JP2015214691A - Oils and fats refining agent - Google Patents
Oils and fats refining agent Download PDFInfo
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- JP2015214691A JP2015214691A JP2015088656A JP2015088656A JP2015214691A JP 2015214691 A JP2015214691 A JP 2015214691A JP 2015088656 A JP2015088656 A JP 2015088656A JP 2015088656 A JP2015088656 A JP 2015088656A JP 2015214691 A JP2015214691 A JP 2015214691A
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- Prior art keywords
- magnesium silicate
- oil
- oils
- sio
- fats
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 54
- 238000007670 refining Methods 0.000 title claims abstract description 33
- 235000014593 oils and fats Nutrition 0.000 title abstract description 5
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000000391 magnesium silicate Substances 0.000 claims abstract description 74
- 229910052919 magnesium silicate Inorganic materials 0.000 claims abstract description 74
- 235000019792 magnesium silicate Nutrition 0.000 claims abstract description 74
- 239000000463 material Substances 0.000 claims abstract description 62
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000011148 porous material Substances 0.000 claims abstract description 43
- 239000004480 active ingredient Substances 0.000 claims abstract description 6
- 230000001186 cumulative effect Effects 0.000 claims abstract description 6
- 239000003921 oil Substances 0.000 claims description 70
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 40
- 239000003925 fat Substances 0.000 claims description 34
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 26
- 238000001179 sorption measurement Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000011777 magnesium Substances 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims 2
- 230000001603 reducing effect Effects 0.000 abstract description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 98
- 235000019198 oils Nutrition 0.000 description 62
- 239000000395 magnesium oxide Substances 0.000 description 50
- 235000021323 fish oil Nutrition 0.000 description 35
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 34
- 235000019197 fats Nutrition 0.000 description 30
- 238000000746 purification Methods 0.000 description 30
- XQAXGZLFSSPBMK-UHFFFAOYSA-M [7-(dimethylamino)phenothiazin-3-ylidene]-dimethylazanium;chloride;trihydrate Chemical compound O.O.O.[Cl-].C1=CC(=[N+](C)C)C=C2SC3=CC(N(C)C)=CC=C3N=C21 XQAXGZLFSSPBMK-UHFFFAOYSA-M 0.000 description 25
- 230000009467 reduction Effects 0.000 description 21
- 239000000243 solution Substances 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000000126 substance Substances 0.000 description 17
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 239000000843 powder Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- 239000004115 Sodium Silicate Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- 229910052911 sodium silicate Inorganic materials 0.000 description 10
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 10
- 238000002835 absorbance Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- 238000005469 granulation Methods 0.000 description 8
- 230000003179 granulation Effects 0.000 description 8
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 8
- 235000019341 magnesium sulphate Nutrition 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 235000019645 odor Nutrition 0.000 description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- 241000269851 Sarda sarda Species 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- 150000001728 carbonyl compounds Chemical class 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 235000013373 food additive Nutrition 0.000 description 5
- 239000002778 food additive Substances 0.000 description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 5
- 239000000347 magnesium hydroxide Substances 0.000 description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000011973 solid acid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000012085 test solution Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000004042 decolorization Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000010335 hydrothermal treatment Methods 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 241000251468 Actinopterygii Species 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 235000019688 fish Nutrition 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 238000010525 oxidative degradation reaction Methods 0.000 description 3
- 235000019512 sardine Nutrition 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 241000555825 Clupeidae Species 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000004111 Potassium silicate Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000010775 animal oil Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 235000020673 eicosapentaenoic acid Nutrition 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 229910052913 potassium silicate Inorganic materials 0.000 description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000008213 purified water Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000010913 used oil Substances 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- DVSZKTAMJJTWFG-SKCDLICFSA-N (2e,4e,6e,8e,10e,12e)-docosa-2,4,6,8,10,12-hexaenoic acid Chemical compound CCCCCCCCC\C=C\C=C\C=C\C=C\C=C\C=C\C(O)=O DVSZKTAMJJTWFG-SKCDLICFSA-N 0.000 description 1
- YYGNTYWPHWGJRM-UHFFFAOYSA-N (6E,10E,14E,18E)-2,6,10,15,19,23-hexamethyltetracosa-2,6,10,14,18,22-hexaene Chemical compound CC(C)=CCCC(C)=CCCC(C)=CCCC=C(C)CCC=C(C)CCC=C(C)C YYGNTYWPHWGJRM-UHFFFAOYSA-N 0.000 description 1
- GZJLLYHBALOKEX-UHFFFAOYSA-N 6-Ketone, O18-Me-Ussuriedine Natural products CC=CCC=CCC=CCC=CCC=CCC=CCCCC(O)=O GZJLLYHBALOKEX-UHFFFAOYSA-N 0.000 description 1
- 241000962514 Alosa chrysochloris Species 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 241001149724 Cololabis adocetus Species 0.000 description 1
- 241000287828 Gallus gallus Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 240000008415 Lactuca sativa Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 241001125046 Sardina pilchardus Species 0.000 description 1
- 241000269821 Scombridae Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- BHEOSNUKNHRBNM-UHFFFAOYSA-N Tetramethylsqualene Natural products CC(=C)C(C)CCC(=C)C(C)CCC(C)=CCCC=C(C)CCC(C)C(=C)CCC(C)C(C)=C BHEOSNUKNHRBNM-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- JAZBEHYOTPTENJ-JLNKQSITSA-N all-cis-5,8,11,14,17-icosapentaenoic acid Chemical compound CC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O JAZBEHYOTPTENJ-JLNKQSITSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000000981 basic dye Substances 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000014121 butter Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
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- 238000007906 compression Methods 0.000 description 1
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- 238000000748 compression moulding Methods 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- 239000002285 corn oil Substances 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 235000020669 docosahexaenoic acid Nutrition 0.000 description 1
- KAUVQQXNCKESLC-UHFFFAOYSA-N docosahexaenoic acid (DHA) Natural products COC(=O)C(C)NOCC1=CC=CC=C1 KAUVQQXNCKESLC-UHFFFAOYSA-N 0.000 description 1
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N dodecahydrosqualene Natural products CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 229960005135 eicosapentaenoic acid Drugs 0.000 description 1
- JAZBEHYOTPTENJ-UHFFFAOYSA-N eicosapentaenoic acid Natural products CCC=CCC=CCC=CCC=CCC=CCCCC(O)=O JAZBEHYOTPTENJ-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
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- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 235000020640 mackerel Nutrition 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
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- 239000004006 olive oil Substances 0.000 description 1
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
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- TUHBEKDERLKLEC-UHFFFAOYSA-N squalene Natural products CC(=CCCC(=CCCC(=CCCC=C(/C)CCC=C(/C)CC=C(C)C)C)C)C TUHBEKDERLKLEC-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Fats And Perfumes (AREA)
Abstract
Description
本発明は、新規な油脂精製剤に関する。 The present invention relates to a novel oil refining agent.
例えばカツオ、イワシ等の魚類から採取される魚油は、それに含まれる成分の生理作用が注目されている。例えば、魚油にはω−３系多価不飽和脂肪酸（エイコサペンタエン酸 （ＥＰＡ） 、ドコサヘキサエン酸 （ＤＨＡ））等が含まれるが、これらの日常的な摂取が成人病を予防できるものと期待されている。このため、魚油に含まれる各種の有効成分を抽出し、これを食品、食品添加剤、サプリメント、栄養剤等として利用する試みが進められている。 For example, fish oil collected from fish such as bonito and sardines has attracted attention for the physiological effects of the components contained therein. For example, fish oil contains ω-3 polyunsaturated fatty acids (eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA)), etc., and these daily intakes are expected to prevent adult diseases. ing. For this reason, attempts are being made to extract various active ingredients contained in fish oil and use them as foods, food additives, supplements, nutrients, and the like.
ところが、単に搾油しただけの未精製の魚油は、例えばアミン、脂肪酸、カルボニル化合物の成分（揮発性成分等）も含まれているため、これらが魚特有の臭気を呈し、製品化の妨げとなっている。また、未精製の魚油は、含有される着色成分により色合いは異なるが、一般的に赤褐色又は茶系統の色合いを呈することが多いことから、これら着色成分を除去し、より淡色化又は澄明性を高めることで製品としての価値を高める必要もある。このため、これらの不要成分を効果的に取り除くことを目的として、魚油を精製する技術の開発も進められている。 However, unrefined fish oil that has just been squeezed contains, for example, components of amines, fatty acids, and carbonyl compounds (volatile components, etc.), so these exhibit a fish-specific odor and hinder commercialization. ing. In addition, unrefined fish oil varies in color depending on the color components contained, but generally has a reddish brown or brown color, so these color components are removed to make the color lighter or clearer. It is also necessary to increase the value as a product by increasing it. For this reason, development of a technique for refining fish oil has been promoted for the purpose of effectively removing these unnecessary components.
例えば、魚油の精製方法として、魚油を減圧水蒸気蒸留にかけ、吸着剤と接触させて高沸点の一層極性の大きい香味化合物並びにその他の望ましくない少量成分を減少させ、次いで精製油を回収する方法が提案されている（特許文献１）。ここに、吸着剤としては、シリカゲル又はケイ酸を使用することが開示されている。 For example, as a method for refining fish oil, a method is proposed in which fish oil is subjected to steam distillation under reduced pressure and brought into contact with an adsorbent to reduce high-boiling, more polar flavor compounds and other undesirable minor components, and then recover the refined oil. (Patent Document 1). Here, it is disclosed that silica gel or silicic acid is used as the adsorbent.
また例えば、魚油を減圧下で極性吸着樹脂と接触させることを特徴とする魚油の精製法が提案されている（特許文献２）。 In addition, for example, a method for purifying fish oil has been proposed in which fish oil is brought into contact with a polar adsorption resin under reduced pressure (Patent Document 2).
