JPH06306386A - Oil and fat refining method - Google Patents

Abstract

(57) [Summary] [Purpose] To provide an efficient method for refining fats and oils, which simplifies the refining process. [Structure] In the step of refining fats and oils, a step of converting phospholipids in fats and oils into water-soluble substances containing a phosphate group and removing them as water-soluble substances is provided. It utilizes the action of enzymes to convert it into a water-soluble substance. As the enzyme, an enzyme having phospholipase C activity is preferably used. [Effect] It becomes possible to refine fats and oils by omitting the deoxidation step of generating industrial waste containing alkaline wastewater and a large amount of oil. Moreover, since the loss of neutral fats and oils that accompany them is lost, the yield can be improved.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for refining fats and oils. More specifically, the present invention relates to a method for purifying fats and oils, which comprises a step of decomposing phospholipids in the fats and oils into water-soluble substances by the action of an enzyme when the fats and oils are purified.

[0002]

[Prior art and its problems] In the manufacturing process of fats and oils,
The oil pressed from the oil / fat raw material or the oil obtained by extracting and removing the solvent (hereinafter, these are collectively referred to as “crude crude oil”) includes
Impurities such as polar lipids mainly consisting of phospholipids, fatty acids, pigments, and odorous components are contained, and these must be removed in the purification process. Therefore, warm water is added to crude crude oil to hydrate polar lipids such as phospholipids, and a degumming step of removing gums with a centrifuge and free fatty acids of degummed oil after degumming are neutralized with caustic soda. Therefore, a deoxidation step of removing this with a centrifuge is required. Furthermore, the purification of oils and fats is completed through a decoloring step of adding activated clay, activated carbon and the like to adsorb and remove a pigment such as chlorophyll, and a deodorizing step of removing odorous components by distillation under vacuum. Further, in the case of producing salad oil, a dewaxing step of crystallizing and removing components such as solid fat and wax that tend to solidify may be added.

However, the above-mentioned deoxidation step is a step in which free fatty acids are neutralized with caustic soda and then removed by a centrifuge. Although residual phospholipids are also removed, a large amount of entrained oil is contained. So-called "soda oil syrup" occurs. Some of them are used as raw materials for producing fatty acids, but most of them are treated as industrial waste. Furthermore, in the subsequent neutralization step, in order to remove the soap content dissolved in the oil after the treatment, a step of washing with warm water is generally incorporated, and a large amount of waste water containing the oil generated here is also treated. It costs.

As described above, the process of refining fats and oils requires complicated and long steps, and it is expected to develop an efficient refining method such as simplification for each step, especially the deoxidizing step. Regarding the omission of the deoxidation step due to the waste-generating alkali, a so-called steam refining method of removing free fatty acids by vacuum steam distillation in the deodorizing step (for example, Japanese Patent Publication No. 53-38281), degumming A method has been proposed in which oil is treated with an enzyme having phospholipase A activity (JP-A-2-153997). However, the former method is limited to the purification of fats and oils having a low phospholipid content derived from raw materials such as palm oil, soybeans, when applied to fats and oils made from common oil seeds such as rapeseed, phospholipids A large amount of oil and fat remains. This is coloring by heating,
Generation of unpleasant odor is significant and it cannot be used as a product. In the latter method, when the oil to be treated and the oxygen aqueous solution are reacted, if the amount of the enzyme solution is reduced, the reaction takes a long time, and in order to process the reaction in a short time, the required amount of the enzyme increases.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an efficient method for refining fats and oils, which simplifies the refining process.

[0006]

Means for Solving the Problems The inventors of the present invention have focused on the fact that the deoxidation step is a post-treatment step of the degumming step in order to improve the efficiency of the method for refining fats and oils, particularly to omit the deoxidation step. Because of the omission of the acid step, further research is promoted to improve the degumming step, which is the preceding step, and the degumming step is to remove the gum substance as a gum substance and then decompose it into a water-soluble substance and remove it. It was found that the oil and fat can be efficiently refined by changing the above method to the present invention, and the present invention was completed.

The present invention changes phospholipids, which are impurities in fats and oils, into water-soluble substances in the process of refining fats and oils,
A purification step is provided to remove as a water-soluble substance. It is by the action of an enzyme that the gum impurities to be removed are changed into water-soluble ones, that is, decomposed. In the purification step of the present invention, in which the gum substance is changed to a water-soluble substance and removed as a water-soluble substance, most preferably, an enzyme having phospholipase C activity is added at the stage of degumming crude oil. Then, it is treated enzymatically.

