JP2016123330A - Method for decreasing chloropropanol in edible oil and fat - Google Patents
Method for decreasing chloropropanol in edible oil and fat Download PDFInfo
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- JP2016123330A JP2016123330A JP2014266356A JP2014266356A JP2016123330A JP 2016123330 A JP2016123330 A JP 2016123330A JP 2014266356 A JP2014266356 A JP 2014266356A JP 2014266356 A JP2014266356 A JP 2014266356A JP 2016123330 A JP2016123330 A JP 2016123330A
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- chloropropanols
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- 238000000034 method Methods 0.000 title claims abstract description 96
- RZWHKKIXMPLQEM-UHFFFAOYSA-N 1-chloropropan-1-ol Chemical compound CCC(O)Cl RZWHKKIXMPLQEM-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000008157 edible vegetable oil Substances 0.000 title abstract description 7
- 230000003247 decreasing effect Effects 0.000 title abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 191
- 239000003921 oil Substances 0.000 claims abstract description 129
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 72
- 239000004927 clay Substances 0.000 claims abstract description 64
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 36
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 239000003925 fat Substances 0.000 claims description 93
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 38
- 239000000920 calcium hydroxide Substances 0.000 claims description 38
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 38
- 239000003513 alkali Substances 0.000 claims description 30
- 230000001603 reducing effect Effects 0.000 claims description 25
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- SSZWWUDQMAHNAQ-UHFFFAOYSA-N 3-chloropropane-1,2-diol Chemical compound OCC(O)CCl SSZWWUDQMAHNAQ-UHFFFAOYSA-N 0.000 abstract description 69
- 239000002023 wood Substances 0.000 abstract description 25
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 3
- 235000014593 oils and fats Nutrition 0.000 abstract description 3
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- 235000019197 fats Nutrition 0.000 description 85
- 230000008569 process Effects 0.000 description 38
- 235000021323 fish oil Nutrition 0.000 description 36
- 239000000126 substance Substances 0.000 description 33
- 230000009467 reduction Effects 0.000 description 18
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 15
- 238000001914 filtration Methods 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 15
- 229910052740 iodine Inorganic materials 0.000 description 15
- 239000011630 iodine Substances 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- 235000014113 dietary fatty acids Nutrition 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 239000000194 fatty acid Substances 0.000 description 11
- 229930195729 fatty acid Natural products 0.000 description 11
- -1 glycidol fatty acid esters Chemical class 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 230000004913 activation Effects 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 235000013305 food Nutrition 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 239000012670 alkaline solution Substances 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000004332 deodorization Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 150000004665 fatty acids Chemical group 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000010561 standard procedure Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 230000001877 deodorizing effect Effects 0.000 description 3
- 125000005456 glyceride group Chemical group 0.000 description 3
- 230000008520 organization Effects 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 235000019485 Safflower oil Nutrition 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000019486 Sunflower oil Nutrition 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000037396 body weight Effects 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 235000019864 coconut oil Nutrition 0.000 description 2
- 239000003240 coconut oil Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 235000005713 safflower oil Nutrition 0.000 description 2
- 239000003813 safflower oil Substances 0.000 description 2
- 235000011803 sesame oil Nutrition 0.000 description 2
- 239000008159 sesame oil Substances 0.000 description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 235000013555 soy sauce Nutrition 0.000 description 2
- 239000002600 sunflower oil Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 235000019487 Hazelnut oil Nutrition 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 235000018330 Macadamia integrifolia Nutrition 0.000 description 1
- 240000000912 Macadamia tetraphylla Species 0.000 description 1
- 235000003800 Macadamia tetraphylla Nutrition 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 235000004347 Perilla Nutrition 0.000 description 1
- 244000124853 Perilla frutescens Species 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 235000019774 Rice Bran oil Nutrition 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 235000019498 Walnut oil Nutrition 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000021324 borage oil Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000010495 camellia oil Substances 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229960004424 carbon dioxide Drugs 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 235000019868 cocoa butter Nutrition 0.000 description 1
- 229940110456 cocoa butter Drugs 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- 239000002285 corn oil Substances 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- QUSSPXNPULRXKG-UHFFFAOYSA-N galleon Natural products O1C(=CC=2)C(OC)=CC=2CCCCC(=O)CCC2=CC=C(O)C1=C2 QUSSPXNPULRXKG-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 231100000025 genetic toxicology Toxicity 0.000 description 1
- 230000001738 genotoxic effect Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 239000010468 hazelnut oil Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 235000021243 milk fat Nutrition 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000010466 nut oil Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 239000003346 palm kernel oil Substances 0.000 description 1
- 235000019865 palm kernel oil Nutrition 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 235000015277 pork Nutrition 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical group CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000008171 pumpkin seed oil Substances 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000008165 rice bran oil Substances 0.000 description 1
- 238000012502 risk assessment Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
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- 239000010497 wheat germ oil Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Landscapes
- Edible Oils And Fats (AREA)
- Fats And Perfumes (AREA)
Abstract
Description
本発明は、食用油脂中のクロロプロパノール類を低減する方法に関する。 The present invention relates to a method for reducing chloropropanols in edible fats and oils.
クロロプロパノール類は、プロパノールに塩素が結合した物質の総称であり、その１つである３−クロロ−１，２−プロパンジオール（３−ＭＣＰＤ）はアミノ酸液や醤油等を製造する際に副産物として生成することが知られている。ＦＡＯ（国際連合食糧農業機関）／ＷＨＯ（世界保健機関）によるリスク評価の結果、３−ＭＣＰＤには遺伝毒性や発がん性は認められないものの、長期間にわたり大量に摂取した場合、腎臓に悪影響を及ぼすことが懸念されている。我が国においては、食品衛生法に基づく基準は設定されていないが、農林水産省では醤油等に対しては、製造法による低減の推進を指導している。また、諸外国においては、ＥＵ（ヨーロッパ連合）が０．０２ｍｇ／ｋｇ体重（乾物ベース）、ＣＯＤＥＸ（国際食品規格委員会）が０．４ｍｇ／ｋｇ体重の規制を設定している。 Chloropropanol is a general term for substances in which chlorine is bonded to propanol, and 3-chloro-1,2-propanediol (3-MCPD), one of which is a by-product in the production of amino acid solutions, soy sauce, and the like. It is known to generate. As a result of risk assessment by FAO (United Nations Food and Agriculture Organization) / WHO (World Health Organization), although 3-MCPD does not show genotoxicity or carcinogenicity, it causes adverse effects on the kidneys when ingested in large quantities over a long period of time. There are concerns about the effects. In Japan, standards based on the Food Sanitation Law have not been set, but the Ministry of Agriculture, Forestry and Fisheries has instructed the promotion of reduction of soy sauce by the manufacturing method. In other countries, the EU (European Union) sets a limit of 0.02 mg / kg body weight (dry matter base) and CODEX (International Food Standards Committee) sets a limit of 0.4 mg / kg body weight.
また、２０００年代に入り、食用油脂中には、３−ＭＣＰＤが脂肪酸と結合したエステル体（３−ＭＣＰＤＥ）で存在していることが報告されている（非特許文献１）。この報告によれば、３−ＭＣＰＤＥを含む食品を人が摂取すると、体内でエステルが加水分解され、３−ＭＣＰＤが生成されることが懸念されている。 In the 2000s, it has been reported that 3-MCPD is present in edible fats and oils in the form of an ester (3-MCPDE) bonded to a fatty acid (Non-patent Document 1). According to this report, there is a concern that when a person ingests a food containing 3-MCPDE, the ester is hydrolyzed in the body to produce 3-MCPD.
このような報告を踏まえ、現在も３−ＭＣＰＤＥが人体に及ぼす影響等について継続的に調査されている。 Based on such reports, the effects of 3-MCPDE on the human body are still being investigated.
実際、３−ＭＣＰＤＥについては、許容摂取量等が定められていないものの、欧州においては、３−ＭＣＰＤＥに結合する脂肪酸が全て遊離して、３−ＭＣＰＤを生成するとみなす、ドイツ公定法（ＤＧＦ Ｓｔａｎｄａｒｄ Ｍｅｔｈｏｄｓ Ｃ−III １８（０９））による定量が広く行われている。この方法においては、クロロプロパノール類である３−ＭＣＰＤや３−ＭＣＰＤＥおよびそれらの形成物質であるグリシドールやグリシドール脂肪酸エステルについても、３−ＭＣＰＤへ変換して測定している。なお、グリシドールについては、ＷＨＯの外部組織であるＩＲＡＣ（国際がん研究機関）により、人に対する発がん性がおそらくある、とされるグループ２Ａの化合物に分類されており、その低減が望ましいとされている（非特許文献２）。このようにして定量された３−ＭＣＰＤ量に基づいて人体に及ぼす影響を評価する動きがある。 In fact, for 3-MCPDE, the allowable intake and the like are not defined, but in Europe, all fatty acids that bind to 3-MCPDE are released to form 3-MCPD, and the official German law (DGF Standard) Quantification by Methods C-III 18 (09)) is widely performed. In this method, 3-MCPD and 3-MCPDE which are chloropropanols and glycidol and glycidol fatty acid esters which are their forming substances are also converted into 3-MCPD and measured. Glicidol is classified as a group 2A compound that is probably carcinogenic to humans by the IRAC (International Agency for Research on Cancer), an external organization of WHO, and its reduction is desirable. (Non-Patent Document 2). There is a movement to evaluate the influence on the human body based on the amount of 3-MCPD determined in this way.
そこで、上記の３−ＭＣＰＤに代表されるクロロプロパノール類を低減させる方法として、脱臭工程を経ていない食用油脂に相当するグリセリド組成物と、アルカリ白土とを接触させるアルカリ白土処理工程を含むクロロプロパノール類の低減方法が提案されている（特許文献１）。また、食用油脂に相当するグリセリド油脂が１００℃以上に加熱される処理以前に、吸着剤処理および／またはアルカリ処理するクロロプロパノール類の低減方法も提案されている（特許文献２）。さらには、クロロプロパノール類を少なくとも１種含有し、および／または、脂肪酸を２つしか持たない食用油脂に相当するジグリセリドを３質量％以上含有するグリセリド油脂を、１００℃〜２４０℃の温度条件にて脱臭処理するクロロプロパノール類の低減方法が提案されている（特許文献３）。また、食用油脂の脱臭工程を１９０℃〜２３０℃の温度範囲で行うクロロプロパノール類の低減方法が提案されている（特許文献４）。 Therefore, as a method for reducing chloropropanols typified by the above-mentioned 3-MCPD, chloropropanols comprising an alkaline clay treatment step in which a glyceride composition corresponding to edible fats and oils not subjected to a deodorizing step and alkaline clay are brought into contact with each other. Has been proposed (Patent Document 1). In addition, a method for reducing chloropropanols by adsorbent treatment and / or alkali treatment before treatment in which glyceride fat corresponding to edible fat is heated to 100 ° C. or higher has also been proposed (Patent Document 2). Furthermore, glyceride fats and oils containing at least one chloropropanols and / or diglycerides corresponding to edible fats and oils having only two fatty acids in an amount of 3% by mass or more are set to a temperature condition of 100 ° C. to 240 ° C. Thus, a method for reducing chloropropanols to be deodorized has been proposed (Patent Document 3). Moreover, the reduction method of chloropropanols which performs the deodorizing process of edible fats and oils in the temperature range of 190 to 230 degreeC is proposed (patent document 4).