ところで、魚油は、酸化的劣化に伴って「戻り臭」と呼ばれる不快な臭いを発するが、その原因となる主な物質はアルデヒド類及びケトン類であることが知られている。そして、魚油の酸化的劣化の度合いを示す指標としては、その対象物質等に応じて種々のものが知られているが、油中の二次酸化生成物（アルデヒド類等）の含有量を評価するための指標としてアニシジン価が採用されている。このため、上記のような不快な臭いをなくすためには、アニシジン価を指標とし、その数値を下げることが必要となる。 By the way, fish oil emits an unpleasant odor called “return odor” along with oxidative degradation, and it is known that main substances that cause this are aldehydes and ketones. Various indicators are known as indicators of the degree of oxidative degradation of fish oil depending on the target substance, etc., but the content of secondary oxidation products (aldehydes, etc.) in the oil is evaluated. The anisidine value is adopted as an index for this. For this reason, in order to eliminate the unpleasant odor as described above, it is necessary to use the anisidine value as an index and lower the numerical value.
しかしながら、これらの従来の魚油の精製技術では、十分なアニシジン価低減効果が得られないことから、さらなる改良が必要とされている。 However, these conventional fish oil refining techniques do not provide a sufficient anisidine value reduction effect, so further improvements are required.
従って、本発明の主な目的は、アニシジン価をより効果的に低減できる油脂精製剤を提供することにある。 Therefore, the main object of the present invention is to provide an oil and fat refining agent that can more effectively reduce the anisidine value.
本発明者は、従来技術の問題点に鑑みて鋭意研究を重ねた結果、特定のケイ酸マグネシウム系材料を採用することによって上記目的を達成できることを見出し、本発明を完成するに至った。 As a result of intensive studies in view of the problems of the prior art, the present inventor has found that the above object can be achieved by employing a specific magnesium silicate-based material, and has completed the present invention.
すなわち、本発明は、下記の油脂精製剤に係る。
１． 油脂のアニシジン価を低減するために用いられる材料であって、有効成分としてケイ酸マグネシウム系材料を含み、前記ケイ酸マグネシウム系材料における細孔径２００〜５００ｎｍにおける累積細孔容積が０．０５ｃｃ／ｇ以上であることを特徴とするケイ酸マグネシウム系油脂精製剤。
２． 前記ケイ酸マグネシウム系材料の水分含有量が８．０重量％以下である、前記項１に記載のケイ酸マグネシウム系油脂精製剤。
３． 前記ケイ酸マグネシウム系材料のメチレンブルー吸着量が０．４０ｍｍｏｌ／ｇ以上である、前記項１に記載のケイ酸マグネシウム系油脂精製剤。
４． 前記ケイ酸マグネシウム系材料において、細孔径２００〜５００ｎｍの細孔における比表面積当たりのメチレンブルー吸着量が１．５ｍｏｌ／ｍ２以上である、前記項１に記載のケイ酸マグネシウム系油脂精製剤。
５． 前記ケイ酸マグネシウム系材料におけるＳｉ及びＭｇの含有比率がＳｉＯ２／ＭｇＯ重量比換算で１．２〜７．６である、前記項１のケイ酸マグネシウム系油脂精製剤。
６． 前記項１〜５のいずれかに記載の油脂精製剤を油脂と接触させる工程を含むことを特徴とする精製油の製造方法。
That is, the present invention relates to the following oil and fat refining agent.
1. A material used to reduce the anisidine value of fats and oils, containing a magnesium silicate material as an active ingredient, and a cumulative pore volume at a pore diameter of 200 to 500 nm in the magnesium silicate material is 0.05 cc / g The magnesium silicate type oil refiner characterized by the above-mentioned.
2. Item 2. The magnesium silicate oil refining agent according to Item 1, wherein the magnesium silicate material has a water content of 8.0% by weight or less.
3. Item 2. The magnesium silicate oil refining agent according to Item 1, wherein the magnesium silicate material has a methylene blue adsorption amount of 0.40 mmol / g or more.
4). Item 2. The magnesium silicate-based oil refining agent according to Item 1, wherein the magnesium silicate-based material has a methylene blue adsorption amount per specific surface area of pores having a pore diameter of 200 to 500 nm of 1.5 mol / m 2 or more.
5. The magnesium silicate oil refining agent according to Item 1, wherein the content ratio of Si and Mg in the magnesium silicate material is 1.2 to 7.6 in terms of SiO 2 / MgO weight ratio.
6). The manufacturing method of the refined oil characterized by including the process of contacting the fats and oils refiner in any one of said claim | item 1-5 with fats and oils.
本発明によれば、より優れたアニシジン価低減性能を発揮する油脂精製剤を提供することができる。本発明の油脂精製剤が従来品よりも高い性能を発現する理由は定かではないが、本発明の油脂精製剤では、揮発性成分を含む低分子量のアミン、アルデヒド等を吸着除去するとともに、これらが重合した分子量の大きな不揮発性物質も吸着除去できるためと考えられる。 According to the present invention, an oil and fat refining agent that exhibits more excellent anisidine value reducing performance can be provided. The reason why the oil refining agent of the present invention exhibits higher performance than conventional products is not clear, but the oil refining agent of the present invention adsorbs and removes low molecular weight amines, aldehydes and the like containing volatile components, and these This is considered to be because the non-volatile substance having a large molecular weight obtained by polymerization can be adsorbed and removed.
アニシジン価に影響を与える物質（関与物質）として、不飽和油脂の酸化生成物であるカルボニル化合物（アルデヒド類及びケトン類）のほか、これらが重合した重合物が例示される。一般に、前記重合物の場合は、低分子のカルボニル化合物に比して分子量及び分子サイズが大きく、それに伴って不揮発性となる傾向にある。このため、従来の蒸留法等では、これらの不揮発性物質を除去することは困難であると考えられる。また、従来の吸着剤においても、その細孔構造との関係で分子量及び分子サイズが大きな不揮発性物質を除去することは難しいものと考えられる。これに対し、本発明では、特定の細孔構造を有するケイ酸マグネシウム系材料を採用することによって、低分子量の関与物質のみならず、高分子量の関与物質も吸着できるようになった結果、アニシジン価をより効果的に低減させることが可能になるものと推察される。 Examples of substances (participating substances) that affect the anisidine value include carbonyl compounds (aldehydes and ketones), which are oxidation products of unsaturated oils, and polymers obtained by polymerizing these compounds. In general, the polymer is larger in molecular weight and molecular size than a low-molecular carbonyl compound, and tends to become non-volatile along with it. For this reason, it is considered difficult to remove these non-volatile substances by a conventional distillation method or the like. In addition, it is considered difficult for conventional adsorbents to remove non-volatile substances having a large molecular weight and molecular size in relation to the pore structure. In contrast, in the present invention, by adopting a magnesium silicate-based material having a specific pore structure, not only low molecular weight participating substances but also high molecular weight participating substances can be adsorbed. It is presumed that the price can be reduced more effectively.
このように、本発明の油脂精製剤によって、特に油脂中のアルデヒド重合物由来の臭気の低減を図ることができ、ひいては高品質の精製油を製造することが可能となる。 As described above, the oil and fat refining agent of the present invention can particularly reduce the odor derived from the aldehyde polymer in the oil and fat, and as a result, high-quality refined oil can be produced.
しかも、本発明の油脂精製剤では、製品価値を低下させる原因となる着色成分を取り除くこともできるので、より良好な外観を呈する精製油を提供することもできる。 In addition, since the oil and fat refining agent of the present invention can also remove colored components that cause a reduction in product value, it is possible to provide a refined oil exhibiting a better appearance.
本発明の油脂精製剤は、例えばカツオ、マグロ、イワシ、サンマ、サバ等の魚油の精製に用いることができるほか、アニシジン価の低減が必要とされる一般的な油類、例えば使用済み油（食用油等）の再生、製品である天然油・合成油を製造する際における粗油（原料油）の精製、天然油・合成油を原料とする製品（例えば医薬品、化粧品、食品、化学品等）の製造における前記原料の精製等に好適に用いることができる。 The oil and fat refining agent of the present invention can be used for refining fish oil such as bonito, tuna, sardine, saury, mackerel, etc., as well as general oils that require a reduction in anisidine value, such as used oil ( Edible oil, etc.), refinement of crude oil (raw oil) when producing natural oils and synthetic oils, products made from natural oils and synthetic oils (eg pharmaceuticals, cosmetics, foods, chemicals, etc.) ) Can be suitably used for purification of the raw materials.
１．油脂精製剤
本発明のケイ酸マグネシウム系油脂精製剤（以下「本発明精製剤」ともいう。）は、油脂のアニシジン価を低減するために用いられる材料であって、有効成分としてケイ酸マグネシウム系材料を含み、前記ケイ酸マグネシウム系材料における細孔径２００〜５００ｎｍにおける累積細孔容積が０．０５ｃｃ／ｇ以上であることを特徴とする。
1. Fat and oil refining agent Magnesium silicate oil and fat refining agent of the present invention (hereinafter also referred to as "the refining agent of the present invention") is a material used for reducing the anisidine value of fats and oils, and magnesium silicate as an active ingredient Including the material, the cumulative pore volume at a pore diameter of 200 to 500 nm in the magnesium silicate-based material is 0.05 cc / g or more.
本発明精製剤は、特に油脂のアニシジン価を低減するために用いられるものである。すなわち、主として油脂中に含まれるアルデヒド類及びケトン類のカルボニル化合物ならびにそれらの重合物の吸着除去に好適に用いられる材料である。これによって、例えば魚油等の酸化的劣化により生ずる物質を取り除くことができる結果、「戻り臭」等の臭気を効果的に低減することが可能となる。本発明精製剤が適用できる油脂は、限定的でなく、例えば各種の魚類から抽出された魚油を挙げることができる。 The purification agent of the present invention is particularly used for reducing the anisidine value of fats and oils. That is, it is a material that is suitably used for adsorption removal of carbonyl compounds of aldehydes and ketones and their polymers mainly contained in fats and oils. As a result, for example, substances resulting from oxidative degradation such as fish oil can be removed, and as a result, odors such as “return odor” can be effectively reduced. The fats and oils to which the purification agent of the present invention can be applied are not limited, and examples thereof include fish oil extracted from various fishes.