In the degumming step in the conventional refining method, in order to remove impurities such as polar lipids mainly containing phospholipids, fatty acids, pigments and odorous components, phospholipids are added to crude crude oil by adding warm water. Is a step of removing the gum as a gum with a centrifuge, the method for purifying fats and oils of the present invention is
In the step of removing phospholipids, the fats and oils are treated with an enzyme that cleaves the ester bond between glycerin and phosphate in the phospholipids, such as an enzyme having phospholipase C activity. Is used to obtain a process oil by washing with water or an acidic aqueous solution.

The enzyme used in the present invention is selected from those capable of enzymatically treating phospholipids to decompose them into water-soluble ones.
In order to convert phospholipid into a water-soluble degradation product, an enzyme that cleaves the ester bond between glycerin and phosphoric acid in the phospholipid is selected. Phospholipase C is known as an enzyme that cleaves the ester bond between glycerin and phosphate in phospholipids. Phospholipase C is genus Bacillus or Clostridium (Cl
ostridium), Pseudomonas (Pseud)
It is known that it exists in organs such as the brain, spleen, and liver of animals, and plants such as carrots and spinach.

In the present invention, these enzymes are dispersed and dissolved in water or an appropriate buffer solution and added to a fat or oil containing gum impurities mainly containing phospholipids to be removed and reacted. As long as the fat or oil contains impurities of phospholipid, the fat or oil at any stage of refining may be used, but it is preferable to add it to the crude crude oil and react it. At that time, in order to enhance the contact efficiency between the oil phase and the water phase, an appropriate emulsifying machine such as a homomixer, a colloid mill or a pipeline mixer can be used.

When added to crude crude oil and reacted, the amount of phospholipase C used is usually 10 to 10,000 units, preferably 100 to 10,000 units per kg of crude crude oil.
2,000 units are suitable. The enzyme treatment is usually performed at 30 to 90 ° C., preferably 40 to 70 ° C. for about 5 minutes to 10 hours, depending on the optimum temperature of the enzyme. The amount of water added by dissolving the enzyme is 5 to 1,000 parts by weight based on 100 parts by weight of crude crude oil, and more preferably 10 to 200 parts by weight based on 100 parts by weight of crude crude oil. For the phospholipase C activity, 1 unit was defined as the amount of enzyme that produced 1 micromol of phosphocholine per minute in the following reaction system. Substrate Phosphatidylcholine (soybean origin) Calcium concentration 6 mM Reaction time 5 minutes Temperature 40 ° C pH Optimal pH of each enzyme

After such enzyme treatment, the enzyme solution is separated by an appropriate means such as a centrifuge to obtain a treated oil. Most of the phosphorus-containing compounds such as phosphocholine and phosphoethanolamine produced by the enzymatic decomposition of gum in this step move to the aqueous phase and are removed from the oil phase. After the enzymatic treatment, if necessary, the treated oil is treated with (warm) water or acetic acid, phosphoric acid,
A step of washing with a (warm) solution of an organic or inorganic acid such as citric acid or a salt thereof can be added.
As the washing conditions, it is preferable to carry out at a temperature of 55 to 80 ° C. and a water / oil ratio of 0.5 to 2.0. Again, it is preferable to use the same emulsifying machine as used in the enzyme treatment. Good.

After the above operation, the amount of phospholipid component remaining in the oil is extremely small. Further, in the decoloring step by a conventional method usually carried out after the treatment, it is adsorbed and removed by an adsorbent such as activated clay or activated carbon, and the quality of the product is lowered to such an extent that it is not adversely affected. On the other hand, the free fatty acid remaining in the process oil is completely removed by vacuum steam distillation in the deodorizing process, so that the deoxidizing process is not required.

[0014]

EXAMPLES The present invention will be described with reference to examples. The present invention is not limited to the examples. Example 1 Crude soybean crude oil (phospholipid content 2,200 ppm) 0.5 k
g was placed in a 2 liter beaker, and 480 ml of a 5 mM calcium chloride solution was added to the beaker for sterilization. An enzyme solution having phospholipase C activity (Boehringer Mannheim Yamanouchi Phospholipase C GI Grade 10
20 units (0 units / ml) were sterile filtered and added.
T. K. Homo mixer (MarkI manufactured by Tokushu Kika Co., Ltd.)
The cylinder part (I2.5 type) was set so as to be positioned at the center of the aqueous phase portion in the container, and the mixture was stirred at 10,000 rpm. The reaction temperature was 40 ° C. and the reaction time was 4 hours. After completion of the reaction, centrifugation (1,500 g, 5 minutes) was performed to collect the oil phase. The enzyme-treated oil was dehydrated under vacuum, and 1.0% of activated clay (NV manufactured by Mizusawa Chemical Industry Co., Ltd.) was added thereto, followed by treatment at 105 ° C. and 30 mmHg for 20 minutes for decolorization. The decolorized oil was further deodorized for 60 minutes while blowing steam at 105 ° C. and 8 mmHg to obtain a deodorized oil as a final product.

