JP5753752B2 - Method for producing oil and fat composition - Google Patents

Description

  The present invention relates to a method for producing an oil and fat composition and a method for solid-liquid fractionation of the oil and fat composition.

  In general, fats and oils such as rapeseed oil and soybean oil are liquid at room temperature, but crystals may precipitate and become cloudy when placed under a low temperature such as a cold district or a refrigerator. In particular, even if the fatty acid composition is the same, diacylglycerol has a higher melting point than triacylglycerol, and thus tends to be easily crystallized at a low temperature.

  As a method for suppressing crystallization of fats and oils, a method of previously removing a high melting point component by wintering is known. In addition, for fats and oils containing diacylglycerol at a high concentration, a method has been reported in which an emulsifier is added as a separation aid during wintering and the precipitated crystals are separated into solid and liquid (Patent Document 1).

JP 2002-20882 A

Wintering consists of a crystallization step for producing crystals and a fractionation step for separating the crystals, but it may be difficult to separate by the composition of the oil or fat. Moreover, since the emulsifier is concentrated in the high melting point component, the method of adding an emulsifier as in Patent Document 1 may affect the flavor and physical properties of the fats and oils. Furthermore, the use of emulsifiers may be restricted in other countries.
In view of such circumstances, the present invention intends to provide a new method for producing an oil and fat composition in which crystallization at low temperature is suppressed.

  The present inventors diligently studied in view of the above problems, and when the oil and fat composition was cooled, when the bubbles were brought into contact with each other, fine crystals floated along with the bubbles and could be easily separated. It has been found that the fats and oils suppress the precipitation of crystals at low temperatures and are difficult to precipitate at low temperatures.

That is, the present invention includes the following steps (1), (2) and (3):
(1) a step of cooling the oil / fat composition within the cloud point +0 to + 10 ° C. of the oil / fat composition;
(2) a step of bringing bubbles into contact with the cooled oil and fat composition;
(3) The process of isolate | separating the foam part formed by the said process from a liquid part,
The manufacturing method of the refined fats and oils composition containing this is provided.
The present invention also includes the following steps (1), (2) and (3):
(1) a step of cooling the oil / fat composition within the cloud point +0 to + 10 ° C. of the oil / fat composition;
(2) a step of bringing bubbles into contact with the cooled oil and fat composition;
(3) The process of isolate | separating the foam part and liquid part which were formed by the said process,
The solid-liquid fractionation method of the oil-fat composition containing this is provided.

  ADVANTAGE OF THE INVENTION According to this invention, the high melting point component of fats and oils can be fractionated easily and efficiently, and the fat and oil composition by which crystallization at low temperature was suppressed can be manufactured. In addition, the method of the present invention can reduce or avoid the use of an emulsifier, and can be expected to simplify the separation equipment and reduce the cost of the oil and fat composition.

It is a figure which shows schematic structure of a cylindrical bubble contact tank.

  In the manufacturing method of the refined fat composition of the present invention and the solid-liquid fractionation method of the fat composition, (1) the step of cooling the fat composition within the cloud point +0 to + 10 ° C. of the fat composition, (2 A step of bringing bubbles into contact with the cooled oil and fat composition, and (3) a step of separating the foamed part formed by the above-mentioned process from the liquid part.

  In this specification, fats and oils refer to those containing any one or more of monoacylglycerol, diacylglycerol, and triacylglycerol. As fats and oils, any of vegetable oils and animal fats may be used. Specific raw materials include rapeseed oil (canola oil), sunflower oil, corn oil, soybean oil, sesame oil, rice oil, safflower oil, cottonseed oil, palm oil, palm oil, olive oil, grape oil, avocado oil, sesame oil Peanut oil, macadamia nut oil, hazelnut oil, walnut oil, lard, beef tallow, chicken oil, butter oil, fish oil and the like. In addition, those obtained by separating and mixing these oils and fats, those obtained by adjusting the fatty acid composition by hydrogenation, transesterification, or the like can be used as raw materials.