本発明精製剤は、特定の細孔構造を有するケイ酸マグネシウム系材料を有効成分として用いる。本発明精製剤中のケイ酸マグネシウム系材料の含有量は限定的ではないが、通常は８０〜１００重量％程度とし、特に９０〜１００重量％が好ましく、さらには９５〜１００重量％がより好ましい。従って、例えばケイ酸マグネシウム系材料１００重量％からなる本発明精製剤も適用可能である。 The purification agent of the present invention uses a magnesium silicate-based material having a specific pore structure as an active ingredient. The content of the magnesium silicate-based material in the purification agent of the present invention is not limited, but is usually about 80 to 100% by weight, particularly preferably 90 to 100% by weight, and more preferably 95 to 100% by weight. . Therefore, the purification agent of the present invention comprising, for example, 100% by weight of a magnesium silicate material is also applicable.
前記ケイ酸マグネシウム系材料の細孔構造に関しては、細孔径２００〜５００ｎｍにおける累積細孔容積が０．０５ｃｃ／ｇ以上であり、好ましくは０．１０ｃｃ／ｇ以上であり、より好ましくは０．２０ｃｃ／ｇ以上であるケイ酸マグネシウム系材料を用いる。本発明精製剤では、細孔径が２００〜５００ｎｍという比較的大きな細孔を０．０５ｃｃ／ｇ以上に設定することによって、カルボニル化合物（低分子）のみならず、その重合物（高分子）を収容できる空間を確保し、それによってアニシジン価を効果的に低減させることが可能となる。 Regarding the pore structure of the magnesium silicate-based material, the cumulative pore volume at a pore diameter of 200 to 500 nm is 0.05 cc / g or more, preferably 0.10 cc / g or more, more preferably 0.20 cc. A magnesium silicate-based material that is at least / g is used. The purification agent of the present invention accommodates not only a carbonyl compound (low molecule) but also a polymer (polymer) thereof by setting relatively large pores having a pore size of 200 to 500 nm to 0.05 cc / g or more. It is possible to secure a space that can be produced, thereby effectively reducing the anisidine value.
前記ケイ酸マグネシウム系材料の水分含有量は限定的ではないが、通常は８．０重量％以下であり、特に７．４重量％以下であり、さらには７．０重量％以下とすることが好ましい。本発明精製剤中に含まれる水分は本発明精製剤表面への関与物質の拡散を抑制し、かつ水分子が例えば、本発明精製剤の細孔表面の固体酸点に対して、自身に含まれる酸素原子の不対電子を介して吸着されることで固体酸点を潰してしまうおそれがあると考えられる。このことから、ケイ酸マグネシウム系材料の水分含有量が８．０重量％より大きい場合は、十分なアニシジン価低減効果が得られないことがある。なお、水分含有量の下限値は限定的ではないが、通常は１．０重量％程度とすれば良い。 The water content of the magnesium silicate-based material is not limited, but is usually 8.0% by weight or less, particularly 7.4% by weight or less, and more preferably 7.0% by weight or less. preferable. Moisture contained in the purification agent of the present invention suppresses diffusion of the participating substances on the surface of the purification agent of the present invention, and water molecules are contained in itself, for example, with respect to the solid acid point on the pore surface of the purification agent of the present invention. It is considered that the solid acid sites may be crushed by being adsorbed via unpaired electrons of oxygen atoms. For this reason, when the water content of the magnesium silicate-based material is greater than 8.0% by weight, a sufficient anisidine value reduction effect may not be obtained. Note that the lower limit of the moisture content is not limited, but is usually about 1.0% by weight.
前記ケイ酸マグネシウム系材料のメチレンブルー吸着量は、特に制約されないが、通常は０．４０ｍｍｏｌ／ｇ以上とすることが好ましい。メチレンブルー吸着量は、メチレンブルーが塩基性色素であることから、一般的に表面固体酸量を表す指標として使用されている。細孔表面に関与物質を安定的に固定化させるためには、全細孔において関与物質が有する塩基点に作用する固体酸が必要であるため、ケイ酸マグネシウム系材料のメチレンブルー吸着量が０．４０ｍｍｏｌ／ｇより小さい場合は、アニシジン価低減性能が低下し、十分な効果が得られない場合がある。 The amount of methylene blue adsorbed by the magnesium silicate-based material is not particularly limited, but is usually preferably 0.40 mmol / g or more. The methylene blue adsorption amount is generally used as an index representing the amount of surface solid acid because methylene blue is a basic dye. In order to stably immobilize the participating substance on the pore surface, a solid acid acting on the base point of the participating substance in all the pores is required, so the methylene blue adsorption amount of the magnesium silicate-based material is 0. When it is less than 40 mmol / g, the anisidine value reduction performance is lowered, and a sufficient effect may not be obtained.
また、特に高分子量の関与物質の捕捉には、前記ケイ酸マグネシウム系材料の２００〜５００ｎｍの有効細孔における比表面積当たりのメチレンブルー吸着量が１．５ｍｏｌ／ｍ２以上とすることが好ましい。２００〜５００ｎｍの細孔における比表面積当たりのメチレンブルー吸着量が１．５ｍｏｌ／ｍ２より小さい場合は、上記理由によりアニシジン価低減性能が低下するおそれがある。 In particular, for capturing high molecular weight related substances, it is preferable that the adsorption amount of methylene blue per specific surface area in the effective pores of 200 to 500 nm of the magnesium silicate-based material is 1.5 mol / m 2 or more. When the amount of methylene blue adsorbed per specific surface area in pores of 200 to 500 nm is smaller than 1.5 mol / m 2 , the anisidine value reduction performance may be lowered due to the above reasons.
前記ケイ酸マグネシウム系材料中におけるＳｉ及びＭｇの含有比率は特に限定されないが、通常はＳｉＯ２／ＭｇＯ重量比で１．２〜７．６とすることが好ましい。上記比率に設定する場合には、より優れたアニシジン価低減効果を得ることができる。ＳｉＯ２／ＭｇＯ重量比が１．２より小さい領域では、塩基性物質である水酸化マグネシウムの残存が確認され、メチレンブルー吸着量が低下することによりアニシジン価低減能も低下することがある。また、ＳｉＯ２／ＭｇＯ重量比が７．６より大きい領域では、塩基性物質であるＳｉＯ２の重量比率が増加し、相対的に固体酸量が減少することにより、メチレンブルー吸着量が低下し、アニシジン価低減能も低下するおそれがある。 Although the content ratio of Si and Mg in the magnesium silicate-based material is not particularly limited, it is usually preferable to set the SiO 2 / MgO weight ratio to 1.2 to 7.6. When it is set to the above ratio, a more excellent anisidine value reduction effect can be obtained. In the region where the weight ratio of SiO 2 / MgO is smaller than 1.2, it is confirmed that magnesium hydroxide, which is a basic substance, remains, and the ability to reduce anisidine value may decrease due to a decrease in the amount of adsorbed methylene blue. Further, the SiO 2 / MgO weight ratio is 7.6 larger area, increasing the weight ratio of SiO 2 is a basic substance, by weight relatively solid acid is reduced, reduces the methylene blue adsorption amount, There is also a possibility that the ability to reduce anisidine value may be lowered.
本発明精製剤では、必要に応じて、本発明の効果を妨げない範囲内において他の添加剤を配合することもできる。例えば、公知又は市販の再生剤、酸化防止剤等を挙げることができる。すなわち、本発明精製剤中におけるケイ酸マグネシウム系材料の含有量が１００重量％未満の場合において、その残部をこれらの添加剤が構成することになる。 In the purification agent of the present invention, if necessary, other additives can be blended within a range not impeding the effects of the present invention. For example, publicly known or commercially available regenerants and antioxidants can be mentioned. That is, when the content of the magnesium silicate-based material in the purification agent of the present invention is less than 100% by weight, these additives constitute the remainder.
本発明精製剤は、通常は粉末の形態で使用することができるが、必要に応じて造粒等の成形を行うこともできる。造粒方法は特に制限されず、例えば転動造粒法、攪拌造粒法、流動層造粒法、圧縮成型法（圧縮造粒法）、成膜処理法、磁気特性処理法、表面改質法、焼結成型法、振動成型法、圧力スイング法、真空成型法、スプレードライ法等のほか、凍結乾燥法、共沈法等を利用する方法等のいずれであっても良い。造粒物の平均粒径は、一般的には１０〜３００μｍ程度とすれば良い。なお、造粒に際しては、ケイ酸マグネシウム系材料の水分含有量の変動を効果的に抑制するために、溶媒としてアルコール類等の有機溶剤を使用したり、あるいは造粒後に乾燥工程を実施することもできる。 The purification agent of the present invention can usually be used in the form of a powder, but can also be subjected to molding such as granulation as necessary. The granulation method is not particularly limited. For example, rolling granulation method, stirring granulation method, fluidized bed granulation method, compression molding method (compression granulation method), film formation method, magnetic property treatment method, surface modification In addition to a method, a sintering molding method, a vibration molding method, a pressure swing method, a vacuum molding method, a spray drying method, etc., any of a method using a freeze drying method, a coprecipitation method, or the like may be used. The average particle size of the granulated material may generally be about 10 to 300 μm. In granulation, in order to effectively suppress fluctuations in the moisture content of the magnesium silicate-based material, an organic solvent such as an alcohol is used as a solvent, or a drying step is performed after granulation. You can also.
