Classifications

• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS OR COOKING OILS
  • A23D9/00—Other edible oils or fats, e.g. shortenings or cooking oils
  • A23D9/02—Other edible oils or fats, e.g. shortenings or cooking oils characterised by the production or working-up
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
  • C11B3/00—Refining fats or fatty oils
  • C11B3/10—Refining fats or fatty oils by adsorption
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
  • C11B3/00—Refining fats or fatty oils
  • C11B3/12—Refining fats or fatty oils by distillation
  • C11B3/14—Refining fats or fatty oils by distillation with the use of indifferent gases or vapours, e.g. steam

Definitions

• the present invention relates to a method for producing refined fats and oils.
• fats and oils used for food in order to improve the quality of fats and oils indicated by flavor and oxidative stability, so-called crude oil collected from animals and plants is degummed, deoxidized, decolorized, and deodorized.
• crude oil collected from animals and plants is degummed, deoxidized, decolorized, and deodorized.
• purification including.
• RBD refined Bleached Deodorized
• NBD Neutralized Bleached Deodorized
• 3-chloropropane-1,2-diol (hereinafter referred to as "3-MCPD") and 2 have been added to refined fats and oils including RBD fats and oils and NBD fats and oils.
• -Chloropropanediols such as chloropropane-1,3-diol (hereinafter referred to as "2-MCPD") and their fatty acid esters (hereinafter collectively referred to as "MCPDs”), glycidol and its fatty acid esters. It has become clear that the species (hereinafter, these are collectively referred to as “glycidols”) are contained.
• MCPDs and glycidols are produced from lipids and chloride ions in fats and oils by exposing them to high temperatures in the process of refining, for example, in the deodorizing step.
• MCPDs and glycidols are concerned about adverse health effects, and various studies are underway to reduce the content of MCPDs and glycidols in fats and oils.
• Patent Document 1 proposes a method of reducing MCPDs in fats and oils by bringing the fats and oils that have undergone the decolorization step and the deodorization step into contact with silica gel and / or basic activated carbon.
• Patent Document 2 proposes a method for producing fats and oils with reduced MCPDs, in which one or more inorganic powders selected from the group consisting of boehmite and hydrotalcite are brought into contact with fats and oils under constant temperature conditions. ing.
• Patent Document 3 proposes a method for producing a purified glyceride composition using a mixture of activated clay and potassium carbonate
• Patent Document 4 proposes a decolorizing agent for refined fats and oils using a mixture of activated clay and a silica magnesia preparation. Has been done.
• Non-Patent Document 1 describes a method for removing 3-MCPD fatty acid ester and its derivative from refined fats and oils by using various adsorbents such as amorphous magnesium silicate and zeolite.
• the method of contacting with an adsorbent is easy to introduce into a conventionally known refining process for fats and oils, but has a problem that it is difficult to sufficiently reduce the content of MCPDs in fats and oils.
• the treatment with the adsorbent is the final step, the flavor derived from the adsorbent is likely to be imparted to the fats and oils.
• Patent Document 2 has a problem that it cannot be used for producing edible oils and fats because it uses an adsorbent that cannot be used for producing foods.
• Patent Document 3 since the method described in Patent Document 3 uses potassium carbonate whose aqueous solution exhibits strong alkalinity, there is a problem that saponification decomposition may proceed at the same time as purification. Further, the fats and oils examined in the examples have not actually undergone deodorization treatment, and even if the method for producing fats and oils described in Patent Document 3 is used, it is not disclosed whether MCPDs are sufficiently reduced, and it is unknown. Met.
• Patent Document 4 is used for the decolorization treatment of RBD palm oil for the purpose of performing the deodorization treatment at a low temperature and in a short time, and MCPDs and glycidol which are said to be produced by the deodorization treatment. Although it was possible to prevent the increase of the types, it was difficult to reduce the already generated MCPDs and glycidols.
• Non-Patent Document 1 shows that 3-MCPD can be reduced to about 4 ppm by adding an adsorbent such as amorphous magnesium silicate or zeolite so as to have 10% by mass of fat and oil.
• an adsorbent such as amorphous magnesium silicate or zeolite
• the adsorbent is removed from the fat and oil, it is industrially removed by filtration, but since the method described in Non-Patent Document 1 removes 3-MCPD by using a large amount of adsorbent, filtration is performed. The efficiency and the yield of fats and oils tend to be low, and there is a problem in terms of production efficiency when applied to the production of fats and oils industrially.
• an object to be solved by the present invention is to provide a method for producing refined fats and oils, which can efficiently obtain fats and oils having a sufficiently reduced content of MCPDs and glycidols.
• the present invention provides: ⁇ 1> A method for producing refined fats and oils, which comprises a contact treatment in which white clay and zeolite are brought into contact with the fats and oils.
• ⁇ 4> The method according to any one of ⁇ 1> to ⁇ 3>, wherein 0.1 to 3.5 parts by mass of zeolite is used with respect to 100 parts by mass of fats and oils in the contact treatment.
• ⁇ 5> The method according to any one of ⁇ 1> to ⁇ 4>, wherein the clay is active clay.
• ⁇ 6> The method according to any one of ⁇ 1> to ⁇ 5>, wherein the zeolite is one or more selected from the group consisting of natural zeolite and synthetic zeolite.
• ⁇ 7> The method according to any one of ⁇ 1> to ⁇ 6>, further comprising a deodorizing treatment for deodorizing the fats and oils subjected to the contact treatment.
• ⁇ 8> The method according to ⁇ 7>, wherein the oil / fat temperature in the deodorizing treatment is 180 to 270 ° C.
• ⁇ 9> The method according to any one of ⁇ 1> to ⁇ 8>, which is performed on fats and oils that have undergone a deodorizing step one or more times.
• ⁇ 10> A refined fat or oil obtained by the method according to any one of ⁇ 1> to ⁇ 9>, wherein the total content of chloropropanediols and fatty acid esters thereof is 4 mass ppm or less.
• ⁇ 11> A refined fat or oil obtained by the method according to any one of ⁇ 1> to ⁇ 9>, wherein the total content of glycidol and its fatty acid esters is 3% by mass or less.
