JP6013746B2 - Production method of refined edible fats and oils - Google Patents

Description

  The present invention relates to a method for producing a refined edible fat / oil for easily and efficiently obtaining a highly purified edible fat / oil from an edible fat / oil raw material.

  The consumption of edible fats and oils is increasing due to changes in eating habits in recent years. Along with this, there are concerns about the effects of harmful substances and functional unknown components contained in edible fats and oils, by-products generated during the production of fats and oils on health.

In conventional edible fat and oil production, after extracting fats and oils using hexane, which is a petroleum product, a process of removing hexane by heating, a process of removing high-temperature steam to remove off-flavors and volatile substances, a high temperature after washing with water In each step, a process for removing moisture and the like accompanied by a heating operation were performed. This heating operation causes oxidation and alteration of fatty acids, and recently, the influence of hexane on the health of trans fatty acids and extraction solvents caused by heating has become a problem.
For this reason, the technique of reducing a heating process as much as possible, or manufacturing fats and oils with high purity is developed.

For example, Patent Document 1 describes a method of extracting by microwave irradiation in a solvent such as water or a polyhydric alcohol as a method for obtaining a plant extract having excellent extract stability and little coloration.
Patent Document 2 describes a method in which an oil / fat component in a vegetable oil / fat raw material is released in an aqueous solution at 30 to 55.5 ° C. and separated by a centrifuge.
Furthermore, Patent Document 3 discloses a method in which a free fatty acid is dissolved together with fats and oils in a polar organic solvent, an aqueous solution of a predetermined salt is added, and the water-containing organic solvent phase containing fatty acids is separated from the fats and oils.

  Patent Document 4 describes a method of removing water using molecular sieves after converting free fatty acids in fats and oils to fatty acid esters in the production of biodiesel oil.

JP 2004-89786 A Special table 2009-519357 JP-A-8-81692 JP 2008-1856 A

However, the extraction method by microwave irradiation as described in Patent Document 1 requires a cost for adding new equipment, distilling off the solvent, and processing. The method described in Patent Document 2 also has a similar problem.
On the other hand, in the method described in Patent Document 3, in the step of dissolving fats and oils with an organic solvent and mixing with a predetermined aqueous solution, emulsification is likely to occur, and separation of the fats and oils becomes difficult.
Moreover, all of the methods described in the above-mentioned Patent Documents 1 to 3 are the oil extraction method by the extraction method and not the oil extraction method by the compression method.

  In addition, in the method described in Patent Document 4, the molecular sieve used when removing moisture in the fats and oils adsorbs moisture, and such inorganic substances containing a lot of moisture must be treated as waste. The problem of not becoming will arise.

  Therefore, in the production of refined edible fats and oils, conventional production facilities can be used as much as possible, and the number of production processes can be reduced easily, and there is little waste, and highly refined edible fats and oils can be efficiently obtained. A method that can be used is desired.

  The present invention has been made in order to solve the above technical problem, and can improve the oil extraction efficiency by the pressing method, and can easily and efficiently produce highly purified edible fats and oils without requiring a heat treatment step. It aims at providing the manufacturing method of the refined edible oil and fat which can be obtained specifically.

The method for producing a refined edible fat according to the present invention includes a pretreatment step in which a solid fat raw material is immersed in a hydrophilic organic solvent as it is, or a pulverized slurry in a hydrophilic organic solvent; An oil extraction process for compressing and oiling the obtained oil and fat raw material, a liquid separation process for separating the oil extracted from the oil and the hydrophilic organic solvent, and a liquid organic oil for the separated oil extraction fat after the liquid separation process Extraction washing with water, and further with an extraction washing process with water, and after the extraction washing process, a dehydration process for dehydrating the washed oil and fat by adding cellulose or passing through a cellulose column . It is characterized by that.
Thus, by using a hydrophilic organic solvent, the oil and fat raw material is immersed or slurried and then squeezed, so that the purification process can be simplified or omitted, and the pigment components and various impurities in the squeezing can be easily and efficiently performed. Things can be effectively reduced.

Moreover, the manufacturing method of the refined edible oil and fat which concerns on this invention is equipped with the extraction washing | cleaning process which carries out extraction washing | cleaning by the hydrophilic organic solvent after the said liquid separation process, and also carrying out extraction washing | cleaning with water .
Such extraction washing is a suitable method for further purification of the oiled fat.

