JP7430562B2 - Adsorbent for purines - Google Patents
Adsorbent for purines Download PDFInfo
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- JP7430562B2 JP7430562B2 JP2020066221A JP2020066221A JP7430562B2 JP 7430562 B2 JP7430562 B2 JP 7430562B2 JP 2020066221 A JP2020066221 A JP 2020066221A JP 2020066221 A JP2020066221 A JP 2020066221A JP 7430562 B2 JP7430562 B2 JP 7430562B2
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- JP
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- Prior art keywords
- clay
- acid
- adsorbent
- purines
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003463 adsorbent Substances 0.000 title claims description 64
- 150000003212 purines Chemical class 0.000 title claims description 38
- 239000004927 clay Substances 0.000 claims description 105
- 239000002253 acid Substances 0.000 claims description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 67
- RYYVLZVUVIJVGH-UHFFFAOYSA-N caffeine Chemical compound CN1C(=O)N(C)C(=O)C2=C1N=CN2C RYYVLZVUVIJVGH-UHFFFAOYSA-N 0.000 claims description 65
- 238000001179 sorption measurement Methods 0.000 claims description 52
- 229960001948 caffeine Drugs 0.000 claims description 33
- LPHGQDQBBGAPDZ-UHFFFAOYSA-N Isocaffeine Natural products CN1C(=O)N(C)C(=O)C2=C1N(C)C=N2 LPHGQDQBBGAPDZ-UHFFFAOYSA-N 0.000 claims description 32
- VJEONQKOZGKCAK-UHFFFAOYSA-N caffeine Natural products CN1C(=O)N(C)C(=O)C2=C1C=CN2C VJEONQKOZGKCAK-UHFFFAOYSA-N 0.000 claims description 32
- 239000011229 interlayer Substances 0.000 claims description 32
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 claims description 30
- NYHBQMYGNKIUIF-UUOKFMHZSA-N Guanosine Chemical compound C1=NC=2C(=O)NC(N)=NC=2N1[C@@H]1O[C@H](CO)[C@@H](O)[C@H]1O NYHBQMYGNKIUIF-UUOKFMHZSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 229910021647 smectite Inorganic materials 0.000 claims description 25
- MIKUYHXYGGJMLM-GIMIYPNGSA-N Crotonoside Natural products C1=NC2=C(N)NC(=O)N=C2N1[C@H]1O[C@@H](CO)[C@H](O)[C@@H]1O MIKUYHXYGGJMLM-GIMIYPNGSA-N 0.000 claims description 15
- NYHBQMYGNKIUIF-UHFFFAOYSA-N D-guanosine Natural products C1=2NC(N)=NC(=O)C=2N=CN1C1OC(CO)C(O)C1O NYHBQMYGNKIUIF-UHFFFAOYSA-N 0.000 claims description 15
- 229940029575 guanosine Drugs 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 239000011973 solid acid Substances 0.000 claims description 12
- 230000001476 alcoholic effect Effects 0.000 claims description 6
- 238000010306 acid treatment Methods 0.000 description 27
- 239000010410 layer Substances 0.000 description 26
- UYTPUPDQBNUYGX-UHFFFAOYSA-N guanine Chemical compound O=C1NC(N)=NC2=C1N=CN2 UYTPUPDQBNUYGX-UHFFFAOYSA-N 0.000 description 25
- LRFVTYWOQMYALW-UHFFFAOYSA-N 9H-xanthine Chemical class O=C1NC(=O)NC2=C1NC=N2 LRFVTYWOQMYALW-UHFFFAOYSA-N 0.000 description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 21
- 235000019441 ethanol Nutrition 0.000 description 21
- 239000000843 powder Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 17
- 239000007864 aqueous solution Substances 0.000 description 15
- 235000013361 beverage Nutrition 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 description 12
- 229930024421 Adenine Natural products 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 229960000643 adenine Drugs 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- -1 xanthine compound Chemical class 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 8
