KR20070084059A - Process for producing fats and oils - Google Patents

Abstract

A free fatty acid contained in raw fats and oils is esterified by adding an alcohol to the raw fats and oils and bringing the mixture into contact with an acid gel-type cation exchange resin. According to this production process, the esterification efficiency of the free fatty acid can be improved as compared with the conventional process using an acid-type solid cation exchange resin. When the raw fats and oils contain metal ions, the metal ions can be removed by the acid gel-type cation exchange resin. Further, according to the production process of the present invention, even when the raw fats and oils contain useful components such as carotene and tocotrienol, a deterioration and disappearance thereof can be prevented.

Description

Production method of fats and oils {PROCESS FOR PRODUCING FATS AND OILS}

This invention relates to the manufacturing method of fats and oils.

In the fats and oils of palm oil, free fatty acid exists by hydrolysis of triglyceride by a lipase. Conventionally, as a method of reducing the content of free fatty acids in fats and oils, methods such as neutralization with an alkaline water solution, removal with an adsorbent, and preesterification with an acid catalyst have been taken.

For example, the alkali deoxidation method (refer patent document 1) of the free fatty acid in fats and oils by the Zenith method, or the method of adsorption-removing free fatty acid using hydroxy apatite (refer patent document 2) are proposed. However, these methods have a problem that the loss of fat or oil itself is large, and the scale of industrial facilities and the like becomes large.

Moreover, the preesterification method of the free fatty acid in fats and oils using at least one of aliphatic and aromatic sulfonic acid as a catalyst is proposed (refer patent document 3). However, this method has a problem in that metal ions contained in fats and oils cannot be removed. In addition to this problem, in this method, when carotene and tocotrienol which are useful components are contained in fats and oils, there exists a problem that they decompose (dissipate) and deteriorate.

And in order to solve these problems, the method of using an acid type solid cation exchange resin is proposed (refer patent document 4). This method is a method of reducing the content of free fatty acids in a fat or oil by treating fat or oil with a lower monohydric alcohol in the presence of an acidic esterification catalyst, and an acidic solid cation exchange resin is used as the catalyst. According to this method, the content of free fatty acids can be reduced, metal ions can be removed, there is little loss of useful components such as carotene, and the scale of implementation is not larger than necessary. However, even in this method, the esterification efficiency of free fatty acid is not sufficient.

Patent Document 1: Japanese Patent Application Laid-Open No. 4-370195

Patent Document 2: Japanese Patent Application Laid-Open No. 63-97696

Patent Document 3: Japanese Patent Application Laid-Open No. 61-140544

Patent Document 4: Japanese Patent Application Laid-Open No. 61-168696

Then, an object of this invention is to provide the manufacturing method of the fats and oils which can further improve the esterification efficiency of the free fatty acid in fats and oils.

Means to solve the problem

In order to achieve the above object, the production method of the present invention is a production method of fat or oil having a step of esterifying the free fatty acid in the raw material holding with alcohol, wherein the esterification step adds alcohol to the raw material holding, It is a manufacturing method of the fats and oils which is a process of making this contact an acidic gel type cation exchange resin.

Effects of the Invention

Thus, the manufacturing method of the fats and oils of this invention uses acidic gel type cation exchange resin as a catalyst used for esterification of the free fatty acid in fats and oils. Thereby, the manufacturing method of this invention can improve the esterification efficiency of free fatty acid compared with the method using the conventional acid type solid cation exchange resin.

It is not clear why the production method of the present invention can improve the esterification efficiency of free fatty acids as compared with the conventional method using an acidic solid cation exchange resin, but the mechanism is inferred as follows. That is, in the conventional system using an acidic solid cation exchange resin, water generated in the esterification of free fatty acids adheres or adsorbs to the exchange resin, and as a result, it is considered that the catalytic performance of the exchange resin is lowered. In contrast, in the production method of the present invention, since an acidic gel-type cation exchange resin is used, water generated in the esterification of free fatty acids is taken into the acidic gel-type cation exchange resin as hydrated water, It is thought that the fall of catalyst capacity is prevented. In addition, this mechanism is only a guess and does not restrict this invention.

Moreover, according to the manufacturing method of the fats and oils of this invention, when a metal ion is contained in the said raw material holding | maintenance, for example, it can remove by the said acidic gel type cation exchange resin. And in the manufacturing method of this invention, when useful raw materials, such as carotene and a tocotrienol, are contained in the said raw material fat and oil, these deterioration and loss | disappearance can be prevented.