Furthermore, the manufacturing method of the refined edible oil and fat which concerns on this invention is equipped with the spin-drying | dehydration process which spin-dry | dehydrates the said oil-squeezed oil and fat after washing | cleaning by adding a cellulose or letting it pass through a cellulose column .
Thus, by dehydrating using cellulose, dehydration in fats and oils can be performed effectively, and impurities can be further reduced.

Here, in the pretreatment step, it is preferable to wash the fat and oil raw material by exchanging the hydrophilic organic solvent at least once.
By such a cleaning treatment in the pretreatment step, it is possible to enhance the effect of removing contaminants in the fat and oil raw material.

As the hydrophilic organic solvent used in the above production method, any one of methanol, ethanol, acetonitrile, and acetone, or a mixed solvent of two or more thereof is suitably used from the viewpoint of liquid separation with fats and oils.
The hydrophilic organic solvent is preferably a hydrous solvent. In the liquid separation step, water or carbonate such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, ammonium dihydrogen phosphate, phosphoric acid triphosphate. It is desirable to add one or more salt solutions of phosphates such as sodium and tripotassium phosphate.

According to the manufacturing method which concerns on this invention, the oil extraction efficiency by a pressing method can be improved, and the pigment | dye, off-flavor, and the amount of foreign substances contained in oil extraction fats can be reduced more simply and efficiently.
Further, according to the present invention, an edible oil / fat having a high degree of purification can be obtained without requiring a heat treatment step. Therefore, it becomes possible to provide an edible oil / fat with less lipid oxidation and less trans-fatty acid.
In addition, because it is possible to recycle the oil used in the mill and the manufacturing process, there is an advantage that less waste is generated, resources are effectively used, and the production cost of edible fats and oils is reduced. ing.

It shows the high performance liquid chromatography (HPLC) detection pattern in Experiment 3 of an Example, (a) is canola oil (standard product), (b) is what squeezed rapeseed seed grain directly, (c) is Pulverized rapeseed seeds directly squeezed, (d) rapeseed seeds squeezed after ethanol soaking, (e) rapeseed seeds soaked in ethanol, sonicated and squeezed, (F) is a pulverized rapeseed seed that has been oil soaked and then oiled. The HPLC detection pattern in Experiment 4 of an Example is shown, (a) is canola oil (preparation), (b) is oil extraction rapeseed oil before extraction washing, (c) is rapeseed oil after extraction washing, (D) is refined rapeseed oil after dehydration.

Hereinafter, the present invention will be described in detail.
The method for producing purified edible fats and oils according to the present invention includes at least a pretreatment step, a pressing step and a liquid separation step with a hydrophilic organic solvent of a solid fat raw material, and other steps as appropriate. May be combined. Hereinafter, each process will be described.

  Here, the edible fats and oils referred to in the present invention are those in which the fat and oil raw materials are solid and vegetable fats and oils are common, but are not particularly limited. Examples thereof include rapeseed oil, soybean oil, safflower oil, corn oil, sesame oil, cottonseed oil, olive oil, coconut oil, palm oil, sunflower oil, rice oil, grape seed oil, and the like.

In the pretreatment step, the fat and oil raw material is immersed or slurried with a hydrophilic organic solvent.
Specifically, 10% by mass or more, preferably 50 to 200% by mass of a hydrophilic organic solvent is added to the fat and oil raw material and immersed as it is. Alternatively, a pre-ground oil / fat raw material is mixed with a hydrophilic organic solvent to form a slurry. The fat and oil raw material immersed in the hydrophilic organic solvent may be pulverized using a mixer or a stone mortar to form a slurry.
In this way, by squeezing the oil raw material after immersing or slurrying it with a hydrophilic organic solvent, the tissue of the seed raw material becomes soft and easy to squeeze, and impurities in the oil extraction are extracted with the hydrophilic organic solvent, Since it can be reduced, simple and efficient purification becomes possible.

In the pretreatment step, whether to immerse the solid fat raw material as it is or pulverize it into a slurry can be appropriately selected according to the size, hardness, etc. of the fat raw material, and can be easily squeezed. Any can be used.
Usually, pulverization tends to increase oil extraction efficiency, although the number of operation steps increases.

