is removed. It is characterized by deodorizing.

　＜第一工程：エステル交換反応＞
　前記エステル交換反応では、アルカリ性物質を触媒として動植物油脂をエステル交換反応させる。具体的には、例えば「油脂の加熱→脱水→触媒投入」の順で常法に従うことができるが、これに限定されない。この反応工程内における触媒投入時に、触媒であるアルカリ性物質と動植物油脂が反応することで、化学エステル交換反応が進行すると共に、副生物のセッケンが生成する。ここでセッケンとは、エステル交換反応に供せられる動植物油脂中に含まれるトリグリセライド、ジグリセライド、又はモノグリセライド由来の脂肪酸とアルカリ性物質が反応して生じる脂肪酸アルカリ金属塩のことである。 <First step: transesterification>
In the transesterification reaction, animal and vegetable fats and oils are transesterified using an alkaline substance as a catalyst. Specifically, for example, the usual method can be followed in the order of “heating of fat / oil → dehydration → injecting catalyst”, but is not limited thereto. When the catalyst is charged in this reaction step, the alkaline substance as a catalyst reacts with animal and vegetable oils and fats, whereby a chemical transesterification reaction proceeds and a by-product soap is generated. Here, soap is a fatty acid alkali metal salt produced by a reaction between a fatty acid derived from triglyceride, diglyceride, or monoglyceride contained in animal or vegetable oils and fats subjected to transesterification and an alkaline substance.

　本発明のエステル交換油の製造に用いる動植物油脂は特に制限されるものではないが、植物油の例として、サフラワー油、大豆油、ナタネ油、パーム油、パーム核油、綿実油、ヤシ油、米糠油、ゴマ油、ヒマシ油、亜麻仁油、オリーブ油、桐油、椿油、落花生油、カポック油、カカオ油、木蝋、ヒマワリ油、コーン油などを例示することができ、動物油としては、魚油、鯨油、牛脂、豚脂、羊脂、牛脚脂などを例示でき、更にそれらの水素添加油やエステル交換油、分別油、さらにはそれらの混合油などを用いても良い。 The animal and vegetable oils and fats used for producing the transesterified oil of the present invention are not particularly limited, but examples of vegetable oils include safflower oil, soybean oil, rapeseed oil, palm oil, palm kernel oil, cottonseed oil, coconut oil, rice bran Oil, sesame oil, castor oil, linseed oil, olive oil, tung oil, coconut oil, peanut oil, kapok oil, cacao oil, wood wax, sunflower oil, corn oil, etc. Examples include pork fat, sheep fat, beef leg fat, and the like, and hydrogenated oils, transesterified oils, fractionated oils, and mixed oils thereof may also be used.

　上記エステル交換反応において、動植物油脂中のモノグリセライド、ジグリセライド、又はトリグリセライドとアルカリ性物質が反応する際に、水分はエステル交換反応を阻害するため、動植物油脂中の水分含有量は少ないほど良い。そこで、触媒を投入する前に、動植物油脂を脱水工程に付して、動植物油脂中の水分含有量を、０．１重量％以下まで減少させておくことが好ましく、より好ましくは０．０５重量％以下、さらに好ましくは０．０３重量％以下、特に好ましくは０．０１重量％以下である。ここで、動植物油脂を脱水するには、加熱真空脱水や窒素バブリングなどを行なえばよい。 In the transesterification reaction, when monoglyceride, diglyceride, or triglyceride in animal and vegetable oils and fats react with an alkaline substance, moisture inhibits the ester exchange reaction, so that the moisture content in animal and vegetable oils and fats is better. Therefore, before adding the catalyst, it is preferable to subject the animal and vegetable oils and fats to a dehydration step to reduce the water content in the animal and vegetable oils and fats to 0.1% by weight or less, more preferably 0.05% by weight. % Or less, more preferably 0.03% by weight or less, particularly preferably 0.01% by weight or less. Here, in order to dehydrate the animal and vegetable fats and oils, heating vacuum dehydration, nitrogen bubbling, or the like may be performed.

　動植物油脂を脱水する前に動植物油脂を加熱する際には、その加熱温度は特に限定されないが、例えば、６０～１１０℃程度の温度に加熱すればよい。６０℃未満であると脱水効率が悪い場合があり、１１０℃を超えると、油脂が劣化し過ぎる場合がある。 When heating the animal and vegetable oils and fats before dehydrating the animal and vegetable oils and fats, the heating temperature is not particularly limited. For example, it may be heated to a temperature of about 60 to 110 ° C. If it is less than 60 ° C, the dehydration efficiency may be poor, and if it exceeds 110 ° C, the oil may be excessively deteriorated.

　本発明のエステル交換油の製造に用いるアルカリ性物質としては、エステル交換能を有している物質であれば何を使用しても良く、アルカリ金属やその化合物が例示でき、具体的にはカリウムナトリウム合金、ナトリウムメチラート、ナトリウムエチラート、カリウムメチラート、水酸化ナトリウム、水酸化カリウム等を例示できる。低温での活性が高いことからはカリウムナトリウム合金が好ましく、経済性や扱い易さからはナトリウムメチラートが好ましい。 As the alkaline substance used in the production of the transesterified oil of the present invention, any substance having transesterification ability may be used, and an alkali metal or a compound thereof can be exemplified. Specifically, potassium sodium Examples include alloys, sodium methylate, sodium ethylate, potassium methylate, sodium hydroxide, potassium hydroxide and the like. A potassium sodium alloy is preferable because of its high activity at low temperatures, and sodium methylate is preferable from the viewpoint of economy and ease of handling.

　前記アルカリ性物質の添加量は、前記動植物油脂１００重量部に対して０．０５～０．５重量部が好ましく、０．１～０．３重量部がより好ましい。０．０５重量部より少ないと、動植物油脂のエステル交換反応速度が遅い、もしくは反応が進行しない場合がある。一方、０．５重量部より多いと、油脂中のモノグリセライド、ジグリセライド、又はトリグリセライドとアルカリ性物質が反応することで生成するセッケンの量が多くなり、得られるエステル交換油の収率が低下するため、好ましくない場合がある。 The amount of the alkaline substance added is preferably 0.05 to 0.5 parts by weight, more preferably 0.1 to 0.3 parts by weight, with respect to 100 parts by weight of the animal or vegetable oil. If the amount is less than 0.05 parts by weight, the transesterification rate of the animal or vegetable oil may be slow or the reaction may not proceed. On the other hand, if the amount is more than 0.5 parts by weight, the amount of soap produced by the reaction of monoglyceride, diglyceride, or triglyceride in the oil and fat with an alkaline substance increases, and the yield of the obtained transesterified oil decreases. It may not be preferable.

　動植物油脂とアルカリ性物質との反応条件は特に限定されず、常法に従うことができるが、例えば０．０３～３時間、５０～１２０℃程度であって、好ましくは外気等から水分が混入しない条件がよく、例えば真空下で反応させたり、油脂のヘッドスペースに窒素を充填した状態で反応させたりすればよい。 The reaction conditions between the animal and vegetable oils and alkaline substances are not particularly limited and can be according to conventional methods. For example, the conditions are about 0.03 to 3 hours and about 50 to 120 ° C., and preferably no moisture is mixed from outside air. For example, the reaction may be performed under vacuum, or the reaction may be performed in a state in which the oil or fat headspace is filled with nitrogen.

　＜第二工程：エステル交換反応後の油脂と中性水との接触＞
　前記エステル交換反応後の油脂に、中性水を接触させる。これにより、油脂に含まれるセッケンを水層に移行させ、油脂中に含まれるセッケン量を低減することができる。 <Second step: Contact between oil and fat after transesterification and neutral water>
Neutral water is brought into contact with the fat after the transesterification reaction. Thereby, the soap contained in fats and oils can be moved to an aqueous layer, and the amount of soap contained in fats and oils can be reduced.

　ここで、中性水とは、わずかにアルカリ性を示す水、及び、わずかに酸性を示すが、セッケンと反応して脂肪酸に変化させる程度の酸性ではない水も含む。具体的には、ｐＨ５～９の範囲の水を好適に用い得る。 Here, neutral water includes water that is slightly alkaline and water that is slightly acidic but is not acidic enough to react with soap and change into fatty acid. Specifically, water having a pH in the range of 5 to 9 can be suitably used.

　前記中性水を油脂と接触させるには、エステル交換反応後の油脂と中性水との接触表面積の総和が大きく且つ乳化が生じにくいように中性水を油脂に添加する方法が好ましい。接触表面積の総和が小さいと、洗浄効率の悪い場合がある。また、乳化が起こると、油脂の歩留りを低下させる場合がある。中性水の水滴径が大きいほど、大半の水滴はセッケンを抱いたまま、比重の差に従い沈降していく。これにより、セッケンを十分に除去できると共に、乳化を生じにくくすることができる。 In order to bring the neutral water into contact with fats and oils, a method of adding neutral water to the fats and oils so that the total surface area of contact between the fats and fats after the transesterification reaction and the neutral water is large and emulsification hardly occurs is preferable. If the total contact surface area is small, the cleaning efficiency may be poor. Moreover, when emulsification occurs, the yield of fats and oils may be reduced. The larger the water droplet size of neutral water, the more water droplets will settle according to the difference in specific gravity while holding the soap. Thereby, soap can be removed sufficiently and emulsification can be made difficult to occur.

　接触表面積の総和と水滴径とのバランスを適切な範囲にするために、具体的には、油層中における水滴径が１～５ｍｍ程度になるように、中性水の液滴を油脂に添加する方法が好ましく、さらには、中性水の添加の勢いが強すぎないように添加することがより好ましい。水滴径が１ｍｍより小さいと、水滴が油脂中に浮遊し続けて沈降しにくい場合があり、また、油層中の油脂全体に接触させるためには中性水の添加の勢いを強くする必要があるので乳化層が生じやすくなる場合がある。５ｍｍより大きいと接触表面積の総和が小さくなり、セッケンの除去が不十分になる場合がある。上記以外の方法としては、ヘッドスペースに中性水を霧状に噴霧し油層表面で合一させて水滴の状態で沈降させる方法や、予め中性水で満たした水層に対して油脂を油滴の状態で添加する方法を例示することができる。 In order to make the balance between the sum of the contact surface areas and the water droplet diameter within an appropriate range, specifically, neutral water droplets are added to the oil so that the water droplet diameter in the oil layer is about 1 to 5 mm. The method is preferred, and more preferably, neutral water is added so that the momentum of addition is not too strong. If the water droplet diameter is smaller than 1 mm, the water droplet may continue to float in the oil and be difficult to settle, and in order to contact the entire oil and fat in the oil layer, it is necessary to increase the momentum of neutral water addition Therefore, an emulsified layer may be easily generated. When it is larger than 5 mm, the total contact surface area becomes small, and the removal of soap may be insufficient. Other than the above, neutral water is sprayed in the head space in the form of a mist and coalesced on the surface of the oil layer and settled in the form of water droplets, or oil is added to the water layer previously filled with neutral water. The method of adding in the state of a drop can be illustrated.