- 229940075420 xanthine Drugs 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 125000000561 purinyl group Chemical group N1=C(N=C2N=CNC2=C1)* 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 4
- 235000013334 alcoholic beverage Nutrition 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 235000013405 beer Nutrition 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 239000002734 clay mineral Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- FDGQSTZJBFJUBT-UHFFFAOYSA-N hypoxanthine Chemical compound O=C1NC=NC2=C1NC=N2 FDGQSTZJBFJUBT-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000012488 sample solution Substances 0.000 description 4
- 230000002522 swelling effect Effects 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000440 bentonite Substances 0.000 description 3
- 229910000278 bentonite Inorganic materials 0.000 description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 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 3
- 238000005259 measurement Methods 0.000 description 3
- 230000000717 retained effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- QUNWUDVFRNGTCO-UHFFFAOYSA-N 1,7-dimethylxanthine Chemical compound N1C(=O)N(C)C(=O)C2=C1N=CN2C QUNWUDVFRNGTCO-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UGQMRVRMYYASKQ-UHFFFAOYSA-N Hypoxanthine nucleoside Natural products OC1C(O)C(CO)OC1N1C(NC=NC2=O)=C2N=C1 UGQMRVRMYYASKQ-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910004283 SiO 4 Inorganic materials 0.000 description 2
- 244000269722 Thea sinensis Species 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- OIRDTQYFTABQOQ-KQYNXXCUSA-N adenosine Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](CO)[C@@H](O)[C@H]1O OIRDTQYFTABQOQ-KQYNXXCUSA-N 0.000 description 2
- 239000002156 adsorbate Substances 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- VWWQXMAJTJZDQX-UYBVJOGSSA-N flavin adenine dinucleotide Chemical compound C1=NC2=C(N)N=CN=C2N1[C@@H]([C@H](O)[C@@H]1O)O[C@@H]1CO[P@](O)(=O)O[P@@](O)(=O)OC[C@@H](O)[C@@H](O)[C@@H](O)CN1C2=NC(=O)NC(=O)C2=NC2=C1C=C(C)C(C)=C2 VWWQXMAJTJZDQX-UYBVJOGSSA-N 0.000 description 2
- 235000019162 flavin adenine dinucleotide Nutrition 0.000 description 2
- 239000011714 flavin adenine dinucleotide Substances 0.000 description 2
- 229940093632 flavin-adenine dinucleotide Drugs 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 235000013616 tea Nutrition 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- YAPQBXQYLJRXSA-UHFFFAOYSA-N theobromine Chemical compound CN1C(=O)NC(=O)C2=C1N=CN2C YAPQBXQYLJRXSA-UHFFFAOYSA-N 0.000 description 2
- ZFXYFBGIUFBOJW-UHFFFAOYSA-N theophylline Chemical compound O=C1N(C)C(=O)N(C)C2=C1NC=N2 ZFXYFBGIUFBOJW-UHFFFAOYSA-N 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- AUHDWARTFSKSAC-HEIFUQTGSA-N (2S,3R,4S,5R)-3,4-dihydroxy-5-(hydroxymethyl)-2-(6-oxo-1H-purin-9-yl)oxolane-2-carboxylic acid Chemical compound [C@]1([C@H](O)[C@H](O)[C@@H](CO)O1)(N1C=NC=2C(O)=NC=NC12)C(=O)O AUHDWARTFSKSAC-HEIFUQTGSA-N 0.000 description 1
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- YKBGVTZYEHREMT-KVQBGUIXSA-N 2'-deoxyguanosine Chemical compound C1=NC=2C(=O)NC(N)=NC=2N1[C@H]1C[C@H](O)[C@@H](CO)O1 YKBGVTZYEHREMT-KVQBGUIXSA-N 0.000 description 1
- 239000002126 C01EB10 - Adenosine Substances 0.000 description 1
- UDMBCSSLTHHNCD-UHFFFAOYSA-N Coenzym Q(11) Natural products C1=NC=2C(N)=NC=NC=2N1C1OC(COP(O)(O)=O)C(O)C1O UDMBCSSLTHHNCD-UHFFFAOYSA-N 0.000 description 1