本発明精製剤は、例えば本発明精製剤と油脂とを接触させる工程を含む方法によって好適に使用することができる。接触させる際の温度は、処理対象となる油脂の種類等に応じて適宜設定すれば良い。例えば、魚油の精製を目的として精製する場合は、１５０℃以下（好ましくは３０〜１００℃、より好ましくは５０〜８０℃）の温度に加熱された魚油と本発明精製剤とを接触させる工程を含む精製方法により精製油の製造を好適に行うことができる。 The purification agent of the present invention can be suitably used, for example, by a method including a step of bringing the purification agent of the present invention into contact with fats and oils. What is necessary is just to set the temperature at the time of contacting suitably according to the kind etc. of fats and oils used as a process target. For example, when refining for the purpose of refining fish oil, a step of bringing the refining agent of the present invention into contact with fish oil heated to a temperature of 150 ° C. or lower (preferably 30 to 100 ° C., more preferably 50 to 80 ° C.). The refined oil can be suitably produced by the refining method including.
油脂と接触させる方法は特に制限されず、例えばａ）油脂に本発明精製剤を分散・攪拌させる方法、ｂ）本発明精製剤を含むフィルター層に油脂を１回又は複数回流通させる方法等を採用することができる。なお、本発明精製剤を用いて精製処理を実施した後において、精製された油脂中に本発明精製剤が含まれている場合は、ろ過等の公知の固液分離方法により本発明精製剤を分離・回収することができる。 The method for bringing the oil and fat into contact is not particularly limited. For example, a) a method of dispersing and stirring the refinement agent of the present invention in the oil and fat, b) a method of circulating the oil and fat one or more times through the filter layer containing the refinement of the invention, and the like. Can be adopted. In addition, after carrying out the purification treatment using the purification agent of the present invention, when the purification agent of the present invention is contained in the refined fat, the purification agent of the present invention is obtained by a known solid-liquid separation method such as filtration. It can be separated and recovered.
接触工程で用いる本発明精製剤の使用量は、用いる油脂のアニシジン価等に応じて適宜設定することができるが、通常は油脂１００重量部に対して本発明精製剤０．１〜５０重量部、特に１〜１０重量部とすることが好ましい。 The amount of the purification agent of the present invention used in the contacting step can be appropriately set according to the anisidine value of the oil used, but usually 0.1 to 50 parts by weight of the purification agent of the present invention per 100 parts by weight of the oil. In particular, it is preferably 1 to 10 parts by weight.
接触工程では、本発明精製剤とともに、脱酸剤を併用することもできる。脱酸剤の併用により、アニシジン価低減効果とともに脱酸効果を得ることができる。すなわち、処理対象である油脂が粗油あるいは劣化油（使用済み油）である場合、脱酸剤により酸性成分を吸着し、酸価を低減することができる。脱酸剤としては、公知のもの又は市販品を使用することができ、例えば酸化マグネシウム、酸化カルシウム、炭酸マグネシウム、炭酸カルシウム、ケイ酸カルシウム、ケイ酸マグネシウム、水酸化カルシウム、水酸化マグネシウム、水酸化アルミニウム、合成フィロケイ酸マグネシウム、シリカ、マグネシア、二酸化ケイ素及び活性白土等の少なくとも１種を好適に用いることができる。 In the contacting step, a deoxidizer can be used in combination with the purification agent of the present invention. By using a deoxidizing agent in combination, a deoxidizing effect can be obtained together with an anisidine value reducing effect. That is, when the fat or oil to be treated is a crude oil or a deteriorated oil (used oil), the acid component can be adsorbed by the deoxidizer and the acid value can be reduced. As the deoxidizer, known or commercially available products can be used. For example, magnesium oxide, calcium oxide, magnesium carbonate, calcium carbonate, calcium silicate, magnesium silicate, calcium hydroxide, magnesium hydroxide, hydroxide At least one of aluminum, synthetic magnesium phyllosilicate, silica, magnesia, silicon dioxide, activated clay and the like can be suitably used.
脱酸剤を使用する場合の使用量は、油脂の酸価に応じて適宜決定することができるが、通常は本発明精製剤１００重量に対して０．１〜１０重量部程度、特に０．４〜４重量部とすることが望ましい。 The amount used in the case of using a deoxidizing agent can be appropriately determined according to the acid value of the oil or fat, but is usually about 0.1 to 10 parts by weight, particularly 0. It is desirable to be 4 to 4 parts by weight.
油脂としては、特に限定的でなく、前記で示した魚油のほか、各種の油脂のいずれにも適用することができる。魚油としては、例えばカツオ、マグロ、イワシ等から採取された魚油が挙げられる。従って、例えばアニシジン価１０以上、特に２０以上の魚油を好適に精製することも可能である。また、魚油のほか、本発明精製剤によりアニシジン価を下げることができる限り、動物性油、植物性油又は鉱物性油のいずれであっても良い。動物性油としては、例えばバター、ラード、鶏油、鯨油、スクワレン等が挙げられる。植物性油としては、例えばパーム油、ショートニング、サラダ油、大豆油、コーン油、ごま油、菜種油、ひまわり油、椿油、オリーブオイル等が挙げられる。鉱物性油としては、例えばシリコンオイル、琥珀油等が挙げられる。 The oil and fat is not particularly limited, and can be applied to any of various oils and fats in addition to the fish oil shown above. Examples of fish oil include fish oil collected from bonito, tuna, sardines and the like. Therefore, for example, fish oil having an anisidine value of 10 or more, particularly 20 or more can be suitably purified. In addition to fish oil, any of animal oil, vegetable oil, or mineral oil may be used as long as the anisidine value can be lowered by the purification agent of the present invention. Examples of animal oils include butter, lard, chicken oil, whale oil, squalene and the like. Examples of vegetable oils include palm oil, shortening, salad oil, soybean oil, corn oil, sesame oil, rapeseed oil, sunflower oil, coconut oil, olive oil and the like. Examples of the mineral oil include silicon oil and cocoon oil.
また、本発明において、油脂としては、使用前の油脂であっても良いし、使用後の油脂（使用済み油脂）であっても良い。すなわち、本発明の製造方法は、例えば粗油の精製、精製油の最終工程での精製、使用済み油脂の再生等を目的として実施することができる。 Moreover, in this invention, as fats and oils, the fats and oils before use may be sufficient, and the fats and oils after use (used fats and oils) may be sufficient. That is, the production method of the present invention can be carried out for the purpose of, for example, refining crude oil, refining refined oil in the final step, regenerating used fats and oils, and the like.
２．魚油精製剤の製造
本発明精製剤は、本発明のケイ酸マグネシウム系材料を調製する工程を含むことを特徴とするものである。より具体的には、マグネシウム原料を含む溶液とケイ酸質原料を含む溶液とをｐＨ６〜１０の条件下で反応させる工程を含む製造方法によって、本発明精製剤を好適に得ることができる。
2. Manufacture of fish oil refining agent The refining agent of the present invention includes a step of preparing the magnesium silicate-based material of the present invention. More specifically, the purification agent of the present invention can be suitably obtained by a production method including a step of reacting a solution containing a magnesium raw material and a solution containing a siliceous raw material under conditions of pH 6-10.
マグネシウム原料としては、公知のケイ酸マグネシウム合成で使用されている原料と同様のものを使用することができる。例えば、水酸化マグネシウム、酸化マグネシウム、塩化マグネシウム、硫酸マグネシウム、炭酸マグネシウム、硝酸マグネシウム等を挙げることができる。これらの中でも特に水溶性のマグネシウム塩である塩化マグネシウム、硫酸マグネシウム、硝酸マグネシウム等を使用することが望ましい。 As the magnesium raw material, the same raw materials used in known magnesium silicate synthesis can be used. Examples thereof include magnesium hydroxide, magnesium oxide, magnesium chloride, magnesium sulfate, magnesium carbonate, and magnesium nitrate. Of these, water-soluble magnesium salts such as magnesium chloride, magnesium sulfate, and magnesium nitrate are particularly preferable.
ケイ酸質原料としては、公知のケイ酸マグネシウム合成で使用されている原料と同様のものを使用することができる。例えば、二酸化ケイ素、ケイ砂、ケイ石、石英、ケイ酸ナトリウム、ケイ酸カリウム等を挙げることができる。これらの中でも特に水溶性の原料であるケイ酸ナトリウム、ケイ酸カリウム等を使用することが望ましい。 As the siliceous material, the same materials as those used in the known magnesium silicate synthesis can be used. Examples thereof include silicon dioxide, silica sand, silica stone, quartz, sodium silicate, potassium silicate and the like. Among these, it is desirable to use sodium silicate, potassium silicate, etc. which are water-soluble raw materials.
反応に際しては、ｐＨを６〜１０の範囲内に調整する。この場合、必要に応じて適宜ｐＨ調整剤（アルカリ又は酸）を使用することができる。アルカリは公知のものを使用すれば良く、例えば水酸化ナトリウム、水酸化カリウム、アンモニア水、炭酸ナトリウム、炭酸水素ナトリウム等を用いることができ、これらは溶液（又は水溶液）の形態で用いることが望ましい。また、酸としては、公知のものを使用すれば良く、例えば硫酸、塩酸、硝酸等を用いることができる。これらは水で適宜希釈して使用しても良い。 During the reaction, the pH is adjusted within the range of 6-10. In this case, a pH adjuster (alkali or acid) can be appropriately used as necessary. Any known alkali may be used. For example, sodium hydroxide, potassium hydroxide, ammonia water, sodium carbonate, sodium hydrogen carbonate and the like can be used, and these are preferably used in the form of a solution (or an aqueous solution). . Moreover, what is necessary is just to use a well-known thing as an acid, for example, a sulfuric acid, hydrochloric acid, nitric acid etc. can be used. These may be used after appropriately diluted with water.