• ⁇ 12> A method for reducing chloropropanediols and fatty acid esters thereof, or glycidol and fatty acid esters thereof in fats and oils, which comprises a contact treatment in which white clay and zeolite are brought into contact with the fats and oils.
• fats and oils having a sufficiently reduced content of MCPDs and glycidols can be efficiently obtained.
• the method for producing a refined fat or oil of the present invention includes a contact treatment in which white clay and zeolite are brought into contact with the fat or oil.
• the order in which the white clay and the zeolite are brought into contact with the fat and oil is not particularly limited, and for example, the following (1) to (4) can be mentioned as specific methods of the contact treatment.
• the contact treatment in which the white clay and the zeolite are brought into contact with the fat and oil can be carried out by using an arbitrary method, and either a batch type or a continuous type may be used, but since many fats and oils can be treated at one time. , It is preferable to perform batch type contact treatment.
• a method of adding one or both of white clay or zeolite to the fat or oil heated to a predetermined temperature to treat the fat or oil or (II) adding white clay or zeolite to the fat or oil.
• a method of heating the fat and oil until the temperature reaches a predetermined temperature after adding one or both of them can be mentioned.
• the contact treatment is performed. During that time, it is preferable to stir the fat and oil to disperse the white clay and zeolite in the fat and oil.
• a filtration step is performed between the contact treatment for contacting the white clay and the contact treatment for contacting the zeolite, and after the white clay or zeolite is filtered out. , The next contact process can be started.
• the white clay and the zeolite are brought into contact with the fat and oil, from the viewpoint of obtaining the fat and oil having an excellent flavor and color tone and from the viewpoint of removing MCPDs and glycidols from the fat and oil to a higher degree, the above ( It is preferable that the white clay and the zeolite are brought into contact with the fat and oil at the same time by either the method of 3) or (4).
• either (3) or (4) above can be set from the viewpoint that the temperature of the fat and oil during the contact treatment, which will be described later, can be set low and the oxidative stability of the fat and oil over time can be further improved. It is preferable that the white clay and the zeolite are brought into contact with the fat and oil at the same time by the method.
• the white clay and zeolite used in the contact treatment will be described below.
• Naturally occurring acidic clay (montmorillonite-based clay) or activated clay obtained by treating the acidic clay with an inorganic acid such as sulfuric acid or hydrochloric acid can be used.
• activated clay having a porous structure having a larger specific surface area for acid treatment it is preferable to use activated clay having a porous structure having a larger specific surface area for acid treatment.
• the specific surface area of the active clay is preferably 50 to 400 m 2 / g, and the acidity (KOHmg / g) of the active clay is preferably 2.50 or less.
• Active white clay contains SiO 2 , Al 2 O 3 , Fe 2 O 3 , CaO, MgO, etc. as general chemical components, and the mass ratio of SiO 2 to Al 2 O 3 (SiO 2). / Al 2 O 3 ratio) is preferably in the range of 3 to 12, and more preferably in the range of 4 to 10. Further, a composition containing 1 to 5% by mass of Fe 2 O 3 , 0 to 1.5% by mass of CaO, and 1 to 7% by mass of MgO is preferable.
• Examples of commercially available products of acid clay used in the present invention include Mizuka Ace # 20, Mizuka Ace # 300, Mizuka Ace # 400, and Mizulite (all manufactured by Mizusawa Industrial Chemicals Co., Ltd.).
• Examples of commercially available products of clay clay include Galleon Earth V2R, Galleon Earth V2, Galleon Earth NVZ, and Galleon Earth NV (all manufactured by Mizusawa Industrial Chemicals Co., Ltd.).
• the zeolite used in the present invention is an aluminosilicate mineral also called boiling stone, and has a porous structure derived from a crystal structure.
• Zeolites can be roughly classified into three types, natural zeolites, synthetic zeolites and artificial zeolites, depending on their origin.
• the synthetic zeolite means a zeolite having a higher purity than a natural zeolite, which is artificially synthesized by using a raw material such as pure silicic acid or aluminum hydroxide.
• the artificial zeolite means a zeolite artificially synthesized from lime charcoal or the like as a raw material.
• the effect of the present invention can be obtained by using one or more selected from the group consisting of natural zeolite, synthetic zeolite and artificial zeolite.
• Zeolites contain SiO 2 , Al 2 O 3 , Fe 2 O 3 , CaO, K 2 O, Na 2 O and the like as general chemical components.
• the zeolite used in the method for producing refined fats and oils of the present invention is not particularly limited, and has, for example, a composition having a mass ratio of SiO 2 and Al 2 O 3 (SiO 2 / Al 2 O 3 ratio) of 2 to 12. Natural zeolite or the like can be used.
• zeolites selected from the group consisting of natural zeolites and synthetic zeolites reduces MCPDs and glycidols. It is preferable from the viewpoint of As the zeolite, calcined zeolite that has been calcined in the process of its production may be used. From the viewpoint of further reducing MCPDs and glycidols, it is preferable to use uncalcined zeolite.
• zeolite products used in the present invention include SGW, SGW-B4, calcined SGW, etc. (all manufactured by Siegrite Co., Ltd.), SP # 600, etc. (manufactured by Nitto Powder Industry Co., Ltd.), Izukalite, etc. (stocks). Companies such as Izuka) and SU (manufactured by Zeo Co., Ltd.) can be mentioned.
• Shirotsuchi and zeolite have different "structures" and "pore diameters".
• the white clay has, for example, a montmorillonite structure, and the average pore diameter thereof is preferably about 60 ⁇ .
• zeolite has, for example, a clinoptilolite structure or a mordenite structure, and its average pore diameter is preferably less than 10 ⁇ .
• the zeolite selected may have a mordenite structure alone, a clinoptilolite structure alone, or a coexistence of these structures.
• the structure of the zeolite is identified by X-ray analysis, and the change in peak shape due to heating identifies it as a clinoptilolite structure, a mordenite structure, and a mixture thereof.