しかしながら、特許文献１、２に記載の方法は、硬化、脱臭といった温度処理を行う前にアルカリ白土やアルカリで処理する技術であり、当該工程で完全にクロロプロパノール類の生成を抑制することは困難である。また、硬化、脱臭といった高温処理工程を経るとクロロプロパノール類が僅かに生成してしまうことが指摘されていた。 However, the methods described in Patent Documents 1 and 2 are techniques for treating with alkali clay or alkali before performing temperature treatment such as curing and deodorization, and it is difficult to completely suppress the production of chloropropanols in this process. It is. In addition, it has been pointed out that chloropropanols are slightly produced through high-temperature treatment steps such as curing and deodorization.
特許文献３、４に記載の方法は、脱臭工程においてクロロプロパノール類を低減化する方法であるが、脱臭温度を通常よりも低くするため、臭気の除去が不十分であるという問題があった。 The methods described in Patent Documents 3 and 4 are methods for reducing chloropropanols in the deodorization step, but there is a problem that odor removal is insufficient because the deodorization temperature is lower than usual.
本発明は、以上の通りの事情に鑑みてなされたものであり、食用油脂中のクロロプロパノール類である３−ＭＣＰＤや３−ＭＣＰＤＥ等を簡便な方法で効率よく低減する方法を提供することを課題としている。 The present invention has been made in view of the circumstances as described above, and provides a method for efficiently reducing 3-MCPD, 3-MCPDE and the like, which are chloropropanols in edible fats and oils, by a simple method. It is an issue.
前記の課題を解決するために、本発明の食用油脂中のクロロプロパノール類を低減する方法は、硬化処理を含む原料油からの食用油脂の製造において、硬化処理前、硬化処理時および硬化処理後のうちのいずれかの工程において、ｐＨ７．０以上の白土、ｐＨ７．０以上の木質系活性炭、炭酸ナトリウムおよび水酸化カルシウムからなる群より選択される少なくとも１種を添加することを特徴としている。 In order to solve the above-mentioned problems, the method for reducing chloropropanols in edible fats and oils of the present invention is the production of edible fats and oils from raw material oils including a curing process, before the curing process, during the curing process, and after the curing process Is characterized by adding at least one selected from the group consisting of white clay having a pH of 7.0 or higher, woody activated carbon having a pH of 7.0 or higher, sodium carbonate and calcium hydroxide.
本発明の食用油脂中のクロロプロパノール類を低減する方法においては、炭酸ナトリウムおよび水酸化カルシウムは、粉状であることが好ましい。 In the method for reducing chloropropanols in the edible fat according to the present invention, the sodium carbonate and calcium hydroxide are preferably powdery.
本発明の食用油脂中のクロロプロパノール類を低減する方法においては、ｐＨ７．０以上の白土、ｐＨ７．０以上の木質系活性炭、炭酸ナトリウムおよび水酸化カルシウムからなる群より選択される少なくとも１種の添加量が、処理対象油に対し０．００５質量％以上５質量％以下であることが好ましい。 In the method for reducing chloropropanols in edible fats and oils of the present invention, at least one selected from the group consisting of white clay having a pH of 7.0 or higher, woody activated carbon having a pH of 7.0 or higher, sodium carbonate and calcium hydroxide. The addition amount is preferably 0.005% by mass or more and 5% by mass or less with respect to the oil to be treated.
本発明の食用油脂中のクロロプロパノール類を低減する方法においては、ｐＨ７．０以上の白土およびｐＨ７．０以上の木質系活性炭は、ナトリウムメトキシドおよび水酸化ナトリウムからなる群より選択される少なくとも１種と併用することが好ましい。 In the method for reducing chloropropanols in edible fats and oils of the present invention, at least 1 selected from the group consisting of sodium methoxide and sodium hydroxide is a clay of pH 7.0 or higher and woody activated carbon of pH 7.0 or higher. It is preferably used in combination with seeds.
本発明の食用油脂中のクロロプロパノール類を低減する方法においては、ｐＨ７．０以上の白土の二酸化ケイ素含量が、白土の全組成の６５質量％以上であることが好ましい。 In the method for reducing chloropropanols in edible fats and oils of the present invention, the silicon dioxide content of the clay with a pH of 7.0 or more is preferably 65% by mass or more of the total composition of the clay.
本発明の食用油脂中のクロロプロパノール類を低減する方法においては、ｐＨ７．０以上の木質系活性炭の灰分が３質量％以上であることが好ましい。 In the method for reducing chloropropanols in edible fats and oils of the present invention, the ash content of the woody activated carbon having a pH of 7.0 or higher is preferably 3% by mass or higher.
本発明の食用油脂中のクロロプロパノール類を低減する方法においては、ｐＨ７．０以上の白土およびｐＨ７．０以上の木質系活性炭は、あらかじめアルカリ処理されたものであることが好ましい。 In the method for reducing chloropropanols in edible fats and oils of the present invention, it is preferable that the white clay having a pH of 7.0 or more and the woody activated carbon having a pH of 7.0 or more have been previously alkali-treated.
本発明によれば、食用油脂中のクロロプロパノール類である３−ＭＣＰＤや３−ＭＣＰＤＥおよびそれらの形成物質であるグリシドールやグリシドール脂肪酸エステルを簡便な方法で効率よく低減することができる。 According to the present invention, 3-MCPD and 3-MCPDE which are chloropropanols in edible fats and oils, and glycidol and glycidol fatty acid esters which are their forming substances can be efficiently reduced by a simple method.
以下に、本発明について詳細に説明する。なお、本発明では、クロロプロパノール類は、食用油脂中において生成された３−クロロ−１，２−プロパンジオール（３−ＭＣＰＤ）や３−クロロ−１，２−プロパンジオール脂肪酸エステル（３−ＭＣＰＤＥ）およびそれらの形成物質であるグリシドールやグリシドール脂肪酸エステルを含むものとする。 The present invention is described in detail below. In the present invention, chloropropanols include 3-chloro-1,2-propanediol (3-MCPD) and 3-chloro-1,2-propanediol fatty acid ester (3-MCPDE) produced in edible fats and oils. And glycidol and glycidol fatty acid esters which are their forming substances.
本発明の食用油脂中のクロロプロパノール類を低減する方法は、硬化処理を含む原料油からの食用油脂の製造において、硬化処理前、硬化処理時および硬化処理後のうちのいずれかの工程において、ｐＨ７．０以上の白土、ｐＨ７．０以上の木質系活性炭、炭酸ナトリウムおよび水酸化カルシウムからなる群より選択される少なくとも１種を添加することを特徴としている。 The method for reducing chloropropanols in the edible fat of the present invention is the production of edible fats and oils from raw material oils including a curing process, in any step of the curing process, during the curing process and after the curing process, It is characterized by adding at least one selected from the group consisting of white clay having a pH of 7.0 or higher, woody activated carbon having a pH of 7.0 or higher, sodium carbonate and calcium hydroxide.
ここで、食用油脂の製造方法は、一般に、原料となる植物や動物油脂を圧搾、加熱、溶剤等で抽出した原料油を脱ガム処理、脱酸処理、脱色処理および脱臭処理を経ることで精製される一連の工程を含んでいる。また、上記の製造方法には、脱ろう処理を含む場合もある。そして、一般に硬化処理は脱ガム、脱酸、脱色等の精製した油脂、精製後脱臭した油脂等を使用できる。 Here, the method for producing edible fats and oils is generally refined by degreasing, deoxidizing, decolorizing and deodorizing raw material oils extracted from plants and animal fats and oils as raw materials by extraction, heating, and solvent. A series of steps to be performed are included. In addition, the above manufacturing method may include a dewaxing process. And generally the hardening process can use refined fats and oils, such as degumming, deoxidation, and decoloring, and deodorized fats and oils after refinement.
本発明では、原料油に対し、硬化処理前、硬化処理時および硬化処理後のうちのいずれの時点においてｐＨ７．０以上の白土、ｐＨ７．０以上の木質系活性炭、炭酸ナトリウムおよび水酸化カルシウムからなる群より選択される少なくとも１種を添加することで、硬化反応中に生成するクロロプロパノール類を低減化する。 In the present invention, for the raw material oil, at any point of time before the curing process, at the time of the curing process, or after the curing process, from white clay having a pH of 7.0 or more, woody activated carbon having a pH of 7.0 or more, sodium carbonate and calcium hydroxide. By adding at least one selected from the group, chloropropanols generated during the curing reaction are reduced.
（ｐＨ７．０以上の白土）
白土は、カオリンやモンモリロン石と呼ばれる粘土鉱物を主成分とした酸性白土や、酸性白土を硫酸や塩酸などで活性化処理を施した活性白土であり、産地により、ｐＨや成分が異なる。本発明において使用する白土は、ｐＨ７．０以上、好ましくはｐＨ８．０以上のものが例示される。白土のｐＨの測定方法としては、ＪＩＳ Ｋ ５１０１−１７−１：２００４ 顔料試験方法等が例示される。
(Soil with pH 7.0 or higher)
The clay is an acid clay with a clay mineral called kaolin or montmorillonite as a main component, or an activated clay obtained by subjecting the acid clay to an activation treatment with sulfuric acid, hydrochloric acid, etc., and the pH and components differ depending on the production area. The clay used in the present invention is exemplified by those having a pH of 7.0 or more, preferably 8.0 or more. Examples of the method for measuring the pH of clay include JIS K 5101-17-1: 2004 pigment test method.
また、本発明において使用する白土の二酸化ケイ素（ＳｉＯ２）含量は、白土の全組成の６５質量％〜８５質量％であることが好ましく、より好ましくは６８質量％〜８３質量％の範囲が例示される。ＳｉＯ２含量が、上記の範囲内であれば、クロロプロパノール類の生成をより抑制することができる。このような白土の市販品としては、例えば、ＭＩＺＵＫＡ−ＡＣＥ ＃３００（ｐＨ８．５、ＳｉＯ２含量７０．５％、水澤化学工業株式会社製）等が例示される。 The silicon dioxide (SiO 2 ) content of the clay used in the present invention 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 clay. Is done. SiO 2 content is within the range described above, it is possible to suppress the formation of chloro propanols. Examples of such a white clay commercial product include MIZUKA-ACE # 300 (pH 8.5, SiO 2 content 70.5%, manufactured by Mizusawa Chemical Co., Ltd.).
さらにまた、白土は、予めアルカリ処理したものも好適に使用することができる。ここで、アルカリ処理とは、白土をアルカリ溶液と混合後、濾過や遠心分離により脱溶媒処理する工程を含む。 Furthermore, the clay that has been previously alkali-treated can be suitably used. Here, the alkali treatment includes a step of removing the solvent by filtration or centrifugation after mixing the clay with the alkali solution.