　中性水を添加する際は、油脂を撹拌しながら一気に中性水を接触させると、特開昭５１－６１５１０号公報に記載のように、水層と油層の間で大量の乳化層が発生し、油脂の歩留りを低下させる恐れがある。従って、乳化層の発生をできるだけ抑制するために、油脂と中性水との接触は穏やかであることが好ましい。前述した水滴径の大きさに関わらず、中性水を添加する際の勢いが強すぎると乳化が起こり易くなる場合があり、勢いが弱すぎると中性水の添加に時間がかかり、生産効率が低下する場合がある。また、油脂に中性水を添加する際、油脂の流動性は低い方が好ましく、油脂は流動させないことが更に好ましい。油脂の流動性は、例えば撹拌速度を変えることで調整すれば良い。 When neutral water is added, if the neutral water is brought into contact with the oil and fat while stirring, a large amount of emulsified layer is generated between the water layer and the oil layer as described in JP-A-51-61510. In addition, the yield of fats and oils may be reduced. Therefore, in order to suppress generation | occurrence | production of an emulsion layer as much as possible, it is preferable that the contact with fats and oils and neutral water is gentle. Regardless of the size of the water droplets described above, if the momentum when adding neutral water is too strong, emulsification may occur easily. If the momentum is too weak, it takes time to add neutral water, and production efficiency is increased. May decrease. Moreover, when adding neutral water to fats and oils, the one where the fluidity | liquidity of fats and oils is low is preferable, and it is still more preferable not to let fats and oils flow. The fluidity of the oil and fat may be adjusted by changing the stirring speed, for example.

　中性水を油脂の上部から添加する場合は、例えばシャワーリングによって中性水を液滴状にして添加する方法などを例示することができる。シャワーリングは、ノズル径の変更や水圧の調節などで水滴径をコントロールし易く、エステル交換反応後の油脂と中性水との接触表面積の総和を制御するのに好適である。また、油層の表面に対して広範囲に均一に中性水を添加することも容易である。さらに、添加する水滴が小粒径であっても、油層表面で水滴同士が合一し易く、適度な粒径になって沈降し易い。 In the case of adding neutral water from the upper part of the oil or fat, for example, a method of adding neutral water in the form of droplets by showering can be exemplified. The shower ring is easy to control the water droplet diameter by changing the nozzle diameter or adjusting the water pressure, and is suitable for controlling the total surface area of contact between the fats and oils and the neutral water after the transesterification reaction. It is also easy to add neutral water uniformly over a wide range with respect to the surface of the oil layer. Furthermore, even if the water droplets to be added have a small particle size, the water droplets are likely to coalesce on the surface of the oil layer, so that they have an appropriate particle size and are likely to settle.

　前記エステル交換反応後の油脂に接触させる中性水の添加量は、原料である動植物油脂１００重量部に対して１０～２００重量部が好ましく、３０～１７０重量部がより好ましく、５０～１５０重量部が更に好ましく、５０～１２０重量部が特に好ましい。１０重量部より少ないと、中性水とセッケンが接触する表面積の総和が少ないために、エステル交換反応後の油脂中からセッケンを十分に除去できない場合がある。２００重量部より多いと、処理しなければならない廃水量が増加するため、経済的に好ましくない場合がある。 The amount of neutral water to be brought into contact with the oil and fat after the transesterification reaction is preferably 10 to 200 parts by weight, more preferably 30 to 170 parts by weight, and more preferably 50 to 150 parts by weight with respect to 100 parts by weight of the animal and vegetable oils and fats that are raw materials. Parts are more preferred, and 50 to 120 parts by weight are particularly preferred. If the amount is less than 10 parts by weight, the total surface area where neutral water and soap are in contact with each other is small, so that soap may not be sufficiently removed from the fat after the transesterification reaction. If the amount is more than 200 parts by weight, the amount of waste water that must be treated increases, which may be economically undesirable.

　この工程により、第一水層及び第一油層を含む液が得られる。また、この工程によると、従来の水洗工程と比較して、乳化層の発生をはるかに抑えることができる。しかし、わずかに乳化層が発生することもあり、その場合には、この工程により、第一水層、乳化層及び第一油層からなる液が得られる。乳化層は、第一水層と第一油層との間に形成される。 By this step, a liquid containing the first aqueous layer and the first oil layer is obtained. Moreover, according to this process, compared with the conventional water washing process, generation | occurrence | production of an emulsion layer can be suppressed much. However, a slightly emulsified layer may be generated, and in this case, a liquid composed of the first aqueous layer, the emulsified layer and the first oil layer is obtained by this step. The emulsified layer is formed between the first aqueous layer and the first oil layer.

　＜第三工程：第一水層の除去＞
　この工程では、第二工程で得られた液から第一水層を除去する。また、上述したように、第二工程で得られた液において乳化層が発生している場合には、第二工程で得られた液から第一水層及び乳化層を除去する。この場合、乳化層は第一水層と共に除去すればよい。 <Third step: removal of the first aqueous layer>
In this step, the first aqueous layer is removed from the liquid obtained in the second step. Moreover, as above-mentioned, when the emulsion layer has generate | occur | produced in the liquid obtained at the 2nd process, a 1st water layer and an emulsion layer are removed from the liquid obtained at the 2nd process. In this case, the emulsified layer may be removed together with the first aqueous layer.

　第二工程で得られた液は、タンク等の容器中で、比重の差に従って、下方から、第一水層、生じている場合には乳化層、及び、第一油層に分離している。従って、容器の下部から、第一水層、及び、生じている場合には乳化層を排出することにより、第二工程で得られた液から第一水層及び乳化層を除去することが出来る。 In the container such as a tank, the liquid obtained in the second step is separated into the first aqueous layer, the emulsified layer, and the first oil layer, if any, from below according to the difference in specific gravity. Therefore, the first aqueous layer and the emulsified layer can be removed from the liquid obtained in the second step by discharging the first aqueous layer and, if any, the emulsified layer from the lower part of the container. .

　なお、第一水層、乳化層、及び第一油層は、第一水層及び乳化層の除去の前に予め十分に分離させておくことが好ましい。各層の分離が十分でないとセッケンと乳化物の除去効率が低下したり、油脂の歩留りが低下する場合がある。前記各層を十分に分離するには、例えば、添加した中性水の沈降後に、容器中で一定時間静置したり、遠心分離すれば良い。 The first aqueous layer, the emulsified layer, and the first oil layer are preferably sufficiently separated in advance before the removal of the first aqueous layer and the emulsified layer. If the separation of each layer is not sufficient, the removal efficiency of soap and emulsion may be reduced, or the yield of fats and oils may be reduced. In order to sufficiently separate the layers, for example, after settling of the added neutral water, the layers may be left in a container for a certain period of time or centrifuged.

　こうして水層を除去して得られたエステル交換油は、この時点で含まれるセッケン濃度が好ましくは３５０～１２００ｐｐｍ（より好ましくは３５０～１０００ｐｐｍ）と非常に少なくなる。 The transesterified oil obtained by removing the aqueous layer in this way has a very low soap concentration of preferably 350 to 1200 ppm (more preferably 350 to 1000 ppm).

　＜第四工程：酸性物質と油層との混合＞
　第三工程で第一水層と、生じている場合には乳化層とを除去した後の第一油層に、酸性物質の水溶液を混合し、撹拌する。これにより、第一油層に残留しているセッケンを脂肪酸に変化させることでセッケンを分解し、生じた脂肪酸を水層に移行させることができる。ここで、撹拌とは油層と酸性物質の水溶液を乱流状態にすることを表す。乱流状態を作り上げるには、例えばタンクの中で撹拌翼を回転させたり、スタティックミキサーを通せばよい。 <Fourth step: Mixing of acidic substance and oil layer>
In the third step, an aqueous solution of an acidic substance is mixed and stirred in the first oil layer after removing the first aqueous layer and, if any, the emulsified layer. Thereby, soap can be decomposed | disassembled by changing the soap remaining in the 1st oil layer into a fatty acid, and the produced fatty acid can be moved to an aqueous layer. Here, the agitation represents making the oil layer and the aqueous solution of the acidic substance into a turbulent state. In order to create a turbulent state, for example, a stirring blade may be rotated in a tank or a static mixer may be passed.

　本発明において使用可能な酸性物質は、セッケンと反応した際に、セッケンからアルカリ金属を奪い脂肪酸に変化させることが可能な酸性物質であれば特に限定はない。例えばクエン酸やリンゴ酸、乳酸などの有機酸、塩酸、硫酸などの無機酸が例示できるが、食用であることを考えると、有機酸が好ましい。 The acidic substance that can be used in the present invention is not particularly limited as long as it is an acidic substance that can take an alkali metal from soap and change it into a fatty acid when reacted with soap. For example, organic acids such as citric acid, malic acid, and lactic acid, and inorganic acids such as hydrochloric acid and sulfuric acid can be exemplified, but considering that they are edible, organic acids are preferable.

　前記酸性物質を水溶液の状態で第一油層に添加する理由は、酸性物質を固体状で添加すると、油脂中のセッケンとの反応が効率的に進まないし、酸性物質を気体状で添加すると、油脂中からすぐに抜けてしまい、同じく反応が効率的に進まないからである。 The reason why the acidic substance is added to the first oil layer in the form of an aqueous solution is that when the acidic substance is added in a solid state, the reaction with soap in the fat or oil does not efficiently proceed. This is because the reaction will not proceed efficiently, as it will quickly escape from the inside.

　前記酸性物質は、下記式１を満足するような量を第一油層に混合する。
Ａ×α＝ｎ×Ｂ　　（式１）
　式中、Ａは、第一油層中のセッケン濃度（ｐｐｍ）／（３.０４４×１０^２×１０^６）により算出される第一油層１ｇ当たりのセッケン総ｍｏｌ数を表す。ｎは、前記酸性物質の価数を表す。Ｂは、第一油層１ｇ当たりに混合する前記酸性物質のｍｏｌ数、α：０．７～５を表す。 The acidic substance is mixed in the first oil layer in an amount that satisfies the following formula 1.
A × α = n × B (Formula 1)
In the formula, A represents the total number of moles of soap per 1 g of the first oil layer calculated by the soap concentration (ppm) in the first oil layer / (3.044 × 10 ² × 10 ⁶ ). n represents the valence of the acidic substance. B represents the number of moles of the acidic substance to be mixed per 1 g of the first oil layer, α: 0.7 to 5.

　前記式１において、定数αは、０．７～５の範囲にある数値となる。好ましくは、０．７～４であり、より好ましくは０．７～３であり、さらに好ましくは０．８～２である。αが０．７より小さいと、酸性物質の添加量が不十分であり、油脂中に残存するセッケンが多くなったり、後工程でセッケンの除去にかかる時間が長くなる場合がある。αが５より大きいと酸性物質の添加量が過剰なため、反応せずに残る酸性物質が多くなり、経済的負担が大きすぎる場合がある。 In the above formula 1, the constant α is a numerical value in the range of 0.7-5. Preferably, it is 0.7-4, more preferably 0.7-3, and still more preferably 0.8-2. If α is smaller than 0.7, the amount of the acidic substance added is insufficient, and there may be a lot of soap remaining in the fat or oil, or the time required for removing the soap in a subsequent process may be long. If α is greater than 5, the amount of acidic substance added is excessive, so that the amount of acidic substance remaining without reacting increases, and the economic burden may be too great.

　式１の第一油層１ｇ当たりのセッケンの総ｍｏｌ数Ａは、次のようにして算出する。まず、社団法人日本油化学協会編「基準油脂分析法」（発行年：１９９６年）の２．６．２－１９９６セッケンに記載された方法に従い、第一油層中のセッケン濃度Ｘ（ｐｐｍ）を算出する。その後、式２：Ａ’＝Ｘ×Ｙ／（３.０４４×１０^２×１０^６）（Ａ’：第一油層中のセッケン総ｍｏｌ数、Ｘ：第一油層中のセッケン濃度Ｘ（ｐｐｍ）、Ｙ：エステル交換反応に供する全動植物油脂量（ｇ））によって、第一油層中のセッケン総ｍｏｌ数Ａ’を算出出来る。従って、第一油層１ｇ当たりのセッケン総ｍｏｌ数Ａは、式２’：Ａ＝Ｘ／（３.０４４×１０^２×１０^６）に従って算出できる。 The total mole number A of soap per 1 g of the first oil layer of Formula 1 is calculated as follows. First, the soap concentration X (ppm) in the first oil layer was determined according to the method described in 2.6.2-1996 soap of “Reference Oil Analysis Method” (issue year: 1996) edited by Japan Oil Chemical Association. calculate. Then, Formula 2: A ′ = X × Y / (3.044 × 10 ² × 10 ⁶ ) (A ′: total number of moles of soap in the first oil layer, X: soap concentration X (ppm) in the first oil layer , Y: Total animal and vegetable fats and oils (g) for use in the transesterification reaction can calculate the total mole number A ′ of soap in the first oil layer. Therefore, the total number of moles A of soap per 1 g of the first oil layer can be calculated according to the formula 2 ′: A = X / (3.044 × 10 ² × 10 ⁶ ).