In the production method of the present invention, as the resin contained in the acidic gel-type cation exchange resin, the mother agent is preferably a styrene type, and as the crosslinking agent contained in the acidic gel-type cation exchange resin, divinylbenzene is used. desirable. The degree of crosslinking (content of crosslinking agent) of the acidic gel-type cation exchange resin is not particularly limited, but is preferably in the range of 3 to 10% by weight. That is, if it is 3 weight% or more, it is more preferable at the point of resin strength, and if it is 10 weight% or less, it becomes possible to further improve the esterification efficiency of free fatty acid. The degree of crosslinking of the acidic gel-type cation exchange resin is more preferably in the range of 3 to 9% by weight, still more preferably in the range of 4 to 8% by weight. Among them, when the esterification efficiency of free fatty acids is the highest, and when useful ingredients such as carotene and tocotrienol are contained in the raw material holding, the deterioration and loss of these substances are sufficiently suppressed, and the mechanical strength of the resin is increased. Particularly preferred is 4% by weight of sufficiently good crosslinking degree. In addition, the "gel type cation exchange resin" in the present invention generally means a cation exchange resin composed of a crosslinked polymer having a uniform particle inside.

In the manufacturing method of this invention, it is preferable that the said esterification process is a process which makes the said raw material holding which added the said alcohol pass through the column which filled the said acidic gel type cation exchange resin. In terms of further improving the esterification efficiency of the free fatty acid in the passage of the column holding the raw material, the column temperature is, for example, in the range of 40 to 70 ° C, preferably in the range of 50 to 65 ° C. More preferably, it is the range of 60-65 degreeC. The column residence time of the raw material holding is, for example, in the range of 60 to 480 minutes, preferably in the range of 100 to 360 minutes, and more preferably in the range of 100 to 240 minutes.

In the manufacturing method of this invention, although the addition amount of the said alcohol is suitably determined by fatty acid distribution of the said raw material holding | maintenance, etc., For example, it is the range of 5-30 weight part with respect to 100 weight part of said raw material holding | maintenance, Preferably the said It is the range of 10-28 weight part with respect to 100 weight part of raw material holdings, More preferably, it is the range of 15-26 weight part with respect to 100 weight part of said raw material holdings.

In the manufacturing method of this invention, the water content in the said alcohol is so preferable that it is low, For example, it is 1500 ppm or less, Preferably it is 1000 ppm or less, More preferably, it is 600 ppm or less. The lower limit of the amount of water in the alcohol is not particularly limited, but is, for example, a detection limit degree (0 ppm), and preferably about 100 ppm.

In the manufacturing method of this invention, it is preferable to use lower monohydric alcohol as said alcohol, for example. As said lower monohydric alcohol, a C1-C4 thing is preferable, For example, methanol, ethanol, propanol, butanol, etc. are mentioned. These may be used independently or may use two or more types together. Among these, it is preferable to use methanol.

In the manufacturing method of this invention, when metal raw material is contained in the said raw material holding | maintenance, it is preferable to remove in the said esterification process. Examples of the metal ions contained in the raw material holding include copper ions, iron ions, sodium ions, potassium ions, calcium ions, magnesium ions and the like.

In the production method of the present invention, it is also preferable to have an alcoholissis step of alcoholicating by adding alcohol to the fats and oils in which the free fatty acid is esterified by the esterification step.

The raw material fats and oils used for the production method of the present invention are not particularly limited, and examples thereof include beef tallow, palm oil, palm oil, palm kernel oil, rapeseed oil, soybean oil, sunflower seed oil, corn oil and the like. These may be used independently or may use two or more types together. Moreover, it is preferable to use what contains useful components, such as carotene, tocopherol, and tocotrienol, as said raw material holding | maintenance. Especially, it is especially preferable to use the palm oil containing many carotene and tocotrienol. In addition, in this invention, the fats and oils before providing to an esterification process are called "raw material holding," and the fats and oils after providing to the esterification process are called "refining fats and oils."

Next, the manufacturing method of this invention is demonstrated, for example.

As described above, in the production method of the present invention, the free fatty acid in the raw material holding is esterified by an esterification step in which alcohol is added to the raw material holding and brought into contact with the acidic gel-type cation exchange resin. In addition, before the application of the production method of the present invention, degum gum may be applied to the raw material holding. In the degum treatment, for example, hot water is added to the raw material holding to hydrate the phospholipid, or coagulation by inorganic acid or heat treatment is followed by sedimentation or centrifugation. It can carry out by removing.