Even if the oil and fat raw material that has undergone the pretreatment process is directly compressed as it is, the effect of reducing the amount of contaminants during oil extraction and improving the oil extraction efficiency is obtained, but in the pretreatment process, at least a hydrophilic organic solvent is used. It is preferable to change and wash once.
In the case of a slurry, specifically, the slurry is allowed to stand, the separated hydrophilic organic solvent layer is removed, a new hydrophilic organic solvent is added, and the mixture is stirred and mixed again. Repeatedly, the pulverized pieces of fats and oils are washed. The solvent exchange of the slurry may be performed by either a batch method or a column method.
By performing slurry washing multiple times in this manner, impurities contained in the oil and fat raw material are effectively extracted into the hydrophilic organic solvent, and the removal effect is enhanced. Therefore, further purification treatment is performed after the subsequent liquid separation step. Even if it is not, high quality edible fats and oils can be obtained.

As the hydrophilic organic solvent , methanol , ethanol, acetonitrile, and acetone can be used. Although methanol is effective from the viewpoint of oil extraction efficiency, ethanol is preferred in the production of edible fats and oils. In addition, when acetone is hard to isolate | separate from fats and oils, it is used with water, or it hydrolyzes after oil extraction and makes it separate from fats and oils.
These solvents can dissolve not only pigments and off-flavors but also contaminants such as free fatty acids and saponins, and even organic solvents will not dissolve evenly with oils and fats, and will be separated if left standing. To do.
Therefore, if a hydrophilic organic solvent is used, not only the amount of pigment and off-flavor components can be reduced, but also the amount of free fatty acids can be effectively reduced.
Moreover, in order to give the selectivity of the extract to a solvent, the said hydrophilic organic solvent can also be used as a hydrous solvent (high concentration aqueous solution), However, In this case, oil extraction efficiency is a little inferior. It should be noted that the specific gravity of the hydrophilic organic solvent is smaller than the specific gravity of the oil and fat.

In the next oil extraction step, the oil or fat raw material that has been immersed or slurried is compressed and extracted.
Specifically, the said fats and oils raw material is thrown into the pressing part of an oil press. At that time, the excess solvent may be separated and recovered in advance before pressing.
By filling the pressing part with the solvent, the gap can be reduced as much as possible, and the filling can be performed precisely, and the pressure for pressing acts uniformly without waste, compared to the case of directly pressing without using the solvent. Efficiency can be improved by 50% or more. Moreover, since the hydrophilic organic solvent has osmose | permeated in fats and oils raw material, it becomes easy to elute the oil in the structure | tissue of this fats and oils raw material, and can reduce the oil which remains in the squeezed sachet.
Furthermore, in this invention, it is not necessary to perform the heating process at the time of pressing, and the quality change by the heat of oil does not arise. In addition, depending on the required quality of the oil, in order to further increase the oil extraction efficiency, the oil may be heated as long as the temperature is equal to or lower than the boiling point of the solvent used.

Next, in the liquid separation step, the oil and fat obtained in the oil extraction step and the hydrophilic organic solvent are separated.
When the oiled oil is put in a tank and allowed to stand, it is separated into a hydrophilic organic solvent layer and an oily oil layer. To facilitate the separation, water or carbonates such as sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, ammonium dihydrogen phosphate, triphosphate Any one or a plurality of salt solutions of phosphates such as sodium and tripotassium phosphate may be added, or may be separated using centrifugal force. However, it is necessary to pay attention so that the specific gravity of the hydrophilic organic solvent layer is smaller than the specific gravity of the oil and fat.
By doing in this way, oil extraction fats and the hydrophilic organic solvent layer containing impurities, such as a harmful substance, can be liquid-separated, and edible fats and oils can be refine | purified.

In the case of further purifying the oil and fat separated from the hydrophilic organic solvent after the liquid separation step, it is preferable to perform an extraction washing step of extracting and washing with a hydrophilic organic solvent and further extracting and washing with water.
By such stepwise extraction and washing, impurities in the oil and fat can be more effectively extracted into a hydrophilic organic solvent and water and purified without emulsifying the oil and fat.

  This extraction washing process can be performed by extraction separation in a batch system. In this case, the extraction and washing with a hydrophilic organic solvent or water can be purified more effectively by repeated multiple times.