　なお、ここで分母の数字（３．０４４×１０^２）はオレイン酸ナトリウムの分子量である。セッケン中の脂肪酸はオレイン酸だけではないが、オレイン酸ナトリウムの分子量を慣例的にセッケンの分子量とする。また、酸性物質を添加する第一油層量は、第三工程で水層や乳化層を除去する際に若干目減りするが、その目減り分は無視することとする。但し、著しく第一油層量が減っている場合や厳密に計算する場合には、式２のＸ値を基に第一油層量を計算すれば良い。 Here, the denominator number (3.044 × 10 ² ) is the molecular weight of sodium oleate. Although the fatty acid in soap is not only oleic acid, the molecular weight of sodium oleate is customarily used as the molecular weight of soap. Further, the amount of the first oil layer to which the acidic substance is added is slightly reduced when the aqueous layer and the emulsified layer are removed in the third step, but the reduced amount is ignored. However, when the amount of the first oil layer is remarkably reduced or when it is strictly calculated, the first oil layer amount may be calculated based on the X value of Equation 2.

　第一油層に酸性物質の水溶液を添加して得られた混合物を撹拌する際には、第一油層が完全に融解している状態に保ちながら撹拌することが好ましい。第一油層が完全に融解していない状態で撹拌すると、セッケンと酸性物質との反応効率が低下し、第一油層中のセッケンを十分に分解できない場合がある。なお、第一油層を融解するために第一油層を昇温することが好ましいが、そのタイミングは、酸性物質の水溶液の添加前でも後でも良い。 When stirring a mixture obtained by adding an aqueous solution of an acidic substance to the first oil layer, it is preferable to stir while keeping the first oil layer completely melted. When stirring in a state where the first oil layer is not completely melted, the reaction efficiency between the soap and the acidic substance is lowered, and the soap in the first oil layer may not be sufficiently decomposed. Although it is preferable to raise the temperature of the first oil layer in order to melt the first oil layer, the timing may be before or after the addition of the aqueous solution of the acidic substance.

　ここで、前記撹拌は、乱流状態の反応系（第一油層と酸性物質の水溶液の混合・撹拌系）において、油脂が酸化劣化しない状態で行われることが好ましい。具体的には、反応容器内を密閉系にしたり、反応を窒素雰囲気下の状態で行えばよい。また、乱流状態が激しい程酸性物質とセッケンとの反応効率が高くなる一方で、乱流状態が激しすぎると、油層中の水滴径が小さくなりすぎ、後の液滴の沈降に時間がかかりすぎてしまう。 Here, the agitation is preferably performed in a turbulent reaction system (mixing and agitation system of the first oil layer and the aqueous solution of the acidic substance) in a state where the fats and oils are not deteriorated by oxidation. Specifically, the inside of the reaction vessel may be a closed system, or the reaction may be performed in a nitrogen atmosphere. In addition, the reaction efficiency between the acidic substance and the soap increases as the turbulent flow condition increases. On the other hand, if the turbulent flow condition is excessive, the water droplet diameter in the oil layer becomes too small, and the subsequent droplet settling time becomes longer. It takes too much.

　そこで、酸性物質の水溶液を添加する際の乱流状態は、以下の条件を満たすことが好ましい。乱流時には酸性物質の水溶液が油層中において液滴状態として存在するが、液滴径分布上、液滴径ｄよりも小さい液滴径の存在割合が１０重量％であるときに、ストークスの沈降速度式（式３）：ｕ＝｛（ρ_Ｓ－ρ）×ｇ×ｄ^２｝／１８μ（式中、ｕ：液滴の終末沈降速度（ｃｍ/ｓ）、ρ_Ｓ：酸性物質水溶液密度（ｇ/ｃｍ^３）、ρ：第一油層密度（ｇ/ｃｍ³）、ｇ：重力加速度（ｃｍ/ｓ^２）、ｄ：液滴の直径（ｃｍ）、μ：第一油層粘度（ｇ・ｃｍ・ｓ））より得られる終末沈降速度ｕを用いた式４：ｔ＝Ｌ／６０ｕ（ｔ：沈降時間（ｍｉｎ）、Ｌ＝液滴を沈降させる際の反応系の深さ（ｃｍ））において、沈降時間ｔ、即ち、撹拌を停止して混合物を静置してから全水滴の内９０重量％が沈降するまでの時間が５～８０分間であることが好ましく、２０～６０分間がより好ましい。 Therefore, it is preferable that the turbulent flow state when adding the aqueous solution of the acidic substance satisfies the following conditions. In an turbulent flow, an aqueous solution of an acidic substance exists as a droplet in the oil layer. However, when the ratio of the droplet diameter smaller than the droplet diameter d is 10% by weight due to the droplet diameter distribution, Stokes sedimentation occurs. Velocity equation (Equation 3): u = {(ρ _S −ρ) × g × d ² } / 18 μ (where u: terminal sedimentation velocity (cm / s) of droplets, ρ _S : density of acidic substance aqueous solution ( g / cm ³ ), ρ: first oil layer density (g / cm ³ ), g: gravitational acceleration (cm / s ² ), d: droplet diameter (cm), μ: first oil layer viscosity (g · cm In the formula 4 using the terminal sedimentation velocity u obtained from s)): t = L / 60u (t: sedimentation time (min), L = depth of the reaction system (cm) when the droplet is sedimented) The sedimentation time t, that is, the time from when the stirring is stopped and the mixture is allowed to stand until 90% by weight of all the water droplets settles is 5 to 80 minutes. Preferably, more preferably 20 to 60 minutes.

　前記沈降時間が８０分間を超える場合は、液滴径が小さくなり過ぎていたり、残存するセッケンが多いために乳化が生じてしまっていることを意味しており、第五工程で第二水層を除去する前に遠心分離の工程を要するなど手間がかかってしまう場合がある。また、５分間より短い場合は、液滴径が大きくなりすぎていることを意味し、接触表面積の総和が不足するためセッケンを十分に分解、除去できない場合がある。 When the sedimentation time exceeds 80 minutes, it means that the droplet diameter is too small or there is a lot of remaining soap and emulsification has occurred. There are cases where it takes time and effort, such as requiring a step of centrifugation before removing. If the time is shorter than 5 minutes, it means that the droplet diameter is too large, and the total surface area of the contact is insufficient, so that the soap may not be sufficiently decomposed and removed.

　第一油層と酸性物質の水溶液との混合・撹拌は、第一油層中のセッケンと酸性物質とを反応させ、セッケンを十分に分解することを目的としているため、混合・撹拌を停止するタイミングは油層中のセッケン量を目安にすればよく、油層中のセッケン濃度が３０ｐｐｍ以下になった段階で混合・撹拌を停止すればよい。油層中のセッケン濃度が３０ｐｐｍよりも多い段階で混合・撹拌を停止すると、残存したセッケンで乳化が起こり、水滴の沈降に時間を要する場合があったり、乳化によって油脂の歩留まりが低下することがあり好ましくない。また、前記セッケン濃度が３０ｐｐｍを下回った以降も撹拌を続けると、油脂中のセッケン量が低下することで、発生していた乳化層が破壊され、歩留まり向上に繋がり、好ましい。しかしながら、場合によっては長時間の撹拌により液滴径が小さくなりすぎて液滴の沈降に時間を要し、油層と水層との分離に時間がかかりすぎることもある。 The mixing / stirring of the first oil layer and the aqueous solution of the acidic substance is intended to cause the soap and the acidic substance in the first oil layer to react and sufficiently decompose the soap. The amount of soap in the oil layer may be used as a guide, and mixing and stirring may be stopped when the soap concentration in the oil layer becomes 30 ppm or less. If mixing / stirring is stopped when the soap concentration in the oil layer is higher than 30 ppm, emulsification may occur in the remaining soap, and it may take time for the water droplets to settle, and the yield of fats and oils may decrease due to emulsification. It is not preferable. Moreover, when stirring is continued even after the soap concentration falls below 30 ppm, the amount of soap in the oil and fat is reduced, so that the generated emulsified layer is destroyed, which leads to an improvement in yield. However, in some cases, the droplet diameter becomes too small due to long-time stirring, so that it takes time to settle the droplet, and it may take too much time to separate the oil layer and the water layer.

　なお、ストークスの沈降速度式（式３）における第一油層の粘度は、社団法人日本油化学協会編「基準油脂分析法」（発行年：１９９６年）の２．２．１０．１－１９９６粘度（動粘度）に記載された方法に従い測定することが可能である。 The viscosity of the first oil layer in the Stokes sedimentation rate equation (Formula 3) is the 2.2.10.1-1996 viscosity of “Standard Oil Analysis Method” (issue year: 1996) edited by Japan Oil Chemical Association. It can be measured according to the method described in (Kinematic viscosity).

　この工程で、第一油層と酸性物質の水溶液との混合・撹拌を行うことで、第二水層と第二油層からなる液が得られる。また、この工程では、極めて少量ではあるが、わずかに乳化層が発生する場合があり、その場合には、この工程により、第二水層、乳化層及び第二油層からなる液が得られる。乳化層は、第二水層と第二油層との間に形成される。 In this step, a liquid composed of the second aqueous layer and the second oil layer is obtained by mixing and stirring the first oil layer and the aqueous solution of the acidic substance. In this step, an emulsified layer may be slightly generated even in a very small amount, and in this case, a liquid composed of the second aqueous layer, the emulsified layer and the second oil layer is obtained in this step. The emulsified layer is formed between the second aqueous layer and the second oil layer.

　＜第五工程：酸性物質と油層との混合後の水層除去＞
　第四工程の混合・撹拌を停止後静置して、第二水層が沈降したら（好ましくは、５～８０分間静置して全添加水のうち９０重量％以上が沈降したら）、第四工程で得られた液から第二水層を除去する。前記において添加水のうち９０重量％以上の水滴が沈降した後、必要に応じてもうしばらく静置しても良い。第二水層の除去方法は特に限定されないが、例えば、第二水層と第二油層からなる液を収容している容器の下部から第二水層を排出すれば良い。また、上述したように、乳化層が発生している場合には、第四工程で得られた液から第二水層及び乳化層を除去する。この場合、乳化層は第二水層と共に除去すればよい。 <Fifth step: removal of aqueous layer after mixing of acidic substance and oil layer>
When the mixing and stirring in the fourth step is stopped, the mixture is allowed to stand and the second aqueous layer settles (preferably, after standing for 5 to 80 minutes and 90% by weight or more of all the added water has settled) The second aqueous layer is removed from the liquid obtained in the step. In the above, after 90% by weight or more of the added water has settled, it may be left still for a while if necessary. Although the removal method of a 2nd water layer is not specifically limited, For example, what is necessary is just to discharge | emit a 2nd water layer from the lower part of the container which accommodates the liquid which consists of a 2nd water layer and a 2nd oil layer. As described above, when the emulsified layer is generated, the second aqueous layer and the emulsified layer are removed from the liquid obtained in the fourth step. In this case, the emulsified layer may be removed together with the second aqueous layer.