Even if the fatty acid composition is the same, diacylglycerol tends to precipitate crystals at a lower temperature than triacylglycerol. Therefore, the production method and solid-liquid fractionation method of the present invention are preferably applied to an oil and fat composition containing a high amount of diacylglycerol.
The content of diacylglycerol in the oil and fat composition is preferably 20% by mass (hereinafter simply referred to as “%”) or more, preferably 40% or more from the viewpoint of effectively exerting physiological functions such as body fat burning action. More preferred is 70% or more. The upper limit is not particularly defined, but is preferably 99% or less, more preferably 98% or less, and still more preferably 97% or less.

  In the oil and fat composition, the content of triacylglycerol is preferably 80% or less, more preferably 1 to 60%, and particularly preferably 2 to 30% from the viewpoint of improving physiological action such as body fat burning action. . In addition, the content of monoacylglycerol is preferably 20% or less, more preferably 0 to 10%, and further preferably 0.1 to 5% in the oil or fat composition from the viewpoint of improving the flavor.

  The oil / fat composition can be obtained by an esterification reaction between a fatty acid and glycerin, a glycerolysis reaction between an oil / fat and glycerin, or the like. These reactions include chemical methods using chemical catalysts such as alkali metals or alloys thereof, oxides or hydroxides of alkali metals or alkaline earth metals, or alkoxides having 1 to 3 carbon atoms, and enzymatic methods using enzymes such as lipases. It is divided roughly into. Of these, it is preferable in terms of flavor and the like that the reaction is performed enzymatically using lipase or the like as a catalyst under mild conditions.

  In the present invention, the fatty acid constituting the fat in the fat composition is not particularly limited, and may be either a saturated fatty acid or an unsaturated fatty acid. It is preferably applied to an oil or fat composition in which 2 to 30%, further 4 to 25%, particularly 6 to 20% of the constituent fatty acid is a saturated fatty acid. The saturated fatty acid is preferably those having 12 to 24 carbon atoms, and more preferably 16 to 22 carbon atoms.

  Of the fatty acids constituting the fats and oils, the unsaturated fatty acid content is preferably 70 to 98% from the viewpoint of the appearance and industrial productivity of the fat and oil composition, more preferably 75 to 96%, and particularly 80 to 80%. 94% is preferred.

  In the present invention, prior to the cooling step, it is preferable that the oil / fat composition is set at a temperature higher by 10 ° C. or more than the cloud point of the oil / fat composition in advance. By setting the temperature to such a temperature, components to be precipitated later can be sufficiently dissolved once, and in the subsequent precipitation, the high melting point component can be selectively precipitated. Although the said temperature depends on the cloud point of an oil-fat composition, for example, 25 degreeC or more is preferable, 30 degreeC or more is more preferable, 40 degreeC or more is further more preferable, 50 degreeC or more is especially preferable.

In this invention, an oil-fat composition is cooled in the range of the cloud point + 0 + 10 degreeC of the said oil-fat composition. “Cloud point +0 to + 10 ° C.” is a notation indicating a temperature range of “more than cloud point and less than cloud point + 10 ° C.” (the same applies hereinafter). By cooling to such a temperature range, the part which deposits in the initial stage among the high melting point components of fats and oils can be finely crystallized and floated to the foam part together with the bubbles, and can be easily separated from the liquid part.
In addition, in this specification, the cloud point of an oil-and-fat composition is the temperature at which a transparent oil-and-fat begins to become cloudy, and can be measured by the method described in Examples below.
When the cooling temperature of the oil / fat composition is lower than the cloud point of the oil / fat, a purified oil / fat composition in which crystal precipitation is suppressed even at a low temperature is obtained, but a component having a relatively low melting point is also precipitated, resulting in the purification obtained. The yield of the oil / fat composition is reduced. When the cooling temperature of the oil / fat composition is higher than the cloud point of the oil / fat by more than 10 ° C., crystals do not precipitate or the amount of crystal precipitation is insufficient, so the suppression of crystal precipitation at low temperatures becomes insufficient.

From this viewpoint, the cooling temperature is preferably a cloud point of the oil or fat composition +0 to + 9 ° C., more preferably +0.5 to + 9 ° C., and particularly preferably +1 to + 7 ° C. By setting to such a temperature range, the high melting point component crystal can be more efficiently accompanied by bubbles and floated to the foam part, and separation becomes easy.
Although cooling temperature depends on a cloud point, for example, 0 to 24 ° C is preferable, 2 to 22 ° C is more preferable, 4 to 20 ° C is further preferable, 6 to 18 ° C is further preferable, and 8 to 15 ° C is further preferable. .