The raw material holding is as described above.

The amount of the alcohol added and the amount of water in the alcohol are as described above. Moreover, as mentioned above, it is preferable to use methanol as said alcohol.

As said acidic gel type cation exchange resin, the sulfonate of a styrene-divinylbenzene copolymer, etc. are mentioned, for example. As said commercially available acidic gel type cation exchange resin, For example, Mitsubishi Chemical Corporation brand name diagram ion SK104, copper SK106, copper SK1B and copper SK110, the brand name of Dow Chemical Co., Ltd. make, product made by Dow Chemical Co., Ltd. The brand name Ambarite etc. are mentioned. The degree of crosslinking of the acidic gel-type cation exchange resin is as described above. In addition, as the pretreatment, it is preferable to wash the acidic gel type cation exchange resin with a cleaning alcohol. As the cleaning alcohol, it is preferable to use the same alcohol as that added to the above-described raw material holding. It is preferable to perform the said washing | cleaning until before and after washing | cleaning until the amount of water in the said washing alcohol does not change. As a result, the water in the acidic gel-type cation exchange resin is replaced with the cleaning alcohol, so that the esterification of the free fatty acid can be performed more efficiently. Specifically, for example, the acidic gel-type cation exchange resin may be washed with 2 to 5 times the capacity of the cleaning alcohol.

Next, by adding the alcohol to the raw material holding and contacting the acidic gel-type cation exchange resin, the free fatty acid in the raw material holding can be esterified. As mentioned above, in the manufacturing method of this invention, it is preferable that this esterification process is a process which makes the said raw material holding which added the said alcohol pass through the column which filled the said acidic gel type cation exchange resin. In this case, the column temperature and the column residence time of the raw material holding are as described above.

In the fats and oils obtained by the said esterification process (henceforth "refining and holding | maintenance"), the deoxidation rate is although it does not restrict | limit especially, For example, it is 70% or more, Preferably it is 80 % Or more, More preferably, it is 90% or more. In addition, the said deoxidation rate means the ratio (weight%) of esterified free fatty acid with respect to all the free fatty acids in raw material holding | maintenance, and can be measured by the method as described in the Example mentioned later, for example. .

In addition, when metal ion is contained in the said raw material holding | maintenance, it is preferable in the said refinement holding | maintenance that the metal ion concentration is below a detection limit. In addition, the said metal ion concentration can be measured by the method as described in the Example mentioned later, for example.

In addition, when carotene and tocotrienol are contained in the said raw material holding | maintenance, in the said refinement holding | maintenance, it is preferable that the carotene loss rate and the tocotrienol alteration rate are all 10 weight% or less, More preferably, All are 6 weight% or less, More preferably, they are all 4 weight% or less. In addition, the said carotene loss rate and a tocotrienol alteration rate can be measured by the method as described in the Example mentioned later, for example.

As mentioned above, the manufacturing method of this invention may also have the alcohol lysing process which adds alcohol and alcoholizes with respect to the said refined fats and oils. In addition, in the case of performing the above alcoholissis step, a dehydration step may be required prior to this. That is, the said refined fats and oils contain the water which arose from esterification of free fatty acid. This moisture content depends on the amount of free fatty acids and the esterification rate in the raw material holding. When the raw material holding is not deteriorated very much, the free fatty acid concentration in the raw material holding is, for example, 5% by weight or less, and the amount of water generated in the esterification is, for example, 5000 ppm or less. If it is this amount of water, sufficient reaction rate can be achieved by increasing an alkali catalyst in the alcoholic process mentioned later. However, when the water content is increased more than this, it is difficult to achieve a sufficient reaction rate. In this case, it is preferable to first perform a dehydration step of dehydrating the water in the above-mentioned tablet holding. As the method of dehydration, for example, thin film distillation under vacuum, evaporation at 150 ° C. under atmospheric pressure, and excess methanol are added and mixed with the refined fat and oil, and the mixture is left still. The upper methanol layer (this layer is water It contains a lot), etc. are mentioned.