マグネシウム原料を含む溶液とケイ酸質原料を含む溶液との反応は、両溶液を混合すれば良く、例えば一方に溶液に他方の溶液を滴下する方法を好適に採用することができる。より具体的には、マグネシウム原料を含む溶液にケイ酸質原料を含む溶液を滴下する方法が挙げられる。なお、滴下方法は、特に制限されず、例えば逐次滴下方法、同時滴下方法等のいずれも採用することができる。 For the reaction between the solution containing the magnesium raw material and the solution containing the siliceous raw material, both solutions may be mixed. For example, a method in which the other solution is dropped into one solution can be suitably employed. More specifically, a method of dropping a solution containing a siliceous raw material into a solution containing a magnesium raw material can be mentioned. The dropping method is not particularly limited, and for example, any of a sequential dropping method and a simultaneous dropping method can be employed.
両溶液を混合する際の温度は、適宜調整することができるが、特に７０℃以上とし、さらには９０℃以上の範囲内で行うことが好ましい。かかる温度範囲に設定することによって、安定した沈殿反応物が効率的に得られる。 The temperature at which the two solutions are mixed can be adjusted as appropriate, but it is particularly preferably 70 ° C. or higher, more preferably 90 ° C. or higher. By setting to such a temperature range, a stable precipitation reaction product can be obtained efficiently.
また、両溶液の混合割合は、得られるケイ酸マグネシウム系材料のＳｉＯ２／ＭｇＯ重量比を１．２〜７．６の範囲内になるように適宜調整すれば良い。例えば、食品添加物ケイ酸マグネシウムを得る場合は、ＳｉＯ２／ＭｇＯ重量比を２．８〜５．４の範囲内になるように適宜調整すれば良い。 The mixing ratio of both solutions, the SiO 2 / MgO weight ratio of magnesium obtained silicate-based material may be appropriately adjusted within the range of 1.2 to 7.6. For example, when obtaining food additive magnesium silicate, the SiO 2 / MgO weight ratio may be appropriately adjusted so as to be in the range of 2.8 to 5.4.
得られた反応生成物は、必要に応じて脱水、水洗、乾燥等（これらをまとめて「精製処理」という。）を行うことによりケイ酸マグネシウム系材料を得る。脱水方法は、公知の固液分離方法、乾燥方法等に従えば良い。固液分離方法としては、例えばろ過、遠心分離等を一般的に採用することができる。また、乾燥方法としては、加熱乾燥又は凍結乾燥がある。乾燥装置は限定的でなく、例えば固定床式送風乾燥機、コンベヤ式送風乾燥機、流動層乾燥機、転動乾燥機、振動乾燥機、ドラム式乾燥機、気流乾燥機、噴霧乾燥機、凍結乾燥機、減圧乾燥機等を用いることができる。 The obtained reaction product is subjected to dehydration, washing with water, drying and the like (collectively referred to as “purification treatment”) as necessary to obtain a magnesium silicate-based material. The dehydration method may follow a known solid-liquid separation method, drying method, or the like. As a solid-liquid separation method, for example, filtration, centrifugation and the like can be generally employed. Further, the drying method includes heat drying or freeze drying. The drying apparatus is not limited. For example, a fixed bed type blower dryer, a conveyor type blower dryer, a fluidized bed dryer, a rolling dryer, a vibration dryer, a drum dryer, an air dryer, a spray dryer, a freezing A dryer, a vacuum dryer or the like can be used.
本発明の製造方法では、必要に応じて、次のような追加工程を実施することもできる。すなわち、前記反応生成物に酸を添加する工程（追加工程１）を実施することができる。この処理によって、ケイ酸マグネシウム系材料のＳｉＯ２／ＭｇＯ重量比を任意に調整することができる。 In the manufacturing method of the present invention, the following additional steps can be performed as necessary. That is, the step of adding an acid to the reaction product (addition step 1) can be performed. By this treatment, the SiO 2 / MgO weight ratio of the magnesium silicate material can be arbitrarily adjusted.
上記の追加工程１において、反応生成物に添加される酸としては、公知のものを使用すれば良く、例えば硫酸、塩酸、硝酸等を用いることができる。これら酸は、水で適宜希釈して使用しても良い。また、酸の添加量は、ケイ酸マグネシウム系材料のＳｉＯ２／ＭｇＯ重量比が１．２〜７．６の範囲内になるようにすることが好ましい。 In the above additional step 1, as the acid added to the reaction product, a known acid may be used, and for example, sulfuric acid, hydrochloric acid, nitric acid and the like can be used. These acids may be used after appropriately diluted with water. The amount of acid is preferably SiO 2 / MgO weight ratio of magnesium silicate-based material is made to be in the range of 1.2 to 7.6.
また、必要に応じて、前記反応生成物又は前記追加工程１で得られた反応生成物を水熱処理する工程（追加工程２）を実施することができる。この処理によってケイ酸マグネシウム系材料の嵩比容積をより効果的に低減することが可能となる。水熱処理の温度は１５０〜２５０℃の範囲が好適である。また、反応時間は、反応温度によって異なるが、通常は１〜５０時間の範囲内とすれば良い。水熱処理は、公知又は市販のオートクレーブ装置等を用いることによって実施することができる。 Moreover, the process (addition process 2) of hydrothermally treating the said reaction product or the reaction product obtained at the said addition process 1 can be implemented as needed. By this treatment, the volume specific volume of the magnesium silicate material can be more effectively reduced. The temperature of the hydrothermal treatment is preferably in the range of 150 to 250 ° C. Moreover, although reaction time changes with reaction temperature, what is necessary is just to be in the range of 1 to 50 hours normally. Hydrothermal treatment can be carried out by using a known or commercially available autoclave apparatus or the like.
以下に実施例及び比較例を示し、本発明の特徴をより具体的に説明する。ただし、本発明の範囲は、実施例に限定されない。 The features of the present invention will be described more specifically with reference to the following examples and comparative examples. However, the scope of the present invention is not limited to the examples.
実施例１
合成用原料として、市販の３号ケイ酸ナトリウム１６３．８ｇ（ＳｉＯ２換算４７．５ｇ）、市販の硫酸マグネシウム２２２．０ｇ（ＭｇＯ換算３６．４ｇ）を用いた。３号ケイ酸ナトリウムは、液量が４２５ｍＬとなるように水を加え、ケイ酸ナトリウム水溶液とした。また、硫酸マグネシウムは、溶解後の液量が２Ｌとなるように水を加え、溶解させて水溶液とした（ＳｉＯ２／ＭｇＯ仕込み重量比＝１．３）。はじめに、硫酸マグネシウム水溶液を容量５Ｌのステンレス鋼製容器に導入し、撹拌しながら、９０℃に加温した。次に、４８％水酸化ナトリウム水溶液１１０ｇに水を加え、全量を１５０ｍＬとした水溶液を滴下し、水酸化マグネシウム沈殿物を得た。滴下終了後、ケイ酸ナトリウム水溶液を滴下し、得られた反応生成物を減圧ろ過により脱水し、脱水ケーキを乾燥器に入れ、１００℃ で一晩乾燥し、粉末状のケイ酸マグネシウム系材料（ＳｉＯ２：５２．０重量％、ＭｇＯ：４１．９重量％、ＳｉＯ２／ＭｇＯ重量比＝１．２）を得た。
Example 1
As a raw material for synthesis, 163.8 g of commercially available No. 3 sodium silicate (47.5 g in terms of SiO 2 ) and 222.0 g of commercially available magnesium sulfate (36.4 g in terms of MgO) were used. No. 3 sodium silicate was added with water so that the liquid volume was 425 mL to obtain a sodium silicate aqueous solution. Magnesium sulfate was dissolved in an aqueous solution by adding water so that the solution volume after dissolution was 2 L (SiO 2 / MgO charge weight ratio = 1.3). First, an aqueous magnesium sulfate solution was introduced into a 5 L stainless steel container and heated to 90 ° C. while stirring. Next, water was added to 110 g of a 48% aqueous sodium hydroxide solution, and an aqueous solution with a total amount of 150 mL was added dropwise to obtain a magnesium hydroxide precipitate. After completion of the dropwise addition, an aqueous sodium silicate solution is dropped, and the resulting reaction product is dehydrated by filtration under reduced pressure. The dehydrated cake is placed in a drier and dried overnight at 100 ° C. to form a powdered magnesium silicate-based material ( SiO 2 : 52.0 wt%, MgO: 41.9 wt%, SiO 2 / MgO weight ratio = 1.2).
実施例２
仕込み重量比を２．０、４８％水酸化ナトリウム水溶液の量を８８．３ｇとした以外は実施例１と同様にサンプルを調製し、粉末状のケイ酸マグネシウム系材料（ＳｉＯ２：６４．５重量％、ＭｇＯ：３３．５重量％、ＳｉＯ２／ＭｇＯ重量比＝１．９）を得た。
Example 2
A sample was prepared in the same manner as in Example 1 except that the charged weight ratio was 2.0 and the amount of 48% sodium hydroxide aqueous solution was 88.3 g, and a powdery magnesium silicate-based material (SiO 2 : 64.5) Wt%, MgO: 33.5 wt%, SiO 2 / MgO weight ratio = 1.9).
実施例３
仕込み重量比を２．８、４８％水酸化ナトリウム水溶液の量を６５．０ｇとした以外は実施例１と同様にサンプルを調製し、粉末状のケイ酸マグネシウム系材料（ＳｉＯ２：７２．０重量％、ＭｇＯ：２６．２重量％、ＳｉＯ２／ＭｇＯ重量比＝２．７）を得た。
Example 3
A sample was prepared in the same manner as in Example 1 except that the charged weight ratio was 2.8 and the amount of 48% sodium hydroxide aqueous solution was 65.0 g, and a powdered magnesium silicate-based material (SiO 2 : 72.0) Wt%, MgO: 26.2 wt%, SiO 2 / MgO weight ratio = 2.7).