Moreover, the said extraction washing | cleaning process can also be performed by the droplet extraction which sends in the droplet of a hydrophilic organic solvent from the bottom part of the container into which the said oil-squeezed oil and fat was put, and performs continuous extraction with this droplet.
Specifically, a liquid drop feeding device such as a pipe having a fine hole or a glass filter is provided at the bottom of a tank filled with oil and fat, and the hydrophilic organic solvent is fed as liquid droplets. Since the hydrophilic organic solvent sent in has a specific gravity smaller than the oil-squeezed fats and oils, it raises in the oil-squeezed fats and oils in a tank. Meanwhile, impurities such as harmful substances contained in the oil and fat are extracted into droplets of the hydrophilic organic solvent. The continuously rising droplets are separated by overflowing from the upper part of the tank. The treatment time for such droplet extraction is appropriately determined by monitoring the concentration of harmful substances contained in the separated solvent.
Then, using water (or an aqueous solution containing a salt) having a specific gravity greater than that of the oil and fat, water is dropped onto the oil surface from above the oil and fat. Extraction of solvents and water-soluble impurities can be performed.

As the hydrophilic organic solvent used in the extraction washing step, the same organic solvent as used in the pretreatment step can be used. Moreover, in the extraction washing | cleaning by water, in order to improve extraction efficiency, it may replace with water and may use the salt aqueous solution similar to the said liquid separation process as needed.
The hydrophilic organic solvent separated in the liquid separation step and the extraction washing step can be recovered by distillation and reused. In addition, the distillation residue contains fat-soluble vitamins, saponins, and the like, and is expected to be used as drug discovery materials and functional food materials.

Although the oil and fat extracted and washed with water as described above has a high degree of purification, turbidity may occur due to the incorporation of moisture. In such a case, it is preferable to go through a dehydration step after extraction and washing.
Specifically, powdery or sheet-like cellulose is used as a dehydrating agent, and this is put into an oil or fat, or dehydrated by passing the oil or fat through the cellulose packed in a column.
According to such dehydration treatment, water-soluble impurities can be adsorbed and removed together with cellulose together with moisture. In addition, since the cellulose after a process can be used for a fuel as it is, the problem of a waste like the case where the conventional molecular sieve is used does not arise.
In addition, the said cellulose is not restricted to cellulose itself, The material containing a cellulose may be sufficient. In this case, from the viewpoint of dehydration efficiency, the cellulose content is preferably 50% or more, and more preferably 80% or more.

  The method for measuring the content of contaminants in the purified edible oil and fat obtained as described above is not particularly limited. For example, after adding methanol to the purified oil and stirring, the mixture is centrifuged, Using the supernatant as an analysis sample, the degree of purification can be compared by comparing the number of detected peaks with the height of each peak by high performance liquid chromatography (HPLC).

  In addition, the refinement | purification process like the manufacturing method which concerns on this invention can be applied suitably for manufacture of the expensive oil which does not refine | purify after squeezing especially among edible fats and oils, such as sesame oil and olive oil. Thereby, oil extraction efficiency can be improved, and since a heating process is not required, it is advantageous in that it is possible to prevent deterioration of oil.

EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to the following Example.
(Experiment 1) Difference in the amount of oil expelled depending on the type of hydrophilic organic solvent Rapeseed seeds were pulverized with a mixer, 15 g was filled into a small oil press (CHS-01; Creative Machine Studio), and various hydrophilic organic materials shown in Table 1 below. 10 ml of solvent was added and immersed, and oil was extracted.
The oil-extracted solution was centrifuged at 4000 rpm for 10 minutes, separated into a solvent and fats and oils, and the volume of fats and oils was measured.
Table 1 summarizes the amount of oil extraction when various hydrophilic organic solvents are used.
In addition, in the case of acetone, since fats and oils melt | dissolved and were not isolate | separated, after oil extraction, 30% water was added and fats and oils were released.

  From the results shown in Table 1, by slurrying pulverized rapeseed seeds with a hydrophilic organic solvent, the seed tissue becomes soft, and the oil extraction efficiency can be increased up to nearly three times compared to the untreated case. Was recognized.