When alcohols are added to the refined fats and oils, the triglyceride in the refined fats and oils is decomposed, and the oil is separated into an oil phase containing a fatty acid lower alkyl ester as a main component and a phase containing glycerin as a main component. . In the case of this separation, when useful tablets, such as carotene and tocotrienol, are contained in the said refined fats and oils, it transfers to the said oil phase. As alcohol for the said alcoholic reaction, lower alcohols, such as methanol, are preferable. The addition amount of the alcohol for alcoholicsis is, for example, in the range of 5 to 50 parts by weight, and preferably in the range of 10 to 40 parts by weight with respect to 100 parts by weight of the above-mentioned tablet holding. The temperature of the alcoholicsis is, for example, in the range of 50 to 100 ° C, preferably in the range of 60 to 80 ° C, and the reaction time of the alcoholicsis is, for example, in the range of 15 to 90 minutes, Preferably it is 40 to 70 minutes. Moreover, it is preferable to perform the said alcoholicsis in presence of a catalyst. As the catalyst, an alkali catalyst is preferable, and for example, sodium hydroxide, potassium hydroxide, sodium methylate and the like can be used. The addition amount of the said catalyst is the range of 0.1-0.5 weight part with respect to 100 weight part of said refined fats and oils, for example, Preferably it is the range of 0.2-0.3 weight part. When the alcoholicsis is carried out with respect to the refining oil and fat, the ester yield is improved and an alkyl ester excellent in oxidative stability can be obtained. Moreover, when recovering useful components, such as carotene and tocotrienol, most of them do not deteriorate and disappear, and a recovery rate improves.

Although the use of the fats and oils manufactured by the manufacturing method of this invention is not restrict | limited at all, For example, it can carry out transesterification reaction again and the obtained ester can be used as a biodiesel fuel by mixing with light oil, for example. Can be. Moreover, surfactant is synthesize | combined by performing ethyleneolside addition, hydrogenation, higher alcoholation, or sulfonation, etc., and can use it as a detergent, for example.

Next, the Example of this invention is described with a comparative example. However, this invention is not restrict | limited by the following Example and a comparative example. In addition, the measuring method of each characteristic in the following Example and a comparative example is as showing below.

(1) deoxidation rate

After removing water or methanol contained in the sample (fats and oils) with an evaporator, each sample is pretreated by passing through a filter paper coated with anhydrous sodium sulfate. Accurately weigh 5-10 g (Wtl) of each sample after the pretreatment and place it in a 200 ml Erlenmeyer flask. About 50 ml of neutralizing alcohol is added there, and a sample is dissolved. Several drops of phenolphthalein are added as indicators and titrated with 1/10 prescribed KOH solution. From this titration water (ml), an acid value is computed by following formula (1).

Acid value (mgKOH / g) = A / B. (One)

A: Factor of titrant number X titrant of 1/10 prescribed KOH

B: sample weight (Wt1)

This measurement is performed about refined holding and raw material holding, and the deoxidation rate is calculated by the following formula (2).

Deoxidation rate (%) = {(C1-C2) / C1} × 100. (2)

C1: Acid value of raw material fats (mgKOH / g)

C2: Acid value of refined oil or fat (mgKOH / g)

(2) carotene loss rate

The sample is pretreated in the same manner as the deoxidation rate measuring method described above. 0.1 g (Wt2) of each sample after the said pretreatment is measured correctly, this is put into a flask, the volume is made up to 50 ml with cyclohexane, and it is set as a sample solution. This sample solution is put into the measuring cell of a spectrophotometer, and the absorbance Ab of wavelength 448nm is measured. From this measured value, carotene concentration is computed by following formula (3).

Carotene concentration (ppm) = D × 200 / E... (3)

D: absorbance (Ab)

E: sample weight (Wt2)

This measurement is handled with respect to refined fats and oils and raw materials, and the carotene loss rate is calculated by the following formula (4).

Carotene loss rate (%) = {(F1-F2) / F1} x 100... (4)

F1: Carotene concentration of raw material oil (ppm)

F2: Carotene Concentration (ppm)

(3) tocotrienol alteration rate

The sample is pretreated in the same manner as the deoxidation rate measuring method described above. 0.5g of each sample after the said pretreatment is measured correctly, this is put into a flask, the volume is made up to 50 ml with methanol, and it is set as a sample solution. On the other hand, for each of the standard tocopherols (α, β, γ, δ), a standard solution is prepared so as to have a predetermined concentration. The standard solution is analyzed by HPLC under the following conditions, and a calibration curve for each tocopherol is prepared in advance. In addition, each tocotrienol sensitivity ((alpha), (beta), (gamma), (delta)) was made to be the same as each tocopherol sensitivity. Next, the said sample solution is analyzed similarly, each concentration is computed from the said analytical curve, it sums, and the total tocotrienol concentration (ppm) is obtained.

