Method for refining oils and fats and method for reducing chloropropanols

Abstract

To provide a production method of oil and fat, capable of reducing chloropropanol in oil and fat by simple processing without causing physical property change of stock oil due to curing processing.SOLUTION: A production method of oil and fat includes a chloropropanol reducing processing step of adding a nickel catalyst to oil and fat containing chloropropanol followed by heating the product.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a method for producing fats and oils and a method for reducing chloropropanols. [Background technology]

[0002] Chloropropanols are a general term for substances in which chlorine is bonded to propanol, and one of these, 3-chloro-1,2-propanediol (3-MCPD), is known to be produced as a by-product when manufacturing amino acid liquid, soy sauce, etc. In addition, 3-MCPD exists in edible oils and fats as an ester form (3-MCPDE) in which it is bonded to fatty acids, and there is concern that when people ingest foods containing 3-MCPDE, the ester is hydrolyzed in the body to produce 3-MCPD.

[0003] And, as a result of a risk assessment by the Food and Agriculture Organization of the United Nations (FAO) / World Health Organization (WHO), 3-MCPD was found to be neither genotoxic nor carcinogenic, but there are concerns that it may have adverse effects on the kidneys if ingested in large quantities over a long period of time. In Japan, no standards have been set under the Food Sanitation Act, but the Ministry of Agriculture, Forestry and Fisheries is promoting the reduction of 3-MCPD in soy sauce and other products through manufacturing methods.

[0004] The present applicant has proposed a method for reducing chloropropanols in edible oils and fats (Patent Document 1). Patent Document 1 describes that in the production of edible oils and fats from raw oils, including hardening treatment, at least one selected from the group consisting of white clay having a pH of 7.0 or more, wood-based activated carbon having a pH of 7.0 or more, sodium carbonate, and calcium hydroxide is added in any of the steps before, during, or after the hardening treatment. It also describes that in the hardening treatment step, for example, raw oil to which a hardening catalyst such as nickel has been added is charged into a reaction vessel, heated and stirred under vacuum, and when the raw oil reaches a predetermined temperature, hydrogen at a required pressure is fed into the reaction vessel to start a hydrogenation reaction and add hydrogen. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2016-123330 A Summary of the Invention [Problem to be solved by the invention]

[0006] However, the method of Patent Document 1 is premised on adding hydrogen to the feedstock oil as a hardening treatment. Conventionally, such hardening treatment has been considered essential to reduce chloropropanols, and it has been unavoidable that the hardening treatment causes changes in the physical properties of the feedstock oil.

[0007] The present invention has been made in consideration of the above-mentioned circumstances, and an object of the present invention is to provide a method for producing fats and oils that can reduce chloropropanols in fats and oils through a simple treatment without causing changes in the physical properties of the raw oil due to hardening treatment, and a method for reducing chloropropanols. [Means for solving the problem]

[0008] In order to solve the above problems, the method for producing fats and oils of the present invention is characterized by including a chloropropanol reduction treatment step in which a nickel catalyst is added to fats and oils containing chloropropanols and then heated.

[0009] Furthermore, the method for reducing chloropropanols of the present invention is a method for reducing chloropropanols in fats and oils, and is characterized by including a step of adding a nickel catalyst to fats and oils containing chloropropanols and heating the resulting mixture. Effect of the Invention

[0010] According to the method for producing fats and oils and the method for reducing chloropropanols of the present invention, chloropropanols in fats and oils can be reduced by a simple treatment without causing changes in the physical properties of the raw oil due to hardening treatment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] It has been known in the past that chloropropanols can be reduced by hardening treatment through hydrogenation (e.g., Patent Document 1). However, the present inventors have discovered the novel finding that chloropropanols can be reduced by adding a nickel catalyst to fats and oils and heating them, without carrying out hardening treatment through hydrogenation, and have completed the present invention.

[0012] Hereinafter, one embodiment of the method for producing fats and oils and the method for reducing chloropropanols of the present invention will be described.