アルカリ処理に用いるアルカリ物質としては、例えば、アルカリ金属やアルカリ土類金属の水酸化物、炭酸塩、リン酸塩、有機酸塩、アルコキシド化合物等が例示される。具体的には、炭酸ナトリウム、炭酸水素ナトリウム、ナトリウムメトキシド、ナトリウムエトキシド、水酸化カルシウム、水酸化ナトリウム、水酸化カリウム、トリポリリン酸ナトリウム等が例示される。特に、水酸化ナトリウムは、強アルカリであり、低添加量で所要の効果を発現するので好ましい。これらは単独で使用してもよく２種以上を併用してもよい。 Examples of the alkali substance used for the alkali treatment include alkali metal and alkaline earth metal hydroxides, carbonates, phosphates, organic acid salts, and alkoxide compounds. Specific examples include sodium carbonate, sodium bicarbonate, sodium methoxide, sodium ethoxide, calcium hydroxide, sodium hydroxide, potassium hydroxide, sodium tripolyphosphate and the like. In particular, sodium hydroxide is a strong alkali and is preferable because a required effect is exhibited with a low addition amount. These may be used alone or in combination of two or more.
このようなアルカリ物質は、白土と接触しやすいことから溶媒に溶解し、アルカリ溶液として使用することが好ましい。アルカリ物質の溶解に用いることができる溶媒としては、水、メタノールやエタノール等のアルコール類が例示される。溶媒としては単独で使用してもよく２種以上を併用してもよいが、水分が少ない方が好ましい。溶媒中の水分が少なければ、白土をよりアルカリ性とすることができる。アルカリ性を高めることにより、クロロプロパノール類をより低減化することができる。 Such an alkaline substance is preferably dissolved in a solvent and used as an alkaline solution because it easily comes into contact with clay. Examples of the solvent that can be used for dissolving 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, but preferably has less water. If the water content in the solvent is small, the clay can be made more alkaline. By increasing the alkalinity, chloropropanols can be further reduced.
アルカリ溶液の好ましい濃度としては、例えば、０．０１ｍｏｌ／Ｌ〜５ｍｏｌ／Ｌの範囲が例示される。 As a preferable density | concentration of an alkaline solution, the range of 0.01 mol / L-5 mol / L is illustrated, for example.
また、ｐＨ７以上の白土は、ナトリウムメトキシドおよび水酸化ナトリウムからなる群より選択される少なくとも１種と併用することも可能である。 Moreover, the clay with a pH of 7 or higher can be used in combination with at least one selected from the group consisting of sodium methoxide and sodium hydroxide.
（ｐＨ７．０以上の木質系活性炭）
本発明で用いることができる活性炭としては、例えば、オガ屑、硬質の木材チップ、木炭（素灰）等を原料とする木質系活性炭が例示される。本発明においては、活性炭の形状については、特に制限はないが、原料油中での分散性が良好であって、かつ、原料油との接触面積が大きくなり、より効率的にクロロプロパノール類を低減させることから、粉状活性炭を用いることが好ましい。
(Woody activated carbon with a pH of 7.0 or higher)
Examples of the activated carbon that can be used in the present invention include wood-based activated carbon made from sawdust, hard wood chips, charcoal (raw ash), and the like. In the present invention, the shape of the activated carbon is not particularly limited, but the dispersibility in the raw material oil is good, and the contact area with the raw material oil is increased, so that the chloropropanols can be more efficiently used. From the viewpoint of reduction, it is preferable to use powdered activated carbon.
これらの活性炭は、賦活処理を施すことにより吸着能を高めることが可能である。活性炭の賦活方法としては、水蒸気、二酸化炭素、空気および燃焼ガス等によるガス賦活と塩化亜鉛やリン酸等を用いた薬品賦活等が例示される。なかでも水蒸気賦活を用いることが好ましい。また、活性炭は、賦活処理時の温度により、５００℃以上の高温で賦活処理した塩基性活性炭と５００℃未満の比較的低温で賦活処理した酸性活性炭に分類することができるが、本発明においては、塩基性活性炭を用いることが好ましい。本発明において使用する塩基性活性炭は、ｐＨ７．０以上、好ましくはｐＨ８．０以上のものが例示される。活性炭のｐＨの測定方法は、ＪＩＳ Ｋ １４７４：２００４ 活性炭試験方法等が例示される。 These activated carbons can increase the adsorption capacity by applying an activation treatment. Examples of activated carbon activation methods include gas activation with water vapor, carbon dioxide, air, and combustion gas, and chemical activation with zinc chloride, phosphoric acid, and the like. Of these, steam activation is preferably used. Activated carbon can be classified into basic activated carbon activated at a high temperature of 500 ° C. or higher and acidic activated carbon activated at a relatively low temperature of less than 500 ° C. depending on the temperature during the activation treatment. It is preferable to use basic activated carbon. Examples of the basic activated carbon used in the present invention include those having a pH of 7.0 or more, preferably pH 8.0 or more. Examples of the method for measuring the pH of activated carbon include the JIS K 1474: 2004 activated carbon test method.
また、本発明において使用する活性炭の灰分は、３％〜８％であることが好ましく、より好ましくは４％〜７％の範囲が例示される。このような活性炭の市販品としては、例えば、梅蜂ＩＥ印活性炭（ｐＨ９．７、灰分４．４％、大平化学産業株式会社製）、ＰＷ−Ｄ（ｐＨ８．８、灰分４．２％、クラレケミカル株式会社製）、ＮＯＲＩＴ ＨＢ−ＰＬＵＳ（ｐＨ１０．１、灰分７％、キャボットノリットジャパン株式会社製）等が例示される。 The ash content of the activated carbon used in the present invention is preferably 3% to 8%, and more preferably 4% to 7%. Examples of such activated carbon commercial products include plum bee IE-sign activated carbon (pH 9.7, ash content 4.4%, manufactured by Ohira Chemical Industry Co., Ltd.), PW-D (pH 8.8, ash content 4.2%, Kuraray Chemical Co., Ltd.), NORIT HB-PLUS (pH 10.1, ash content 7%, manufactured by Cabot Norit Japan Co., Ltd.) and the like.
さらに、活性炭の水分含量は低い方が好ましい。活性炭の水分含量が少なければ、原料油に対する活性炭の添加量が少なくて済み、また、油脂の加水分解を防ぐことも可能である。 Furthermore, the water content of the activated carbon is preferably low. If the water content of the activated carbon is low, the amount of activated carbon added to the raw material oil can be reduced, and hydrolysis of the fats and oils can be prevented.
ｐＨが高い活性炭は、ｐＨの低い活性炭を高温で賦活処理すること、アルカリ処理すること、または賦活処理後さらにアルカリ処理することによっても得ることができる。ここで、アルカリ処理とは、活性炭をアルカリ溶液と混合後、濾過や遠心分離により脱溶媒処理する工程を含む。 Activated carbon having a high pH can be obtained by subjecting activated carbon having a low pH to activation treatment at high temperature, alkali treatment, or further alkali treatment after activation treatment. Here, the alkali treatment includes a step of removing the solvent by filtration or centrifugation after mixing the activated carbon with the alkali solution.
アルカリ処理に用いるアルカリ物質としては、例えば、アルカリ金属やアルカリ土類金属の水酸化物、炭酸塩、リン酸塩、有機酸塩、アルコキシド化合物等が例示される。具体的には、炭酸ナトリウム、炭酸水素ナトリウム、ナトリウムメトキシド、ナトリウムエトキシド、水酸化カルシウム、水酸化ナトリウム、水酸化カリウム、トリポリリン酸ナトリウム等が例示される。特に、水酸化ナトリウムは、強アルカリであり、低添加量で効果を発現するので好ましい。これらは単独で使用してもよく２種以上を併用してもよい。 Examples of the alkali substance used for the alkali treatment include alkali metal and alkaline earth metal hydroxides, carbonates, phosphates, organic acid salts, and alkoxide compounds. Specific examples include sodium carbonate, sodium bicarbonate, sodium methoxide, sodium ethoxide, calcium hydroxide, sodium hydroxide, potassium hydroxide, sodium tripolyphosphate and the like. Particularly, sodium hydroxide is preferred because it is a strong alkali and exhibits an effect with a low addition amount. These may be used alone or in combination of two or more.
このようなアルカリ物質は、活性炭と接触しやすいことから溶媒に溶解し、アルカリ溶液として使用することが好ましい。アルカリ物質の溶解に用いることができる溶媒としては、水、メタノールやエタノール等のアルコール類が例示される。これらの溶媒は単独で使用してもよく２種以上を併用してもよいが、水分が少ない方が好ましい。溶媒中の水分が少なければ、活性炭をよりアルカリ性とすることができる。アルカリ性を高めることによりクロロプロパノール類をより低減化することができる。 Such an alkaline substance is preferably dissolved in a solvent and used as an alkaline solution because it easily comes into contact with activated carbon. Examples of the solvent that can be used for dissolving the alkaline substance include water and alcohols such as methanol and ethanol. These solvents may be used alone or in combination of two or more, but preferably have less water. If there is little water in a solvent, activated carbon can be made more alkaline. By increasing alkalinity, chloropropanols can be further reduced.
アルカリ溶液の好ましい濃度としては、例えば、０．０１ｍｏｌ／Ｌ〜５ｍｏｌ／Ｌの範囲が例示される。 As a preferable density | concentration of an alkaline solution, the range of 0.01 mol / L-5 mol / L is illustrated, for example.
また、ｐＨ７以上の木質系活性炭は、ナトリウムメトキシドおよび水酸化ナトリウムからなる群より選択される少なくとも１種と併用することも可能である。 Further, the woody activated carbon having a pH of 7 or higher can be used in combination with at least one selected from the group consisting of sodium methoxide and sodium hydroxide.
（炭酸ナトリウムおよび水酸化カルシウム）
本発明においては、上記の白土および活性炭に加えて、特定のアルカリ物質を硬化処理前、硬化処理時または硬化処理後に添加することによっても、原料油中のクロロプロパノール類の低減化を図ることができる。
(Sodium carbonate and calcium hydroxide)
In the present invention, in addition to the clay and activated carbon, a specific alkaline substance may be added before, during or after the curing process to reduce chloropropanols in the raw material oil. it can.
アルカリ物質としては、炭酸ナトリウムおよび水酸化カルシウムを用いることができる。これらは食品や医薬品用として一般に用いられているもので良く、単独あるいは両方を組み合わせて用いることができる。 Sodium carbonate and calcium hydroxide can be used as the alkaline substance. These may be those generally used for foods and pharmaceuticals, and can be used alone or in combination.
炭酸ナトリウムおよび水酸化カルシウムは、原料油中での分散性が良好であって、かつ、原料油との接触面積が大きくなることから、粉状または顆粒状のものを用いることが好ましく、より好ましくは粉状である。 Sodium carbonate and calcium hydroxide are preferably used in the form of powder or granules, because dispersibility in the raw material oil is good and the contact area with the raw material oil is large. Is powdery.
（原料油への白土、木質系活性炭、炭酸ナトリウムおよび水酸化カルシウムの添加）
上記の白土、木質系活性炭、炭酸ナトリウムおよび水酸化カルシウムの添加は、硬化処理前、硬化処理時および硬化処理後のいずれの時点においても可能であるが、硬化処理前または硬化処理後に添加する場合、それぞれ硬化処理工程の前後いずれかに添加のための工程を追加する必要がある。一方、硬化処理時に添加する場合、従来の硬化処理工程と同時にクロロプロパノール類の低減が可能となるため、生産効率が良好となる。また、硬化処理時に添加すると、クロロプロパノール類の低減率が高くなるため好ましい。
(Addition of white clay, wood-based activated carbon, sodium carbonate and calcium hydroxide to raw oil)
The above clay, wood-based activated carbon, sodium carbonate and calcium hydroxide can be added at any time before the curing process, at the time of the curing process and after the curing process, but when added before or after the curing process. In addition, it is necessary to add a process for addition either before or after the curing treatment process. On the other hand, when added during the curing process, chloropropanols can be reduced at the same time as the conventional curing process, so that the production efficiency is improved. Moreover, when adding at the time of a hardening process, since the reduction rate of chloropropanols becomes high, it is preferable.