- HMFHBZSHGGEWLO-SOOFDHNKSA-N D-ribofuranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H]1O HMFHBZSHGGEWLO-SOOFDHNKSA-N 0.000 description 1
- 239000004278 EU approved seasoning Substances 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 201000005569 Gout Diseases 0.000 description 1
- 229930010555 Inosine Natural products 0.000 description 1
- UGQMRVRMYYASKQ-KQYNXXCUSA-N Inosine Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1N1C2=NC=NC(O)=C2N=C1 UGQMRVRMYYASKQ-KQYNXXCUSA-N 0.000 description 1
- GRSZFWQUAKGDAV-UHFFFAOYSA-N Inosinic acid Natural products OC1C(O)C(COP(O)(O)=O)OC1N1C(NC=NC2=O)=C2N=C1 GRSZFWQUAKGDAV-UHFFFAOYSA-N 0.000 description 1
- BAWFJGJZGIEFAR-NNYOXOHSSA-N NAD zwitterion Chemical compound NC(=O)C1=CC=C[N+]([C@H]2[C@@H]([C@H](O)[C@@H](COP([O-])(=O)OP(O)(=O)OC[C@@H]3[C@H]([C@@H](O)[C@@H](O3)N3C4=NC=NC(N)=C4N=C3)O)O2)O)=C1 BAWFJGJZGIEFAR-NNYOXOHSSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- PYMYPHUHKUWMLA-LMVFSUKVSA-N Ribose Natural products OC[C@@H](O)[C@@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-LMVFSUKVSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229960005305 adenosine Drugs 0.000 description 1
- UDMBCSSLTHHNCD-KQYNXXCUSA-N adenosine 5'-monophosphate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(O)=O)[C@@H](O)[C@H]1O UDMBCSSLTHHNCD-KQYNXXCUSA-N 0.000 description 1
- 229950006790 adenosine phosphate Drugs 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- HMFHBZSHGGEWLO-UHFFFAOYSA-N alpha-D-Furanose-Ribose Natural products OCC1OC(O)C(O)C1O HMFHBZSHGGEWLO-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000013532 brandy Nutrition 0.000 description 1
- 238000009933 burial Methods 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- HAAZLUGHYHWQIW-KVQBGUIXSA-N dGTP Chemical compound C1=NC=2C(=O)NC(N)=NC=2N1[C@H]1C[C@H](O)[C@@H](COP(O)(=O)OP(O)(=O)OP(O)(O)=O)O1 HAAZLUGHYHWQIW-KVQBGUIXSA-N 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000007876 drug discovery Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229940094952 green tea extract Drugs 0.000 description 1
- 235000020688 green tea extract Nutrition 0.000 description 1
- ZDPUTNZENXVHJC-UUOKFMHZSA-N guanosine 3'-monophosphate Chemical compound C1=NC=2C(=O)NC(N)=NC=2N1[C@@H]1O[C@H](CO)[C@@H](OP(O)(O)=O)[C@H]1O ZDPUTNZENXVHJC-UUOKFMHZSA-N 0.000 description 1
- 235000013928 guanylic acid Nutrition 0.000 description 1
- 239000004226 guanylic acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229960003786 inosine Drugs 0.000 description 1
- 235000013902 inosinic acid Nutrition 0.000 description 1
- 239000004245 inosinic acid Substances 0.000 description 1
- 229940028843 inosinic acid Drugs 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000012633 leachable Substances 0.000 description 1
- 235000020094 liqueur Nutrition 0.000 description 1
- 229940083747 low-ceiling diuretics xanthine derivative Drugs 0.000 description 1
- 235000021577 malt beverage Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229940043348 myristyl alcohol Drugs 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 229940101270 nicotinamide adenine dinucleotide (nad) Drugs 0.000 description 1
- 239000002777 nucleoside Substances 0.000 description 1
- 150000003833 nucleoside derivatives Chemical class 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 239000002212 purine nucleoside Substances 0.000 description 1