実施例４
仕込み重量比を３．２、４８％水酸化ナトリウム水溶液の量を５１．７ｇとした以外は実施例１と同様にサンプルを調製し、粉末状のケイ酸マグネシウム系材料（ＳｉＯ２：７４．１重量％、ＭｇＯ：２３．６重量％、ＳｉＯ２／ＭｇＯ重量比＝３．１）を得た。
Example 4
A sample was prepared in the same manner as in Example 1 except that the charging weight ratio was 3.2 and the amount of 48% sodium hydroxide aqueous solution was 51.7 g, and a powdery magnesium silicate-based material (SiO 2 : 74.1) was prepared. Wt%, MgO: 23.6 wt%, SiO 2 / MgO weight ratio = 3.1).
実施例５
実施例２で得られた脱水前のスラリーに薄硫酸（７０重量％硫酸水溶液）２１．１ｇを加えた後、得られたスラリーを減圧ろ過により脱水し、脱水ケーキを乾燥器に入れ、１００℃ で一晩乾燥し、粉末状のケイ酸マグネシウム系材料（ＳｉＯ２：６８．０重量％、ＭｇＯ：３０．２重量％、ＳｉＯ２／ＭｇＯ重量比＝２．３）を得た。
Example 5
After adding 21.1 g of thin sulfuric acid (70% by weight sulfuric acid aqueous solution) to the slurry before dehydration obtained in Example 2, the resulting slurry was dehydrated by vacuum filtration, and the dehydrated cake was put in a drier, 100 ° C. And dried overnight to obtain a powdered magnesium silicate-based material (SiO 2 : 68.0 wt%, MgO: 30.2 wt%, SiO 2 / MgO weight ratio = 2.3).
実施例６
加えた薄硫酸の量を３６．１ｇとした以外は実施例５と同様にサンプルを調製し、粉末状のケイ酸マグネシウム系材料（ＳｉＯ２：７２．３重量％、ＭｇＯ：２６．０重量％、ＳｉＯ２／ＭｇＯ重量比＝２．８）を得た。
Example 6
A sample was prepared in the same manner as in Example 5 except that the amount of added thin sulfuric acid was changed to 36.1 g, and a powdered magnesium silicate-based material (SiO 2 : 72.3 wt%, MgO: 26.0 wt%) , SiO 2 / MgO weight ratio = 2.8).
実施例７
加えた薄硫酸の量を６３．２ｇとした以外は実施例５と同様にサンプルを調製し、粉末状のケイ酸マグネシウム系材料（ＳｉＯ２：７７．８重量％、ＭｇＯ：２０．７重量％、ＳｉＯ２／ＭｇＯ重量比＝３．８）を得た。
Example 7
A sample was prepared in the same manner as in Example 5 except that the amount of added thin sulfuric acid was changed to 63.2 g, and a powdered magnesium silicate-based material (SiO 2 : 77.8 wt%, MgO: 20.7 wt%) SiO 2 / MgO weight ratio = 3.8).
実施例８
加えた薄硫酸の量を７２．６ｇとした以外は実施例５と同様にサンプルを調製し、粉末状のケイ酸マグネシウム系材料（ＳｉＯ２：８１．３重量％、ＭｇＯ：１７．２重量％、ＳｉＯ２／ＭｇＯ重量比＝４．７）を得た。
Example 8
A sample was prepared in the same manner as in Example 5 except that the amount of the added thin sulfuric acid was changed to 72.6 g, and a powdered magnesium silicate-based material (SiO 2 : 81.3 wt%, MgO: 17.2 wt%) , SiO 2 / MgO weight ratio = 4.7).
実施例９
加えた薄硫酸の量を７９．６ｇとした以外は実施例５と同様にサンプルを調製し、粉末状のケイ酸マグネシウム系材料（ＳｉＯ２：８２．５重量％、ＭｇＯ：１６．５重量％、ＳｉＯ２／ＭｇＯ重量比＝５．０）を得た。
Example 9
A sample was prepared in the same manner as in Example 5 except that the amount of the added thin sulfuric acid was changed to 79.6 g, and a powdery magnesium silicate-based material (SiO 2 : 82.5 wt%, MgO: 16.5 wt%) , SiO 2 / MgO weight ratio = 5.0).
実施例１０
加えた薄硫酸の量を８４．３ｇとした以外は実施例５と同様にサンプルを調製し、粉末状のケイ酸マグネシウム系材料（ＳｉＯ２：８４．２重量％、ＭｇＯ：１４．７重量％、ＳｉＯ２／ＭｇＯ重量比＝５．７）を得た。
Example 10
A sample was prepared in the same manner as in Example 5 except that the amount of added thin sulfuric acid was changed to 84.3 g, and a powdered magnesium silicate-based material (SiO 2 : 84.2 wt%, MgO: 14.7 wt%) SiO 2 / MgO weight ratio = 5.7).
実施例１１
加えた薄硫酸の量を９０．３ｇとした以外は実施例５と同様にサンプルを調製し、粉末状のケイ酸マグネシウム系材料（ＳｉＯ２：８６．２重量％、ＭｇＯ：１３．３重量％、ＳｉＯ２／ＭｇＯ重量比＝６．５）を得た。
Example 11
A sample was prepared in the same manner as in Example 5 except that the amount of the added thin sulfuric acid was 90.3 g, and a powdered magnesium silicate-based material (SiO 2 : 86.2 wt%, MgO: 13.3% wt) SiO 2 / MgO weight ratio = 6.5).
実施例１２
加えた薄硫酸の量を９４．８ｇとした以外は実施例５と同様にサンプルを調製し、粉末状のケイ酸マグネシウム系材料（ＳｉＯ２：８７．７重量％、ＭｇＯ：１１．６重量％、ＳｉＯ２／ＭｇＯ重量比＝７．６）を得た。
Example 12
A sample was prepared in the same manner as in Example 5 except that the amount of the added thin sulfuric acid was 94.8 g, and a powdered magnesium silicate-based material (SiO 2 : 87.7 wt%, MgO: 11.6 wt%) SiO 2 / MgO weight ratio = 7.6).
実施例１３
実施例６の粉末の水分含有量を７．０重量％に調整したものを使用した。
Example 13
What adjusted the moisture content of the powder of Example 6 to 7.0 weight% was used.
実施例１４
実施例６の粉末の水分含有量を５．２重量％に調整したものを使用した。
Example 14
What adjusted the moisture content of the powder of Example 6 to 5.2 weight% was used.
実施例１５
実施例６の粉末の水分含有量を３．５重量％に調整したものを使用した。
Example 15
What adjusted the moisture content of the powder of Example 6 to 3.5 weight% was used.
比較例１
比較例１では、市販されている製品「ブリスコールＭＴ」（富田製薬株式会社製、食品添加物規格、ケイ酸マグネシウム）を使用した。
Comparative Example 1
In Comparative Example 1, a commercially available product “Briscol MT” (produced by Tomita Pharmaceutical Co., Ltd., food additive standard, magnesium silicate) was used.
なお、実施例及び比較例で得られた各粉末について、食品添加物ケイ酸マグネシウムの品質規格への適合性を調査した結果、実施例４及び実施例６〜９のケイ酸マグネシウムについては、当該食品添加物規格に合格するものであった。 In addition, as a result of investigating the conformity to the quality standard of food additive magnesium silicate for each powder obtained in the examples and comparative examples, the magnesium silicate of Example 4 and Examples 6 to 9 It passed the food additive standard.
試験例１
実施例及び比較例で得られた各粉末について、カツオ魚油（アニシジン価＝２５．１）に対するアニシジン価低減能等の物性を調べた。その結果を表１に示す。
Test example 1
About each powder obtained by the Example and the comparative example, physical properties, such as an anisidine number reduction ability with respect to bonito fish oil (anisidine number = 25.1), were investigated. The results are shown in Table 1.
なお、表１中の各物性は次のようにして測定した。 In addition, each physical property in Table 1 was measured as follows.
（１）ＭｇＯ、ＳｉＯ２含量
「平成２２年１０月２０日、平成２２年厚生労働省告示第３７２号、食品、添加物等の規格基準の一部を改正する件」記載のＭｇＯ、ＳｉＯ２含量測定方法に従い、測定した。
(1) MgO, SiO 2 content "2010 October 20, 2010 the Ministry of Health, Labor and Welfare Notification No. 372, food, matter to amend the part of the specifications and standards of additives, such as" the description of MgO, SiO 2 content It measured according to the measuring method.
（２）水分含有量
試料皿に試料を測り、１５０℃×３０分間後の試料の重量から赤外線水分計（型式「ＦＤ−６００」、（株）ケツト科学研究所製）を用いて水分量を算出した。
(2) Moisture content Measure the sample in a sample pan and use the infrared moisture meter (model "FD-600", manufactured by Ketto Scientific Laboratory) to determine the moisture content from the weight of the sample after 150 ° C x 30 minutes. Calculated.
（３）ＢＥＴ比表面積
測定装置としてＱｕａｎｔａｃｈｒｏｍｅ社製の高速比表面積・細孔分布測定装置「Ｎ
ＯＶＡ４０００ｅ型」を用いた。試料の前処理として、試料０．０５ｇを正確に測り、試
験管に封入し、１０５℃で３時間脱気を行った。比表面積の測定は、前処理終了後、液体
窒素ガス温度下で窒素ガスの吸着等温線を求め、その吸着等温線を用いてＢＥＴ法により算出した。
(3) BET specific surface area High-speed specific surface area / pore distribution measuring device “N” manufactured by Quantachrome as a measuring device
OVA4000e type "was used. As a pretreatment of the sample, 0.05 g of the sample was accurately measured, sealed in a test tube, and deaerated at 105 ° C. for 3 hours. The measurement of the specific surface area was carried out by obtaining a nitrogen gas adsorption isotherm under the liquid nitrogen gas temperature after completion of the pretreatment and using the adsorption isotherm to calculate the BET method.