　＜任意工程：残留酸性物質の除去＞
　後述の「濾過助剤による補助的セッケン分除去」を行わない場合は、第二油層中に残留している酸性物質を除去するために、以下の方法を実施してもよい。添加した酸性物質の融点が油脂の温度より低い場合、第二水層を除去した後、真空脱水を行うと第二油層中に酸性物質が結晶として析出するので、例えばフィルターに第二油層を通過させるなどの方法で酸性物質を除去することが可能である。また、酸性物質を析出させずに除去する方法としては、第二水層を除去した後、更に遠心分離を行い得られた水層を除去することにより水層に溶解した状態で酸性物質を除去する方法や、油脂と酸性物質との比重の差を利用して遠心分離後に油脂の下層に得られる酸性物質を除去する方法も可能である。この方法の場合、第二水層を除去した後に水を再添加してから遠心分離しても良い。また、添加した酸性物質が塩酸などの沸点の低い酸である場合、酸性物質は揮発するため、第二油層を蒸留することにより酸性物質を除去することが可能である。後述の「濾過助剤による補助的セッケン分除去」を行う場合は、そこで残留酸性物質も除去され得る。 <Optional step: Removal of residual acidic substances>
In the case where the “subsidiary soap removal by the filter aid” described later is not performed, the following method may be performed in order to remove the acidic substance remaining in the second oil layer. If the melting point of the added acidic substance is lower than the temperature of the oil or fat, removing the second aqueous layer and then performing vacuum dehydration causes the acidic substance to precipitate as crystals in the second oil layer. It is possible to remove the acidic substance by a method such as In addition, as a method for removing the acidic substance without precipitating, after removing the second aqueous layer, the acidic substance is removed in the dissolved state in the aqueous layer by removing the aqueous layer obtained by further centrifugation. And a method of removing the acidic substance obtained in the lower layer of the oil and fat after centrifugation using the difference in specific gravity between the oil and fat and the acidic substance. In the case of this method, after removing the second aqueous layer, water may be added again and then centrifuged. Further, when the added acidic substance is an acid having a low boiling point such as hydrochloric acid, the acidic substance is volatilized, and therefore, the acidic substance can be removed by distilling the second oil layer. In the case of performing “subsidiary soap removal by filter aid” described later, residual acidic substances can also be removed there.

　＜任意工程：濾過助剤による補助的セッケン分除去＞
　必須の工程ではないが、少しでも第二油層中のセッケンの残留量を減らし、エステル交換油の脱色効果を十分に得るために、第五工程で第二水層を除去した後、続けて、第二油層に濾過助剤を混合・撹拌した後、濾過助剤を第二油層から分離・除去する方法が挙げられる。前記混合・撹拌の際には、第二油層、残留酸性物質、残留セッケン分、残留水分及び濾過助剤の合計量の内、水分を１重量％以下にすることが好ましい。水分が１重量％より多いと、濾過助剤の有する吸着効果が十分に発揮されない場合がある。なお、反応系中の水分を減らした状態で混合・撹拌するためには、例えば濾過助剤を添加後に加熱真空状態で撹拌すればよい。また、濾過助剤を添加前に、第二水層除去後の第二油層（残留酸性物質、残留セッケン分、残留水分等を含む）、濾過助剤それぞれを加熱真空状態で脱水してもよい。 <Optional step: Removal of auxiliary soap by filter aid>
Although it is not an essential process, in order to reduce the residual amount of soap in the second oil layer as much as possible and sufficiently obtain the decoloring effect of the transesterified oil, after removing the second aqueous layer in the fifth process, continue, A method of separating and removing the filter aid from the second oil layer after mixing and stirring the filter aid in the second oil layer can be mentioned. In the mixing / stirring, the water content is preferably 1% by weight or less in the total amount of the second oil layer, the residual acidic substance, the residual soap, the residual water and the filter aid. If the water content is more than 1% by weight, the adsorption effect of the filter aid may not be sufficiently exhibited. In addition, in order to mix and stir in the state which reduced the water | moisture content in the reaction system, what is necessary is just to stir in a heating vacuum state, for example after adding a filter aid. Further, before the addition of the filter aid, each of the second oil layer after removal of the second aqueous layer (including residual acidic substances, residual soap, residual moisture, etc.) and the filter aid may be dehydrated in a heated vacuum state. .

　前記濾過助剤としては、セッケン分を吸着して除去する効果があること、また付随して、結果的に濾過速度の低下を抑える効果を有していれば、何を使用しても良い。後者の理由は、セッケン分は濾過中に凝集したりしてフィルターの目詰まりを引き起こし、濾過速度が低下しやすいためである。具体的には、活性白土、酸性白土、パーライト、二酸化珪素、珪藻土、活性炭などが挙げられ、特にセッケン分除去の効果の面から、活性白土や酸性白土を用いることが好ましい。また、濾過助剤は２種類以上を用いても構わないが、経済性や作業の簡便さなどを考え、１種類のみを使用することが好ましい。 Any filter aid may be used as long as it has an effect of adsorbing and removing soap and, as a result, an effect of suppressing a decrease in filtration rate. The reason for the latter is that soap is agglomerated during filtration, causing clogging of the filter, and the filtration rate tends to decrease. Specific examples include activated clay, acid clay, pearlite, silicon dioxide, diatomaceous earth, activated carbon, and the like. In particular, activated clay and acid clay are preferably used from the viewpoint of the effect of removing soap. Further, two or more types of filter aids may be used, but it is preferable to use only one type in consideration of economic efficiency and ease of work.

　前記濾過助剤の添加量は、前記第二水層除去後の第二油層１００重量部に対して１．０重量部以下が好ましく、０．１～１．０重量部がより好ましく、０．２～１．０重量部が更に好ましく、０．３～１．０重量部が特に好ましく、０．４～１．０重量部が極めて好ましい。１．０重量部より多いと、濾過助剤特有の好ましくない風味がエステル交換油に移行したり、濾過助剤に付着するエステル交換油量が比例的に増えることで、エステル交換油の収率が低下する場合がある。 The amount of the filter aid added is preferably 1.0 part by weight or less, more preferably 0.1 to 1.0 part by weight, with respect to 100 parts by weight of the second oil layer after the removal of the second aqueous layer. It is more preferably 2 to 1.0 part by weight, particularly preferably 0.3 to 1.0 part by weight, and very preferably 0.4 to 1.0 part by weight. When the amount is more than 1.0 part by weight, the unfavorable flavor unique to the filter aid is transferred to the transesterified oil, or the amount of the transesterified oil adhering to the filter aid is proportionally increased. May decrease.

　なお、セッケン分は次の脱臭工程では除去できないため、脱臭工程の前に、濾過助剤を用いてセッケン分を除去しておくことが好ましい。 In addition, since a soap part cannot be removed in the following deodorizing process, it is preferable to remove a soap part using a filter aid before a deodorizing process.

　＜第六工程：脱臭＞
　この工程では、第二油層を脱臭工程に付して、エステル交換油である食用油脂を得る。前記脱臭は、例えば水蒸気蒸留により実施することができ、具体的には、第二油層を水蒸気蒸留装置に移送し、第二油層を加熱しながら、４００Ｐａ以下の減圧下、第二油層１００重量部に対して０．５～１０重量部／ｈｒで水蒸気を吹き込むことで実行できる。 <Sixth step: Deodorization>
In this step, the second oil layer is subjected to a deodorization step to obtain an edible fat that is a transesterified oil. The deodorization can be performed, for example, by steam distillation. Specifically, the second oil layer is transferred to a steam distillation apparatus, and the second oil layer is heated to 100 parts by weight under reduced pressure of 400 Pa or less while heating the second oil layer. On the other hand, it can be carried out by blowing water vapor at 0.5 to 10 parts by weight / hr.

　前記水蒸気蒸留による脱臭工程に供する第二油層のセッケン濃度は、１５ｐｐｍ以下が好ましく、１０ｐｐｍ以下が更に好ましい。１５ｐｐｍより高いと、得られる食用油脂がえぐみのような異味を呈する場合がある。 The soap concentration of the second oil layer subjected to the deodorizing step by steam distillation is preferably 15 ppm or less, and more preferably 10 ppm or less. If it is higher than 15 ppm, the resulting edible fat may have an off-flavored taste.

　前記水蒸気蒸留による脱臭温度は、１８０～２３０℃が好ましく、１９０～２３０℃がより好ましく、２００～２３０℃が更に好ましい。１８０℃より低いと、エステル交換油中に含まれる遊離脂肪酸を除去できず酸価が高くなり、得られる食用油脂がえぐみのような異味を残す場合がある。２３０℃より高いと、油脂中の酸化安定物質の減少や、良好な風味成分まで除去してしまう場合がある。得られる食用油脂の酸価は、０．１以下が好ましく、０．０７以下がより好ましく、０．０５以下が更に好ましい。酸価が０．０７以下であれば、エステル交換油の脱臭が十分であるといえる。なお、実際の製造においては、酸価の下限値は０．０２が限界である。 The deodorization temperature by the steam distillation is preferably 180 to 230 ° C, more preferably 190 to 230 ° C, and further preferably 200 to 230 ° C. If it is lower than 180 ° C., the free fatty acid contained in the transesterified oil cannot be removed, the acid value becomes high, and the resulting edible fat may leave a bitter taste such as gummy. When it is higher than 230 ° C., there may be a case where a decrease in oxidation-stable substances in fats and oils and a good flavor component are removed. The acid value of the resulting edible oil / fat is preferably 0.1 or less, more preferably 0.07 or less, and even more preferably 0.05 or less. If the acid value is 0.07 or less, it can be said that the deodorization of the transesterified oil is sufficient. In actual production, the lower limit of the acid value is 0.02.

　また前記水蒸気蒸留による脱臭時間は、２０～５０分間が好ましく、３０～５０分間がより好ましく、４０～５０分間が更に好ましい。２０分間より短いと、エステル交換油中に含まれる遊離脂肪酸を除去できず、得られる食用油脂の酸価が高くなったり、えぐみのような異味を残す場合がある。５０分間より長いと、油脂中の酸化安定物質の減少や、良好な風味成分まで除去してしまう場合がある。 Further, the deodorization time by the steam distillation is preferably 20 to 50 minutes, more preferably 30 to 50 minutes, and further preferably 40 to 50 minutes. If it is shorter than 20 minutes, the free fatty acid contained in the transesterified oil cannot be removed, and the acid value of the resulting edible oil or fat may increase or leave an off-flavored taste. If it is longer than 50 minutes, the oxidation-stable substances in the fats and oils may be reduced, and even good flavor components may be removed.

　脱臭としては、薄膜蒸留法も使えるが、その場合の脱臭温度や脱臭時間は、お常法に準拠して適宜行えばよい。 As the deodorization, a thin film distillation method can also be used, but the deodorization temperature and deodorization time in that case may be appropriately performed in accordance with ordinary methods.

　以下に実施例を示し、本発明をより具体的に説明するが、本発明はこれらの実施例に何ら限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

　＜酸価＞
　社団法人日本油化学協会編「基準油脂分析法」（発行年：１９９６年）の基準油脂分析試験法「２．３．１－１９９６酸価」に準拠して酸価を測定した。 <Acid value>
The acid value was measured according to the standard oil analysis method “2.3.1-1996 Acid Value” of “Standard Oil Analysis Method” (issue year: 1996) edited by Japan Oil Chemical Association.

　＜エステル交換油の官能評価＞
　実施例・比較例で得られたエステル交換油を４０℃に温調した後、熟練したパネラー５人に食してもらい、異味・異臭の強さ、良好な風味の強さの観点で評価した結果を集約した。その際の評価基準は以下の通りであった。 <Sensory evaluation of transesterified oil>
After the temperature of the transesterified oil obtained in Examples / Comparative Examples was adjusted to 40 ° C., 5 experienced panelists ate and evaluated from the viewpoint of strength of off-flavor, off-flavor, and good flavor. Was consolidated. The evaluation criteria at that time were as follows.