[0013] In the method for producing fats and oils of the present invention, as a chloropropanols reduction treatment step, a nickel catalyst is added to fats and oils containing chloropropanols, and the resulting mixture is heated.

[0014] In the present invention, chloropropanols include 3-chloro-1,2-propanediol (3-MCPD) and 3-chloro-1,2-propanediol fatty acid esters (3-MCPDE) produced in edible fats and oils, as well as glycidol and glycidol fatty acid esters which are formed from these substances.

[0015] The raw oil for the oil may be one obtained by a method for obtaining oil from plants or animals (by pressing, heating, or solvents), or may be edible oil or a fractionated oil or an interesterified oil obtained by subjecting two or more kinds of edible oils to fractionation, interesterification, or the like, which is commonly performed in the field of edible oils and fats, or may be a triglyceride obtained by esterifying glycerin with a fatty acid.

[0016] Furthermore, the method for producing fats and oils of the present invention may include treatment steps such as degumming, deacidification, bleaching, dewaxing and deodorization, and such treatments may be treatments that are commonly carried out in the field of edible fats and oils.

[0017] The fats and oils are not particularly limited as long as they are usable as edible fats and oils, and may be in any form, such as liquid or solid, at room temperature.Specific examples of the fats and oils include vegetable oils such as soybean oil, rapeseed oil, corn oil, sesame oil, perilla oil, linseed oil, peanut oil, safflower oil, high oleic acid safflower oil, sunflower oil, high oleic acid sunflower oil, cottonseed oil, grape seed oil, macadamia nut oil, hazelnut oil, pumpkin seed oil, walnut oil, camellia oil, tea seed oil, perilla oil, borage oil, olive oil, rice bran oil, wheat germ oil, coconut oil, cacao butter, palm oil, palm kernel oil, and algae oil, and animal oils such as fish oil, lard, beef tallow, and milk fat.

[0018] The nickel catalyst is not particularly limited, and a conventionally known one can be used, and examples thereof include nickel supported on a porous carrier such as diatomaceous earth, or nickel further coated with fat or oil to form flakes, particles, etc. Examples of commercially available nickel catalysts include flake nickel catalysts SO-100A, SO-100AR, SO-250, SO-350, SO-650, SO-750, SO-750R, SO-850, SN-250, SN-300, SN-750, SN-570, SN-705, SN-780, etc. manufactured by Sakai Chemical Industry Co., Ltd.

[0019] The lower limit of the amount of the nickel catalyst added is preferably 0.050% by mass or more, more preferably 0.10% by mass or more, even more preferably 0.20% by mass or more, and particularly preferably 0.30% by mass or more, based on the fat or oil, from the viewpoint of efficiently reducing chloropropanols. The upper limit of the amount of the nickel catalyst added is preferably 5.0% by mass or less, more preferably 4.0% by mass or less, even more preferably 3.0% by mass or less, and particularly preferably 2.0% by mass or less, based on the fat or oil, from the viewpoint of suppressing the amount of nickel eluted into the oil.

[0020] Moreover, the lower limit of the heating temperature of the oil or fat is preferably 60° C. or higher, more preferably 80° C. or higher, and even more preferably 100° C. or higher, from the viewpoint of efficiently reducing chloropropanols. The upper limit of the heating temperature of the oil or fat is preferably less than 220° C., more preferably less than 200° C., even more preferably less than 190° C., and particularly preferably less than 185° C., from the viewpoint of suppressing the production of chloropropanols.

[0021] In addition, although it depends on the heating temperature, the lower limit of the heating time of the oil is preferably 20 minutes or more, more preferably 40 minutes or more, even more preferably 60 minutes or more, and particularly preferably 70 minutes or more, from the viewpoint of efficiently reducing 3-MCPD. The upper limit of the heating time of the oil is preferably 240 minutes or less, more preferably 200 minutes or less, and even more preferably 160 minutes or less, from the viewpoint of suppressing deterioration of the oil.