(Experiment 2) Oil extraction from fat and oil raw material with low fat content Soybeans are pulverized with a coffee mill, 15 ml of ethanol is added to 15 g and immersed in a slurry, heated under the conditions shown in Table 2 below, then Experiment 1 Squeezed in the same manner.
The oil extraction liquid was centrifuged at 4000 rpm for 10 minutes, separated into a solvent and oil and fat, the weight of the oil and fat was measured, and this was defined as the amount of oil extraction.
Table 2 summarizes the amount of expression under various heating conditions.

  Soybeans are generally produced by hexane extraction because they have a low fat content and are difficult to extract. In Experiment 2 above, it was not possible to squeeze the oil at all when it was not slurried (no treatment), but it was confirmed that the oil could be squeezed by the slurry. Moreover, the influence of heating was not recognized.

(Experiment 3) Difference in degree of purification by pre-treatment The degree of purification of oil and fat when rapeseed seed grain or ground rapeseed seed was directly squeezed and when squeezed by immersing (pre-treatment) in ethanol was compared. Oil extraction was performed by the method according to Experiment 1. In addition, regarding the ethanol immersion treatment of the rapeseed seed grains, those subjected to ultrasonic treatment were also evaluated.
The comparison of the degree of purification was performed by adding and mixing the same amount of methanol to each oil and fat, and comparing the HPLC detection pattern of the methanol-soluble component with commercially available canola oil (standard product).
FIG. 1 shows the measured HPLC patterns.

  From each HPLC pattern shown in FIG. 1, it is recognized that the peak of impurities is reduced by the ethanol immersion treatment of rapeseed seeds, and a purification degree close to that of commercially available canola oil (standard product) can be obtained without going through a purification step. It was.

(Experiment 4) Difference in degree of purification by extraction and purification Extraction of rapeseed oil obtained by the compression method was extracted three times with the same amount of ethanol, and then extracted and purified three times with distilled water, resulting in turbidity. .
When 1/50 (w / v) amount of cellulose powder was added to the refined oil and fat and allowed to stand for 1 hour, turbidity due to moisture disappeared and a clear and transparent oil and fat was obtained.
The oils and fats in each stage were mixed with the same amount of methanol, and the HPLC detection patterns for the methanol-soluble components were compared with commercial canola oil (standard product) to compare the degree of purification.
FIG. 2 shows the measured HPLC patterns.

  From the respective HPLC patterns shown in FIG. 2, it is recognized that purified rapeseed oil having a higher degree of purification than (c) and commercially available canola oil (standard product) (a) can be obtained by extraction and purification with ethanol and distilled water. It was. Furthermore, it was confirmed that dehydration (d) with cellulose also functions effectively, and the amount of impurities is further reduced.

Claims (5)

A pretreatment step of immersing a solid fat raw material as it is in a hydrophilic organic solvent, or pulverizing it into a slurry in a hydrophilic organic solvent;
An oiling step of squeezing and squeezing the oil or fat raw material that has been immersed or slurried;
A liquid separation step for separating the squeezed fat and the hydrophilic organic solvent;
After the liquid separation step, the separated oil and fat is extracted and washed with a hydrophilic organic solvent, and further extracted and washed with water,
The manufacturing method of the refined edible oil and fat characterized by including the dehydration process which spin-dry | dehydrates the said oiled fats and oils wash | cleaned after the said extraction washing | cleaning process by adding a cellulose or letting it pass through a cellulose column . The method for producing a purified edible fat / oil according to claim 1, wherein in the pretreatment step, the hydrophilic organic solvent is exchanged at least once and the fat / oil raw material is washed. The said hydrophilic organic solvent is any one of methanol, ethanol, acetonitrile, and acetone, or a mixed solvent of 2 or more types, The manufacturing method of the refined edible oil and fat of Claim 1 or Claim 2 characterized by the above-mentioned. The said hydrophilic organic solvent is a hydrous solvent, The manufacturing method of the refine | purified edible oil and fat of any one of Claim 1 thru | or 3 characterized by the above-mentioned. In the liquid separation step, water or carbonate such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, ammonium dihydrogen phosphate, trisodium phosphate The manufacturing method of the refined edible fats and oils of any one of Claims 1 thru | or 4 which add any 1 type or multiple salt solutions of phosphates, such as tripotassium phosphate.

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