  The cooling operation can be performed by jacket cooling of a bubble contact tank, a heat exchanger, or the like.

In this invention, it has a process which makes a bubble contact the oil-fat composition cooled to the said cooling temperature range. You may start the bubble contact process, after adjusting an oil-fat composition to the said temperature range. In this case, the cooling rate of the oil and fat composition is not particularly limited.
Moreover, you may start the bubble contact process in the cooling process before becoming the said temperature range. In this case, the cooling rate of the fats and oils to the cloud point +0 to + 10 ° C. is 0.5 to 30 ° C./h, more preferably 1 to 15 ° C./h, especially from the viewpoint of facilitating the floating separation of the crystals. 2 to 10 ° C./h is preferable.

  The contact between the oil and fat composition and the bubbles can be performed using a bubble contact tank having a bubble generator. It is preferable that the bubble generating device is located in the lower part of the bubble contact tank. Moreover, it is preferable that a bubble contact tank is a jacket structure for temperature control of an oil-fat composition. Moreover, it is preferable that a bubble contact tank has the space for isolate | separating the liquid part and foam part of an oil-fat composition.

  As the bubble generating device, a device that refines bubbles by shearing, a device that dissolves pressurized gas in the oil and fat composition and generates bubbles by depressurization, and the like can be used. Moreover, the air stone which can generate | occur | produce a bubble by distribute | circulating gas to a porous body can be used.

  The type of gas to be supplied is not particularly limited, and examples include air, nitrogen, oxygen, carbon dioxide, ozone, hydrogen, argon, and helium. In particular, an inert gas such as nitrogen, carbon dioxide, and helium is preferable from the viewpoint of suppressing deterioration of the oil and fat composition.

  The amount of bubbles to be generated can be adjusted by the flow rate of gas, the pressure of the dissolution tank, and the circulation flow rate. From the viewpoint of suppressing the entrainment of the liquid part into the foam part, 1-1000 ml / min per 1 kg of the oil and fat composition, and 2 500 ml / min, especially 4 to 200 ml / min is preferred.

  The average bubble diameter is preferably 1 to 1000 μm, more preferably 10 to 600 μm, and particularly preferably 20 to 400 μm from the viewpoint of facilitating the floating separation of crystals. The average cell diameter is determined by the measurement method described in the examples.

  The time for the step of bringing the cooled oil and fat composition into contact with the bubbles is 0.1 to 48 hours, 0.3 to 24 hours, particularly 0 to 0, from the viewpoint of sufficiently separating and removing the fat and oil containing the saturated fatty acid as a constituent fatty acid. .5-12 hours are preferred. In addition, time here means the sum total of the time when an oil-fat composition exists in the temperature range of the cloud point + 0 + 10 degreeC of the said fat-and-oil composition.

Bubbles float after contact with the oil / fat composition, and form a foam part on top of the liquid part (liquid oil / fat composition). By separating this foam part from the liquid part, a purified fat composition can be obtained. Separation of the foam portion can be performed by a method such as overflow or suction from the bubble contact tank.
Although the ratio of the foam part with respect to fats and oils composition is determined by the saturated fatty acid density | concentration in fats and oils composition, from a viewpoint of fully removing the high melting-point component which precipitated, 3-45%, Furthermore, 5-40%, Furthermore 8 -30%, more preferably 10-25%.

  A foam part can be fractionated into a foam part isolation | separation oil part fat composition and a foam part isolation | separation liquid part fat composition by stationary separation, filtration, centrifugation, etc., for example. In the case of stationary separation, from the viewpoint of sufficiently separating the solid part and the liquid part, the temperature is within the temperature range of +0 to 10 ° C., further +0.5 to 9 ° C., and further +1 to 7 ° C. with respect to the temperature in the bubble separation tower. And preferably 2 to 48 hours, more preferably 3 to 24 hours. The ratio of the foam part separation solid part fat composition to the fat composition is determined by the saturated fatty acid concentration in the fat composition, but from the viewpoint of sufficiently separating the precipitated high melting point component, 1.5 to 35%, Further, 3 to 25%, further 4 to 20%, and further 5 to 15% are preferable. You may reuse the collect | recovered foam part isolation | separation liquid part oil-fat composition as a part of oil-fat composition.