（硬化処理工程）
本発明は、硬化処理を行うものであり、硬化反応としては、例えば原料油に硬化触媒を添加したものを反応釜に投入し、真空下で加熱攪拌する。通常、原料油が１２０℃〜２２０℃、好ましくは１３０℃〜１９５℃未満の温度範囲に到達した時点で加熱をやめ、所要圧（０．０１ＭＰａ〜２．０ＭＰａ）の水素を反応釜に送入し、水素添加反応を開始し、所望により水素を付加させる。硬化反応の終点としては、ヨウ素価、屈折率、融点、水素の消費量等の値を目安として反応の終点を見極め、水素を排気する。その後、油脂を冷却し、油脂中の触媒を除去する。
(Curing process)
In the present invention, a curing treatment is performed. As a curing reaction, for example, a raw material oil added with a curing catalyst is put into a reaction kettle and heated and stirred under vacuum. Usually, when the raw material oil reaches a temperature range of 120 ° C. to 220 ° C., preferably 130 ° C. to 195 ° C., heating is stopped and hydrogen of a required pressure (0.01 MPa to 2.0 MPa) is fed into the reaction kettle. The hydrogenation reaction is started and hydrogen is added as desired. As the end point of the curing reaction, the end point of the reaction is determined using values such as iodine value, refractive index, melting point, hydrogen consumption, etc., and hydrogen is exhausted. Thereafter, the fat is cooled and the catalyst in the fat is removed.
硬化反応に用いる触媒は、我が国の食品衛生法で認可されている食用油脂の硬化触媒であれば特に制限されない。例えば、ニッケルを珪藻土等の多孔質体担体に担持させたもの、あるいはこれを更に油脂で被覆してフレーク状、粒状等にしたもの等が例示される。 The catalyst used for the curing reaction is not particularly limited as long as it is a curing catalyst for edible fats and oils approved by the Japanese Food Sanitation Law. Examples thereof include those in which nickel is supported on a porous carrier such as diatomaceous earth, or those that are further coated with oils and fats to form flakes, granules, and the like.
市販のニッケル触媒としては、例えば、堺化学工業株式会社製のフレークニッケル触媒のＳＯ−１００Ａ、ＳＯ−７５０Ｒ、ＳＯ−８５０等が例示される。 As a commercially available nickel catalyst, SO-100A, SO-750R, SO-850 etc. of the flake nickel catalyst by Sakai Chemical Industry Co., Ltd. are illustrated, for example.
ニッケル触媒の使用量は、原料油の０．０５質量％〜１．０質量％の範囲内であることが好ましい。 The amount of the nickel catalyst used is preferably in the range of 0.05% by mass to 1.0% by mass of the raw material oil.
硬化処理前に白土、木質系活性炭、炭酸ナトリウムおよび水酸化カルシウムを添加する場合、原料油に硬化処理前に白土、木質系活性炭、炭酸ナトリウムおよび水酸化カルシウムを添加して５分以上１８０分以下、より好ましくは１０分以上９０分以下の範囲内で混合加熱して行われる。硬化処理前における加熱温度は、８０℃〜２５０℃、好ましくは１５０℃〜２５０℃の範囲が例示される。 When adding clay, wood-based activated carbon, sodium carbonate and calcium hydroxide before hardening treatment, add clay, wood-based activated carbon, sodium carbonate and calcium hydroxide to the raw oil before hardening treatment, and add 5 to 180 minutes. More preferably, it is carried out by mixing and heating within the range of 10 minutes to 90 minutes. Examples of the heating temperature before the curing treatment include a range of 80 ° C. to 250 ° C., preferably 150 ° C. to 250 ° C.
その後、上記のとおりの硬化処理が行われるが、白土、木質系活性炭、炭酸ナトリウムおよび水酸化カルシウムを濾過してから硬化処理を行ってもよいし、濾過せずに硬化処理を行い硬化後に濾過することも可能である。 Thereafter, the curing process is performed as described above, and the curing process may be performed after filtering the clay, the wooden activated carbon, the sodium carbonate, and the calcium hydroxide, or the curing process may be performed without filtering and the filtration may be performed after the curing. It is also possible to do.
また、上記のとおりの硬化処理時に白土、木質系活性炭、炭酸ナトリウムおよび水酸化カルシウムを添加する場合、原料油に白土、木質系活性炭、炭酸ナトリウムおよび水酸化カルシウムを添加して硬化反応が行われる。硬化処理時における加熱温度は、上記のとおり通常油脂の硬化反応が行われる温度範囲が例示される。なお、白土、木質系活性炭、炭酸ナトリウムおよび水酸化カルシウムは、硬化後に濾過することが好ましい。 In addition, when clay, wood-based activated carbon, sodium carbonate and calcium hydroxide are added during the curing treatment as described above, the curing reaction is performed by adding clay, wood-based activated carbon, sodium carbonate and calcium hydroxide to the raw material oil. . As for the heating temperature at the time of a hardening process, the temperature range in which hardening reaction of fats and oils is normally performed as above-mentioned is illustrated. In addition, it is preferable to filter white clay, wood type activated carbon, sodium carbonate, and calcium hydroxide after hardening.
さらに、上記のとおりの硬化処理後に白土、木質系活性炭、炭酸ナトリウムおよび水酸化カルシウムを添加する場合、硬化した食用油脂に白土、木質系活性炭、炭酸ナトリウムおよび水酸化カルシウムを添加して５分以上１８０分以下、より好ましくは１０分以上９０分以下の範囲内で混合加熱して行われる。硬化処理後における加熱温度は、１２０℃〜２５０℃、好ましくは１５０℃〜２５０℃の範囲が例示される。なお、白土、木質系活性炭、炭酸ナトリウムおよび水酸化カルシウムは、所定の時間の経過後に濾過することが好ましい。 Furthermore, when adding clay, wood-based activated carbon, sodium carbonate and calcium hydroxide after the curing treatment as described above, adding clay, wood-based activated carbon, sodium carbonate and calcium hydroxide to the cured edible oil and fat for 5 minutes or more It is carried out by mixing and heating within a range of 180 minutes or less, more preferably 10 minutes or more and 90 minutes or less. Examples of the heating temperature after the curing treatment are 120 ° C. to 250 ° C., preferably 150 ° C. to 250 ° C. In addition, it is preferable to filter white clay, woody activated carbon, sodium carbonate, and calcium hydroxide after a predetermined time has elapsed.
なお、ヨウ素価は基準油脂分析試験法（公益社団法人日本油化学会）の２．３．４．１−２０１３（ウィイス−シクロヘキサン法）に従い測定することが例示される。 In addition, it is illustrated that the iodine value is measured according to 2.3.4.1-2013 (Wyeth-cyclohexane method) of the standard fat analysis method (Japan Oil Chemical Society).
また製造工程を考慮すると、硬化処理前（前処理時）の加熱温度と硬化開始温度が同じであること、硬化終了温度と硬化処理後（後処理時）の加熱温度が同じであることが好ましい。硬化処理前（前処理時）の加熱温度が硬化開始温度より高いと、硬化する際に冷却する必要があり、また、硬化処理前（前処理時）の加熱温度が硬化開始温度より低いと硬化する際に加熱する必要があり、生産が煩雑となる。同様に硬化処理後（後処理時）の温度が硬化終了温度より高いと、硬化終了後に一旦加熱する必要があり、また、硬化処理後（後処理時）の温度が硬化終了温度より低いと、硬化終了後に冷却工程が必要であり、生産が煩雑となる。 In consideration of the production process, it is preferable that the heating temperature before the curing treatment (during pretreatment) and the curing start temperature are the same, and the curing end temperature and the heating temperature after the curing treatment (during post-treatment) are the same. . If the heating temperature before the curing process (during pretreatment) is higher than the curing start temperature, cooling is required when curing, and if the heating temperature before the curing process (during pretreatment) is lower than the curing start temperature, curing is performed. When it is necessary to heat, production becomes complicated. Similarly, if the temperature after the curing treatment (at the time of post-processing) is higher than the curing end temperature, it is necessary to heat once after the completion of curing, and if the temperature after the curing treatment (at the time of post-processing) is lower than the curing end temperature, A cooling step is required after the curing is completed, and the production becomes complicated.
白土、木質系活性炭、炭酸ナトリウムおよび水酸化カルシウムの添加量は、対油０．００５質量％以上５質量％以下、好ましくは０．０１質量％以上４質量％以下、より好ましくは０．０１質量％以上３質量％以下の範囲が例示される。添加量が０．００５質量％未満では、クロロプロパノール類の低減効果が低下し、５質量％を上回ると処理後の濾過に時間を要し生産効率の低下やコストの増加をもたらす。 The added amount of clay, wood-based activated carbon, sodium carbonate and calcium hydroxide is 0.005% by mass to 5% by mass, preferably 0.01% by mass to 4% by mass, more preferably 0.01% by mass. A range of not less than 3% and not more than 3% by mass is exemplified. If the addition amount is less than 0.005% by mass, the effect of reducing chloropropanols is reduced, and if it exceeds 5% by mass, it takes time for filtration after treatment, resulting in a decrease in production efficiency and an increase in cost.
（原料油）
原料油は、植物や動物から油を得る方法（圧搾、加熱、溶剤）で得られたものの他、食用油脂または２種以上の食用油脂を食用油脂分野において通常行われる水素添加、分別、エステル交換等を施した水素添加油、分別油、エステル交換油でよく、また、グリセリンと脂肪酸をエステル化したトリグリセリドでもよい。また、脱ガム、脱酸、脱色、脱ロウおよび脱臭等の各処理は食用油脂分野において通常行われる処理であってよい。
(Raw oil)
In addition to those obtained by the method of obtaining oil from plants and animals (pressing, heating, solvent), raw oil is edible fat or oil or two or more kinds of edible fats and oils usually used in the edible fat field, hydrogenation, fractionation, transesterification It may be a hydrogenated oil, a fractionated oil, a transesterified oil, or a triglyceride obtained by esterifying glycerin and a fatty acid. Further, each treatment such as degumming, deoxidation, decolorization, dewaxing and deodorization may be a treatment usually performed in the field of edible fats and oils.
本発明で利用される原料油は、食用油脂として用いられるものであれば特に制限はなく、また、常温で液体、固体等の形態は問わない。処理対象油の具体例としては、大豆油、菜種油、コーン油、ゴマ油、シソ油、亜麻仁油、落花生油、紅花油、高オレイン酸紅花油、ひまわり油、高オレイン酸ひまわり油、綿実油、ブドウ種子油、マカデミアナッツ油、ヘーゼルナッツ油、カボチャ種子油、クルミ油、椿油、茶実油、エゴマ油、ボラージ油、オリーブ油、米糠油、小麦胚芽油、ヤシ油、カカオ脂、パーム油、パーム核油および藻類油等の植物油、魚油、豚脂、牛脂、乳脂等の動物油が例示される。 The raw material oil used in the present invention is not particularly limited as long as it is used as an edible oil and fat, and may be in the form of liquid, solid, etc. at room temperature. Specific examples of oils to be treated include soybean oil, rapeseed oil, corn oil, sesame oil, perilla oil, linseed oil, peanut oil, safflower oil, safflower oil, sunflower oil, sunflower oil with high oleic acid, cottonseed oil, grape seeds Oil, macadamia nut oil, hazelnut oil, pumpkin seed oil, walnut oil, coconut oil, tea seed oil, sesame oil, borage oil, olive oil, rice bran oil, wheat germ oil, coconut oil, cocoa butter, palm oil, palm kernel oil and algae Examples include animal oils such as vegetable oils such as oil, fish oil, pork fat, beef tallow and milk fat.