（４）マクロ細孔の比表面積及び累積細孔容積
測定装置としてＱｕａｎｔａｃｈｒｏｍｅ社製水銀ポロシメーター「ｐｏｒｅｍａｓｔｅｒ６０ＧＴ」にて以下の条件で測定を行った。試料０．０５ｇを測定用セルに封入し、水銀の接触角を１４０°、水銀の表面張力を４８０ｄｙｎ／ｃｍとして測定を行った。細孔容積の算出は解析ソフト「Ｐｏｒｅｍａｓｔｅｒ」を用いて行った。なお、解析範囲は、５０〜１０００ｎｍの範囲で行った。
(4) Specific surface area and cumulative pore volume of macropores Measurement was performed using a mercury porosimeter “poremaster 60GT” manufactured by Quantachrome under the following conditions. A sample 0.05 g was sealed in a measurement cell, and the measurement was performed with a mercury contact angle of 140 ° and a mercury surface tension of 480 dyn / cm. The pore volume was calculated using analysis software “Poremaster”. The analysis range was 50 to 1000 nm.
（５）アニシジン価低減能評価試験
カツオ魚油（アニシジン価＝２５．１）１０ｍＬに実施例及び比較例で調製した精製剤５００ｍｇを添加した後、５０℃のオイルバス中、振とう器にて１３０回／分の条件で６０分間振とうした。振とう後、直ちにメンブランフィルタ（目開き０．８０μｍ）にてろ過した。得られたろ過液０．５ｇを精密に量り、基準油脂分析試験法２００３年度版（日本油化学会制定）記載のアニシジン価測定法に準じて、アニシジン価を測定した。なお、アニシジン価低減率は、次式Ａにより算出した。
・アニシジン価低減率＝（（処理前の魚油のアニシジン価−処理後の魚油のアニシジン価）／処理前の魚油のアニシジン価）×１００…式Ａ
(5) Anisidine value reduction ability evaluation test After adding 500 mg of the purifying agent prepared in the examples and comparative examples to bonito fish oil (anisidine value = 25.1) 10 mL, in a 50 ° C. oil bath, 130 Shake for 60 minutes under conditions of times / minute. Immediately after shaking, it was filtered through a membrane filter (aperture 0.80 μm). 0.5 g of the obtained filtrate was precisely weighed, and the anisidine value was measured according to the anisidine value measurement method described in the standard oil analysis test method 2003 version (established by the Japan Oil Chemists' Society). The anisidine value reduction rate was calculated by the following formula A.
Anisidine value reduction rate = ((anisidine value of fish oil before treatment−anisidine value of fish oil after treatment) / anisidine value of fish oil before treatment) × 100 Formula A
（６）メチレンブルー吸着量
メチレンブルー溶液（メチレンブルー３水和物４ｇを１００ｍＬのエタノールに溶解後、精製水で全量を１Ｌとしたもの）１０ｍＬに実施例及び比較例で調製した精製剤１００ｍｇを添加した後、３０℃の水浴中、振とう器にて１３０回／分の条件で３０分間振とうした。振とう後、直ちにメンブランフィルタ（目開き０．８０μｍ）にてろ過した。得られたろ過液１ｍＬを精密に量り取り、精製水で２００倍希釈したものを検液とした。測定装置として日本分光社製「Ｖ−６６０型紫外可視分光光度計」を用いて６６０ｎｍにおける検液の吸光度を測定し、次式Ｂ及びＣによりメチレンブルー吸着量を求めた。
・メチレンブルー吸着率＝（（処理前の検液の吸光度−処理後の検液の吸光度）／処理前の検液の吸光度）×１００…式Ｂ
・メチレンブルー吸着量（ｍｍｏｌ／ｇ）＝１．０７（ｍｍｏｌ）×メチレンブルー吸着率×０．０１…式Ｃ
(6) Methylene blue adsorption amount Methylene blue solution (4 g of methylene blue trihydrate was dissolved in 100 mL of ethanol and then made up to 1 L with purified water) After adding 100 mg of the purification agent prepared in Examples and Comparative Examples to 10 mL The mixture was shaken in a 30 ° C. water bath with a shaker at 130 times / minute for 30 minutes. Immediately after shaking, it was filtered through a membrane filter (aperture 0.80 μm). 1 mL of the obtained filtrate was precisely weighed and diluted 200 times with purified water to obtain a test solution. The absorbance of the test solution at 660 nm was measured using a “V-660 type UV-visible spectrophotometer” manufactured by JASCO Corporation as a measuring device, and the methylene blue adsorption amount was determined by the following formulas B and C.
Methylene blue adsorption rate = ((absorbance of test solution before treatment−absorbance of test solution after treatment) / absorbance of test solution before treatment) × 100 Formula B
Methylene blue adsorption amount (mmol / g) = 1.07 (mmol) × methylene blue adsorption rate × 0.01 Formula C
（７）２００〜５００ｎｍの細孔における比表面積当たりのメチレンブルー吸着量
前記（３）及び（４）で得られた実施例及び比較例で調製した精製剤の比表面積及び前記（６）で得られたメチレンブルー吸着量から、次式Ｄにより２００〜５００ｎｍの細孔における比表面積当たりのメチレンブルー吸着量を算出した。
・２００〜５００ｎｍの細孔における比表面積当たりのメチレンブルー吸着量（ｍｏｌ／ｍ２）＝メチレンブルー吸着量（ｍｍｏｌ／ｇ）×２００〜５００ｎｍの細孔における比表面積（ｍ２／ｇ）×１０００（ｍｏｌ／ｍｍｏｌ）／（ＢＥＴ比表面積＋（５０〜１０００ｎｍの比表面積））（ｍ２／ｇ）…式Ｄ
(7) Methylene blue adsorption amount per specific surface area in pores of 200 to 500 nm Specific surface area of the purification agents prepared in the examples and comparative examples obtained in the above (3) and (4) and obtained in the above (6) From the adsorbed amount of methylene blue, the adsorbed amount of methylene blue per specific surface area in the pores of 200 to 500 nm was calculated by the following formula D.
Adsorption amount of methylene blue per specific surface area in pores of 200 to 500 nm (mol / m 2 ) = Adsorption amount of methylene blue (mmol / g) × Specific surface area of pores of 200 to 500 nm (m 2 / g) × 1000 (mol / Mmol) / (BET specific surface area + (specific surface area of 50 to 1000 nm)) (m 2 / g) Formula D
表１の結果からも明らかなように、２００〜５００ｎｍの細孔における比表面積が小さいケイ酸マグネシウム（比較例１）は、５０％程度のアニシジン価低減率にとどまっていることがわかる。 As is clear from the results in Table 1, it can be seen that magnesium silicate (Comparative Example 1) having a small specific surface area in pores of 200 to 500 nm has an anisidine value reduction rate of about 50%.
図１は、水分含有量とアニシジン価低減率の関係を示すグラフである。図１に示すように、より高いアニシジン価低減率を得るためには、ケイ酸マグネシウム系材料の水分含有量を８．０重量％以下とすることが好ましいことがわかる。 FIG. 1 is a graph showing the relationship between the water content and the anisidine value reduction rate. As shown in FIG. 1, it can be seen that the moisture content of the magnesium silicate-based material is preferably 8.0% by weight or less in order to obtain a higher anisidine value reduction rate.
図２は、２００〜５００ｎｍの細孔における比表面積当たりのメチレンブルー吸着量とアニシジン価低減率の関係を示すグラフである。図２に示すように、アニシジン価低減率には、ケイ酸マグネシウム系材料の２００〜５００ｎｍの細孔における比表面積当たりのメチレンブルー吸着量が大きく関与していることがわかる。 FIG. 2 is a graph showing the relationship between the amount of methylene blue adsorbed per specific surface area and the anisidine value reduction rate in pores of 200 to 500 nm. As shown in FIG. 2, it can be seen that the amount of methylene blue adsorbed per specific surface area in the 200-500 nm pores of the magnesium silicate-based material is greatly involved in the anisidine value reduction rate.
図３は、実施例６と比較例１の細孔分布を示すグラフである。図３に示すように、比較例１については、５０ｎｍ以下の細孔における比表面積を多く有しているが、５０ｎｍ以上の細孔における比表面積は小さく、１００ｎｍ以上の細孔における比表面積は有していない。これに対し、実施例６では、５０ｎｍ未満の細孔における比表面積は小さいが、５０ｎｍ以上の細孔における比表面積を多く有しているため、高分子量のアニシジン価関連物質を効果的に除去することができる。 FIG. 3 is a graph showing the pore distributions of Example 6 and Comparative Example 1. As shown in FIG. 3, Comparative Example 1 has a large specific surface area in pores of 50 nm or less, but has a small specific surface area in pores of 50 nm or more and a specific surface area in pores of 100 nm or more. Not done. On the other hand, in Example 6, although the specific surface area in the pores of less than 50 nm is small, the specific surface area in the pores of 50 nm or more is large, so that the high molecular weight anisidine value related substance is effectively removed. be able to.
図４は、ＳｉＯ２／ＭｇＯ重量比とアニシジン価低減率の関係を示すグラフである。図４に示すように、優れたアニシジン価低減能をより確実に得られるＳｉＯ２／ＭｇＯ重量比は１．２〜７．６の範囲であることがわかる。 FIG. 4 is a graph showing the relationship between the SiO 2 / MgO weight ratio and the anisidine value reduction rate. As shown in FIG. 4, it can be seen that the SiO 2 / MgO weight ratio in which excellent anisidine value reducing ability can be obtained more reliably is in the range of 1.2 to 7.6.
これらの結果からも明らかなように、本発明精製剤を用いる場合（特に上記のような物性を満たすケイ酸マグネシウム系材料を用いる場合）には、それ以外の粉末を使用する場合に比べてより高いアニシジン価低減能を発揮できることがわかる。 As is clear from these results, when the purification agent of the present invention is used (especially when a magnesium silicate material satisfying the above physical properties is used), it is more than when other powders are used. It can be seen that high anisidine value reducing ability can be exhibited.