  By the method of the present invention, a high melting point component is separated and removed from the oil and fat composition, and a purified oil and fat composition in which crystallization at low temperature is suppressed is obtained.

  The recovery rate (yield) of the purified fat composition from the fat composition depends on the high melting point component concentration of the fat composition, but is preferably 50 to 99%, more preferably 60 to 98%, and more preferably 70 to 97%. More preferred is 75 to 96%.

In the method of the present invention, as a high melting point component, fats and oils having saturated fatty acids as constituent fatty acids can be suitably separated and removed, and fats and oils having saturated fatty acids having 12 to 24 carbon atoms as constituent fatty acids are more preferably separated and removed. be able to.
When the oil / fat composition is an oil / fat composition containing a high content of diacylglycerol derived from rapeseed oil, 1,3-disaturated diacylglycerol is suitably fractionated and removed as the high melting point component. As the high melting point component, 1,3-disaturated diacylglycerol can be used as an index, and for example, 1,3-dipalmitine diacylglycerol can be preferably used as an index.

  When the oil / fat composition is an oil / fat composition containing a high content of diacylglycerol derived from rapeseed oil, the content of 1,3-dipalmitine diacylglycerol in the purified oil / fat composition is 1,3-dipalglycerol in the oil / fat composition. It is preferable that the content of dipalmitin diacylglycerol is reduced by 5% or more and further by 10 to 60% from the viewpoint of suppressing crystallization in a low temperature state.

  In addition, when the oil and fat composition is an oil and fat composition containing a high content of diacylglycerol derived from rapeseed oil, the content of 1,3-dipalmitin diacylglycerol in the refined oil and fat composition is low in crystallization at low temperatures. From this point, 0.09% or less, further 0.08% or less, and particularly 0.07% or less are preferable. The lower limit is not particularly defined, but is preferably 0.01% or more, more preferably 0.02% or more, and particularly preferably 0.03% or more from the viewpoint of industrial productivity.

  The content of diacylglycerol in the refined fat composition is preferably 20% or more, more preferably 40% or more, and still more preferably 70% or more from the viewpoint of physiological effects and industrial productivity of the fat. The upper limit is not particularly defined, but is preferably 99% or less, more preferably 98% or less, and still more preferably 97% or less.

  The refined fat composition obtained by the production method of the present invention and the solid-liquid fractionation method can be used in the same manner as general edible fats and oils, and can be widely applied to various foods and drinks using fats and oils.

[Analysis method]
(I) Fatty Acid Composition of Fats and Oils Fatty acid methyl esters were prepared and obtained according to “Preparation Method of Fatty Acid Methyl Esters (2.4.1.-1996)” in “Standard Fat and Fat Analysis Test Method” edited by Japan Oil Chemists' Society. The samples were measured by American Oil Chemist's Society Official Method Ce 1-96 (GLC method).

(Ii) Glycerol composition of fat and oil Along with the glyceride composition of fat and oil, 1,3-diacylglycerol (1,3-DAG), 1,2-diacylglycerol (1,2-DAG) and 1,3-di of high melting point component Palmitic diacylglycerol (1,3-PP-DAG) and 1-monopalmitin monoacylglycerol (1-P-MAG) were subjected to gas chromatography (GLC) and analyzed. To a glass sample bottle, about 10 mg of an oil and fat sample and 0.5 mL of a trimethylsilylating agent (“silylating agent TH”, manufactured by Kanto Chemical) were added, sealed, and heated at 70 ° C. for 15 minutes. To this, 1.0 mL of water and 1.5 mL of hexane were added and shaken. After standing, the upper layer was analyzed by gas chromatography (GLC).
<GLC conditions>
(conditions)
Equipment: Agilent 6890 series (manufactured by Agilent Technologies)
Integrator: ChemStation B 02.01 SR2 (manufactured by Agilent Technologies)
Column: DB-1ht, 10 m (manufactured by Agilent Technologies)
Carrier gas: 1.0 mL He / min
Injector: Split (1:50), T = 320 ° C.
Detector: FID, T = 350 ° C
Oven temperature: raised from 80 ° C to 340 ° C at a rate of 1 ° C / min and held at 340 ° C for 15 minutes

(Iii) Measurement of cloud point of oil / fat composition Cooling at 0.5 ° C./min using a METLER FR900 thermosystem 81HT (manufactured by METTLER TOLEDO), which is a method of detecting the light transmittance by putting a sample in a capillary tube. The crystal precipitation temperature was measured.