[0022] In the method for producing fats and oils of the present invention, a nickel catalyst is added to fats and oils and then heated. This makes it possible to efficiently reduce the chloropropanols 3-MCPD and 3-MCPDE in fats and oils, as well as their precursors glycidol and glycidol fatty acid esters, without causing any change in the physical properties of the raw oil, as occurs in the case of a hardening reaction by hydrogenation, in a simple manner.

[0023] In the method for producing fats and oils of the present invention, it is preferable to further add a fatty acid in the chloropropanols reduction treatment step. By adding a fatty acid together with nickel to fats and oils (raw oil) and heating the mixture, the effect of reducing chloropropanols in the fats and oils can be enhanced. The fatty acid may be added to the fats and oils together with nickel and then heat-treated, or the nickel may be added to the fats and oils and then filtered out after the heat treatment, and then added. However, it is preferable to add the fatty acid to the fats and oils together with nickel and then heat-treated.

[0024] The fatty acid is one or more of the saturated fatty acids S or the unsaturated fatty acids U.

[0025] Examples of saturated fatty acids S include, but are not limited to, butyric acid (4), caproic acid (6), caprylic acid (8), capric acid (10), lauric acid (12), myristic acid (14), palmitic acid (16), stearic acid (18), arachidic acid (20), behenic acid (22), lignoceric acid (24), etc. The above numerical notations refer to the number of carbon atoms in the fatty acid.

[0026] The unsaturated fatty acid U is not particularly limited, but examples thereof include myristoleic acid (14:1), palmitoleic acid (16:1), heliconic acid (16:3), oleic acid (18:1), linoleic acid (18:2), linolenic acid (18:3), eicosenoic acid (20:1), erucic acid (22:1), selacholeic acid (24:1), etc. The numerical values ​​in parentheses for the above unsaturated fatty acids indicate the number of carbon atoms of the fatty acid on the left and the number of double bonds on the right.

[0027] Among them, the fatty acid is preferably a saturated fatty acid, more preferably a saturated fatty acid having 22 or less carbon atoms, and even more preferably a saturated fatty acid having 18 or less carbon atoms. In this case, the effect of reducing chloropropanols can be further enhanced.

[0028] The lower limit of the amount of fatty acid added is preferably 0.10% by mass or more, more preferably 0.20% by mass or more, even more preferably 0.30% by mass or more, and particularly preferably 0.40% by mass or more, based on the oil and fat, from the viewpoint of efficient reduction of chloropropanols. The upper limit of the amount of fatty acid added is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 12% by mass or less, and particularly preferably 8.0% by mass or less, based on the oil and fat, from the viewpoint of removal efficiency from the oil and fat.

[0029] In the method for producing fats and oils of the present invention, it is preferable to further add a silicate in the chloropropanols reduction treatment step. By adding a silicate together with nickel to fats and oils (raw oil) and heating the mixture, the effect of reducing chloropropanols in the fats and oils can be enhanced. The silicate may be added to the fats and oils together with nickel and then heat-treated, or the nickel may be added to the fats and oils and then filtered after heat treatment, and then added. However, it is preferable to add the silicate to the fats and oils together with nickel and then heat-treated.

[0030] Examples of silicate include sodium silicate, calcium silicate, potassium silicate, magnesium silicate, aluminum silicate, and silica gel, and among these, magnesium silicate is particularly preferred. Examples of commercially available silicate include magnesium silicate SMW (magnesium silicate, manufactured by Tomita Pharmaceutical Co., Ltd.), Mizuka Life F-2G (magnesium silicate, manufactured by Mizusawa Chemical Industry Co., Ltd.), Kyoward 600 (magnesium silicate, manufactured by Kyowa Chemical Industry Co., Ltd.), and Kyoward 700 (aluminum silicate, manufactured by Kyowa Chemical Industry Co., Ltd.). Examples of minerals containing silicate include wollastonite, xonotlite, talc, clay, mica, montmorillonite, bentonite, white clay, sepiolite, imogolite, and sericite.