　○：好ましい風味が感じられ、異味・異臭がなく、エステル交換油の風味として好ましい。 ○: A favorable flavor is felt, there is no off-flavor and off-flavor, and it is preferable as a flavor of the transesterified oil.

　△：好ましい風味が弱いもしくはやや感じられ、異味・異臭が無いもしくはやや感じられエステル交換油の風味としてあまり好ましくない。 Δ: The preferred flavor is weak or slightly felt, and there is no or slightly off-flavor or odor, which is not very favorable as the flavor of the transesterified oil.

　×：異味・異臭がはっきりと感じられ、エステル交換油の風味として問題がある。 X: A nasty taste / odour is clearly felt, and there is a problem as a flavor of the transesterified oil.

　＜廃濾過助剤の産生割合＞
　エステル交換油を製造した際に産生された廃濾過助剤の重量を、濾過助剤に処したエステル交換油の重量で除して１００を乗じ、％で表した値を廃濾過助剤の産生割合（％）とした。常法で白土処理を行った場合、廃白土には分離困難な油脂が付着しており、前記産生割合は、２．５～６％となる。従って、前記割合が２．０％未満であれば、エステル交換油の製造で産生される廃濾過助剤の量は少ないと言える。 <Production rate of waste filter aid>
Divide the weight of the waste filter aid produced when producing the transesterified oil by the weight of the transesterified oil treated with the filter aid and multiply by 100 to produce the waste filter aid value in% It was set as a percentage (%). When the white clay is treated by a conventional method, the oil and fat that are difficult to separate adhere to the waste white clay, and the production ratio is 2.5 to 6%. Therefore, if the said ratio is less than 2.0%, it can be said that the quantity of the waste filter aid produced by manufacture of transesterified oil is small.

　＜ＣＤＭ試験（酸化安定性）＞
　社団法人日本油化学協会編「基準油脂分析法」（発行年：１９９６年）の「２．５．１．２－１９９６ＣＤＭ試験」に準じてＣＤＭ値を測定した。前記ＣＤＭ値は、原料とする動植物油脂のヨウ素価とエステル交換油の製造条件に依存するが、ＣＤＭ値が大きくなるほど、酸化安定性が良好であるといえる。 <CDM test (oxidation stability)>
The CDM value was measured according to “2.5.1.2-1996 CDM test” of “Standard Oil Analysis Method” (issue year: 1996) edited by Japan Oil Chemists' Association. The CDM value depends on the iodine value of animal and plant oils and fats used as raw materials and the production conditions of the transesterified oil, but it can be said that the higher the CDM value, the better the oxidation stability.

　（実施例１）　エステル交換油１の作製
　パーム分別油（ヨウ素価：６０、融点１７℃）１００重量部をセパラブルフラスコに入れ、１５０ｒｐｍの撹拌速度で撹拌しながら、１００℃、真空状態（４００Ｐａ）の条件下で加熱真空脱水を行い、前記油脂中の水分を０．００８５重量％に調整した。その後、油脂１００重量部に対しナトリウムメチラートを０．１５重量部添加し、真空状態のまま２０分間撹拌した。撹拌を停止し、真空を開放した後、原料であるパーム分別油１００重量部に対し１００重量部の中性水（ｐＨ７．６（以下、全て同じｐＨ））を、油層の上からシャワーリングしながら注いで、該油脂と中性水とを接触させた。この時、乳化はほとんど生じていなかった。そのまま４０分間静置して油層、乳化層、水層を十分に分離させた後に、フラスコ下部から水層と乳化層とを排出し、９８重量部の油層を得た。該油層には、油層１ｇ当たりセッケンが１．６１×１０^－６ｍｏｌ（５００ｐｐｍ）含まれており、油脂の歩留りは９８．０％であった。 Example 1 Preparation of Transesterified Oil 1 100 parts by weight of palm fractionated oil (iodine number: 60, melting point: 17 ° C.) was put in a separable flask and stirred at a stirring speed of 150 rpm, at 100 ° C. in a vacuum state (400 Pa ) And vacuum dehydration under heating to adjust the water content in the oil to 0.0085% by weight. Thereafter, 0.15 parts by weight of sodium methylate was added to 100 parts by weight of the oil and fat, and the mixture was stirred for 20 minutes while maintaining the vacuum state. After the stirring was stopped and the vacuum was released, 100 parts by weight of neutral water (pH 7.6 (hereinafter all the same pH)) was showered from the top of the oil layer with respect to 100 parts by weight of the palm fractionated oil. Then, the oil and fat was brought into contact with neutral water. At this time, almost no emulsification occurred. After leaving still for 40 minutes to sufficiently separate the oil layer, the emulsified layer and the aqueous layer, the aqueous layer and the emulsified layer were discharged from the bottom of the flask to obtain 98 parts by weight of an oil layer. The oil layer contained 1.61 × 10 ⁻⁶ mol (500 ppm) soap per gram of the oil layer, and the yield of fats and oils was 98.0%.

　それから該油層９８重量部に対し、３００重量部の水に０．０１７重量部のクエン酸を溶解させたクエン酸水溶液を添加し、１５０ｒｐｍ、８０℃、常圧の条件下で６０分間撹拌し、その後静置した。この時、式１のＡ：第一油層１ｇ当たりのセッケン総ｍｏｌ数、ｎ：酸性物質の価数、Ｂ：第一油層１ｇ当たりに混合する酸性物質のｍｏｌ数、α：定数はそれぞれ、Ａ＝１．６１×１０^－６ｍｏｌ、ｎ＝３、Ｂ＝８．９１×１０^－７ｍｏｌ、α＝１．６６であった。即ち、クエン酸水溶液は、油層１ｇ当たりクエン酸の純分が８．９１×１０^－７ｍｏｌとなるように添加した。 Then, an aqueous citric acid solution in which 0.017 parts by weight of citric acid is dissolved in 300 parts by weight of water is added to 98 parts by weight of the oil layer, and the mixture is stirred for 60 minutes under conditions of 150 rpm, 80 ° C. and atmospheric pressure, Then it was left to stand. At this time, A in Formula 1 is the total number of moles of soap per gram of the first oil layer, n is the valence of the acidic substance, B is the number of moles of the acidic substance mixed per gram of the first oil layer, and α is the constant. = 1.61 × 10 ⁻⁶ mol, n = 3, B = 8.91 × 10 ⁻⁷ mol, α = 1.66. That is, the citric acid aqueous solution was added so that the pure content of citric acid was 8.91 × 10 ⁻⁷ mol per 1 g of the oil layer.

　静置開始より３５分後には９０重量％の水分が水層に沈降していた。この時、乳化層は生じていなかった。静置開始より４５分後にフラスコ下部から水層を排出した後、１５０ｒｐｍの撹拌速度で撹拌しながら、１００℃、真空状態（４００Ｐａ）の条件下で加熱真空脱水を行い油脂中の水分を０．０１重量％に調整し、ろ紙（Ａｄｖａｎｔｅｃ定性ろ紙Ｎｏ１）を通過させて析出したクエン酸を除去し、セッケン濃度０ｐｐｍのエステル交換油を９７.５重量部得た。 After 35 minutes from the start of standing, 90% by weight of water had settled in the aqueous layer. At this time, no emulsified layer was formed. After 45 minutes from the start of standing, the aqueous layer was discharged from the bottom of the flask, and then heated under vacuum dehydration under conditions of 100 ° C. and vacuum (400 Pa) while stirring at a stirring speed of 150 rpm, and the water content in the fats and oils was reduced to 0.00. The content was adjusted to 01% by weight and passed through a filter paper (Advantec qualitative filter paper No1) to remove the precipitated citric acid, thereby obtaining 97.5 parts by weight of a transesterified oil having a soap concentration of 0 ppm.

　クエン酸で処理した後のエステル交換油全量９７．５重量部を水蒸気蒸留装置に仕込み、２１０℃、真空度：２７０Ｐａ、水蒸気吹き込み量２重量部／ｈｒ、４５分間の条件で脱臭処理し、９６．５重量部のエステル交換油１を得た（歩留り：９６．５％）。得られたエステル交換油１の酸価は０．０３であり、風味の評価結果は良好であった。また、濾過助剤によるセッケン除去を行っていないため、廃濾過助剤／エステル交換油（重量比）は０％であり、エステル交換油１のＣＤＭ値は、９．５ｈｒであった。 A total of 97.5 parts by weight of the transesterified oil after the treatment with citric acid was charged into a steam distillation apparatus, and deodorized under conditions of 210 ° C., vacuum degree: 270 Pa, steam blowing rate of 2 parts by weight / hr, 45 minutes, 96 Obtained 5 parts by weight of transesterified oil 1 (yield: 96.5%). The acid value of the obtained transesterified oil 1 was 0.03, and the evaluation result of flavor was good. Moreover, since the soap removal was not performed by the filter aid, the waste filter aid / transesterified oil (weight ratio) was 0%, and the CDM value of the transesterified oil 1 was 9.5 hr.

　（実施例２）　エステル交換油２の作製
　パーム分別油（ヨウ素価：５２、融点３３℃）１００重量部をセパラブルフラスコに入れ、１５０ｒｐｍの撹拌速度で撹拌しながら、１００℃、真空状態（１０００Ｐａ）の条件下で脱水を行い、油脂中の水分を０．０２５重量％に調整した。その後、前記油脂１００重量部に対しナトリウムメチラートを０．２５重量部添加し、真空状態のまま３０分間撹拌した。真空を開放した後、１４０重量部の中性水を油層の上からシャワーリングしながら注いで、該油脂と中性水とを接触させた。この時、乳化はほとんど生じていなかった。そのまま４０分間静置して油層、乳化層、水層を十分に分離させた後に、フラスコ下部から水層と乳化層とを排出させ、９７．２重量部の油層を得た。該油層には、油層１ｇ当たりセッケンが１．４４×１０^－６ｍｏｌ（４５０ｐｐｍ）含まれており、油脂の歩留りは９７．２％であった。 Example 2 Production of Transesterified Oil 2 100 parts by weight of palm fractionated oil (iodine number: 52, melting point: 33 ° C.) was put into a separable flask and stirred at a stirring speed of 150 rpm, at 100 ° C. in a vacuum state (1000 Pa ) Was dehydrated and the water content in the fats and oils was adjusted to 0.025% by weight. Thereafter, 0.25 parts by weight of sodium methylate was added to 100 parts by weight of the fat and oil, and the mixture was stirred for 30 minutes in a vacuum state. After releasing the vacuum, 140 parts by weight of neutral water was poured from above the oil layer while showering to bring the oil and fat into contact with neutral water. At this time, almost no emulsification occurred. The mixture was allowed to stand for 40 minutes to sufficiently separate the oil layer, the emulsified layer and the aqueous layer, and then the aqueous layer and the emulsified layer were discharged from the bottom of the flask to obtain 97.2 parts by weight of an oil layer. The oil layer contained 1.44 × 10 ⁻⁶ mol (450 ppm) soap per gram of the oil layer, and the yield of fats and oils was 97.2%.