- 239000002213 purine nucleotide Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 125000000548 ribosyl group Chemical group C1([C@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 235000019992 sake Nutrition 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 235000020083 shōchū Nutrition 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 229940012831 stearyl alcohol Drugs 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229960004559 theobromine Drugs 0.000 description 1
- 229960000278 theophylline Drugs 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 235000015041 whisky Nutrition 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Distillation Of Fermentation Liquor, Processing Of Alcohols, Vinegar And Beer (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
Description
本発明は、カフェインに代表されるキサンチン化合物やグアニン、グアノシンに代表されるアデニンまたはグアニン化合物を構成成分に含む化合物等のプリン体を吸着し得るプリン体用吸着剤に関する。 The present invention relates to an adsorbent for purines that is capable of adsorbing purines, such as compounds containing xanthine compounds typified by caffeine, guanine, and adenine or guanine compounds typified by guanosine as constituent components.
現在、健康志向等の観点から、カフェインレス飲料が市販されている。このカフェインレス飲料は、お茶やコーヒー等からカフェインを除いた飲料である。また、ビール等のアルコール飲料は、痛風等の原因となるプリン体を含んでいるため、このプリン体の含有量が低減されたアルコール飲料も販売されている。 Currently, from the viewpoint of health consciousness, etc., decaffeinated drinks are commercially available. This decaffeinated beverage is a beverage obtained by removing caffeine from tea, coffee, or the like. Furthermore, since alcoholic beverages such as beer contain purine, which causes gout and the like, alcoholic beverages with a reduced purine content are also on sale.
ところで、カフェイン、キサンチン、グアニン、グアノシンなどは、何れもプリン骨格を有する化合物（総称して、プリン体）である。これらを飲料から除去するための吸着剤としては、ゼオライトやジオクタヘドラル型スメクタイト系粘土（酸性白土）等が知られている（特許文献１）。 Incidentally, caffeine, xanthine, guanine, guanosine, and the like are all compounds having a purine skeleton (collectively, purines). Zeolite, dioctahedral type smectite clay (acid clay), and the like are known as adsorbents for removing these from drinks (Patent Document 1).
しかしながら、ゼオライトは、プリン体に対する選択性が乏しく、飲料中に含まれる有効成分まで吸着してしまうため、工業的には使用されていない。 However, zeolite is not used industrially because it has poor selectivity for purines and even the active ingredients contained in beverages are adsorbed.
また、酸性白土等の粘土は、プリン体に対する選択吸着性は高く、安価であるという利点を有しているものの、濾過性が低いという問題を有する。即ち、この種の粘土は、水中で一部がコロイド分散してしまい、濾過時にフィルターの目詰りが生じてしまう。これを
回避するために、濾過を行わず遠心分離をすると、有効成分のロスも生じてしまうし、処理コストも高くなってしまう。
Furthermore, although clay such as acid clay has the advantage of having high selective adsorption to purines and being inexpensive, it has the problem of low filterability. That is, a portion of this type of clay is colloidally dispersed in water, resulting in clogging of the filter during filtration. In order to avoid this, if centrifugation is performed without filtration, the effective ingredients will be lost and the processing cost will also increase.
更に、特許文献１には、酸性白土を酸処理して得られる活性白土がカフェイン（キサンチン化合物）に対する吸着性に優れていることが開示されており、例えば、その実施例では、本出願人により製造販売されている活性白土（ガレオンアースＮＦ－２，ガレオナイトＮｏ．２５１、水澤化学工業（株）製）がカフェインに対して高い吸着性を示している。 Furthermore, Patent Document 1 discloses that activated clay obtained by acid-treating acid clay has excellent adsorption properties for caffeine (xanthine compound). Activated clay (Galleon Earth NF-2, Galleonite No. 251, manufactured by Mizusawa Chemical Industry Co., Ltd.) manufactured and sold by Activated Clay has a high adsorption property for caffeine.