• the shapes of the white clay and zeolite used in the present invention are not particularly limited, and various shapes such as powder, lump, bead, and pellet can be taken. From the viewpoint of increasing the contact area with fats and oils, the white clay and zeolite are preferably in the form of powder. Since the effect of reducing MCPDs and glycidols is particularly excellent, it is preferable to use powdered zeolite having an average particle size of, for example, 200 ⁇ m or less, 150 ⁇ m or less, 100 ⁇ m or less, or 50 ⁇ m or less, preferably 15 ⁇ m or less or 12 ⁇ m or less. It is more preferable to use powdered zeolite.
• the amount of white clay used is preferably 0.25 parts by mass or more, more preferably 0.5 parts by mass with respect to 100 parts by mass of fats and oils. It is 7 parts by mass or more, more preferably 0.75 parts by mass or more, 0.8 parts by mass or more, or 1.0 part by mass or more.
• the upper limit of the amount of white clay used is not particularly limited, but from the viewpoint of enhancing industrial productivity such as filterability and yield, it is preferably 4.5 parts by mass or less, more preferably 3.0 parts by mass with respect to 100 parts by mass of fats and oils.
• mass or less By mass or less, more preferably 2.5 parts by mass or less, 2.3 parts by mass or less, 2.1 parts by mass or less, 2.0 parts by mass or less, 1.8 parts by mass or less, 1.6 parts by mass or less or 1 It is 5.5 parts by mass or less.
• the amount of zeolite used is preferably 0.1 part by mass or more, more preferably 0.3 part by mass or more, still more preferably 0.5 part by mass or more, 0.75 with respect to 100 parts by mass of fats and oils. It is 0 parts by mass or more, 0.8 parts by mass or more, 0.9 parts by mass or more, or 1.0 part by mass or more.
• the upper limit of the amount of zeolite used is not particularly limited, but is preferably 3.5 parts by mass or less, more preferably 2.5 parts by mass or less, still more preferably 2.2 parts by mass or less, and 2 by mass with respect to 100 parts by mass of fats and oils.
• zeolite 0.1 to 3.5 parts by mass of zeolite is used with respect to 100 parts by mass of fats and oils in the contact treatment.
• the total amount of white clay and zeolite used is 100 parts by mass of fats and oils from the viewpoint of sufficiently reducing MCPDs and glycidols. More preferably 0.3 parts by mass or more, more preferably 0.5 parts by mass or more, still more preferably 0.75 parts by mass or more, 0.8 parts by mass or more, 1.0 parts by mass or more, 1.2 parts by mass. As mentioned above, it is 1.4 parts by mass or more or 1.5 parts by mass or more.
• the production method of the present invention including a contact treatment in which white clay and zeolite are brought into contact with fats and oils
• MCPDs and glycidols can be sufficiently reduced even if the total amount of white clay and zeolite used for fats and oils is set low.
• the total amount of white clay and zeolite used may be 8 parts by mass or less, 7.5 parts by mass or less, or less than 7.5 parts by mass, preferably 5.0 parts by mass, based on 100 parts by mass of fats and oils.
• the production method of the present invention which includes a contact treatment in which white clay and zeolite are brought into contact with fats and oils, sufficiently reduces MCPDs and glycidols even when the total amount of white clay and zeolite used is set low as described above. It is possible to achieve both industrial productivity such as filterability and yield and sufficient reduction of MCPDs and glycidols, which is an exceptionally excellent effect.
• the white clay used for the contact treatment is used.
• Zeolite is preferably 0.1 part by mass or more, more preferably 0.3 part by mass or more, still more preferably 0.5 part by mass or more, 0.6 part by mass with respect to 1 part by mass of white clay. Or more or 0.7 parts by mass or more.
• the upper limit of the amount ratio is preferably 2.5 parts by mass or less, more preferably 2.2 parts by mass or less, still more preferably 2.0 parts by mass or less, and 1.8 parts by mass with respect to 1 part by mass of white clay.
• zeolite is in the range of 0.5 to 1.2 parts by mass with respect to 1 part by mass of white clay, the reduction efficiency of MCPDs and glycidols tends to be exceptionally excellent. ing.
• the oil / fat temperature during the contact treatment is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, still more preferably 70 ° C. or higher or 80 ° C. or higher.
• the upper limit of the temperature of the fat and oil during the contact treatment is, for example, 280 ° C. or lower, preferably 260 ° C. or lower. Therefore, in one preferred embodiment, the fat and oil temperature in the contact treatment is 50 to 260 ° C.
• the temperature of the fat and oil during the contact treatment in contact with the white clay is preferably 80 ° C. or higher, 90 ° C. or higher, or 100 ° C. or higher, and the upper limit thereof is preferably 150 ° C. or higher. ° C or lower, 140 ° C or lower, 130 ° C or lower, or 120 ° C or lower.
• the temperature of the fat and oil during the contact treatment in which the zeolite is brought into contact is preferably 180 ° C. or higher, more preferably 200 ° C. or higher, and the upper limit thereof is preferably. It is 270 ° C or lower or 260 ° C or lower.
• the temperature of the fats and oils during the treatment is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, still more preferably 70 ° C. or higher or 80 ° C. or higher.
• the upper limit of the temperature is preferably 180 ° C. or lower, more preferably 160 ° C. or lower, still more preferably 150 ° C. or lower, 140 ° C. or lower, or 130 ° C.
• the temperature of the fats and oils during the contact treatment is in the range of 80 to 150 ° C.
• the effect of reducing MCPDs and glycidols is excellent, the acid value and peroxide value are low, and the color tone is clear and the flavor is good.
• the present inventors have confirmed that fats and oils tend to be obtained.
• the fat and oil temperature during the contact treatment in which the zeolite is brought into contact with the fat and oil is relatively high, and the white clay and the zeolite are brought into contact with each other at the same time.
• the preferable oil / fat temperature range for performing the contact treatment tends to differ depending on the contact treatment method.
• the contact treatment may be performed under reduced pressure, and the contact treatment may be performed under normal pressure. Although this may be carried out, it is preferable to carry out the contact treatment under reduced pressure from the viewpoint of suppressing the oxidation of fats and oils during the treatment.
• the contact treatment When the contact treatment is performed under reduced pressure, it is preferably 1.0 ⁇ 10 4 Pa or less, more preferably 1.0 ⁇ 10 3 Pa or less, still more preferably 8.0 ⁇ 10 2 Pa or less, and particularly preferably.