HPLC column conditions

Column: DuPont, trade name Zorbax ODS

       4.6φ × 250mm, 5㎛ particle size

Eluent: Methanol / water = 98/2 (v / v)

Flow rate: 0.65ml / min

Detector: UV284 nm

Sample volume: 20 μL

This measurement is performed on refined fats and oils and raw materials, and the tocotrienol alteration rate is calculated by the following formula (5).

Tocotrienol alteration rate (%) = [(T1-T2) / T1] × 100. (5)

T1: Total tocotrienol concentration of raw material oil (ppm)

T2: Total tocotrienol concentration (ppm)

(4) metal ion concentration

The metal ion concentration of the sample was measured by the atomic absorption method after the incineration treatment.

Example  One

20 parts by weight of 99.5% by volume methanol was added to 100 parts by weight of raw material fats and oils (palm oil: crude palm oil from Malaysia; acid values 6 to 10 and iodine 50), and heated to 60 ° C in a heater. Purified oil was passed through a column (8 cm in diameter and 30 cm in length) packed with an acidic gel-type cation exchange resin (manufactured by Mitsubishi Chemical Corporation, trade name Diaion SK104, 4% by weight of crosslinking degree (divinylbenzene); 1.5L). Got. The column temperature was 60 ° C., and the column residence time of the raw material holding (2 kg) was 120 minutes. In addition, the acidic gel type cation exchange resin was washed with 4 times (volume) of methanol in advance.

Example  2

Purified oil and fat was obtained in the same manner as in Example 1 except that the added amount of methanol was 10 parts by weight based on 100 parts by weight of the raw material holding.

Example  3

Purified oil was obtained similarly to Example 1 except having made the addition amount of methanol into 30 weight part with respect to 100 weight part of raw material fats and oils.

Example  4

As the acidic gel-type cation exchange resin, tablet oil was obtained in the same manner as in Example 1 except that a crosslinking degree of 6% by weight (from Mitsubishi Chemical Corporation, trade name Diaion SK106) was used.

Example  5

As the acidic gel-type cation exchange resin, tablet oil was obtained in the same manner as in Example 1 except that 8% by weight of a crosslinking agent (trade name Diaion SK1B manufactured by Mitsubishi Chemical Corporation) was used.

Example  6

As the acidic gel-type cation exchange resin, tablet oil was obtained in the same manner as in Example 1 except that 10% by weight of a crosslinking agent (trade name Diaion SK110, manufactured by Mitsubishi Chemical Corporation) was used.

(Comparative Example 1)

20 parts by weight of 99.5% by volume methanol was added to 100 parts by weight of raw material fats and oils (palm oil; same as Example 1), and sulfuric acid (1.0% by weight to fats and oils) was used as a catalyst and the mixture was stirred at 60 ° C for 120 minutes. The free fatty acid in fats and oils was esterified and the refined fats and oils were obtained.

(Comparative Example 2)

Purified oil was obtained in the same manner as in Example 1, except that an acidic solid cation exchange resin (Mitsubishi Chemical Co., Ltd., trade name Diaion PK208, crosslinking degree 4% by weight) was used in place of the acidic gel-type cation exchange resin.

(Comparative Example 3)

Purified oil was obtained in the same manner as in Example 1 except that an acidic solid cation exchange resin (trade name Diaion PK212, manufactured by Mitsubishi Chemical Corporation, trade name 6% by weight) was used in place of the acidic gel-type cation exchange resin.

(Comparative Example 4)

Purified oil and fat were obtained in the same manner as in Example 1, except that an acidic solid cation exchange resin (trade name Diaion PK216, manufactured by Mitsubishi Chemical Corporation, cross-linking degree 8% by weight) was used instead of the acidic gel-type cation exchange resin.

The deoxidation rate, carotene loss rate, and tocotrienol loss rate of the refined fats and oils obtained in Examples 1 to 6 and Comparative Examples 1 to 4 were measured by the method described above. The measurement results are shown in Tables 1 and 2 below. And following Table 1 is the said measurement result about Examples 1-6, and following Table 2 is the said measurement result about Comparative Examples 1-4. In addition, regarding Example 1, metal ion concentration was also measured. The measurement results are shown in Table 3 below. The moisture content in the following Tables 1 and 2 indicates the amount of water in the cation exchange resin before treatment by methanol washing.