[0031] The lower limit of the amount of silicate added is preferably 0.10% by mass or more, more preferably 0.50% by mass or more, even more preferably 1.0% by mass or more, and particularly preferably 2.0% by mass or more, based on the fat or oil, from the viewpoint of efficient reduction of chloropropanols. The upper limit of the amount of silicate added is preferably 10% by mass or less, more preferably 8.0% by mass or less, even more preferably 6.0% by mass or less, and particularly preferably 4.0% by mass or less, based on the fat or oil, from the viewpoint of filtration efficiency of the fat or oil.

[0032] In the method for producing fats and oils of the present invention, it is more preferable to add white clay in the chloropropanols reduction treatment step. By adding white clay together with nickel to fats and oils (raw oil) and heating the mixture, the effect of reducing chloropropanols in the fats and oils can be enhanced. The white clay may be added to the fats and oils simultaneously with nickel and then subjected to heat treatment, or nickel may be added to the fats and oils and then filtered out after heat treatment, and then added. However, it is preferable to add the white clay to the fats and oils simultaneously with nickel and then subjected to heat treatment.

[0033] The white clay is an acidic white clay mainly composed of clay minerals called kaolin or montmorillonite, or an activated white clay obtained by activating the acidic white clay with sulfuric acid or hydrochloric acid. The pH is not particularly limited, but examples include a pH of 7.0 or more, preferably a pH of 8.0 or more. Examples of methods for measuring the pH of white clay include JIS K 5101-17-1:2004 Pigment Test Method.

[0034] The silicon dioxide (SiO2) content of the white clay is preferably 65% ​​by mass to 85% by mass, more preferably 68% by mass to 83% by mass, based on the total composition of the white clay. If the SiO2 content is within the above range, the generation of chloropropanols can be further suppressed. Examples of commercially available products of such white clay include MIZUKA-ACE #300 (pH 8.5, SiO2 content 70.5%, manufactured by Mizusawa Industrial Chemicals Co., Ltd.) and GALLEON EARTH V2 (pH 3.3, SiO2 content 79.8%, manufactured by Mizusawa Industrial Chemicals Co., Ltd.).

[0035] Furthermore, clay that has been previously treated with an alkali may also be used preferably. Here, the alkali treatment includes a step of mixing the clay with an alkali solution, followed by filtration or centrifugation to remove the solvent.

[0036] Examples of the alkaline substance used in the alkali treatment include hydroxides, carbonates, phosphates, organic acid salts, and alkoxide compounds of alkali metals and alkaline earth metals. Specific examples include sodium carbonate, sodium hydrogen carbonate, sodium methoxide, sodium ethoxide, calcium hydroxide, sodium hydroxide, potassium hydroxide, and sodium tripolyphosphate. In particular, sodium hydroxide is preferred because it is a strong alkali and exerts the required effect with a small amount added. These substances may be used alone or in combination of two or more.

[0037] Since such an alkaline substance is easily brought into contact with the white clay, it is preferable to dissolve it in a solvent and use it as an alkaline solution. Examples of solvents that can be used to dissolve the alkaline substance include water and alcohols such as methanol and ethanol. The solvent may be used alone or in combination of two or more kinds, but it is preferable that the solvent contains less water. If the solvent contains less water, the white clay can be made more alkaline. By increasing the alkalinity, the amount of chloropropanols can be further reduced.

[0038] A preferred concentration of the alkaline solution is, for example, in the range of 0.01 mol / L to 5 mol / L.

[0039] Furthermore, the white clay having a pH of 7 or more can be used in combination with at least one selected from the group consisting of sodium methoxide and sodium hydroxide.

[0040] The lower limit of the amount of white clay added is preferably 0.050% by mass or more, more preferably 0.10% by mass or more, even more preferably 0.50% by mass or more, and particularly preferably 0.80% by mass or more, based on the fat or oil, from the viewpoint of efficient reduction of chloropropanols. The upper limit of the amount of white clay added is preferably 10% by mass or less, more preferably 8.0% by mass or less, even more preferably 6.0% by mass or less, and particularly preferably 4.0% by mass or less, based on the fat or oil, from the viewpoint of filtration efficiency of the fat or oil.