• the decompression condition can be 5.0 ⁇ 10 2 Pa or less.
• the contact time between the fat and the white clay is preferably 5 minutes or more, more preferably 10 minutes or more, or 15 minutes. More than a minute. From the viewpoint of industrial productivity, the upper limit of the contact time is preferably 60 minutes or less.
• the contact time between the fat and oil and the zeolite is preferably 5 minutes or more, more preferably 10 minutes or more or 15 minutes or more, and the contact time is The upper limit is preferably 120 minutes or less, more preferably 90 minutes or less.
• the contact time is preferably 5 from the viewpoint of efficiently reducing MCPDs and glycidols. Minutes or more, more preferably 10 minutes or more, still more preferably 15 minutes or more.
• the upper limit of the contact time is not particularly limited, but from the viewpoint of industrial productivity, it is, for example, 180 minutes or less, preferably 150 minutes or less, 120 minutes or less, 90 minutes or less, or 60 minutes or less.
• the starting point of the contact time is the time when one or both of the white clay and the zeolite are brought into contact with the fat and oil heated to a predetermined temperature. Therefore, in the case of batch type contact treatment, the starting point of the contact time is when one or both of white clay and zeolite are added to the fat and oil heated to a predetermined temperature.
• the starting point is when the temperature reaches the predetermined temperature.
• the end point of the contact treatment is when a predetermined contact time has passed with reference to the above start point, and when other steps other than the contact treatment are performed after reaching the end point, the oil and fat, white clay and zeolite are conventionally used. It is preferable to filter out.
• the above contact treatment may be performed a plurality of times. From the viewpoint of industrial productivity and cost-effectiveness related to the reduction of MCPDs and glycidols, the contact treatment is preferably performed twice or less, and more preferably once. When the contact treatment is performed a plurality of times, the conditions of each treatment may be the same or different.
• the white clay and the zeolite may be filtered off for each contact treatment, and the white clay and the zeolite may be newly added before the contact treatment (2) for each contact treatment.
• the next contact treatment may be carried out as it is without filtering, but it is preferable that the white clay and the zeolite are separated by filtration in each contact treatment, and the white clay and the zeolite are newly added and then the contact treatment is carried out.
• additives in addition to white clay and zeolite when performing the above contact treatment.
• the additive used for the contact treatment in the present invention include an adsorbent such as silica gel and a pH adjuster such as citric acid.
• the amount of pure content added per 100 parts by mass of fats and oils is within the above range.
• the method for producing refined fats and oils of the present invention may include other treatments (steps) provided in the conventional method for producing fats and oils.
• Other treatments include, for example, degumming treatment for removing phospholipids, deoxidizing treatment for removing free fatty acids, dewaxing treatment, decolorization treatment, deodorizing treatment and the like. These processes can be performed by a conventional method.
• the conditions and order of these treatments are not particularly limited, and the conditions and order usually set at the time of manufacturing fats and oils may be used (for example, edited by Japan Oil Chemists' Society, Basics and Applications of fats and oils, April 2005). 1st edition issued on the 1st, see pages 215-219).
• the fats and oils are deodorized at least once in addition to the above-mentioned contact treatment. Is preferable.
• the contact treatment and the deodorizing treatment are preferably performed alternately, and either the contact treatment or the deodorizing treatment may be performed first, but from the viewpoint of the reduction effect of MCPDs and glycidols and the viewpoint of obtaining fats and oils having a good flavor. It is preferable to perform the deodorizing treatment after the contact treatment. Therefore, in a preferred embodiment, the method for producing a refined fat or oil of the present invention further includes a deodorizing treatment for deodorizing the fat or oil subjected to the contact treatment.
• the deodorizing treatment can be performed by a conventional method, and the conditions of the deodorizing treatment are not particularly limited.
• a specific deodorizing treatment a deodorizing treatment by vacuum steam distillation in which steam and fats and oils are brought into contact with each other under reduced pressure will be described.
• the lower limit of the oil / fat temperature when the water vapor is brought into contact with the oil / fat is preferably 180 ° C. or higher, more preferably 200 ° C. or higher, from the viewpoint of sufficiently reducing the content of MCPDs and glycidols and obtaining a fat / oil having a good flavor. More preferably, it is 210 ° C. or higher, and most preferably 220 ° C. or higher.
• the upper limit of the fat and oil temperature when the steam and the fat and oil are brought into contact is preferably 270 ° C. or lower, more preferably 270 ° C. or lower, from the viewpoint of suppressing an increase in acid value, peroxide value, etc. and preventing deterioration of the fat or oil during production. It is 260 ° C. or lower, most preferably 250 ° C. or lower. Therefore, in one preferred embodiment, the fat and oil temperature in the deodorizing treatment is 180 to 270 ° C.
• the lower limit of the contact time when the water vapor and the fat and oil are brought into contact is preferably 30 minutes or more, more preferably 45 minutes or more, and most preferably 60 minutes or more, and the upper limit of the contact time when the water vapor and the fat and oil are brought into contact with each other. Is preferably 180 minutes or less, more preferably 150 minutes or less, and most preferably 120 minutes or less.
• the deodorizing treatment preferably has a reduced pressure of 8.0 ⁇ 10 2 Pa or less, more preferably 5.0 ⁇ 10 2 Pa or less, from the viewpoint of suppressing oxidation during the treatment and efficiently removing low boiling point components. It is done below.
• the amount of water vapor blown is preferably 1% by mass or more, more preferably 1.5% by mass or more, based on the amount of oil and fat (that is, when the mass of the fat is 100% by mass), and the upper limit thereof is It is preferably 5% by mass or less, more preferably 4% by mass or less.
• the conditions of each treatment may be different or the same.
• the deodorizing treatment is preferably performed twice or more when crude oil is used as a raw material, and is preferably performed once or more when using RBD oil or NBD oil, which will be described later.
• the refined fats and oils obtained even after being deodorized have a feature that the content of MCPDs and glycidols is small and the flavor is good.
• the above-mentioned contact treatment can be carried out as a decolorization treatment.
• the above-mentioned contact treatment can be performed separately from the decolorization treatment.
• the decolorization treatment can be performed before the contact treatment or between the contact treatment and the deodorization treatment.