実施例１６
３号ケイ酸ナトリウム１８６．２ｇ（ＳｉＯ２換算５４．０ｇ）、市販の硫酸マグネシウム１８２．９ｇ（ＭｇＯ換算３０．０ｇ）を用いた。３号ケイ酸ナトリウムは、液量が２４０ｍＬとなるように水を加え、ケイ酸ナトリウム水溶液とした。また、硫酸マグネシウムは、溶解後の液量が３６５．８ｇとなるように水を加え、溶解させて水溶液とした（ＳｉＯ２／ＭｇＯ仕込み重量比＝１．８）。はじめに、硫酸マグネシウム水溶液を容量５Ｌのステンレス鋼製容器に導入し、水を適量加え、撹拌しながら、９０℃に加温した。次に、４８％水酸化ナトリウム水溶液６３．３ｇに水を加え、全量を８５ｍＬとした水溶液と、炭酸ナトリウム１０．３ｇに水を適量加え、溶解した水溶液とを混合し、水酸化ナトリウム水溶液と炭酸ナトリウム水溶液の合計量を１５０ｍＬとした混合液を滴下し、水酸化マグネシウム沈殿物を得た。滴下終了後、ケイ酸ナトリウム水溶液を滴下し、さらに薄硫酸（７０重量％硫酸水溶液）４２．０ｇを加え、スラリーを得た。得られたスラリーを減圧ろ過により脱水し、脱水ケーキを乾燥器に入れ、１００℃ で一晩乾燥し、粉末状のケイ酸マグネシウム系材料（ＳｉＯ２：７３．７重量％、ＭｇＯ：２５．６重量％、ＳｉＯ２／ＭｇＯ重量比＝２．９）を得た。
Example 16
No. 3 sodium silicate 186.2 g (SiO 2 equivalent 54.0 g) and commercially available magnesium sulfate 182.9 g (MgO equivalent 30.0 g) were used. No. 3 sodium silicate was added with water so that the liquid volume was 240 mL to obtain a sodium silicate aqueous solution. Magnesium sulfate was dissolved in an aqueous solution by adding water so that the liquid volume after dissolution was 365.8 g (SiO 2 / MgO charge weight ratio = 1.8). First, an aqueous magnesium sulfate solution was introduced into a stainless steel container having a capacity of 5 L, an appropriate amount of water was added, and the mixture was heated to 90 ° C. while stirring. Next, water was added to 63.3 g of a 48% sodium hydroxide aqueous solution, the total amount was 85 mL, and an appropriate amount of water was added to 10.3 g of sodium carbonate, and the dissolved aqueous solution was mixed. A mixed solution in which the total amount of the aqueous sodium solution was 150 mL was added dropwise to obtain a magnesium hydroxide precipitate. After completion of dropping, a sodium silicate aqueous solution was added dropwise, and 42.0 g of thin sulfuric acid (70% by weight sulfuric acid aqueous solution) was further added to obtain a slurry. The obtained slurry was dehydrated by filtration under reduced pressure, and the dehydrated cake was put in a drier and dried at 100 ° C. overnight. The powdered magnesium silicate-based material (SiO 2 : 73.7 wt%, MgO: 25.6) % By weight, SiO 2 / MgO weight ratio = 2.9).
実施例１７
実施例１で得られた脱水前のスラリーに薄硫酸（７０重量％硫酸水溶液）６７．２ｇを加えた後、容量１リットルのＴＡＳ−０９−２０−３００型耐圧反応容器（耐圧硝子工業株式会社製）に、得られたスラリーを添加し、撹拌しながら、約１５分で２００℃ まで昇温した。昇温後、２００℃にて３時間水熱処理を行った。得られたスラリーを減圧ろ過により脱水し、脱水ケーキを乾燥器に入れ、１００℃ で一晩乾燥し、粉末状のケイ酸マグネシウム系材料（ＳｉＯ２：７２．８重量％、ＭｇＯ：２５．４重量％、ＳｉＯ２／ＭｇＯ重量比＝２．９）を得た。
Example 17
After adding 67.2 g of thin sulfuric acid (70 wt% sulfuric acid aqueous solution) to the slurry before dehydration obtained in Example 1, a 1-liter TAS-09-20-300 pressure-resistant reaction vessel (Pressure-resistant Glass Industrial Co., Ltd.) The obtained slurry was added to the product, and the temperature was raised to 200 ° C. in about 15 minutes while stirring. After the temperature increase, hydrothermal treatment was performed at 200 ° C. for 3 hours. The obtained slurry was dewatered by vacuum filtration, the dehydrated cake was put in a drier and dried at 100 ° C. overnight, and powdered magnesium silicate material (SiO 2 : 72.8 wt%, MgO: 25.4). % By weight, SiO 2 / MgO weight ratio = 2.9).
実施例１８
容量１リットルのＴＡＳ−０９−２０−３００型耐圧反応容器（耐圧硝子工業株式会社製）に、実施例２で得られた脱水前のスラリーを添加し、撹拌しながら、約１５分で２００℃ まで昇温した。昇温後、２００℃にて３時間水熱処理を行った。得られたスラリーに薄硫酸（７０重量％硫酸水溶液）２８．０ｇを加えた後、減圧ろ過により脱水し、脱水ケーキを乾燥器に入れ、１００℃ で一晩乾燥し、粉末状のケイ酸マグネシウム系材料（ＳｉＯ２：７３．２重量％、ＭｇＯ：２６．１重量％、ＳｉＯ２／ＭｇＯ重量比＝２．８）を得た。
Example 18
The slurry before dehydration obtained in Example 2 was added to a 1-liter TAS-09-20-300 pressure-resistant reaction vessel (made by Pressure Glass Industry Co., Ltd.) and stirred at 200 ° C. in about 15 minutes. The temperature was raised to. After the temperature increase, hydrothermal treatment was performed at 200 ° C. for 3 hours. After adding 28.0 g of thin sulfuric acid (70% by weight sulfuric acid aqueous solution) to the resulting slurry, dehydration was performed by filtration under reduced pressure, and the dehydrated cake was placed in a drier and dried overnight at 100 ° C. to obtain powdered magnesium silicate A system material (SiO 2 : 73.2 wt%, MgO: 26.1 wt%, SiO 2 / MgO weight ratio = 2.8) was obtained.
試験例２
実施例６、実施例１６〜１８及び比較例１で得られた各粉末について、カツオ魚油（アニシジン価＝２９．５）に対するアニシジン価低減能、脱色能等の物性を調べた。その結果を表２に示す。
Test example 2
About each powder obtained in Example 6, Examples 16-18, and the comparative example 1, physical properties, such as an anisidine number reduction ability with respect to skipjack fish oil (anisidine number = 29.5), and a decoloring ability, were investigated. The results are shown in Table 2.
なお、表２中の脱色率及び嵩比容積は次のようにして測定し、それ以外の各物性は試験例１と同様の方法で測定した。 The decolorization rate and bulk specific volume in Table 2 were measured as follows, and the other physical properties were measured in the same manner as in Test Example 1.
（８）脱色率
カツオ魚油（アニシジン価＝２９．５）１０ｍＬに実施例及び比較例で調製した精製剤５００ｍｇを添加した後、５０℃のオイルバス中、振とう器にて１３０回／分の条件で３０分間振とうした。振とう後、直ちにメンブランフィルタ（目開き０．８０μｍ）にてろ過した。得られたろ過液の４３０ｎｍにおける吸光度を測定した。未処理魚油をブランクとし、同様な処理を行って、ろ過液の吸光度を測定した。なお、脱色率は、次式Ｆにより算出した。
・脱色率＝（（処理前の魚油の吸光度−処理後の魚油の吸光度）／処理前の魚油の吸光度）×１００…式Ｆ
(8) Decolorization rate After adding 500 mg of the purification agent prepared in Examples and Comparative Examples to bonito fish oil (anisidine value = 29.5) 10 mL, in a 50 ° C. oil bath, 130 times / min with a shaker. Shake for 30 minutes under conditions. Immediately after shaking, it was filtered through a membrane filter (aperture 0.80 μm). The absorbance at 430 nm of the obtained filtrate was measured. The untreated fish oil was used as a blank, the same treatment was performed, and the absorbance of the filtrate was measured. The decolorization rate was calculated by the following formula F.
Decolorization rate = ((absorbance of fish oil before treatment−absorbance of fish oil after treatment) / absorbance of fish oil before treatment) × 100 Formula F
（９）嵩比容積
試料５．０ｇを量りとり、５０ｍＬメスシリンダーに入れ、４ｃｍの高さにて１００回／２５０秒の速度でタッピングを行い、粉体の体積を測定し、次式により嵩比容積を算出した。
嵩比容積（ｍＬ／ｇ）＝ 粉体体積（ｍＬ）／粉体重量（ｇ）
(9) Bulk specific volume A sample of 5.0 g is weighed and placed in a 50 mL graduated cylinder, tapped at a rate of 100 cm / 250 seconds at a height of 4 cm, and the volume of the powder is measured. Specific volume was calculated.
Bulk specific volume (mL / g) = powder volume (mL) / powder weight (g)
表２の結果からも明らかなように、本発明精製剤を用いる場合には、高いアニシジン価低減能を発揮できるとともに、５０％以上の高い脱色能を発揮できることがわかる。 As is clear from the results in Table 2, it can be seen that when the purification agent of the present invention is used, a high anisidine value reducing ability can be exhibited and a high decolorizing ability of 50% or more can be exhibited.
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| JP2005008675A (en) * | 2003-06-16 | 2005-01-13 | Mizusawa Ind Chem Ltd | Silica-magnesia formulation and method for producing the same |
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