　それから該油層９７．２重量部に対し、２００重量部の水に０．００８５重量部のクエン酸を溶解させたクエン酸水溶液を添加し、１５０ｒｐｍ、８０℃、常圧の条件下で６０分間撹拌し、その後静置した。この時、式１のＡ：第一油層１ｇ当たりのセッケン総ｍｏｌ数、ｎ：酸性物質の価数、Ｂ：第一油層１ｇ当たりに混合する酸性物質のｍｏｌ数、α：定数はそれぞれ、Ａ＝１．４４×１０^－６ｍｏｌ、ｎ＝３、Ｂ＝４．４５×１０^－７ｍｏｌ、α＝０．９３であった。即ち、クエン酸水溶液は、クエン酸の純分が油層１ｇ当たり４．４５×１０^－７ｍｏｌとなるように添加した。 Then, an aqueous citric acid solution in which 0.0085 parts by weight of citric acid is dissolved in 200 parts by weight of water is added to 97.2 parts by weight of the oil layer, and the mixture is stirred for 60 minutes at 150 rpm, 80 ° C. and atmospheric pressure. And then left to stand. At this time, A in Formula 1 is the total number of moles of soap per gram of the first oil layer, n is the valence of the acidic substance, B is the number of moles of the acidic substance mixed per gram of the first oil layer, and α is the constant. = 1.44 × 10 ⁻⁶ mol, n = 3, B = 4.45 × 10 ⁻⁷ mol, α = 0.93. That is, the citric acid aqueous solution was added so that the pure content of citric acid was 4.45 × 10 ⁻⁷ mol per 1 g of the oil layer.

　静置開始より４０分後には９０重量％の水分が沈殿しており、静置開始より５０分後に沈降した水層を除去した。この時、乳化層は生じていなかった。その後、１００℃、真空状態（４００Ｐａ）の条件下で加熱真空脱水により油脂中の水分を０．０１重量％に調整し、ろ紙（Ａｄｖａｎｔｅｃ定性ろ紙Ｎｏ１）を通過させて析出したクエン酸を除去し、セッケン濃度３５ｐｐｍの油層を９６.２重量部得た。 After 40 minutes from the start of standing, 90% by weight of water was precipitated, and the precipitated aqueous layer was removed 50 minutes after the start of standing. At this time, no emulsified layer was formed. Then, the moisture in the fats and oils is adjusted to 0.01 wt% by heating vacuum dehydration under conditions of 100 ° C and vacuum (400 Pa), and the precipitated citric acid is removed by passing through a filter paper (Advantec qualitative filter paper No1). 96.2 parts by weight of an oil layer having a soap concentration of 35 ppm was obtained.

　クエン酸処理後の油層全量９６．２重量部をセパラブルフラスコに入れ、０．３８重量部（クエン酸処理後の油層全量１００重量部に対して０．４０重量部）の活性白土を添加した後、９０℃、１５０ｒｐｍ、真空状態（１３３０Ｐａ）の条件下で２０分間撹拌し、混合物全体の水分量を１重量％に調整した後、白土を分離してセッケン濃度０ｐｐｍのエステル交換油を９５．８重量部得た。 96.2 parts by weight of the oil layer after citric acid treatment was put in a separable flask, and 0.38 parts by weight (0.40 parts by weight with respect to 100 parts by weight of the oil layer after citric acid treatment) was added. Then, after stirring for 20 minutes under the conditions of 90 ° C., 150 rpm, and vacuum (1330 Pa), the water content of the whole mixture was adjusted to 1% by weight, and then the white clay was separated and 95% of transesterified oil having a soap concentration of 0 ppm was obtained. 8 parts by weight were obtained.

　上記で得られたエステル交換油を水蒸気蒸留装置に仕込み、２３０℃、真空度２７０Ｐａ、水蒸気吹き込み量２重量部／ｈｒ、４５分間の条件下で脱臭処理し、９４．７重量部のエステル交換油２を得た（歩留り：９４．７％）。得られたエステル交換油２の酸価は０．０４であり、風味の評価結果は良好であった。また、分離した白土には油脂が０．４重量部付着しており、廃濾過助剤／エステル交換油（重量比）は０．８２％であり、エステル交換油２のＣＤＭ値は、１１．５ｈｒであった。 The transesterified oil obtained above was charged into a steam distillation apparatus and deodorized under conditions of 230 ° C., vacuum degree 270 Pa, steam blown amount 2 parts by weight / hr, 45 minutes, and 94.7 parts by weight of transesterified oil 2 was obtained (yield: 94.7%). The acid value of the obtained transesterified oil 2 was 0.04, and the evaluation result of flavor was good. Moreover, 0.4 weight part of fats and oils adhered to the separated white clay, waste filter aid / transesterified oil (weight ratio) was 0.82%, and the CDM value of transesterified oil 2 was 11. It was 5 hours.

　（実施例３）　エステル交換油３の作製
　豚脂（融点３７℃）１００重量部をセパラブルフラスコに入れ、１５０ｒｐｍの撹拌速度で撹拌しながら、１００℃、真空状態（６７０Ｐａ）での脱水を行い、油脂中の水分を０．０１５重量％に調整した。その後、前記油脂１００重量部に対し０．１８重量部のナトリウムメチラートを添加し、真空状態のまま２５分間撹拌した。真空を開放した後、８０重量部の中性水を油層の上からシャワーリングしながら注いだ。この時、乳化はほとんど生じていなかった。 (Example 3) Production of transesterified oil 3 100 parts by weight of pork fat (melting point: 37 ° C) was put into a separable flask and dehydrated at 100 ° C in a vacuum state (670 Pa) while stirring at a stirring speed of 150 rpm. The water in the oil was adjusted to 0.015% by weight. Thereafter, 0.18 parts by weight of sodium methylate was added to 100 parts by weight of the oil and fat, and the mixture was stirred for 25 minutes in a vacuum state. After releasing the vacuum, 80 parts by weight of neutral water was poured from above the oil layer while showering. At this time, almost no emulsification occurred.

　そのまま４０分間静置して油層、乳化層、水層を十分に分離させた後に、フラスコ下部から水層と乳化層とを排出し、９７.８重量部の油層を得た。該油層には、油層１ｇ当たりセッケンが２．４１×１０^－６ｍｏｌ（７５０ｐｐｍ）含まれており、油脂の歩留りは９７．７％であった。 After leaving still for 40 minutes to sufficiently separate the oil layer, the emulsified layer and the aqueous layer, the aqueous layer and the emulsified layer were discharged from the bottom of the flask to obtain 97.8 parts by weight of an oil layer. The oil layer contained 2.41 × 10 ⁻⁶ mol (750 ppm) of soap per 1 g of the oil layer, and the yield of fats and oils was 97.7%.

　それから該油層９７.８重量部に対し、４００重量部の水に０．０５重量部のリンゴ酸を溶解させたリンゴ酸水溶液を添加し、１５０ｒｐｍ、９０℃、常圧で４０分間撹拌し、その後静置した。この時、式１のＡ：第一油層１ｇ当たりのセッケン総ｍｏｌ数、ｎ：酸性物質の価数、Ｂ：第一油層１ｇ当たりに混合する酸性物質のｍｏｌ数、α：定数はそれぞれ、Ａ＝２．４１×１０^－６ｍｏｌ、ｎ＝２、Ｂ＝３．８４×１０^－６ｍｏｌ、α＝３．１９であった。即ち、リンゴ酸水溶液は、リンゴ酸の純分が油層１ｇ当たり３．８４×１０^－６ｍｏｌとなるように添加した。 Then, an aqueous malic acid solution in which 0.05 parts by weight of malic acid was dissolved in 400 parts by weight of water was added to 97.8 parts by weight of the oil layer, and the mixture was stirred at 150 rpm, 90 ° C. and normal pressure for 40 minutes. Left to stand. At this time, A in Formula 1 is the total number of moles of soap per gram of the first oil layer, n is the valence of the acidic substance, B is the number of moles of the acidic substance mixed per gram of the first oil layer, and α is the constant. = 2.41 × 10 ⁻⁶ mol, n = 2, B = 3.84 × 10 ⁻⁶ mol, α = 3.19. That is, the malic acid aqueous solution was added so that the pure content of malic acid was 3.84 × 10 ⁻⁶ mol per 1 g of the oil layer.

　静置開始より３０分後には９０重量％の水分が沈降し、油層、水層が十分に分離したので、そのまま水層を除去した。この時、乳化層は生じていなかった。その後、１００℃、真空状態（４００Ｐａ）の条件下で加熱真空脱水により油脂中の水分を０．０１重量％に調整し、ろ紙（Ａｄｖａｎｔｅｃ定性ろ紙Ｎｏ１）を通過させ析出したリンゴ酸を除去し、セッケン濃度０ｐｐｍのエステル交換油を９７.３重量部得た。 After 30 minutes from the start of standing, 90% by weight of water settled and the oil layer and the water layer were sufficiently separated, so the water layer was removed as it was. At this time, no emulsified layer was formed. Then, the moisture content in the fats and oils is adjusted to 0.01 wt% by heating under vacuum dehydration under conditions of 100 ° C and vacuum (400 Pa), and the precipitated malic acid is removed by passing through a filter paper (Advantec qualitative filter paper No1). 97.3 parts by weight of a transesterified oil having a soap concentration of 0 ppm was obtained.

　リンゴ酸で処理した後の油層全量を水蒸気蒸留装置に仕込み、２２０℃、真空度：２７０Ｐａ、水蒸気吹き込み量：３重量部／ｈｒ、４０分間の脱臭条件で処理し、９６．５重量部のエステル交換油３を得た（歩留り：９６．５％）。得られたエステル交換油３の酸価は０．０３であり、風味の評価結果は良好であった。また、濾過助剤によるセッケン除去を行っていないため、廃濾過助剤／エステル交換油（重量比）は０％であった。 The whole oil layer after treatment with malic acid was charged into a steam distillation apparatus, treated at 220 ° C., vacuum degree: 270 Pa, steam blowing amount: 3 parts by weight / hr, deodorizing conditions for 40 minutes, and 96.5 parts by weight of ester Exchange oil 3 was obtained (yield: 96.5%). The acid value of the obtained transesterified oil 3 was 0.03, and the evaluation result of flavor was good. Moreover, since the soap removal was not performed by the filter aid, the waste filter aid / transesterified oil (weight ratio) was 0%.

　（比較例１）　エステル交換油４の作製
　パーム分別油（ヨウ素価４５、融点３２℃）１００重量部をセパラブルフラスコに入れ、１５０ｒｐｍの撹拌速度で撹拌しながら、１００℃、真空状態（９３０Ｐａ）での脱水を行い、油脂中の水分を０．０２２重量％に調整した。その後、０．３５重量部のナトリウムメチラートを添加し、真空状態のまま３０分間撹拌した。真空を開放した後、１８０重量部の中性水を油層の上からシャワーリングしながら注いだ。この時、乳化はほとんど生じていなかった。 Comparative Example 1 Production of Transesterified Oil 4 100 parts by weight of palm fractionated oil (iodine value 45, melting point 32 ° C.) was put into a separable flask and stirred at a stirring speed of 150 rpm, 100 ° C., vacuum state (930 Pa). The water in the fats and oils was adjusted to 0.022% by weight. Thereafter, 0.35 parts by weight of sodium methylate was added, and the mixture was stirred for 30 minutes in a vacuum state. After releasing the vacuum, 180 parts by weight of neutral water was poured from above the oil layer while showering. At this time, almost no emulsification occurred.

　そのまま４０分間静置させた後に、水を排出して油層、乳化層、水層を十分に分離させた後に、フラスコ下部から水層と乳化層とを排出し、９７.３重量部の油層を得た。該油層には、油層１ｇ当たり１．７６×１０^－６ｍｏｌ（５５０ｐｐｍ）のセッケンが含まれており、油脂の歩留りは９７．２％であった。 After leaving it to stand for 40 minutes, after draining water and sufficiently separating the oil layer, the emulsified layer and the water layer, the water layer and the emulsified layer are drained from the bottom of the flask, and 97.3 parts by weight of the oil layer is removed. Obtained. The oil layer contained 1.76 × 10 ⁻⁶ mol (550 ppm) soap per gram of the oil layer, and the yield of fats and oils was 97.2%.