• the RBD fats and oils can be subjected to a decolorization treatment, followed by the above-mentioned contact treatment and then a deodorization treatment.
• the RBD fats and oils can be subjected to the above-mentioned contact treatment, then decolorized, and then deodorized.
• the decolorization treatment when the contact treatment and the decolorization treatment are performed separately, the decolorization treatment can be performed by a conventional method.
• the conditions for the decolorization treatment are not particularly limited, and the decolorization treatment may be performed under the same conditions as the decolorization treatment usually set in the method for producing fats and oils.
• a decolorization material typified by white clay is preferably added to the fat and oil to be decolorized by about 0.1 to 2% by mass, and the pressure is preferably 1.0 ⁇ 10 4 Pa or less.
• the heating time is preferably 5 to 60 minutes.
• Decolorized fats and oils can be obtained by filtering the white clay from the fats and oils after heating the fats and oils.
• the conditions of each process may be different or the same.
• the decolorization treatment is preferably performed twice or more when crude oil is used as a raw material, and is preferably performed once or more when using RBD oil or NBD oil, which will be described later.
• Edible oils and fats include, for example, palm oil, palm kernel oil, palm oil, corn oil, olive oil, cottonseed oil, soybean oil, rapeseed oil, rice oil, sunflower oil, saflower oil, coconut oil, shea butter, mango kernel oil, and monkey.
• Vegetable fats and oils such as fats and ilippe fats, animal fats and oils such as beef tallow, milk fat, lard, fish oil and whale oil, and processed fats and oils that have been subjected to one or more treatments selected from hydrogenation, fractionation and ester exchange. Can be mentioned.
• the present invention may be applied to a single edible oil or fat selected from these, or may be applied to an edible oil or fat in which two or more kinds are mixed in combination.
• the method for producing refined fats and oils of the present invention may be applied to crude oils and fats and oils that have already been refined.
• MCPDs and glycidols are known to be produced by exposure to high temperatures in the process of producing fats and oils, and the refined fats and oils of the present invention are used for fats and oils that have undergone one or more deodorization steps of steam distillation at high temperatures. It is preferable to apply the production method of. Therefore, in one preferred embodiment, the method for producing a refined fat or oil of the present invention is applied to a fat or oil that has undergone a deodorization step at least once.
• the deodorizing step may be carried out according to the same procedure and conditions as the above-mentioned deodorizing treatment. In particular, it is preferable to select RBD fats and oils that are primary refined by physically refining crude oils and NBD fats and oils that are primary refined by chemical refining crude oils.
• the method for producing refined fats and oils of the present invention is preferably applied to palm-based fats and oils because its effect is particularly remarkable.
• the palm-based oil and fat is one or more physical or chemical treatments selected from palm oil, palm kernel oil, and palm oil or palm kernel oil, which are selected from hydrogenation, fractionation, transesterification, and the like. Refers to fats and oils. Regardless of which palm-based fat or oil is selected, according to the method of the present invention, a fat or oil having an extremely low content of MCPD or glycidol can be produced.
• the fats and oils obtained by the production method of the present invention are characterized by having an extremely low content of MCPDs and glycidols.
• the production method of the present invention when the production method of the present invention is applied to RBD palm-based fats and oils having an MCPD content of more than 4 ppm and a glycidol content of more than 3 ppm, it is obtained.
• the total content of MCPDs in the obtained fats and oils is preferably 4 ppm or less, more preferably 0 to 3 ppm, and the total content of glycidols in the obtained fats and oils is preferably 3 ppm or less, more preferably 0 to 2.5 ppm.
• a direct analysis method and an indirect analysis method are known due to the difference in principle.
• any method may be used for quantification, but since the types of standard substances used are small and economical, it is preferable to quantify MCPDs and glycidols by an indirect analysis method.
• an indirect analysis method the method described in Japanese Patent No. 5864278, Oleoscience Vol. 17, No. 4 (2017) p171-178, and the like can be used.
• 3-MCPD fatty acid ester, 2-MCPD fatty acid ester, and glycidyl fatty acid ester in fats and oils are hydrolyzed to convert them into free components, which are derivatized with phenylboric acid and then subjected to GC-MS.
• GC-MS a measuring method.
• the measurement conditions by GC-MS can be arbitrarily set with reference to the above documents, and for example, the measurement can be performed under the following conditions.
• the fats and oils obtained by the production method of the present invention preferably have an acid value of 0.5 or less, more preferably 0.3 or less, from the viewpoint of obtaining fats and oils having a good flavor.
• the acid value of fats and oils can be measured by, for example, the method shown in the standard fats and oils analysis test method (2013 edition) 2.3.1-2013 established by the Japan Oil Chemists' Society.
• the fats and oils obtained by the production method of the present invention preferably have a peroxide value of 0.3 or less, and more preferably 0.1 or less, from the viewpoint of obtaining fats and oils having a good flavor.
• the peroxide value of fats and oils can be measured by the method shown in, for example, the standard fats and oils analysis test method (2013 edition) 2.5.2 established by the Japan Oil Chemists' Society.
• the fats and oils obtained by the production method of the present invention can be used for manufacturing foods and drinks in the same manner as general fats and oils.
• Foods and drinks using fats and oils obtained by the production method of the present invention are characterized in that the content of MCPDs and glycidols is suppressed to be lower than that of conventional foods and drinks using fats and oils.
• Examples of the above foods and drinks include, for example, processed foods such as margarine, shortening, fat spread, dressing, mayonnaise, chilled confectionery, oil for spraying, oil for frying, oil for chocolate, oil for batter, oil powder, and flowers.
• Confectionery and bread ingredients such as paste and chocolate, Western confectionery, Japanese confectionery, bread, snacks, curry, stew, gratin, seasonings, instant cooked foods, processed livestock products, processed marine products, processed vegetables and other foods and drinks It can also be used as a raw material for foods and drinks that are required to have a high reduction in MCPDs and glycidols, such as prepared powdered milk for raising infants.
• the present invention also provides a method for reducing MCPDs or glycidols in fats and oils (hereinafter, also simply referred to as "method for reducing the present invention").