本発明の製造方法により得られる食用油脂では、硬化油脂中のクロロプロパノール類の含有量が低減化されている。 In the edible oil / fat obtained by the production method of the present invention, the content of chloropropanols in the hardened oil / fat is reduced.
したがって、本発明の食用油脂の製造方法によれば、食用油脂中のクロロプロパノール類である３−ＭＣＰＤや３−ＭＣＰＤＥおよびそれらの形成物質であるグリシドールやグリシドール脂肪酸エステルを簡便な方法で効率よく低減することができる。 Therefore, according to the method for producing edible fats and oils of the present invention, 3-MCPD and 3-MCPDE which are chloropropanols in edible fats and glycidol and glycidol fatty acid esters which are their forming substances are efficiently reduced by a simple method. can do.
以下、本発明の実施例に基づいてさらに詳細に説明するが、本発明はこれらの実施例に何ら限定されるものではない。 EXAMPLES Hereinafter, although it demonstrates still in detail based on the Example of this invention, this invention is not limited to these Examples at all.
なお、実施例においては、以下の処理工程の手順に従っている。 In addition, in the Example, the procedure of the following process steps is followed.
また、ヨウ素価は基準油脂分析試験法（公益社団法人日本油化学会）の２．３．４．１−２０１３（ウィイス−シクロヘキサン法）に従い測定した。 Moreover, the iodine value was measured according to 2.3.4.1-2013 (Wyeth-cyclohexane method) of the standard fats and oils analysis test method (Japan Oil Chemical Society).
＜硬化処理前工程（前処理）＞
魚油（ヨウ素価１６１）４５０ｇに表１に示した白土、表２に示した活性炭を添加し、各時間・各温度、真空下で加熱撹拌した後、白土、活性炭を吸引濾過し、前処理油脂を得た。その後、１リットルのオートクレーブに前処理した魚油（ヨウ素価＝１６１）３５０ｇ、ニッケル触媒（堺化学工業株式会社製ＳＯ−７５０Ｒ）を対油０．３質量％（１．０５ｇ）添加し、真空下で１８０℃まで加熱後、表の水素圧（ゲージ圧）、攪拌数７５０ｒｐｍで攪拌しながら水素添加反応を行い、油脂のヨウ素価が７０に低下するまで硬化を行なった。その後ニッケル触媒を吸引濾過し硬化油を得た。
<Pre-curing process (pre-treatment)>
450 g of fish oil (iodine number 161) is added with the white clay shown in Table 1 and the activated carbon shown in Table 2. After heating and stirring at each temperature and temperature and under vacuum, the white clay and activated carbon are suction filtered and pretreated oil and fat Got. Thereafter, 350 g of fish oil (iodine number = 161) pretreated in a 1 liter autoclave and 0.3% by mass (1.05 g) of anti-oil were added to nickel catalyst (SO-750R manufactured by Sakai Chemical Industry Co., Ltd.) After heating to 180 ° C., the hydrogenation reaction was carried out while stirring at a hydrogen pressure (gauge pressure) in the table and a stirring speed of 750 rpm, and curing was carried out until the iodine value of the fat decreased to 70. Thereafter, the nickel catalyst was suction filtered to obtain a hardened oil.
上記で得た硬化油をドイツ公定法（ＤＧＦ Ｓｔａｎｄａｒｄ Ｍｅｔｈｏｄｓ Ｃ−III １８（０９））に準じて３−ＭＣＰＤに換算した値としてクロロプロパノール類の総量を求めた。 The total amount of chloropropanols was determined as a value obtained by converting the hydrogenated oil obtained above into 3-MCPD according to the German official method (DGF Standard Methods C-III 18 (09)).
＜硬化処理時工程（硬化中）＞
１リットルのオートクレーブに魚油（ヨウ素価１６１）３５０ｇ、ニッケル触媒（堺化学工業株式会社製ＳＯ−７５０Ｒ）を対油０．３質量％（１．０５ｇ）、表１に示した白土、表２〜４に示した活性炭、および表４、５に示したアルカリを添加し、真空下で表に示した硬化温度まで加熱後、表の水素圧（ゲージ圧）、攪拌数７５０ｒｐｍで攪拌しながら水素添加反応を行い、油脂のヨウ素価が７０まで低下するまで硬化を行なった。その後ニッケル触媒および白土、活性炭、アルカリを吸引濾過し硬化油を得た。上記で得た硬化油をドイツ公定法（ＤＧＦ Ｓｔａｎｄａｒｄ Ｍｅｔｈｏｄｓ Ｃ−III １８（０９））に準じて３−ＭＣＰＤに換算した値としてクロロプロパノール類の総量を求めた。
<Curing process (during curing)>
In a 1 liter autoclave, 350 g of fish oil (iodine number 161), nickel catalyst (SO-750R manufactured by Sakai Chemical Industry Co., Ltd.) 0.3 mass% (1.05 g) of oil, white clay shown in Table 1, Table 2 After adding the activated carbon shown in 4 and the alkali shown in Tables 4 and 5 to the curing temperature shown in the table under vacuum, hydrogenation was performed while stirring at a hydrogen pressure (gauge pressure) in the table and a stirring speed of 750 rpm. The reaction was carried out and curing was performed until the iodine value of the fat decreased to 70. Thereafter, nickel catalyst, clay, activated carbon, and alkali were suction filtered to obtain a hardened oil. The total amount of chloropropanols was determined as a value obtained by converting the hydrogenated oil obtained above into 3-MCPD according to the German official method (DGF Standard Methods C-III 18 (09)).
＜硬化処理後（後処理）＞
１リットルのオートクレーブに魚油（ヨウ素価１６１）３５０ｇ、ニッケル触媒（堺化学工業株式会社製ＳＯ−７５０Ｒ）を対油０．３質量％（１．０５ｇ）添加し、真空下で表に示した硬化温度まで加熱後、表の水素圧（ゲージ圧）、攪拌数７５０ｒｐｍで攪拌しながら水素添加反応を行い、油脂のヨウ素価が７０に低下するまで硬化を行なった。その後ニッケル触媒を吸引濾過した。上記で得た硬化油(処理前)に表２に示した活性炭、表５に示した水酸化カルシウムを添加し、真空下で、各温度で加熱を行なった後、活性炭、水酸化カルシウムを吸引濾過し硬化油(処理後)を得た。
<After curing (post treatment)>
350 g of fish oil (iodine number 161) and nickel catalyst (SO-750R manufactured by Sakai Chemical Industry Co., Ltd.) 0.3% by mass (1.05 g) of oil were added to a 1 liter autoclave and cured as shown in the table under vacuum. After heating to temperature, a hydrogenation reaction was performed while stirring at a hydrogen pressure (gauge pressure) in the table and a stirring speed of 750 rpm, and curing was performed until the iodine value of the fat decreased to 70. Thereafter, the nickel catalyst was suction filtered. Activated carbon shown in Table 2 and calcium hydroxide shown in Table 5 are added to the hardened oil obtained above (before treatment), heated at various temperatures under vacuum, and then the activated carbon and calcium hydroxide are sucked. Filtration gave a hardened oil (after treatment).
上記で得た硬化油をドイツ公定法（ＤＧＦ Ｓｔａｎｄａｒｄ Ｍｅｔｈｏｄｓ Ｃ−III １８（０９））に準じて３−ＭＣＰＤに換算した値としてクロロプロパノール類の総量を求めた。 The total amount of chloropropanols was determined as a value obtained by converting the hydrogenated oil obtained above into 3-MCPD according to the German official method (DGF Standard Methods C-III 18 (09)).
（参考例１）
１リットルのオートクレーブに魚油（ヨウ素価１６１）３５０ｇ、ニッケル触媒（堺化学工業株式会社製ＳＯ−７５０Ｒ）を対油０．３質量％（１．０５ｇ）添加し、水素圧０．５ＭＰａ（ゲージ圧）を維持するように水素を吹き込んで、攪拌数７５０ｒｐｍで攪拌しながら水素添加反応を行い、油脂のヨウ素価が７０に低下するまで硬化を行なった。その後ニッケル触媒を吸引濾過し硬化油を得た。上記で得た硬化油をドイツ公定法（ＤＧＦ Ｓｔａｎｄａｒｄ Ｍｅｔｈｏｄｓ Ｃ−III １８（０９））に準じて３−ＭＣＰＤに換算した値としてクロロプロパノール類の総量を求めた。（以下、３−ＭＣＰＤ生成量と表記する）
（参考例２）
水素圧０．１２ＭＰａ（ゲージ圧）に変えた以外は参考例１と同様に硬化させ、その後硬化油脂中の３−ＭＣＰＤ生成量を求めた。
(Reference Example 1)
350 g of fish oil (iodine number 161), nickel catalyst (SO-750R manufactured by Sakai Chemical Industry Co., Ltd.) 0.3 mass% (1.05 g) of oil were added to a 1 liter autoclave, and hydrogen pressure 0.5 MPa (gauge pressure) The hydrogenation reaction was performed while stirring at a stirring speed of 750 rpm, and curing was performed until the iodine value of the fat decreased to 70. Thereafter, the nickel catalyst was suction filtered to obtain a hardened oil. The total amount of chloropropanols was determined as a value obtained by converting the hydrogenated oil obtained above into 3-MCPD according to the German official method (DGF Standard Methods C-III 18 (09)). (Hereinafter referred to as 3-MCPD generation amount)
(Reference Example 2)
Except for changing to a hydrogen pressure of 0.12 MPa (gauge pressure), it was cured in the same manner as in Reference Example 1, and then the amount of 3-MCPD produced in the cured oil was determined.
［白土による試験］
（実施例１）
前記の前処理の手順に従って、魚油に白土として対油３質量％の酸性白土（ＭＩＺＵＫＡ−ＡＣＥ ＃３００、以下ＭＡ３００と表記、ｐＨ８．５、ＳｉＯ２含量７０．５％、水澤化学工業株式会社製）を添加し、真空下１００℃で２０分処理した後、濾過により白土を取り除き、前処理油脂を得た。前処理油脂を参考例１と同様の条件で硬化し、３−ＭＣＰＤ生成量を求めた。
[Examination with white clay]
Example 1
According to the above pretreatment procedure, 3% by weight acid clay (MIZUKA-ACE # 300, hereinafter referred to as MA300, pH 8.5, SiO 2 content 70.5%, made by Mizusawa Chemical Co., Ltd.) ) And treated at 100 ° C. for 20 minutes under vacuum, and then the white clay was removed by filtration to obtain a pretreated oil and fat. The pretreated oil was cured under the same conditions as in Reference Example 1, and the amount of 3-MCPD produced was determined.