　それから該油層９７.３重量部に対して、２００重量部の水に０．００７３重量部のクエン酸を溶解させた水溶液を添加し、１５０ｒｐｍ、７０℃、常圧で６０分間撹拌し、その後静置させた。この時、式１のＡ：第一油層１ｇ当たりのセッケン総ｍｏｌ部、ｎ：酸性物質の価数、Ｂ：第一油層１ｇ中に混合する酸性物質のｍｏｌ数、α：定数はそれぞれ、Ａ＝１．７６×１０^－６ｍｏｌ、ｎ＝３、Ｂ＝３．８１×１０^－７ｍｏｌ、α＝０．６５であった。即ち、クエン酸水溶液は、クエン酸の純分が油層１ｇ当たり３．８１×１０^－７ｍｏｌとなるように添加した。 Then, an aqueous solution in which 0.0073 parts by weight of citric acid is dissolved in 200 parts by weight of water is added to 97.3 parts by weight of the oil layer, and the mixture is stirred for 60 minutes at 150 rpm, 70 ° C. and normal pressure, and then statically. I put it. In this case, A in Formula 1: total mole part of soap per 1 g of the first oil layer, n: valence of the acidic substance, B: mol number of the acidic substance mixed in 1 g of the first oil layer, α: constant is A = 1.76 × 10 ⁻⁶ mol, n = 3, B = 3.81 × 10 ⁻⁷ mol, α = 0.65. That is, the citric acid aqueous solution was added so that the pure content of citric acid was 3.81 × 10 ⁻⁷ mol per 1 g of the oil layer.

　やや乳化が生じていたが、静置開始より９０分後には９０重量％の水分が沈殿したので、そのまま水層及び乳化層を除去した。その後、加熱真空脱水により油脂中の水分を０．０１重量％に調整し、ろ紙（Ａｄｖａｎｔｅｃ定性ろ紙Ｎｏ１）を通過させ、析出したクエン酸を除去し、セッケン濃度５０ｐｐｍのエステル交換油を９６.５重量部得た。 Although some emulsification occurred, 90% by weight of water precipitated after 90 minutes from the start of standing, so the aqueous layer and the emulsified layer were removed as they were. Then, the moisture in the fats and oils is adjusted to 0.01% by weight by heat vacuum dehydration, passed through a filter paper (Advantec qualitative filter paper No1), the precipitated citric acid is removed, and a transesterified oil having a soap concentration of 50 ppm is added to 96.5. Part by weight was obtained.

　クエン酸で処理した後のエステル交換油全量を水蒸気蒸留装置に仕込み、２３０℃、真空度２７０Ｐａ、水蒸気吹き込み量２重量部／ｈｒ、４５分間の条件で処理し、９５．８重量部のエステル交換油４を得た。得られたエステル交換油４の酸価は０．０８であり、風味評価では、えぐみの様な異味と異臭がはっきりと感じられた。また、濾過助剤によるセッケン除去を行っていないため、廃濾過助剤／エステル交換油の値（重量比）は０％であった。エステル交換油４のＣＤＭ値は、１１．３ｈｒであった。 The total amount of the transesterified oil after treatment with citric acid is charged into a steam distillation apparatus, treated at 230 ° C., a vacuum of 270 Pa, a steam blowing rate of 2 parts by weight / hr for 45 minutes, and 95.8 parts by weight of the ester exchange Oil 4 was obtained. The acid value of the obtained transesterified oil 4 was 0.08, and in taste evaluation, a taste and a strange odor like an sardine were clearly felt. Moreover, since the soap removal was not performed by the filter aid, the value (weight ratio) of waste filter aid / transesterified oil was 0%. The CDM value of the transesterified oil 4 was 11.3 hr.

　（比較例２）　エステル交換油５の作製
　パーム分別油（ヨウ素価６０、融点２２℃）１００重量部をセパラブルフラスコに入れ、撹拌（１５０ｒｐｍ）しながら、１００℃、真空状態（５３０Ｐａ）での脱水を行い、油脂中の水分を０．０１３重量％に調整した。その後、０．１５重量部のナトリウムメチラートを添加し、真空状態のまま２０分撹拌した。真空を開放した後、１２０重量部の中性水を油層の上からシャワーリングしながら注いだ。この時、乳化はほとんど生じていなかった。そのまま４０分間静置させた後に、水を排出させ、９８重量部の油層を得た。該油層には、油層１ｇ当たり１．１３×１０^－６ｍｏｌ（３５０ｐｐｍ）のセッケンが含まれており、油脂の歩留りは９８．０％であった。 (Comparative Example 2) Production of transesterified oil 5 100 parts by weight of palm fractionated oil (iodine value 60, melting point 22 ° C) was put into a separable flask and stirred (150 rpm) at 100 ° C in a vacuum state (530 Pa). Dehydration was performed, and the water content in the fat was adjusted to 0.013% by weight. Thereafter, 0.15 parts by weight of sodium methylate was added, and the mixture was stirred for 20 minutes in a vacuum state. After releasing the vacuum, 120 parts by weight of neutral water was poured from above the oil layer while showering. At this time, almost no emulsification occurred. After leaving still for 40 minutes, water was discharged to obtain 98 parts by weight of an oil layer. The oil layer contained 1.13 × 10 ⁻⁶ mol (350 ppm) soap per gram of the oil layer, and the yield of fats and oils was 98.0%.

　油層全量９８重量部をセパラブルフラスコに入れ、２．４５重量部（油層全量１００重量部に対して２．５０重量部）の活性白土を添加した後、９０℃、１５０ｒｐｍ、３０分間真空状態（１３３０Ｐａ）で放置し、混合物全体の水分量を１重量％に調整した後、白土を分離してセッケン濃度０ｐｐｍのエステル交換油を９３重量部得た。 Place 98 parts by weight of the total oil layer in a separable flask, add 2.45 parts by weight (2.50 parts by weight with respect to 100 parts by weight of the total oil layer), and then apply vacuum (90 ° C., 150 rpm, 30 minutes) 1330 Pa), the water content of the whole mixture was adjusted to 1% by weight, and the white clay was separated to obtain 93 parts by weight of transesterified oil having a soap concentration of 0 ppm.

　上記で得られたエステル交換油全量を水蒸気蒸留装置に仕込み、２３０℃、真空度２７０Ｐａ、水蒸気吹き込み量２重量部／ｈｒ、４５分間の条件で処理し、９１．７重量部のエステル交換油５を得た（歩留り：９１．７％）。得られたエステル交換油５の酸価は０．１５であり、風味評価では、えぐみと白土独特の異味と異臭がやや感じられた。また、分離した白土には油脂が５.０重量部付着しており、廃濾過助剤／エステル交換油（重量比）は５．４１％であった。また、エステル交換油５のＣＤＭ値は、８．５ｈｒであった。 The total amount of the transesterified oil obtained above was charged into a steam distillation apparatus and treated under the conditions of 230 ° C., vacuum degree of 270 Pa, steam blown amount of 2 parts by weight / hr, 45 minutes, and 91.7 parts by weight of transesterified oil 5 (Yield: 91.7%). The acid value of the obtained transesterified oil 5 was 0.15, and in taste evaluation, the taste and odor peculiar to egumi and white clay were slightly felt. The separated white clay had 5.0 parts by weight of fats and oils, and the waste filter aid / ester exchange oil (weight ratio) was 5.41%. The CDM value of the transesterified oil 5 was 8.5 hr.

　（比較例３）　エステル交換油６の作製
　大豆油１００重量部をセパラブルフラスコに入れ、撹拌（１５０ｒｐｍ）しながら、１００℃、真空状態（１０００Ｐａ）での脱水を行い、油脂中の水分を０．０１７重量％に調整した。その後、０．２０重量％のナトリウムメチラートを添加し、真空状態のまま２０分撹拌し、真空を開放し、９９．８重量部の油層（水層は無いが、ここでは油層という）を得た。該油層には、油層１ｇ当たり１．５４×１０^－４ｍｏｌ（４８０００ｐｐｍ）のセッケン分が含まれており、油脂の歩留りは９５．０％であった。 (Comparative Example 3) Production of transesterified oil 6 100 parts by weight of soybean oil was put into a separable flask, and dehydration was performed at 100 ° C in a vacuum state (1000 Pa) while stirring (150 rpm). Adjusted to 0.017 wt%. Thereafter, 0.20% by weight of sodium methylate was added, and the mixture was stirred for 20 minutes in a vacuum state, then the vacuum was released to obtain 99.8 parts by weight of an oil layer (there is no water layer, but here referred to as an oil layer). It was. The oil layer contained 1.54 × 10 ⁻⁴ mol (48000 ppm) of soap per gram of oil layer, and the yield of fats and oils was 95.0%.

　それから該油層９９．８重量部に対して、８０重量部の水に１．２２重量部のリンゴ酸を溶解させた水溶液を添加し、１５０ｒｐｍ、９０℃、常圧で４０分間撹拌し、その後静置させた。この時、式１のＡ：第一油層１ｇ当たりのセッケン総ｍｏｌ数、ｎ：酸性物質の価数、Ｂ：第一油層１ｇ当たりに混合する酸性物質のｍｏｌ数、α：定数はそれぞれ、Ａ＝１．５４×１０^－４ｍｏｌ、ｎ＝２、Ｂ＝９．１×１０^－５ｍｏｌ、α＝１．１８であった。即ち、リンゴ酸水溶液は、リンゴ酸の純分が油層１ｇ当たり９．１×１０^-５ｍｏｌとなるように添加した。 Then, an aqueous solution in which 1.22 parts by weight of malic acid was dissolved in 80 parts by weight of water was added to 99.8 parts by weight of the oil layer, and the mixture was stirred at 150 rpm, 90 ° C. and normal pressure for 40 minutes, and then statically. I put it. At this time, A in Formula 1 is the total number of moles of soap per gram of the first oil layer, n is the valence of the acidic substance, B is the number of moles of the acidic substance mixed per gram of the first oil layer, and α is the constant. = 1.54 × 10 ⁻⁴ mol, n = 2, B = 9.1 × 10 ⁻⁵ mol, α = 1.18. That is, the malic acid aqueous solution was added so that the pure content of malic acid was 9.1 × 10 ⁻⁵ mol per 1 g of the oil layer.

　静置開始より４０分後には９０重量％の水分が沈殿したので、そのまま水層を除去した。この時乳化は生じていなかった。その後、加熱真空脱水により油層中の水分を０．０１重量％に調整し、ろ紙（Ａｄｖａｎｔｅｃ定性ろ紙Ｎｏ１）を通過させ析出したリンゴ酸を除去し、セッケン濃度０ｐｐｍのエステル交換油を９８．８重量部得た。 After 40 minutes from the start of standing, 90% by weight of water precipitated, so the aqueous layer was removed as it was. At this time, no emulsification occurred. Thereafter, the moisture in the oil layer is adjusted to 0.01% by weight by heat vacuum dehydration, the precipitated malic acid is removed by passing through a filter paper (Advantec qualitative filter paper No. 1), and the transesterified oil having a soap concentration of 0 ppm is 98.8%. I got a part.

　リンゴ酸で処理した後のエステル交換油全量を水蒸気蒸留装置に仕込み、２５０℃、真空度２７０Ｐａ、水蒸気吹き込み量２重量部／ｈｒ、４５分間の条件で処理し、９８．０重量部のエステル交換油６を得た（歩留り：９８．０％）。 The total amount of transesterified oil after the treatment with malic acid was charged into a steam distillation apparatus and treated under the conditions of 250 ° C., vacuum degree of 270 Pa, steam blowing amount of 2 parts by weight / hr, 45 minutes, and 98.0 parts by weight of transesterification. Oil 6 was obtained (yield: 98.0%).