• the reduction method of the present invention is characterized by including a contact treatment of bringing white clay and zeolite into contact with fats and oils.
• activated clay is preferable to use activated clay as the clay, and it is preferable to use one or more selected from the group consisting of natural zeolite and synthetic zeolite as the zeolite.
• the preferable composition of white clay and zeolite, the amount used, and the like are as described above.
• the contact treatment and then the deodorization treatment it is preferable to perform the contact treatment and then the deodorization treatment.
• the conditions for the deodorizing treatment are as described above.
• the present invention also provides a decolorizing agent for fats and oils and a reducing agent for MCPDs or glycidols in fats and oils.
• the decolorizing agent for fats and oils and the reducing agent for MCPDs or glycidols in fats and oils of the present invention contain white clay and zeolite, and are used in contact with fats and oils during the production of fats and oils.
• the fat and oil decolorizing agent of the present invention contains 0.1 to 2.5 parts by mass of zeolite with respect to 1 part by mass of white clay.
• the decolorizing agent for fats and oils of the present invention may be a one-dose type decolorizing agent in which white clay and zeolite are mixed, or a two-dosage form in which a first agent made of white clay and a second agent made of zeolite are combined.
• the reducing agent for MCPDs or glycidols in the fats and oils of the present invention contains 0.1 to 2.5 parts by mass of zeolite with respect to 1 part by mass of white clay.
• the reducing agent for MCPDs or glycidols in the fats and oils of the present invention may be a one-dosage form reducing agent in which white clay and zeolite are mixed, and the first agent made of white clay and the second agent made of zeolite It may be a two-dosage form reducing agent that is a combination of the above.
• the decolorizing agent for fats and oils of the present invention and the reducing agent for MCPDs or glycidols in fats and oils may contain any additive in addition to white clay and zeolite.
• examples of such an additive include an adsorbent such as silica gel and a pH adjuster such as citric acid.
• the content of the additive is not particularly limited as long as the effect of the present invention is not impaired, and the amount to be blended in the fat or oil may be determined as described above.
• the decolorizing agent for fats and oils of the present invention and the reducing agent for MCPDs or glycidols in fats and oils are one-dose type agents in which white clay, zeolite and additives are mixed.
• It may be a three-dosage form agent in which the first agent composed of white clay, the second agent composed of zeolite, and the third agent composed of additives are combined, and two kinds selected from white clay, zeolite and additives. It may be a two-agent type agent in which the first agent composed of the above components and the second agent composed of the remaining components are combined.
• the decolorizing agent for fats and oils and the reducing agent for MCPDs or glycidols in fats and oils of the present invention from the viewpoint of enhancing the reducing effect of MCPDs and glycidols, the decolorizing agent for fats and oils of the present invention or It is preferable to perform a deodorizing treatment of the fat and oil after a contact treatment in which the reducing agent of MCPDs or glycidols in the fat and oil is brought into contact with the fat and oil.
• the conditions for contact treatment and deodorization treatment are as described above.
• RBD palm oil was used as the raw material.
• the RBD palm oil used is as follows. Unless otherwise specified, the following were used for white clay and zeolite. Further, unless otherwise specified, the deodorizing treatment was carried out under the conditions shown below.
• RBD palm oil manufactured by AAA, MCPD content 4.32 ppm, glycidols 3.69 ppm obtained by physically refining palm crude oil was used as a raw material.
• ⁇ Deodorizing treatment> As the deodorizing treatment, a deodorizing treatment by steam distillation was performed. Except as otherwise specified in Examinations 1 to 9, which will be described later, specifically, the dissolved fats and oils were steam-distilled at 230 ° C. for 90 minutes under a reduced pressure of 5.0 ⁇ 10 2 Pa or less. The amount of water vapor blown was 3% by mass / h with respect to oil and fat.
• MCPDs and glycidol content in fats and oils were measured by the following procedure using an indirect analysis method.
• the fatty acid ester of 3-MCPD, the fatty acid ester of 2-MCPD, and the fatty acid of glycidol in the fat and oil according to the method described in [Example] of Patent No. 5864278.
• the ester was hydrolyzed to convert it into free components 3-MCPD, 2-MCPD, and glycidol, respectively, which were derivatized with phenylboric acid and then quantified using GC-MS.
• the content of MCPDs was quantified in the same method for the RBD palm oil used for screening.
• the conditions of the gas chromatograph (GC) section and the mass spectrometry (MS) section were as follows.
• the “sum of MCPDs” in the table below means the sum of the contents of MCPDs contained in fats and oils, and the unit is mass ppm.
• the “sum of glycidols” means the total content of glycidols contained in fats and oils, and the unit is mass ppm.
• the "reduction rate of MCPDs” and “reduction rate of glycidols” in the table below are contact treatments based on the total amount of MCPDs in RBD palm oil before treatment or the total amount of glycidols. It shows how much the contents of MCPDs and glycidols could be reduced by passing through the above, and is calculated from the following formula.
• the contents of MCPDs and glycidols increase after the treatment based on the sum of the MCPDs and glycidols in the RBD palm oil before the treatment. Means to be.
• Reduction rate of MCPDs [(Contents of MCPDs before treatment-Contents of MCPDs after treatment) / (Contents of MCPDs before treatment)] ⁇ 100
• Reduction rate of glycidols [(content of glycidols before treatment-content of glycidols after treatment) / (content of glycidols before treatment)] ⁇ 100
• the color tone of fats and oils is the standard fats and oils analysis test method established by the Japan Oil Chemists' Society (1996 version) 2.2.1.1.
• the R and Y values were measured according to the Robibond method shown in -1996. In the table shown below, the R / Y values are shown.
• Example 1-1 white clay and zeolite were separately brought into contact with fats and oils.
• zeolite was brought into contact with the heated and dissolved RBD palm oil. Specifically, after adding 1.5% by mass of zeolite to the dissolved RBD palm oil, the oil and fat temperature is adjusted to 250 ° C., and the mixture is stirred for 30 minutes under a reduced pressure of 1.0 ⁇ 10 3 Pa or less. did. After the contact treatment with the zeolite, the zeolite was filtered off. Next, 2% by mass of white clay was added to the RBD palm oil contacted with zeolite.