（実施例２）
あらかじめ活性白土（ＧＡＬＬＥＯＮ ＥＡＲＴＨ Ｖ２、以下Ｖ２と表記、ｐＨ３．３、ＳｉＯ２含量７９．８％、水澤化学工業株式会社製）に対して５倍量の１ｍｏｌ／Ｌ水酸化ナトリウム水溶液を加え、常温・常圧で３０分間攪拌後、濾過により白土を回収し、その後真空下３００℃で４時間乾燥させてアルカリ処理を行った。前記の硬化中の手順に従って、魚油に白土として対油０．４６質量％のアルカリ処理したＶ２（ｐＨ１１．１）を添加し、アルカリ処理白土を入れたまま参考例２と同様の条件で硬化させ、その後硬化油脂中の３−ＭＣＰＤ生成量を求めた。
(Example 2)
Add 5 mol of 1 mol / L sodium hydroxide aqueous solution in advance to activated clay (GALLEON EARTH V2, hereinafter referred to as V2, pH 3.3, SiO 2 content 79.8%, manufactured by Mizusawa Chemical Co., Ltd.) -After stirring for 30 minutes at normal pressure, the white clay was recovered by filtration, and then dried at 300 ° C under vacuum for 4 hours for alkali treatment. In accordance with the above curing procedure, V2 (pH 11.1) of 0.46% by mass of oil as a white clay was added to fish oil and cured under the same conditions as in Reference Example 2 while the alkali-treated white clay was left. Thereafter, the amount of 3-MCPD produced in the hardened fat was determined.
（実施例３）
あらかじめ酸性白土（ＭＩＺＵＫＡ−ＡＣＥ ＃３００、以下ＭＡ３００と表記、ｐＨ８．５、ＳｉＯ２含量７０．５％、水澤化学工業株式会社製）に対して５倍量の１ｍｏｌ／Ｌ水酸化ナトリウム水溶液を加え、常温・常圧で３０分間攪拌後、濾過により白土を回収し、その後真空下３００℃で４時間乾燥させてアルカリ処理を行った。前記の硬化中の手順に従って、白土としてアルカリ処理した酸性白土ＭＡ３００（ｐＨ１１．２）を、対油１．５質量％添加したこと以外は、実施例２と同様にして魚油を硬化させ、その後硬化油脂中のクロロプロパノール類の総量を３−ＭＣＰＤに換算した値として求めた。
Example 3
Add 5 mol of 1 mol / L sodium hydroxide aqueous solution in advance to acid clay (MIZUKA-ACE # 300, hereinafter referred to as MA300, pH 8.5, SiO 2 content 70.5%, manufactured by Mizusawa Chemical Co., Ltd.) After stirring at room temperature and normal pressure for 30 minutes, the white clay was recovered by filtration, and then dried at 300 ° C. for 4 hours under vacuum to perform alkali treatment. According to the procedure during curing, acid oil clay MA300 (pH 11.2) treated with alkali as clay was added to the oil oil in the same manner as in Example 2 except that 1.5% by mass of the oil was added, and then cured. The total amount of chloropropanols in the oil was determined as a value converted to 3-MCPD.
実施例１における３−ＭＣＰＤの低減率（％）は、参考例１における３−ＭＣＰＤ生成量（ｐｐｍ）を基準として、実施例２、３における３−ＭＣＰＤの低減率（％）は、参考例２における３−ＭＣＰＤ生成量（ｐｐｍ）を基準として以下の計算式で算出された。 The reduction rate (%) of 3-MCPD in Example 1 is based on the 3-MCPD generation amount (ppm) in Reference Example 1, and the reduction rate (%) of 3-MCPD in Examples 2 and 3 is a reference example. Based on the 3-MCPD production amount (ppm) in 2, the following calculation formula was used.
３−ＭＣＰＤ低減率（％）＝１００−
｛（各実施例での３−ＭＣＰＤ生成量（ｐｐｍ））／
（参考例１または２での３−ＭＣＰＤ生成量（ｐｐｍ））｝×１００
結果を表１に示す。
3-MCPD reduction rate (%) = 100-
{(3-MCPD production amount in each example (ppm)) /
(3-MCPD production amount (ppm) in Reference Example 1 or 2)} × 100
The results are shown in Table 1.
表１に示したように、実施例１では、硬化工程の前処理としてｐＨ７以上の白土を原料油に添加することにより、添加なしの参考例１と比較して約２０％程度クロロプロパノール類を低減可能であることが確認された。また、実施例２、３では、硬化工程時にアルカリ処理した白土を添加することで、実施例１よりもさらにクロロプロパノール類の低減率の向上が可能であることが示された。 As shown in Table 1, in Example 1, about 20% of chloropropanols were added to the raw material oil by adding white clay having a pH of 7 or more to the raw material oil as a pretreatment in the curing step. It was confirmed that it could be reduced. Moreover, in Example 2, 3, it was shown that the reduction rate of chloropropanols can be improved further than Example 1 by adding the white clay which carried out the alkali process at the time of a hardening process.
［活性炭添加による試験］
（実施例４）
前記の前処理の手順に従って、魚油に木質系活性炭として対油３質量％のアルカリ性活性炭（ＰＷ−Ｄ（ｐＨ８．８）、クラレケミカル株式会社製）を添加し、真空下１８０℃で１時間加熱撹拌した後、濾過により活性炭を取り除き、前処理油脂を得た。前処理油脂を参考例２と同様に硬化させ、その後硬化油脂中の３−ＭＣＰＤ生成量を求めた。
[Test by adding activated carbon]
Example 4
In accordance with the above pretreatment procedure, 3% by mass of alkaline activated carbon (PW-D (pH 8.8), manufactured by Kuraray Chemical Co., Ltd.) as a wood-based activated carbon is added to fish oil and heated at 180 ° C. for 1 hour under vacuum. After stirring, the activated carbon was removed by filtration to obtain a pretreated oil and fat. The pretreated oil and fat was cured in the same manner as in Reference Example 2, and then the amount of 3-MCPD produced in the cured oil and fat was determined.
（実施例５）
前記の硬化中の手順に従って、魚油に木質系活性炭として対油０．５質量％のＰＷ−Ｄ（ｐＨ８．８）を添加し、参考例２と同様に硬化させ、その後硬化油脂中の３−ＭＣＰＤ生成量を求めた。
(Example 5)
According to the above-mentioned procedure during curing, 0.5% by mass of PW-D (pH 8.8) to the oil is added to the fish oil as a wood-based activated carbon, cured in the same manner as in Reference Example 2, and then 3- The amount of MCPD produced was determined.
（実施例６）
ＰＷ−Ｄの添加量を対油１質量％に増量したこと以外は、実施例５と同様にして魚油を硬化させ、その後硬化油脂中の３−ＭＣＰＤ生成量を求めた。
(Example 6)
Fish oil was hardened in the same manner as in Example 5 except that the amount of PW-D added was increased to 1% by mass with respect to oil, and then the amount of 3-MCPD produced in the hardened fat was determined.
（実施例７）
ＰＷ−Ｄの添加量を対油３質量％に増量したこと以外は、実施例５と同様にして魚油を硬化させ、その後硬化油脂中の３−ＭＣＰＤ生成量を求めた。
(Example 7)
Fish oil was hardened in the same manner as in Example 5 except that the amount of PW-D added was increased to 3% by mass with respect to the oil, and then the amount of 3-MCPD produced in the hardened fat was determined.
（実施例８）
参考例２と同様に硬化し硬化油脂を得た。前記の後処理の手順に従って、対油３質量％のＰＷ−Ｄ（ｐＨ８．８）を添加して、１００℃を維持したまま１５分間攪拌混合した。続いて、１５分かけて１８０℃まで昇温し、１８０℃を維持したまま１５分間攪拌混合した後、濾過により活性炭を取り除き、後処理油脂を得た。その後硬化油脂中の３−ＭＣＰＤ生成量を求めた。
(Example 8)
Cured in the same manner as in Reference Example 2 to obtain a hardened fat. According to the post-treatment procedure, 3% by mass of PW-D (pH 8.8) with respect to oil was added, and the mixture was stirred and mixed for 15 minutes while maintaining 100 ° C. Then, it heated up to 180 degreeC over 15 minutes, and stirred and mixed for 15 minutes, maintaining 180 degreeC, Then, activated carbon was removed by filtration and the post-processing fats and oils were obtained. Thereafter, the amount of 3-MCPD produced in the hardened fat was determined.
（実施例９）
参考例２と同様に硬化し硬化油脂を得た。前記の後処理の手順に従って、硬化油脂と活性炭を１８０℃からさらに１５分かけて２２０℃まで昇温し、２２０℃を維持したまま１５分間攪拌混合したこと以外は、実施例８と同様にして硬化油脂中の３−ＭＣＰＤ生成量を求めた。
Example 9
Cured in the same manner as in Reference Example 2 to obtain a hardened fat. According to the post-treatment procedure, the hardened oil and activated carbon and activated carbon were heated from 180 ° C. to 220 ° C. over 15 minutes, and stirred and mixed for 15 minutes while maintaining 220 ° C. As in Example 8. The amount of 3-MCPD produced in the hardened fat was determined.
（実施例１０）
前記の硬化中の手順に従って、魚油に木質系活性炭として対油０．３質量％の梅蜂ＩＥ印活性炭（以下梅蜂ＩＥ印と表記する、ｐＨ９．７、大平化学産業株式会社製）を添加し、参考例２と同様に硬化させ、その後硬化油脂中の３−ＭＣＰＤ生成量を求めた。
(Example 10)
According to the above curing procedure, add 0.3% by mass of oil-based activated carbon Plum Bee IE Marked Activated Carbon (hereinafter referred to as Plum Bee IE Mark, pH 9.7, manufactured by Ohira Chemical Industry Co., Ltd.) to the fish oil. Then, it was cured in the same manner as in Reference Example 2, and then the amount of 3-MCPD produced in the cured oil was determined.
（実施例１１）
梅蜂ＩＥ印の添加量を対油０．５質量％に増量したこと以外は、実施例１０と同様にして魚油を硬化させ、その後硬化油脂中の３−ＭＣＰＤ生成量を求めた。
(Example 11)
Fish oil was hardened in the same manner as in Example 10 except that the addition amount of plum bee IE was increased to 0.5% by mass with respect to oil, and then the amount of 3-MCPD produced in the hardened fat was determined.
（実施例１２）
梅蜂ＩＥ印の添加量を対油１質量％に増量したこと以外は、実施例１０と同様にして魚油を硬化させ、その後硬化油脂中の３−ＭＣＰＤ生成量を求めた。
(Example 12)
The fish oil was hardened in the same manner as in Example 10 except that the addition amount of the plum bee IE mark was increased to 1% by mass with respect to the oil, and then the amount of 3-MCPD produced in the hardened fat was determined.
（実施例１３）
梅蜂ＩＥ印の添加量を対油３質量％に増量したこと以外は、実施例１０と同様にして魚油を硬化させ、その後硬化油脂中の３−ＭＣＰＤ生成量を求めた。
(Example 13)
The fish oil was hardened in the same manner as in Example 10 except that the addition amount of the plum bee IE mark was increased to 3% by mass with respect to the oil, and then the amount of 3-MCPD produced in the hardened fat was determined.