　得られたエステル交換油６の酸価は０．１８であり、風味評価では、えぐみのような異味と異臭がはっきりと感じられた。また、濾過助剤によるセッケン除去を行っていないため、廃濾過助剤／エステル交換油の値（重量比）は０％であり、エステル交換油６のＣＤＭ値は、２．９ｈｒであった。 The acid value of the obtained transesterified oil 6 was 0.18, and the taste evaluation clearly felt a taste and a strange odor like an igumi. Moreover, since the soap removal was not performed by the filter aid, the value (weight ratio) of waste filter aid / transesterified oil was 0%, and the CDM value of transesterified oil 6 was 2.9 hr.

　（比較例４）　エステル交換油７の作製
　パーム分別油（ヨウ素価：６０、融点１７℃）１００重量部をセパラブルフラスコに入れ、１５０ｒｐｍの撹拌速度で撹拌しながら、１００℃、真空状態（４００Ｐａ）の条件下で加熱真空脱水を行い、前記油脂中の水分を０．００９２重量％に調整した。その後、油脂１００重量部に対しナトリウムメチラートを０．１５重量部添加し、真空状態のまま２０分間撹拌した。撹拌を停止し、真空を開放した後、原料であるパーム分別油１００重量部に対し５重量部の中性水を、油層の上からシャワーリングしながら注いだ。その後、１５０ｒｐｍで５分間撹拌し、該油脂と水とを接触させた。この時、乳化が生じていた為、９０分間静置して油層、乳化層、水層を十分に分離させた後に、フラスコ下部から水層と乳化層とを排出し、９５重量部の油層を得た。該油層には、油層１ｇ当たりセッケンが４．６８×１０^－５ｍｏｌ（１５０００ｐｐｍ）含まれており、油脂の歩留りは９３．６％であった。 Comparative Example 4 Production of Transesterified Oil 7 100 parts by weight of palm fractionated oil (iodine number: 60, melting point: 17 ° C.) was placed in a separable flask and stirred at a stirring speed of 150 rpm, at 100 ° C. under vacuum (400 Pa ) And vacuum dehydration by heating, and the water content in the oil was adjusted to 0.0092% by weight. Thereafter, 0.15 parts by weight of sodium methylate was added to 100 parts by weight of the oil and fat, and the mixture was stirred for 20 minutes while maintaining the vacuum state. After the stirring was stopped and the vacuum was released, 5 parts by weight of neutral water was poured over 100 parts by weight of the palm fraction oil as a raw material while showering from above the oil layer. Then, it stirred at 150 rpm for 5 minutes and made this fat and water contact. At this time, since emulsification occurred, the mixture was allowed to stand for 90 minutes to sufficiently separate the oil layer, the emulsified layer and the aqueous layer, and then the aqueous layer and the emulsified layer were discharged from the bottom of the flask, and 95 parts by weight of the oil layer was removed. Obtained. The oil layer contained 4.68 × 10 ⁻⁵ mol (15000 ppm) soap per gram of the oil layer, and the yield of fats and oils was 93.6%.

　それから該油層９５重量部に対し、２００重量部の水に１．０５重量部のクエン酸を溶解させたクエン酸水溶液を添加し、１５０ｒｐｍ、８０℃、常圧の条件下で６０分間撹拌し、その後静置した。この時、式１のＡ：第一油層１ｇ当たりのセッケン総ｍｏｌ数、ｎ：酸性物質の価数、Ｂ：第一油層１ｇ当たりに混合する酸性物質のｍｏｌ数、α：定数はそれぞれ、Ａ＝４．８２×１０^－５ｍｏｌ、ｎ＝３、Ｂ＝３．６９×１０^－５ｍｏｌ、α＝２．３０であった。即ち、クエン酸水溶液は、油層１ｇ当たりクエン酸の純分が３．６９×１０^－５ｍｏｌとなるように添加した。 Then, an aqueous citric acid solution in which 1.05 parts by weight of citric acid is dissolved in 200 parts by weight of water is added to 95 parts by weight of the oil layer, and the mixture is stirred for 60 minutes at 150 rpm, 80 ° C. and atmospheric pressure. Then it was left to stand. At this time, A in Formula 1 is the total number of moles of soap per gram of the first oil layer, n is the valence of the acidic substance, B is the number of moles of the acidic substance mixed per gram of the first oil layer, and α is the constant. = 4.82 × 10 ⁻⁵ mol, n = 3, B = 3.69 × 10 ⁻⁵ mol, α = 2.30. That is, the citric acid aqueous solution was added so that the pure content of citric acid was 3.69 × 10 ⁻⁵ mol per 1 g of the oil layer.

　静置開始より４０分後には９０重量％の水分が水層に沈降していた。静置開始より４５分後にフラスコ下部から水層を排出した後、１５０ｒｐｍの撹拌速度で撹拌しながら、１００℃、真空状態（４００Ｐａ）の条件下で加熱真空脱水を行い油脂中の水分を０．０１重量％に調整し、ろ紙（Ａｄｖａｎｔｅｃ定性ろ紙Ｎｏ１）を通過させて析出したクエン酸を除去し、セッケン濃度０ｐｐｍのエステル交換油を９５．５重量部得た。 After 40 minutes from the start of standing, 90% by weight of water had settled in the aqueous layer. After 45 minutes from the start of standing, the aqueous layer was discharged from the bottom of the flask, and then heated under vacuum dehydration under conditions of 100 ° C. and vacuum (400 Pa) while stirring at a stirring speed of 150 rpm, and the water content in the fats and oils was reduced to 0.00. The content was adjusted to 01% by weight and passed through a filter paper (Advantec qualitative filter paper No1) to remove the precipitated citric acid, thereby obtaining 95.5 parts by weight of a transesterified oil having a soap concentration of 0 ppm.

　クエン酸で処理した後のエステル交換油全量９５．５重量部を水蒸気蒸留装置に仕込み、２５０℃、真空度：２７０Ｐａ、水蒸気吹き込み量２重量部／ｈｒ、４５分間の条件で脱臭処理し、９４．０重量部のエステル交換油７を得た（歩留り：９４．０％）。得られたエステル交換油１の酸価は０．１３であり、風味評価ではややえぐみが感じられた。また、濾過助剤によるセッケン除去を行っていないため、廃濾過助剤／エステル交換油（重量比）は０％であった。また、エステル交換油７のＣＤＭ値は、９．０ｈｒであった。 A total of 95.5 parts by weight of the transesterified oil after the treatment with citric acid was charged into a steam distillation apparatus, and deodorized at a temperature of 250 ° C., a degree of vacuum of 270 Pa, a steam blowing rate of 2 parts by weight / hr, and 45 minutes. 0.0 part by weight of transesterified oil 7 was obtained (yield: 94.0%). The acid value of the obtained transesterified oil 1 was 0.13, and a slight tingling was felt in flavor evaluation. Moreover, since the soap removal was not performed by the filter aid, the waste filter aid / transesterified oil (weight ratio) was 0%. The CDM value of the transesterified oil 7 was 9.0 hr.

Claims (7)

1. 　動植物油脂を、アルカリ性物質を用いたエステル交換反応に付する第一工程、
   　前記エステル交換反応後に得られた油脂と、前記動植物油脂１００重量部に対して１０～２００重量部の中性水とを接触させて、第一水層及び第一油層を含む液を得る第二工程、
   　第二工程で得られた液から第一水層を除去する第三工程、
   　酸性物質の使用量が下記式１を満足するように当該酸性物質の水溶液を、第三工程で得られた第一油層に混合して、第二水層と第二油層からなる液を得る第四工程、
   　第四工程で得られた液から第二水層を除去する第五工程、及び
   　第五工程で得られた第二油層を脱臭工程に付して、エステル交換油を得る第六工程
   を含む、食用油脂の製造方法。
   Ａ×α＝ｎ×Ｂ　　（式１）
   （Ａ：第一油層中のセッケン濃度（ｐｐｍ）／（３.０４４×１０^８）により算出される第一油層１ｇ当たりのセッケン総ｍｏｌ数、ｎ：前記酸性物質の価数、Ｂ：第一油層１ｇ当たりに混合する前記酸性物質のｍｏｌ数、α：０．７～５） The first step of subjecting animal and vegetable oils and fats to a transesterification reaction using an alkaline substance,
   A second oil is obtained by bringing the oil and fat obtained after the transesterification reaction into contact with 10 to 200 parts by weight of neutral water with respect to 100 parts by weight of the animal and vegetable oils and fats to obtain a liquid containing a first aqueous layer and a first oil layer. Process,
   A third step of removing the first aqueous layer from the liquid obtained in the second step;
   The aqueous solution of the acidic substance is mixed with the first oil layer obtained in the third step so that the amount of the acidic substance used satisfies the following formula 1 to obtain a liquid composed of the second aqueous layer and the second oil layer. Four steps,
   A fifth step of removing the second aqueous layer from the liquid obtained in the fourth step, and a sixth step of subjecting the second oil layer obtained in the fifth step to a deodorizing step to obtain a transesterified oil, A method for producing edible fats and oils.
   A × α = n × B (Formula 1)
   (A: soap concentration in the first oil layer (ppm) / (3.044 × 10 ⁸ ) calculated by total mol number of soap per 1 g of the first oil layer, n: valence of the acidic substance, B: first Mol number of the acidic substance to be mixed per 1 g of oil layer, α: 0.7 to 5)
2. 　酸性物質が有機酸であることを特徴とする請求項１に記載の食用油脂の製造方法。 The method for producing edible fat according to claim 1, wherein the acidic substance is an organic acid.
3. 　第四工程において、第一油層に酸性物質の水溶液を添加して混合物を得、当該混合物を、第一油層が融解している温度以上の温度に保ちながら撹拌し、次いで、５～８０分間静置して全水滴のうち９０重量％以上が沈降した後、第五工程を実施することを特徴とする請求項１又は２に記載の食用油脂の製造方法。 In the fourth step, an aqueous solution of an acidic substance is added to the first oil layer to obtain a mixture. The mixture is stirred while maintaining a temperature equal to or higher than the temperature at which the first oil layer is melted, and then allowed to stand for 5 to 80 minutes. The method for producing edible fats and oils according to claim 1 or 2, wherein the fifth step is performed after 90% by weight or more of all the water droplets have settled.
4. 　第五工程後の第二油層１００重量部に対して０．１～１．０重量部の濾過助剤を添加して濾過助剤による処理を行い、次いで、濾過助剤を第二油層から除去した後、第六工程を実施することを特徴とする請求項１～３の何れかに記載の食用油脂の製造方法。 Add 0.1 to 1.0 part by weight of filter aid to 100 parts by weight of second oil layer after the fifth step and perform treatment with filter aid, then remove filter aid from second oil layer The method for producing edible fats and oils according to any one of claims 1 to 3, wherein the sixth step is performed after the step.
5. 　第六工程における脱臭温度が１８０～２３０℃であることを特徴とする請求項１～４の何れかに記載の食用油脂の製造方法。 The method for producing edible fats and oils according to any one of claims 1 to 4, wherein the deodorizing temperature in the sixth step is 180 to 230 ° C.
6. 　第六工程における脱臭時間が２０～５０分であることを特徴とする請求項１～５の何れかに記載の食用油脂の製造方法。 6. The method for producing edible fats and oils according to any one of claims 1 to 5, wherein the deodorizing time in the sixth step is 20 to 50 minutes.
7. 　第二工程において、第一水層、乳化層及び第一油層を含む液を得、
   　第三工程において、第二工程で得られた液から第一水層及び乳化層を除去することを特徴とする請求項１～６の何れかに記載の食用油脂の製造方法。 In the second step, a liquid containing the first aqueous layer, the emulsified layer and the first oil layer is obtained,
   The method for producing edible fats and oils according to any one of claims 1 to 6, wherein in the third step, the first aqueous layer and the emulsified layer are removed from the liquid obtained in the second step.