Example 2 An equal amount of water was added to the enzyme-treated oil obtained by treating in the same manner as in Example 1, and the mixture was stirred under the same conditions as in the above reaction for 10 minutes. The washing oil was recovered by centrifugation and dehydrated under vacuum. Thereafter, decolorization and deodorization were performed in the same manner as in Example 1 to obtain a deodorized oil as a final product.

Comparative Example 1 A decolorized oil was obtained by the same procedure as in Example 1 except that water was added instead of the enzyme solution in Example 1, and the same operation as in Example 1 was performed to obtain a deodorized oil. . Properties of the decolorized oil and the deodorized oil obtained as described above are collectively shown in Table 1 (property of process oil).

[0017]

[Table 1] Hue and phospholipid content: Measured by the standard oil and fat analysis test method (hue is measured by the Lovibond method for decolorized oil at 25.4 mm cell and deodorized oil at 133,4 mm cell respectively) Cold flavor and heating odor are sensory tests by panelists

As is apparent from Table 1, the product oil obtained by using the method of the present invention was satisfactory in hue, flavor and the like, and its quality was extremely good. On the other hand, the product oil obtained from the process oil not subjected to the phospholipase C enzyme treatment according to the present invention has insufficient removal of phospholipids, so that coloration and the formation of precipitates are observed upon heating, and its flavor is also remarkable. It was inferior.

[0019]

In the prior art, the deoxidation step has been a major problem because it produces alkaline wastewater and industrial waste containing a large amount of oil. However, in the method of the present invention, the soda generated in this deoxidation step is generated. No generation of industrial waste such as oil pans and alkaline cleaning wastewater. In addition, the loss of neutral fats and oils that accompany them is lost and the yield is improved.

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[Procedure amendment]

[Submission date] May 19, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0006

[Correction method] Change

[Correction content]

[0006]

Means for Solving the Problems The inventors of the present invention have focused on the fact that the deoxidation step is a post-treatment step of the degumming step in order to improve the efficiency of the method for refining fats and oils, particularly to omit the deoxidation step. Because of the omission of the acid step, further research is promoted to improve the degumming step, which is the preceding step, and the degumming step is to remove the gum substance as a gum substance and then decompose it into a water-soluble substance and remove it. The present invention was completed by finding that efficient purification of oils and fats can be carried out by adding or changing to the step .

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction content]

According to the present invention, in the step of purifying fats and oils, a purification step is performed in which phospholipids, which are impurities in the fats and oils, are converted into water-soluble substances and removed as water-soluble substances. It is by the action of an enzyme that the gum impurities to be removed are changed into water-soluble ones, that is, decomposed. In the purification step of the present invention, in which the gum substance is changed to a water-soluble substance and removed as a water-soluble substance, most preferably, an enzyme having phospholipase C activity is added at the stage of degumming crude oil. Then, it is treated enzymatically.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction content]

In the present invention, these enzymes are dispersed and dissolved in water or an appropriate buffer solution and added to a fat or oil containing gum impurities mainly composed of phospholipids to be removed and reacted. Oils and fats at any stage of refining may be used as long as they contain phospholipid impurities, but crude oil or degummed oil
It is preferably added to oil and reacted. At that time, in order to enhance the contact efficiency between the oil phase and the water phase, an appropriate emulsifying machine such as a homomixer, a colloid mill or a pipeline mixer can be used.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction content]

When added to crude crude oil or degummed oil and reacted, the amount of phospholipase C used is usually
10 to 10,000 per 1 kg of crude crude oil or degummed oil
0 units, more preferably 100 to 2,000 units are suitable. The enzyme treatment is usually performed at 30 to 90 ° C., preferably 40 to 70 ° C. for about 5 minutes to 10 hours, depending on the optimum temperature of the enzyme. The amount of water added by dissolving the enzyme is 5 to 1,000 parts by weight, more preferably crude crude oil , relative to 100 parts by weight of crude crude oil or degummed oil.
Alternatively, it is 10 to 200 parts by weight with respect to 100 parts by weight of degummed oil . For the phospholipase C activity, 1 unit was defined as the amount of enzyme that produced 1 micromol of phosphocholine per minute in the following reaction system. Substrate Phosphatidylcholine (soybean origin) Calcium concentration 6 mM Reaction time 5 minutes Temperature 40 ° C pH Optimal pH of each enzyme