（実施例１４）
前記の硬化中の手順に従って、魚油に木質系活性炭として対油０．１質量％のＮＯＲＩＴ ＨＢ−ＰＬＵＳ（以下ＨＢ−ＰＬＵＳと表記する、ｐＨ１０．１、キャボットノリットジャパン株式会社製）を添加し、参考例２と同様に硬化させ、その後硬化油脂中の３−ＭＣＰＤ生成量を求めた。
(Example 14)
In accordance with the above curing procedure, 0.1% by mass of NORIT HB-PLUS (hereinafter referred to as HB-PLUS, pH 10.1, manufactured by Cabot Norit Japan Co., Ltd.) as a wood-based activated carbon is added to the fish oil. Then, it was cured in the same manner as in Reference Example 2, and then the amount of 3-MCPD produced in the cured oil was determined.
（実施例１５）
ＨＢ−ＰＬＵＳの添加量を対油０．５質量％に増量したこと以外は、実施例１４と同様にして魚油を硬化させ、その後硬化油脂中の３−ＭＣＰＤ生成量を求めた。
(Example 15)
The fish oil was hardened in the same manner as in Example 14 except that the amount of HB-PLUS was increased to 0.5% by mass of the oil, and then the amount of 3-MCPD produced in the hardened fat was determined.
（比較例１）
木質系活性炭であるＰＷ−Ｄの代わりに石炭系活性炭であるＫＷ−Ｐ（ｐＨ９．２、クラレケミカル株式会社製）を用いたこと以外は、実施例５と同様にして魚油を硬化させ、その後硬化油脂中の３−ＭＣＰＤ生成量を求めた。
(Comparative Example 1)
The fish oil is cured in the same manner as in Example 5 except that KW-P (pH 9.2, manufactured by Kuraray Chemical Co., Ltd.), which is a coal-based activated carbon, is used instead of PW-D, which is a wooden activated carbon. The amount of 3-MCPD produced in the hardened fat was determined.
（比較例２）
木質系活性炭であるＰＷ−Ｄの代わりにヤシ殻由来活性炭であるＧＷ−ＨＰ（ｐＨ７．５、クラレケミカル株式会社製）を用いたこと以外は、実施例５と同様にして魚油を硬化させ、その後硬化油脂中の３−ＭＣＰＤ生成量を求めた。
(Comparative Example 2)
The fish oil is cured in the same manner as in Example 5 except that GW-HP (pH 7.5, manufactured by Kuraray Chemical Co., Ltd.), which is coconut shell-derived activated carbon, is used instead of PW-D, which is a wood-based activated carbon. Thereafter, the amount of 3-MCPD produced in the hardened fat was determined.
（比較例３）
木質系活性炭であるＰＷ−Ｄの代わりにヤシ殻由来活性炭であるＧＷ−Ｐ（ｐＨ８．５、クラレケミカル株式会社製）を用いたこと以外は、実施例５と同様にして魚油を硬化させ、その後硬化油脂中の３−ＭＣＰＤ生成量を求めた。
(Comparative Example 3)
The fish oil is cured in the same manner as in Example 5 except that GW-P (pH 8.5, manufactured by Kuraray Chemical Co., Ltd.), which is coconut shell-derived activated carbon, is used instead of PW-D, which is a wood-based activated carbon. Thereafter, the amount of 3-MCPD produced in the hardened fat was determined.
（比較例４）
ＰＷ−Ｄの代わりに木質系活性炭であるＡ−Ｗ５０（ｐＨ５．８、フタムラ化学株式会社製）を対油１％使用したこと以外は、実施例５と同様にして魚油を硬化させ、その後硬化油脂中の３−ＭＣＰＤ生成量を求めた。
(Comparative Example 4)
The fish oil was cured in the same manner as in Example 5 except that A-W50 (pH 5.8, manufactured by Phutamura Chemical Co., Ltd.), which is a wood-based activated carbon, was used instead of PW-D, and then cured. The amount of 3-MCPD produced in the fat was determined.
結果を表２に示す。 The results are shown in Table 2.
表２に示したように、ｐＨ７以上の木質系由来の活性炭を原料油に添加することにより、クロロプロパノール類の低減が可能であることが確認された。この効果は、硬化処理時に活性炭を添加した場合に特に顕著であることが示唆された。また、活性炭の添加量に量依存的にクロロプロパノール類の低減率が増大することも示唆された。さらに、活性炭の灰分が３％以上であることも、クロロプロパノール類の低減率に効果的であることが示唆された。 As shown in Table 2, it was confirmed that chloropropanols can be reduced by adding wood-based activated carbon having a pH of 7 or higher to the raw material oil. It was suggested that this effect is particularly remarkable when activated carbon is added during the curing process. It was also suggested that the reduction rate of chloropropanols increased depending on the amount of activated carbon added. Furthermore, it was suggested that the ash content of activated carbon being 3% or more is effective for the reduction rate of chloropropanols.
一方、比較例１〜４の結果から、活性炭が木質系由来以外のものである場合、また、活性炭のｐＨが７未満の場合、クロロプロパノール類の低減が認められなかった。 On the other hand, from the results of Comparative Examples 1 to 4, when the activated carbon was other than wood-based, or when the pH of the activated carbon was less than 7, no reduction of chloropropanols was observed.
［アルカリ処理した活性炭による試験］
（実施例１６）
あらかじめ木質系活性炭であるＨＢ−ＰＬＵＳに、５倍量の１ｍｏｌ／Ｌの水酸化ナトリウム水溶液を加え、常温・常圧で６０分間攪拌混合し、濾過により活性炭を回収後、８０℃で２１０分間乾燥させてアルカリ処理を行った。前記の硬化中の手順に従って、魚油に活性炭として対油０．１質量％のアルカリ処理したＨＢ−ＰＬＵＳ（ｐＨ１０．８）を添加し、活性炭を入れたまま参考例２と同様に硬化させ、その後硬化油脂中の３−ＭＣＰＤ生成量を求めた。
[Testing with alkali-treated activated carbon]
(Example 16)
Add 5 times volume of 1 mol / L sodium hydroxide aqueous solution to HB-PLUS, which is a wood-based activated carbon, and stir and mix at room temperature and normal pressure for 60 minutes. Collect the activated carbon by filtration and dry at 80 ° C for 210 minutes. The alkali treatment was performed. According to the procedure during the curing described above, 0.1% by mass of alkali-treated HB-PLUS (pH 10.8) as an activated carbon was added to the fish oil, and cured in the same manner as in Reference Example 2 while the activated carbon was added. The amount of 3-MCPD produced in the hardened fat was determined.
（実施例１７）
あらかじめ木質系活性炭であるＨＢ−ＰＬＵＳに、５倍量の１ｍｏｌ／Ｌの水酸化ナトリウム／エタノール溶液を加え、常温・常圧で３時間攪拌混合し、濾過により活性炭を回収後、７０℃で６０分間乾燥させてアルカリ処理を行った。前記の硬化中の手順に従って、魚油に活性炭として対油０．１質量％のアルカリ処理したＨＢ−ＰＬＵＳ（ｐＨ１１．９）を添加し、活性炭を入れたまま参考例２と同様に硬化させ、その後硬化油脂中の３−ＭＣＰＤ生成量を求めた。
(Example 17)
Add 5 times 1 mol / L sodium hydroxide / ethanol solution to wood based activated carbon HB-PLUS in advance, stir and mix at room temperature and pressure for 3 hours, collect the activated carbon by filtration, and then add 60% at 70 ° C. Alkali treatment was performed by drying for a minute. According to the procedure during the curing, 0.1% by mass of an oil-treated HB-PLUS (pH 11.9) as an activated carbon was added to the fish oil and cured in the same manner as in Reference Example 2 while the activated carbon was added. The amount of 3-MCPD produced in the hardened fat was determined.
表３に示すように、実施例１７では、あらかじめｐＨ７以上の木質系活性炭にアルカリ溶液処理することにより、クロロプロパノール類の低減率を増強可能であることが示唆された。実施例１６では、アルカリ溶液の溶媒として水を用いているため、エタノールを用いた実施例１７よりクロロプロパノール類の低減効果が減少したものと考えられる。 As shown in Table 3, in Example 17, it was suggested that the reduction rate of chloropropanols can be enhanced by previously treating the wood-based activated carbon having a pH of 7 or higher with an alkaline solution. In Example 16, since water was used as the solvent of the alkaline solution, it is considered that the effect of reducing chloropropanols was reduced compared to Example 17 using ethanol.
［活性炭とアルカリ物質の併用による試験］
（実施例１８）
前記の硬化中の手順に従って、魚油に木質系活性炭として対油０．１質量％のＨＢ−ＰＬＵＳと対油０．１質量％の粉状の炭酸ナトリウム（関東化学株式会社製）を添加し、参考例２と同様に硬化させ、その後硬化油脂中の３−ＭＣＰＤ生成量を求めた。
[Test using activated carbon and alkaline substances in combination]
(Example 18)
According to the procedure during the curing, 0.1% by mass of HB-PLUS for oil and 0.1% by mass of powdered sodium carbonate (manufactured by Kanto Chemical Co., Ltd.) for oil as wood-based activated carbon are added to the fish oil, It hardened similarly to the reference example 2, and calculated | required 3-MCPD production amount in hardened fats and oils after that.
（実施例１９）
炭酸ナトリウムの代わりに対油０．０１質量％の粉状の水酸化カルシウムを添加したこと以外は、実施例１８と同様に魚油を硬化させ、その後硬化油脂中の３−ＭＣＰＤ生成量を求めた。
(Example 19)
Fish oil was hardened in the same manner as in Example 18 except that 0.01% by mass of powdered calcium hydroxide for oil was added instead of sodium carbonate, and then the amount of 3-MCPD produced in the hardened fat was determined. .
（実施例２０）
水酸化カルシウムの添加量を０．０５質量％に増量したこと以外は、実施例１９と同様に魚油を硬化させ、その後硬化油脂中の３−ＭＣＰＤ生成量を求めた。
(Example 20)
Fish oil was hardened in the same manner as in Example 19 except that the amount of calcium hydroxide added was increased to 0.05 mass%, and then the amount of 3-MCPD produced in the hardened fat was determined.
（実施例２１）
水酸化カルシウムの添加量を０．１質量％に増量したこと以外は、実施例１９と同様に魚油を硬化させ、その後硬化油脂中の３−ＭＣＰＤ生成量を求めた。
(Example 21)
Fish oil was hardened in the same manner as in Example 19 except that the amount of calcium hydroxide added was increased to 0.1% by mass, and then the amount of 3-MCPD produced in the hardened fat was determined.
（実施例２２）
炭酸ナトリウムの代わりに対油０．０１質量％の粉状のナトリウムメトキシドを添加したこと以外は、実施例１８と同様に魚油を硬化させ、その後硬化油脂中の３−ＭＣＰＤ生成量を求めた。
(Example 22)
Fish oil was hardened in the same manner as in Example 18 except that 0.01% by mass of powdered sodium methoxide was added in place of sodium carbonate, and then the amount of 3-MCPD produced in the hardened fat was determined. .