• Example 1-2 white clay and zeolite were brought into contact with fats and oils at the same time.
• 2% by mass of white clay and 1.5% by mass of zeolite were weighed in advance with respect to the weight of fats and oils, and dry-mixed so as to be uniform.
• the heated and dissolved RBD palm oil was subjected to a contact treatment.
• the oil and fat temperature was adjusted to 250 ° C., and the mixture was stirred for 30 minutes under a reduced pressure of 1.0 ⁇ 10 3 Pa or less.
• the white clay and the zeolite were separated by filtration.
• the contact-treated RBD palm oil was deodorized to obtain refined fats and oils.
• REx1-1 the obtained refined fats and oils of Reference Example 1-1
• Ex1-1 to 1-2 the refined fats and oils of Examples 1-1 to 1-2
• the following reference examples and examples may be described in the same manner.
• Example 2-1 The treatment was carried out in the same manner as in Example 1-2 except that the temperature of the fats and oils during the contact treatment was adjusted to 120 ° C. to obtain refined fats and oils.
• Example 2-2 The treatment was carried out in the same manner as in Example 1-2 except that the temperature of the fats and oils during the contact treatment was adjusted to 90 ° C. to obtain refined fats and oils.
• Example 2-3 The treatment was carried out in the same manner as in Example 1-2 except that the temperature of the fats and oils during the contact treatment was adjusted to 60 ° C. to obtain refined fats and oils.
• Table 2 shows the MCPD content, glycidol content, and the reduction rate, acid value, peroxide value, color tone, and flavor of these Ex2-1 to 2-3 from RBD palm oil.
• MCPDs and glycidols can be used in a wide range of fats and oils temperatures of 60 to 250 ° C. It was confirmed that the reduction effect could be achieved. It was also confirmed that the temperature of fats and oils during the contact treatment tends to affect the effect of reducing MCPDs and glycidols, and the acid value, peroxide value, color tone, and flavor of the finally obtained refined fats and oils. ..
• Example 3-1 The treatment was carried out in the same manner as in Example 2-2 except that the contact treatment time was 60 minutes, and refined fats and oils were obtained.
• Example 3-2 The treatment was carried out in the same manner as in Example 2-2 except that the contact treatment time was 180 minutes, and refined fats and oils were obtained.
• Table 3 shows the MCPD content, glycidol content, reduction rate from RBD palm oil, acid value, peroxide value, color tone, and flavor of the obtained Ex3-1 and Ex3-2.
• Example 4-1 The treatment was carried out in the same manner as in Example 2-2 except that the contact treatment was carried out under normal pressure to obtain refined fats and oils.
• Table 4 shows the MCPD content, glycidol content, and the reduction rate, acid value, peroxide value, color tone, and flavor of these Ex4-1 from RBD palm oil.
• Example 5-1 The same treatment as in Example 2-2 was carried out to obtain refined fats and oils, except that the amount of white clay and the amount of zeolite used for the contact treatment were 1% by mass and 0.75% by mass of fats and oils, respectively.
• the amount ratio of white clay to zeolite was 0.75 parts by mass of zeolite with respect to 1 part by mass of white clay.
• Example 5-2 The treatment was carried out in the same manner as in Example 2-2 except that the amount of zeolite used for the contact treatment was 0.75% by mass based on the fat and oil, and refined fats and oils were obtained.
• the amount ratio of white clay to zeolite was 0.38 parts by mass of zeolite with respect to 1 part by mass of white clay.
• Example 5-3 The treatment was carried out in the same manner as in Example 2-2 except that the amount of white clay used for the contact treatment was 1% by mass with respect to the fat and oil, and refined fats and oils were obtained.
• the amount ratio of white clay to zeolite was 1.5 parts by mass of zeolite with respect to 1 part by mass of white clay.
• Example 5-4 The treatment was carried out in the same manner as in Example 2-2 except that the amount of zeolite used for the contact treatment was 3% by mass based on the fat and oil, and refined fats and oils were obtained.
• the amount ratio of white clay to zeolite was 1.5 parts by mass of zeolite with respect to 1 part by mass of white clay.
• Example 5-5 The treatment was carried out in the same manner as in Example 2-2, except that the amount of white clay and the amount of zeolite used for the contact treatment were 4% by mass and 3% by mass, respectively, to obtain refined fats and oils.
• the amount ratio of white clay to zeolite was 0.75 parts by mass of zeolite with respect to 1 part by mass of white clay.
• Table 5 shows the MCPD content, glycidol content, reduction rate from RBD palm oil, acid value, peroxide value, color tone, and flavor of the obtained Ex5-1 to Ex5-5.
• the amount ratio of white clay and zeolite used for the contact treatment is in the range of 0.5 to 1.2 parts by mass of zeolite with respect to 1 part by mass of white clay, such as 0.75 parts by mass of zeolite with respect to 1 part by mass of white clay.
• the effect of reducing MCPDs and zeolites tended to be particularly excellent.
• Example 6-1 Instead of natural zeolite (product name "SGW”, manufactured by Siegrite Co., Ltd., average particle size 10 ⁇ m), natural zeolite (product name "SGW-B4", manufactured by Siegrite Co., Ltd., average particle size 18 ⁇ m, clinoptilolite)
• SGW natural zeolite
• SGW-B4 manufactured by Siegrite Co., Ltd., average particle size 18 ⁇ m, clinoptilolite
• Example 6-2 Instead of natural zeolite (product name “SGW”, manufactured by Siegrite Co., Ltd., average particle size 10 ⁇ m), calcined zeolite (product name “calcined SGW” (when manufacturing "SGW", calcin and cool before classifying) (Partially ceramicized), manufactured by Siegrite Co., Ltd., with an average particle size of 10 ⁇ m, and a structure in which a clinoptilolite structure and a mordenite structure coexist) are the same as in Example 2-2. Was treated to obtain refined fats and oils.
• Example 6-3 Instead of natural zeolite (product name "SGW”, manufactured by Siegrite Co., Ltd., average particle size 10 ⁇ m), natural zeolite (product name "SP # 600", manufactured by Nitto Flour Chemical Co., Ltd., average particle size 1.9 ⁇ m, A refined fat or oil was obtained by carrying out the same treatment as in Example 2-2 except that the one having a mordenite structure was used.