[0041] In the method for producing fats and oils of the present invention, it is preferable to further add silicon dioxide in the chloropropanols reduction treatment step. By adding silicon dioxide together with nickel to fats and oils (raw oil) and heating the mixture, the effect of reducing chloropropanols in the fats and oils can be enhanced. Silicon dioxide may be added to fats and oils simultaneously with nickel and then heat-treated, or nickel may be added to fats and oils and then filtered after heat treatment, but it is preferable to add silicon dioxide to fats and oils simultaneously with nickel and then heat-treated. From the viewpoint of efficiently reducing chloropropanols, the amount of silicon dioxide added is preferably 0.10% by mass or more, more preferably 0.20% by mass or more, even more preferably 0.30% by mass or more, and particularly preferably 0.40% by mass or more, based on the fats and oils. From the viewpoint of removal efficiency from fats and oils, the upper limit of the amount of silicon dioxide added is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 12% by mass or less, and particularly preferably 8.0% by mass or less, based on the fats and oils.

[0042] Examples of commercially available silicon dioxide products include Cylopute 71R, Cylopute 80, Cylopute 81, Cylopute 82, Cylopute 130, Cylopute 200, Cylopute 202, and Cylopute 230 manufactured by Fuji Silysia Chemical Ltd.

[0043] From the viewpoint of efficiently reducing chloropropanols, the pH of silicon dioxide is preferably not more than 4. Examples of commercially available silicon dioxide of this type include Cylopute 230.

[0044] Thus, in the method for producing fats and oils of the present invention, it is preferable to add, in addition to the nickel catalyst, one or more of fatty acids, silicates, clay and silicon dioxide, and then heat the mixture.

[0045] Furthermore, the method for reducing chloropropanols of the present invention is a method for reducing chloropropanols in fats and oils, and includes a step of adding a nickel catalyst to fats and oils containing chloropropanols and heating the resulting mixture.

[0046] Embodiments of the method for reducing chloropropanols of the present invention include the configurations described in the above-mentioned method for producing fats and oils of the present invention.

[0047] According to the method for reducing chloropropanols of the present invention, by adding a nickel catalyst to fats and oils and heating the oils and oils, it is possible to efficiently reduce the chloropropanols 3-MCPD and 3-MCPDE in fats and oils, as well as their precursors, glycidol and glycidol fatty acid esters, in a simple manner without causing any change in the physical properties of the raw material oil due to the hardening reaction caused by hydrogenation.

[0048] The method for producing fats and oils and the method for reducing chloropropanols of the present invention are not limited to the above embodiments. In the method for producing fats and oils and the method for reducing chloropropanols of the present invention, a hardening treatment by hydrogenation can be performed as necessary. In this case, the physical properties of the raw oil may change due to the hardening reaction, but chloropropanols may be effectively reduced. EXAMPLES

[0049] The method for producing fats and oils and the method for reducing chloropropanols of the present invention will be described below with reference to examples. However, the method for producing fats and oils and the method for reducing chloropropanols of the present invention are not limited to the following examples. <1> material Nickel was added to the oil, and one or two of fatty acids, silicates, clay, and silicon dioxide were also added. (Oils and fats) RBD palm oil (RBD-PO) was used. The total amount of chloropropanols was calculated as 3-MCPD according to the American Oil Chemists' Society Official Method (AOCS Official Method Cd 29c-13 Assay B). The amount of 3-MCPD in the RBD palm oil was 3.00 ppm. (Nickel catalyst) Nickel catalysts SO-100A, SO-100AR, SO-250, SO-350, SO-650, SO-750, SO-850, SN-250, SN-300, SN-570, SN-705, SN-750, and SN-780 (manufactured by Sakai Chemical Industry Co., Ltd.) were used. The nickel catalyst was added at 0.30 to 1.0% relative to the fat or oil. (fatty acid) Capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, and linoleic acid were used. Fatty acids were added at 0.50 to 10% of the oil. (Silicate) Magnesium silicate SMW (Tomita Pharmaceutical Co., Ltd.) and Mizuka Life F-2G (Mizusawa Industrial Chemicals Co., Ltd.) were used. The silicate was added at 3.0% relative to the fat and oil. (Shirato) Acid clay (MIZUKA-ACE #300, pH 8.5, SiO2 content 70.5%, Mizusawa Chemical Industry Co., Ltd.) was used. Activated clay (GALLEON EARTH V2, pH 3.3, SiO2 content 79.8%, Mizusawa Chemical Industry Co., Ltd.) was also used. The clay was added at 1.0 to 3.0% relative to the fat and oil. (Silicon dioxide) Silicon dioxide Silopute 71R, Silopute 80, Silopute 81, Silopute 82, Silopute 130, Silopute 200, Silopute 202, and Silopute 230 (manufactured by Fuji Silysia Chemical Co., Ltd.) were used. Silicon dioxide was added at 3.0% relative to the fat and oil.