TABLE 1

Example One 2 3 4 5 6 Methanol addition amount (part by weight) 20 10 30 20 20 20 Cation exchange resin crosslinking degree (% by weight) Water content (%) Gel 4 57--67 Gel 4 57--67 Gel 4 57--67 Ezekiel 6 47--57 Gel 9 43-50 Gel 10 35-45 Deoxidation rate (%) Carotene loss rate (%) Tocotrienol alteration rate (%) 95 3 5 70 3 5 96 3 5 80 2 4 70 2 3 20 1 2

TABLE 2

Comparative example One 2 3 4 Methanol addition amount (part by weight) 20 20 20 20 Cation exchange resin crosslinking degree (% by weight) Water content (%) (Sulfuric Acid)-- Solid 4- Solid 6- Solid 8- Deoxidation rate (%) Carotene loss rate (%) Tocotrienol alteration rate (%) 40 90 50 10 1 2 10 1 2 10 1 2

TABLE 3

Metal ion Raw material maintenance (ppm) Refining Copper Ion Iron Ion Sodium Ion Potassium Ion Calcium Ion Magnesium Ion 0.1 3.0 3.3 2.3 2.5 2.5 Below detection limit Below detection limit Below detection limit Below detection limit Below detection limit Below detection limit

From Table 1 and Table 2, it was found that the refined fats and oils obtained in Examples 1 to 6 were lower in carotene loss rate and tocotrienol alteration rate as compared with the refined fats and oils obtained in Comparative Example 1. Moreover, it turned out that the refined fats and oils obtained by Examples 1-6 are high in deoxidation rate compared with the refined fats and oils obtained by Comparative Examples 2-4.

As can be seen from Table 3, the metal ion concentration was below the detection limit by the production method of the present invention.

According to the production method of the present invention, the free fatty acid in the raw material holding can be efficiently esterified, and when the raw material holding contains metal ions, it can be removed as well. When useful components, such as an enol, are contained, the deterioration and a loss can be prevented. Therefore, when the production method of the present invention is applied to, for example, palm oil or the like, fats and oils excellent in oxidative stability and rich in useful components such as carotene and tocotrienol can be obtained.

The fats and oils obtained by the manufacturing method of this invention can perform transesterification reaction further, and the obtained ester can be used as a biodiesel fuel by mixing with light oil, for example. Moreover, surfactant is synthesize | combined by providing the said ester further with ethyleneol side addition, hydrogen addition, higher alcoholation, sulfonation, etc., and can be used as a detergent, for example.

Claims (11)

A process for producing a fat or oil having a step of esterifying free fatty acid in a raw material holding with alcohol, wherein the esterification step is a step of adding alcohol to the raw material holding and contacting it with an acidic gel-type cation exchange resin. Manufacturing method of fats and oils made with. The method of claim 1, The crosslinking degree of the said acidic gel type cation exchange resin is 3 to 10 weight% of the manufacturing method of the fats and oils characterized by the above-mentioned. The method of claim 1, The said esterification process is a process of passing the said raw material holding which added the said alcohol through the column which filled the said acidic gel type cation exchange resin, The manufacturing method of the fats and oils characterized by the above-mentioned. The method of claim 3, wherein In the passage of the column of the raw material holding, the column temperature is in the range of 40 to 70 ℃ characterized in that the manufacturing method of fats and oils. The method of claim 3, wherein In the passage of the column of the raw material holding, the column residence time of the raw material holding is in the range of 100 to 480 minutes. The method of claim 1, The addition amount of the said alcohol is 5-30 weight part with respect to 100 weight part of said raw material fats and oils, The manufacturing method of the fats and oils characterized by the above-mentioned. The method of claim 1, The amount of moisture in the alcohol is 1500 ppm or less. The method of claim 1, The said alcohol contains methanol, The manufacturing method of the fats and oils characterized by the above-mentioned. The method of claim 1, The said esterification process WHEREIN: Furthermore, the metal ion contained in the said fats and oils is removed, The manufacturing method of the fats and oils characterized by the above-mentioned. The method of claim 1, Furthermore, the manufacturing method of the fats and oils which has an alcoholissis process which adds alcohol to the fats and oils which esterified free fatty acid by the said esterification process is carried out. The method of claim 1, At least one selected from the group consisting of tallow, palm oil, palm oil, palm kernel oil, rapeseed oil, soybean oil, sunflower seed oil and corn oil is used as the raw material fat and oil.