(Iv) Measurement of average bubble diameter The average bubble diameter was determined by measuring bubbles from a 2 mm wide slit filled with an oil and fat composition and measuring the image directly from a camera.

(V) Method for calculating yield of foam part-separated solid part fat composition The yield of the fat composition was calculated according to the following equation.
Foam part separated solid part oil / fat composition weight / fat composition / weight x 100 (%)

[Preparation of oil and fat composition a]
870 parts by weight of fatty acid obtained by hydrolyzing rapeseed oil and 50 parts by weight of 1,3-position-selective immobilized lipase (Lipozyme RM IM: manufactured by Novoldisk Industries) as a catalyst were mixed, and 130 parts by weight of glycerin was added. The esterification reaction was performed. After the lipase preparation was filtered off, the reaction-finished product was subjected to molecular distillation, further decolorized, acid-treated and washed with water, and then deodorized at 245 ° C. for 34 minutes to obtain an oil and fat composition a.

[Preparation of oil and fat composition b]
The oil and fat composition b was obtained in the same manner as in the preparation of the oil and fat composition a except that the rapeseed oil was changed to soybean oil.

[Preparation of Oil and Fat Composition c]
828 parts by mass of high oleic sunflower oil and 1,3-position selective immobilized lipase (Lipozyme RM IM: NOVOLDIS INDUSTRY Co., Ltd.) 100 parts by mass and distilled water 20 parts by mass were mixed with 172 parts by mass of glycerin. The glycerolysis reaction was performed by addition. After the lipase preparation was filtered off, the reaction finished product was deglycerinized to obtain an oil and fat composition c.

  Table 1 shows composition of oil and fat compositions a to c, cloud point, and high melting point component name, high melting point component concentration in fat and oil compositions a to c, and saturation of 12 to 24 carbon atoms in constituent fatty acids of glycerides. The amount of fatty acid is shown.

Test example 1
6.0 kg of the oil and fat composition a was charged in a jacket-cooled cylindrical bubble contact tank (inner diameter 100 mm × height 1000 mm, the same applies hereinafter) shown in FIG. 1 and completely dissolved at 50 ° C. It was circulated at a rate of about 120 ml / min between the bubble generation standing (OM4-MDG-045, Auratec) and the cylindrical bubble contact tank. The oil and fat composition a was cooled at 4 ° C./h at 13 ° C. while adjusting the pressure for generating bubbles to 0.26 MPa and continuously generating bubbles by depressurizing immediately before the cylindrical bubble contact tank. Hold for 10 hours. The average bubble diameter at this time was 79 μm. In addition, the contact time between the oil and fat composition and the bubbles within the range of the cloud point +0 to + 10 ° C. of the oil and fat composition a was 11 hours (in the table, expressed as “bubble contact time in the cooling temperature range”. the same.). The refined fat composition was extracted from a sampling port attached at a position 100 mm higher from the lower part of the cylindrical bubble contact tank. Moreover, the foam part was extracted into an eggplant flask and allowed to stand at 15 ° C. for 12 hours to separate the separated foam part separated liquid part fat composition, thereby obtaining a foam part separated solid part fat composition.

Test example 2
In a jacket-cooled cylindrical bubble contact tank, 6.0 kg of the oil / fat composition b was charged and completely dissolved at 50 ° C. It was circulated at a rate of about 120 ml / min between the bubble generation standing (OM4-MDG-045, Auratec) and the cylindrical bubble contact tank. The oil and fat composition b was cooled at 4 ° C./h at 17 ° C. while adjusting the pressure for bubble generation to 0.26 MPa and continuously generating bubbles by releasing the pressure immediately before the cylindrical bubble contact tank. Hold for 4 hours. The contact time between the oil and fat composition and the bubbles in the range of cloud point +0 to + 10 ° C. of the oil and fat composition b was 5.15 hours. The refined fat composition was extracted from a sampling port attached at a position 100 mm higher from the lower part of the cylindrical bubble contact tank.