（実施例２３）
前記の硬化中の手順に従って、魚油に木質系活性炭として対油０．０９質量％のＨＢ−ＰＬＵＳと粉状の水酸化ナトリウム（粒状の水酸化ナトリウム（関東化学株式会社製）を乳鉢ですり潰して得た）を対油０．０１質量％添加し、参考例２と同様に硬化させ、その後硬化油脂中３−ＭＣＰＤ生成量を求めた。
(Example 23)
In accordance with the above-mentioned curing procedure, 0.09% by mass of HB-PLUS and oily sodium hydroxide (granular sodium hydroxide (manufactured by Kanto Chemical Co., Ltd.)) as a wood-based activated carbon in fish oil is ground in a mortar. Obtained) was added in an amount of 0.01% by mass to the oil and cured in the same manner as in Reference Example 2, and then the amount of 3-MCPD produced in the cured oil was determined.
実施例１８〜２３における３−ＭＣＰＤの低減率（％）は、参考例２における３−ＭＣＰＤ生成量（ｐｐｍ）を基準として、白土による試験と同様の計算式で求められた。 The reduction rate (%) of 3-MCPD in Examples 18 to 23 was obtained by the same calculation formula as in the test using white clay, based on the 3-MCPD generation amount (ppm) in Reference Example 2.
結果を表４に示す。 The results are shown in Table 4.
表４に示すように、実施例１４のｐＨ７以上の木質系活性炭とアルカリとを併用することによって、実施例１４に対して、クロロプロパノール類の低減率が約２〜５倍に増強されることが確認された。また、実施例１９〜２１の結果から、アルカリの添加量が増大するにつれてクロロプロパノール類の低減率も増強されることが示唆された。 As shown in Table 4, the reduction rate of chloropropanols is enhanced by about 2 to 5 times compared to Example 14 by using together woody activated carbon of pH 7 or more of Example 14 and alkali. Was confirmed. Moreover, from the results of Examples 19 to 21, it was suggested that the reduction rate of chloropropanols was enhanced as the amount of alkali added increased.
［アルカリ物質の添加による試験］
（実施例２４）
前記の硬化中の手順に従って、魚油にアルカリ物質として対油０．１質量％の粉状の炭酸ナトリウム（関東化学株式会社製）を添加し、参考例２と同様に硬化させ、その後硬化油脂中の３−ＭＣＰＤ生成量を求めた。
[Test by adding alkaline substances]
(Example 24)
In accordance with the procedure during curing described above, 0.1% by mass of powdered sodium carbonate (manufactured by Kanto Chemical Co., Ltd.) as an alkaline substance is added to fish oil and cured in the same manner as in Reference Example 2, and then in the cured oil and fat. The amount of 3-MCPD produced was determined.
（実施例２５）
炭酸ナトリウムを対油０．０１質量％の粉状の水酸化カルシウムに変更したこと以外は、実施例２４と同様に魚油を硬化させ、その後硬化油脂中の３−ＭＣＰＤ生成量を求めた。
(Example 25)
Fish oil was hardened in the same manner as in Example 24 except that sodium carbonate was changed to powdered calcium hydroxide with 0.01% by mass of oil, and then the amount of 3-MCPD produced in the hardened fat was determined.
（実施例２６）
水酸化カルシウムの添加量を０．０２５質量％に増量したこと以外は、実施例２５と同様に魚油を硬化させ、その後硬化油脂中の３−ＭＣＰＤ生成量を求めた。
(Example 26)
Fish oil was hardened in the same manner as in Example 25 except that the amount of calcium hydroxide added was increased to 0.025% by mass, and then the amount of 3-MCPD produced in the hardened fat was determined.
（実施例２７）
水酸化カルシウムの添加量を０．０５質量％に増量したこと以外は、実施例２５と同様に魚油を硬化させ、その後硬化油脂中の３−ＭＣＰＤ生成量を求めた。
(Example 27)
Fish oil was hardened in the same manner as in Example 25 except that the amount of calcium hydroxide added was increased to 0.05 mass%, and then the amount of 3-MCPD produced in the hardened fat was determined.
（実施例２８）
水酸化カルシウムの添加量を０．１質量％に増量したこと以外は、実施例２５と同様に魚油を硬化させ、その後硬化油脂中の３−ＭＣＰＤ生成量を求めた。
(Example 28)
Fish oil was hardened in the same manner as in Example 25 except that the amount of calcium hydroxide added was increased to 0.1% by mass, and then the amount of 3-MCPD produced in the hardened fat was determined.
（実施例２９）
参考例２と同様に硬化し硬化油脂を得た。その後、前記の後処理の手順に従って、対油０．３質量％の粉状の水酸化カルシウムを添加して、１８０℃を維持したまま６０分間攪拌混合した後、濾過により水酸化カルシウムを取り除き、後処理油脂を得た。その後硬化油脂中の３−ＭＣＰＤ生成量を求めた。
(Example 29)
Cured in the same manner as in Reference Example 2 to obtain a hardened fat. Thereafter, in accordance with the above-mentioned post-treatment procedure, 0.3% by mass of powdered calcium hydroxide with respect to oil was added, and after stirring and mixing for 60 minutes while maintaining 180 ° C., calcium hydroxide was removed by filtration, A post-treated oil was obtained. Thereafter, the amount of 3-MCPD produced in the hardened fat was determined.
（比較例５）
炭酸ナトリウムを対油０．１質量％の粉状の炭酸カルシウムに変更したこと以外は、実施例２４と同様に魚油を硬化させ、その後硬化油脂中の３−ＭＣＰＤ生成量を求めた。
(Comparative Example 5)
Fish oil was hardened in the same manner as in Example 24 except that sodium carbonate was changed to powdery calcium carbonate with 0.1% by mass of oil, and then the amount of 3-MCPD produced in the hardened fat was determined.
（比較例６）
炭酸ナトリウムを対油０．１質量％の粉状のリン酸二水素カリウムに変更したこと以外は、実施例２４と同様に魚油を硬化させ、その後硬化油脂中の３−ＭＣＰＤ生成量を求めた。
(Comparative Example 6)
Fish oil was hardened in the same manner as in Example 24 except that sodium carbonate was changed to powdered potassium dihydrogen phosphate with 0.1% by weight of oil, and then the amount of 3-MCPD produced in the hardened fat was determined. .
（比較例７）
実施例２４と同様の処理において、炭酸ナトリウムを粉状の水酸化ナトリウム（粒状の水酸化ナトリウム（関東化学株式会社製）を乳鉢ですり潰して得た）を対油０．１質量％に変更し、硬化したが、ヨウ素価は低下せず、硬化反応は進まなかった。
(Comparative Example 7)
In the same treatment as in Example 24, sodium carbonate was changed to powdered sodium hydroxide (obtained by grinding granular sodium hydroxide (manufactured by Kanto Chemical Co., Ltd.) with a mortar) to 0.1% by mass of oil. However, the iodine value did not decrease and the curing reaction did not proceed.
（比較例８）
実施例２４と同様の処理において、炭酸ナトリウムを対油０．０１質量％の粉状のナトリウムメトキシドに変更し、硬化したがヨウ素価は低下せず、硬化反応は進まなかった。
(Comparative Example 8)
In the same treatment as in Example 24, sodium carbonate was changed to powdered sodium methoxide with an oil content of 0.01% by mass and cured, but the iodine value did not decrease and the curing reaction did not proceed.
（比較例９）
比較例８と同様の処理において、ナトリウムメトキシドの添加量を対油０．１質量％に増量し、硬化したがヨウ素価は低下せず、硬化反応は進まなかった。
(Comparative Example 9)
In the same treatment as in Comparative Example 8, the amount of sodium methoxide was increased to 0.1% by mass with respect to oil and cured, but the iodine value did not decrease and the curing reaction did not proceed.
実施例２４〜２９および比較例５〜６における３−ＭＣＰＤの低減率（％）は、参考例２における３−ＭＣＰＤ生成量（ｐｐｍ）を基準として、白土による試験と同様の計算式で求められた。 The reduction rate (%) of 3-MCPD in Examples 24 to 29 and Comparative Examples 5 to 6 is obtained by the same calculation formula as in the test using white clay based on the 3-MCPD generation amount (ppm) in Reference Example 2. It was.
結果を表５に示す。 The results are shown in Table 5.
表５に示すように、アルカリ物質として、原料油に炭酸ナトリウムと水酸化カルシウムを添加した場合、クロロプロパノール類を低減可能であることが示された。水酸化カルシウムに関しては、硬化工程時に添加量が増大するにつれて、クロロプロパノール類の低減作用も増大することが確認された。また、実施例２５〜２８と実施例２９との対比から、硬化工程時にアルカリ物質を添加することで、クロロプロパノール類の低減効果が高まることが示唆された。すなわち、本発明は、硬化処理前や硬化処理後にアルカリ物質を添加する工程や、この工程のための新たな設備導入を追加しなくても、良好なクロロプロパノール類の低減効果を得ることができると考えられる。 As shown in Table 5, it was shown that chloropropanols can be reduced when sodium carbonate and calcium hydroxide are added to the raw material oil as an alkaline substance. Regarding calcium hydroxide, it was confirmed that the reducing effect of chloropropanols increased as the amount added increased during the curing step. Moreover, it was suggested from the comparison with Examples 25-28 and Example 29 that the reduction effect of chloropropanols increases by adding an alkaline substance at the time of a hardening process. That is, the present invention can obtain a good effect of reducing chloropropanols without adding a step of adding an alkaline substance before or after the curing treatment or introducing a new facility for this step. it is conceivable that.
一方、比較例５、６の結果から、アルカリ物質であっても、炭酸カルシウムを添加した場合や酸性物質であるリン酸二水素カリウムを添加した場合には、クロロプロパノール類の低減効果が認められなかった。また、比較例７〜９の結果から、水酸化ナトリウム粉末、ナトリウムメトキシドを添加した場合には、油脂の硬化反応自体が起こらなくなることが確認された。このことから、本発明は、単にアルカリ性の物質を添加するのではなく、特定のアルカリ性の物質を添加することが、クロロプロパノール類の低減には有効であることを示唆しているものと考えられる。
On the other hand, from the results of Comparative Examples 5 and 6, even if it is an alkaline substance, when calcium carbonate is added or when potassium dihydrogen phosphate, which is an acidic substance, is added, an effect of reducing chloropropanols is recognized. There wasn't. Further, from the results of Comparative Examples 7 to 9, it was confirmed that when the sodium hydroxide powder and sodium methoxide were added, the oil and fat curing reaction itself did not occur. From this, it is considered that the present invention suggests that the addition of a specific alkaline substance, not simply adding an alkaline substance, is effective in reducing chloropropanols. .
Claims (7)
前記硬化処理前、硬化処理時および硬化処理後のうちのいずれかの工程において、ｐＨ７．０以上の白土、ｐＨ７．０以上の木質系活性炭、炭酸ナトリウムおよび水酸化カルシウムからなる群より選択される少なくとも１種を添加することを特徴とする食用油脂中のクロロプロパノール類を低減する方法。 In the production of edible fats and oils from raw material oil including curing treatment,
In any step of the curing treatment, at the time of the curing treatment and after the curing treatment, selected from the group consisting of white clay having a pH of 7.0 or more, woody activated carbon having a pH of 7.0 or more, sodium carbonate and calcium hydroxide. A method for reducing chloropropanols in edible fats and oils, comprising adding at least one kind.
The chloropropanol in edible fats and oils according to any one of claims 1 to 6, wherein the white clay having a pH of 7.0 or higher and the woody activated carbon having a pH of 7.0 or higher have been previously alkali-treated. To reduce the kind.
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