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0014

[Correction method] Change

[Correction content]

[0014]

EXAMPLES The present invention will be described with reference to examples. The present invention is not limited to the examples. Example 1 Unrefined soybean oil (degummed oil, phospholipid content of 2,200 pp
m) 0.5 kg was placed in a 2 liter beaker, and 480 ml of a 5 mM calcium chloride solution was added thereto to sterilize it. An enzyme solution having phospholipase C activity (Boehringer Mannheim Yamanouchi Phospholipase C G
20 units of I grade 100 units / ml) were sterile filtered and added. T. K. The cylinder part of a homomixer (MarkII2.5 type manufactured by Tokushu Kika Co., Ltd.) was set so that it was located at the center of the water phase part in the container.
It was stirred at 00 rpm. The reaction temperature was 40 ° C. and the reaction time was 4 hours. After the reaction was completed, centrifugation (1,500 g,
5 minutes) was carried out and the oil phase was recovered. The enzyme-treated oil was dehydrated under vacuum, and activated clay (N, manufactured by Mizusawa Chemical Industry Co., Ltd.)
V) is added at 1.0%, and 20 at 105 ° C. and 30 mmHg.
It was treated for a minute and decolorized. Decolorized oil is 105 ℃, 8
Deodorization treatment was performed for 60 minutes while blowing water vapor at mmHg to obtain a deodorized oil as a final product. ─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] May 24, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

[Correction method] Change

[Correction content]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0003

[Correction method] Change

[Correction content]

However, the above-mentioned deoxidation step is a step in which free fatty acids are neutralized with caustic soda and then removed by a centrifuge. Although residual phospholipids are also removed, a large amount of entrained oil is contained. So-called "soda oil syrup" occurs. Some of them are used as raw materials for producing fatty acids, but most of them are treated as industrial waste. Furthermore, in the subsequent neutralization step, in order to remove the soap content dissolved in the oil after the treatment, a step of washing with warm water is generally incorporated, and a large amount of waste water containing the oil generated here is also treated. It costs. that's all
In the deoxidation and neutralization process of oil, the decrease in oil and fat yield is a big loss.
It has been lost.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0004

[Correction method] Change

[Correction content]

[0004] Thus, the process of refining oils and fats is in need of complicated long step, for each process, especially deacidification process, the development of efficient purification methods such simplification is expected. Regarding the omission of the deoxidation step due to the alkali that generates waste and lowers the oil yield , a so-called steam purification method of removing free fatty acids by vacuum steam distillation in the deodorization step ( For example, Japanese Examined Patent Publication Sho 53-3828
No. 1), a method of treating degummed oil with an enzyme having phospholipase A activity (JP-A-2-153997). However, the former method is Ru limited to purification of low fat of phospholipid content derived from the raw material of palm oil.
When applied to oils and fats made from general oil seeds such as soybeans and rapeseed, the oils and fats have a large amount of phospholipids remaining.
This is not suitable as a product because it is markedly colored by heating and produces an offensive odor. In the latter method, when the oil to be treated and the oxygen aqueous solution are reacted, if the amount of the enzyme solution is reduced, the reaction takes a long time, and in order to process the reaction in a short time, the required amount of the enzyme increases. Separate phospholipids using phosphatase
Solution removal method (EP-70269) has been proposed.
This is mainly due to the low phospholipid oils and fats (degumming) such as palm oil.
With less than 100 ppm)
It Soybean oil or rapeseed oil (1,000-5000p after degumming
pm) is difficult to apply. In fact, we received this patent
Soybean oil was effective against phospholipase C.
There is a report that there is no end (EP-513709).

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction content]

[0017]

[Table 1] Hue and phospholipid content: Measured by the standard oil and fat analysis test method (hue is measured by Lovibond method for decolorized oil at 25.4 mm cell and deodorized oil at 133.4 mm cell respectively) Cold flavor and heating odor are sensory tests by panelists As apparent from Table 1, obtained using the method of the present invention
The product oil is satisfactory in hue, flavor, etc.,
Its quality was extremely good. On the other hand, according to the present invention,
Phospholipase C obtained from process oil without enzyme treatment
The product oil has insufficient phospholipid removal,
Coloring and the formation of precipitates are observed, and the flavor is significantly inferior
It was a thing.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction content]