Test example 3
In a jacket-cooled cylindrical bubble contact tank, 6.0 kg of the oil / fat composition c was charged, completely dissolved at 50 ° C, and then cooled to 25 ° C. It was circulated at a rate of about 120 ml / min between the bubble generation standing (OM4-MDG-045, Auratec) and the cylindrical bubble contact tank. The oil-and-fat composition c was cooled to 15 ° C. at 1 ° C./h while continuously generating bubbles by adjusting the pressure for leaving the bubbles to 0.26 MPa and releasing the pressure immediately before the cylindrical bubble contact tank. The contact time between the oil and fat composition and the bubbles in the range of cloud point +0 to + 10 ° C. of the oil and fat composition c was 5.2 hours. The refined fat composition was extracted from a sampling port attached at a position 100 mm higher from the lower part of the cylindrical bubble contact tank. Moreover, the foam part was extracted into an eggplant flask and allowed to stand at 20 ° C. for 48 hours to separate the entrained foam part separated liquid part oil and fat composition to obtain a foam part separated solid part oil and fat composition.

Test example 4
In a jacket-cooled cylindrical bubble contact tank, 6.0 kg of the oil composition a was charged and completely dissolved at 50 ° C. Three air stones (25φ round # 180, manufactured by Ibuki Air Stone) were attached to the bottom surface of the cylindrical bubble contact tank. Nitrogen gas was supplied at about 50 ml / min per air stone, and the oil and fat composition a was cooled at 12 ° C./h while continuously generating bubbles, and held at 10 ° C. for 10 hours. The contact time between the oil and fat composition and the bubbles in the range of cloud point +0 to + 10 ° C. of the oil and fat composition a was 10.58 hours. At this time, the average bubble diameter was 725 μm. The refined fat composition was extracted from a sampling port attached at a position 100 mm higher from the lower part of the cylindrical bubble contact tank.

Table 1 shows the yield of the foam-part separated liquid oil composition, the composition of the foam-separated solid oil composition, the high-melting-point component name, and the high-melting-point component in the foam-separated solid oil composition. Content, the amount of saturated fatty acid having 12 to 24 carbon atoms in the constituent fatty acid of glyceride, and the yield.
In addition, the composition of the refined fat and oil composition, cloud point, high melting point component name, content of the high melting point component in the refined fat and oil composition, the amount of saturated fatty acid having 12 to 24 carbon atoms in the constituent fatty acid of the glyceride, and the yield Indicated.

  As is apparent from Table 1, according to the method of the present invention, the glyceride composition in fats and oils, the ratio of 1,2-DAG and 1,3-DAG, and the amount of saturated fatty acid hardly change, and the high melting point component, particularly 1 , 3-PP, 1-P, and other components that become crystal nuclei can be efficiently separated and removed, and it has been confirmed that an excellent refined oil and fat composition in which crystallization is suppressed at low temperatures can be produced.

Claims (5)

Next steps (1), (2) and (3):
(1) a step of cooling the oil / fat composition within the cloud point +0 to + 10 ° C. of the oil / fat composition;
(2) a step of bringing bubbles into contact with the cooled oil and fat composition;
(3) The process of isolate | separating the foam part formed by the said process from a liquid part,
The manufacturing method of the refined fats and oils composition containing this.   The manufacturing method of the refined fat composition of Claim 1 whose average bubble diameter is 1-1000 micrometers.   The manufacturing method of the refined oil-fat composition of Claim 1 or 2 whose oil-fat composition contains 20 mass% or more of diacylglycerols. Next steps (1), (2) and (3):
(1) a step of cooling the oil / fat composition within the cloud point +0 to + 10 ° C. of the oil / fat composition;
(2) a step of bringing bubbles into contact with the cooled oil and fat composition;
(3) The process of isolate | separating the foam part and liquid part which were formed by the said process,
The solid-liquid fractionation method of fats and oils composition containing this.   The solid-liquid fractionation method of the oil-fat composition according to claim 4, wherein the oil-fat composition contains 20% by mass or more of diacylglycerol.