[0050] <2> Heat Treatment Oils and fats to which nickel or other additives had been added were heated at 160°C to 200°C for 40 to 120 minutes. The total amount of chloropropanols in the oils and fats after heating was calculated as a value converted to 3-MCPD in accordance with the American Oil Chemists' Society Official Method (AOCS Official Method Cd 29c-13 Assay B).

[0051] <3> result The results are shown in Tables 1 to 3.

[0052] [Table 1]

[0053] [Table 2]

[0054] [Table 3]

[0055] As shown in Tables 1 to 3, in Examples 1 to 80 in which nickel was added to the oils and fats, it was confirmed that the chloropropanols in the oils and fats were reduced by the nickel treatment without carrying out hardening treatment by hydrogen addition.

[0056] Furthermore, it was confirmed that in Examples 15 to 40, 42 to 50, 52, 54, 56, 58, 60, 62 to 78, and 80, in which one or two of fatty acids, silicates, clay, and silicon dioxide were added in addition to the nickel catalyst, the chloropropanols in the oils and fats were further reduced.

[0057] On the other hand, in Comparative Examples 1 to 10 in which no nickel catalyst was added to the fat or oil, it was confirmed that there was no change in the amount of 3-MCPD or that the reduction effect was insufficient.

Claims

1. A method for refining fats and oils, comprising a chloropropanol reduction treatment step in which a nickel catalyst is added to fats and oils containing chloropropanols and the fats and oils are heated without being subjected to a hardening treatment by hydrogenation.

2. The method for refining oils and fats described in claim 1, characterized in that the chloropropanol reduction treatment process reduces the content of chloropropanols in the oil and fat compared to the content before the chloropropanol reduction treatment.

3. A method for refining fats and oils described in claim 1 or 2, characterized in that the fats and oils are vegetable fats and oils.

4. A method for refining oils and fats as described in claim 3, characterized in that the vegetable oil and fat is palm oil.

5. A method for refining fats and oils described in any one of claims 1 to 4, characterized in that the heating temperature of the fats and oils is less than 190°C, and the amount of nickel catalyst added is 0.050 mass% or more and 2.0 mass% or less relative to the fats and oils.

6. The method for refining fats and oils according to any one of claims 1 to 5, characterized in that a fatty acid is further added in the chloropropanols reduction treatment step.

7. The method for refining fats and oils according to any one of claims 1 to 5, further comprising adding a silicate in the chloropropanols reduction treatment step.

8. The method for refining fats and oils according to any one of claims 1 to 5, further comprising adding clay in the chloropropanols reduction treatment step.

9. The method for refining fats and oils according to any one of claims 1 to 5, characterized in that silicon dioxide is further added in the chloropropanols reduction treatment step.

10. A method for reducing chloropropanols in fats and oils, comprising: A method for reducing chloropropanols, comprising the steps of adding a nickel catalyst to fats and oils containing chloropropanols and heating the fats and oils without carrying out a hardening treatment by hydrogenation.

Images