Comparative Example 2 Unrefined soybean oil (degummed oil, phospholipid content of 2,200 pp
m) Sterilize 0.5kg into a 1 liter beaker
And then sterilized by filtration and having phospholipase C activity
Liquid (phosphorase made by Boehringer Mannheim Yamanouchi)
C, GII grade, 200 units / ml, 5 mM salt
2 minutes using a stirring blade added with 10 ml of calcium chloride)
After stirring vigorously (1,000 rpm) for a while,
The stirring was continued at 00 rpm). Reaction at 40 ° C for 4 hours
The treated oil obtained was decolorized in the same manner as in Example 1. Decolorizing oil
Has a phospholipid content of 1,300ppm and a hue of 12Y +
It was 1.0 R and was insufficiently purified. ─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] June 2, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction content]

When added to crude crude oil or degummed oil and reacted, the amount of phospholipase C used is usually 10 to 10,000 per 1 kg of crude crude oil or degummed oil.
Units, and more preferably 100 to 5, 000 units is appropriate. The enzyme treatment is usually performed at 30 to 90 ° C., preferably 40 to 70 ° C. for about 5 minutes to 10 hours, depending on the optimum temperature of the enzyme. The amount of water added after dissolving the enzyme is 30 parts by weight or more based on 100 parts by weight of crude crude oil or degummed oil , and more preferably 50 to 200 parts by weight based on 100 parts by weight of crude crude oil or degummed oil. Is. Reasons such as an increase in the amount of wastewater in the oil and fat purification process
For this reason, the method of using a large amount of water is not usually adopted. However
According to the present invention, a method of acting an enzyme in an emulsified state is adopted.
Around the time, we saw many benefits based on high water usage.
I did. In other words, the increase in the boundary area between water and oil
Water, which promotes the enzymatic reaction and the transfer of decomposition products to water.
Since the separation of oil and oil becomes clear, it is easy to recover the enzyme solution.
The concentration of the extracted decomposition products is lower than that in the case of using a small amount of water.
Since reaction inhibition and pH change are less likely to occur, separation after reaction
It is said that the number of times that the enzyme solution can be reused as it is will increase.
It is possible to mention. Use of water for EP-70269
There is no description of the amount, and 100 parts by weight of oil is used in the examples.
Only the example using 2 parts by weight is shown. For the phospholipase C activity, 1 unit was defined as the amount of enzyme that produced 1 micromol of phosphocholine per minute in the following reaction system. Substrate Phosphatidylcholine (soybean origin) Calcium concentration 6 mM Reaction time 5 minutes Temperature 40 ° C pH Optimal pH of each enzyme

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0014

[Correction method] Change

[Correction content]

[0014]

EXAMPLES The present invention will be described with reference to examples. The present invention is not limited to the examples. Example 1 Crude soybean crude oil (phospholipid content 2,200 ppm) 0.5 k
g was placed in a 2 liter beaker, and 480 ml of a 5 mM calcium chloride solution was added to the beaker for sterilization. An enzyme solution having phospholipase C activity (Boehringer Mannheim Yamanouchi Phospholipase C GI Grade 10
20 units (0 units / ml) were sterile filtered and added.
T. K. Homo mixer (MarkI manufactured by Tokushu Kika Co., Ltd.)
The cylinder part (I2.5 type) was set so as to be located at the center of the aqueous phase portion in the container, and the mixture was stirred at 10,000 rpm. The reaction temperature was 40 ° C. and the reaction time was 4 hours. After completion of the reaction, centrifugation (1,500 g, 5 minutes) was performed to collect the oil phase. The enzyme-treated oil was dehydrated under vacuum, and 1.0% of activated clay (NV manufactured by Mizusawa Chemical Industry Co., Ltd.) was added thereto, followed by treatment at 105 ° C. and 30 mmHg for 20 minutes for decolorization. The decolorized oil was further deodorized for 60 minutes while blowing steam at 250 ° C. and 8 mmHg to obtain a deodorized oil as a final product.

Claims (4)

[Claims] 1. A method for purifying fats and oils, which comprises a step of converting phospholipids in the fats and oils into water-soluble substances containing a phosphate group and removing them as water-soluble substances in the step of refining fats and oils. 2. The method for purifying oil and fat according to claim 1, wherein the phospholipid in the oil and fat is changed to a water-soluble substance containing a phosphate group by the action of an enzyme. 3. The method for purifying fats and oils according to claim 2, wherein the enzyme is an enzyme that cleaves an ester bond between glycerin and phosphoric acid in a phospholipid. 4. The method for purifying fats and oils according to claim 2, wherein the enzyme is an enzyme having phospholipase C activity.