• Example 6-4 Instead of natural zeolite (product name "SGW”, manufactured by Siegrite Co., Ltd., average particle size 10 ⁇ m), natural zeolite (product name "Izukalite”, manufactured by Izuka Co., Ltd., average particle size 63 ⁇ m or less, having a mordenite structure)
• natural zeolite product name "Izukalite”, manufactured by Izuka Co., Ltd., average particle size 63 ⁇ m or less, having a mordenite structure
• Example 6-5 Instead of natural zeolite (product name "SGW”, manufactured by Siegrite Co., Ltd., average particle size 10 ⁇ m), natural zeolite (product name "SU”, manufactured by Zeo Co., Ltd., average particle size 180 ⁇ m or less, clinoptilolite structure)
• SGW synthetic zeolite
• SU synthetic zeolite
• Comparative Example 6-1 Refined fats and oils were obtained in the same manner as in Example 2-2, except that acidic clay was used instead of natural zeolite (product name "SGW", manufactured by Siegrite Co., Ltd., average particle size 10 ⁇ m).
• Table 6 shows the MCPD content, glycidol content, and the reduction rate, acid value, peroxide value, color tone, and flavor of these Ex6-1 to Ex6-5 and CEx6-1 from RBD palm oil. Shown.
• the zeolite having a clinoptilolite structure tended to have a higher effect of reducing MCPDs than the zeolite having a mordenite structure.
• the test using acid clay instead of zeolite although the effect of reducing glycidols was obtained, the effect of reducing MCPDs was hardly obtained.
• Example 7-1 In addition to white clay and zeolite, silica gel (product name "Syropute 130", manufactured by Fuji Silysia Chemical Ltd.) was further added in an amount of 1% by mass based on fats and oils, and the same treatment as in Example 2-2 was performed to remove refined fats and oils. Obtained.
• Example 7-2 In addition to the white clay and zeolite, a 50% by mass citric acid aqueous solution was added so that the added pure citric acid content was 0.33% by mass with respect to the oil and fat, and the same treatment as in Example 2-2 was carried out. , Refined fats and oils were obtained.
• Table 7 shows the MCPD content, glycidol content, and the reduction rate, acid value, peroxide value, color tone, and flavor of these Ex7-1 and Ex7-2 from RBD palm oil.
• Example 8-1 The refined fats and oils obtained in Example 2-2 were used as raw materials, and the same treatment as in Example 2-2 was carried out to obtain refined fats and oils.
• This refined fat and oil is a fat and oil obtained by subjecting RBD palm oil to contact treatment with white clay and zeolite twice.
• RBD palm oils of different lots (manufactured by AAA, MCPD content 5.45 ppm, glycidols 8.38 ppm) were targeted for purification.
• the RBD palm oils having different lots were indicated as "RBD palm oil lot2" in Table 9.
• Example 9-1 First, 2% by mass of white clay and 1.5% by mass of zeolite were weighed in advance with respect to the weight of fats and oils, and dry-mixed so as to be uniform. Next, using this mixture, the heated and dissolved RBD palm oil was subjected to a contact treatment. During the contact treatment, the oil and fat temperature was adjusted to 90 ° C., and the mixture was stirred for 30 minutes under a reduced pressure of 1.0 ⁇ 10 3 Pa or less. After the contact treatment, the white clay and the zeolite were separated by filtration. Then, the contact-treated RBD palm oil was deodorized to obtain refined fats and oils. The deodorizing treatment was carried out by steam distillation.
• the dissolved fats and oils were adjusted to have a fats and oils temperature of 200 ° C. under a reduced pressure of 5.0 ⁇ 10 2 Pa or less, and steam distillation was performed for 40 minutes.
• the amount of water vapor blown was 3% by mass / h with respect to oil and fat.
• Example 9-2 When the deodorizing treatment was performed, the treatment was carried out in the same manner as in Example 9-1 except that the steam distillation time was changed to 90 minutes to obtain refined fats and oils.
• Example 9-3 When the deodorizing treatment was performed, the treatment was carried out in the same manner as in Example 9-1 except that the fat and oil temperature was changed to 230 ° C. to obtain refined fats and oils.
• Example 9-4 When the deodorizing treatment was performed, the treatment was carried out in the same manner as in Example 9-1 except that the fat and oil temperature was changed to 230 ° C. and the steam distillation time was changed to 90 minutes to obtain refined fats and oils.
• Example 9-5 When the deodorizing treatment was performed, the treatment was carried out in the same manner as in Example 9-1 except that the fat and oil temperature was changed to 260 ° C. to obtain refined fats and oils.
• Example 9-6 When the deodorizing treatment was performed, the treatment was carried out in the same manner as in Example 9-1 except that the fat and oil temperature was changed to 260 ° C. and the steam distillation time was changed to 90 minutes to obtain refined fats and oils.
• Table 9 shows the MCPD content, glycidol content, and the reduction rate, acid value, peroxide value, color tone, and flavor of these Ex9-1 to 9-6 from RBD palm oil.
• Example 10-1 Instead of RBD palm oil, RBD palm olein (separated soft tissue oil obtained by separating RBD palm oil, manufactured by AAA, iodine value 56, MCPD content 6.87 ppm) was used for refining. The same treatment as in Example 2-2 was carried out to obtain refined fats and oils.
• RBD palm olein separated soft tissue oil obtained by separating RBD palm oil, manufactured by AAA, iodine value 56, MCPD content 6.87 ppm
• Example 10-2 RBD super olein (fractional soft tissue oil obtained by further fractionating RBD palm olein, manufactured by AAA, iodine value 65, MCPD content 5.26 ppm) was used for refining instead of RBD palm oil. The same treatment as in Example 2-2 was carried out to obtain refined fats and oils.
• Example 10-3 RBD palm oils of different lots (manufactured by AAA, MCPD content 5.13 ppm, glycidols 5.78 ppm) were treated in the same manner as in Example 2-2 to obtain refined fats and oils. ..
• Table 10 shows the MCPD content, reduction rate from these raw material fats and oils, acid value, peroxide value, color tone, and flavor of the obtained Ex10-1 to 10-3.

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