しかしながら、特許文献１でのカフェインに対する吸着性は、緑茶抽出物粉末（カフェイン含有物）４０ｍｇを水５ｍｌに溶解させ、得られた水溶液に活性白土等の吸着剤を１ｇ（水１００質量部あたり２０質量部）も加えて、評価されている。即ち、この実験は、カフェイン含有粉末を多量に含んでいるペーストに、多量の吸着剤を添加して行われており、カフェインに対する吸着性を適正に評価しているとは言い難い。実際に、このような多量の吸着剤を飲料に添加してカフェインを除去することはコスト的にありえない。また、処理後の吸着剤分離の観点からも問題である。しかも、本出願人が、実際の吸着処理に準じて０．２ｇ／Ｌ濃度のカフェイン水溶液３０ｇに活性白土（ガレオンアースＮＦ－２，ガレオナイトＮｏ．２５１）０．１ｇを加えて吸着試験をしたところ、これらの活性白土（ガレオンアースＮＦ－２，ガレオナイトＮｏ．２５１）のカフェイン吸着性は酸性白土に比して著しく劣っていることがわかった。 However, the adsorptivity for caffeine in Patent Document 1 is as follows: 40 mg of green tea extract powder (caffeine-containing material) is dissolved in 5 ml of water, and 1 g of an adsorbent such as activated clay is added to the resulting aqueous solution (100 parts by mass of water). 20 parts by mass) was also added and evaluated. That is, this experiment was conducted by adding a large amount of adsorbent to a paste containing a large amount of caffeine-containing powder, and it cannot be said that the adsorptivity for caffeine was properly evaluated. In fact, it is not cost-effective to remove caffeine by adding such a large amount of adsorbent to beverages. It is also a problem from the viewpoint of adsorbent separation after treatment. Moreover, the present applicant conducted an adsorption test by adding 0.1 g of activated clay (Galleon Earth NF-2, Galleonite No. 251) to 30 g of a caffeine aqueous solution with a concentration of 0.2 g/L, in accordance with an actual adsorption treatment. However, it has been found that the caffeine adsorption properties of these activated clays (Galleon Earth NF-2, Galleonite No. 251) are significantly inferior to those of acid clay.
そこで、本発明者等は、ジオクタヘドラル型スメクタイト系粘土の酸処理により得られる酸処理物についての吸着性能について多くの実験を行い、検討した結果、種々の用途に使用されている活性白土と呼ばれる領域までの酸処理をせず、それよりも弱いレベルで酸処理しているもの（以下、弱酸処理白土と呼ぶ）が、酸処理されていない粘土（酸性白土）よりも優れた吸着性能を示し、しかも濾過性にも優れており、吸着処理後の溶液からの分離を容易に行うことができるという知見を見出した（特許文献２）。 Therefore, the present inventors conducted many experiments and studied the adsorption performance of acid-treated products obtained by acid treatment of dioctahedral-type smectite clay. Clay that has not been acid-treated up to this point, but has been acid-treated at a weaker level (hereinafter referred to as weak acid-treated clay), has better adsorption performance than clay that has not been acid-treated (acid clay). Moreover, it has been found that it has excellent filterability and can be easily separated from the solution after adsorption treatment (Patent Document 2).
本発明の目的は、ジオクタヘドラル型スメクタイト系粘土の酸処理物から成る、プリン体に対する吸着性の優れた吸着剤を提供することにある。 An object of the present invention is to provide an adsorbent that is made of an acid-treated dioctahedral smectite clay and has excellent adsorption properties for purines.
本発明者等は、弱酸処理白土の層間水の量について多くの実験を行い、検討した結果、層間水の量が特定の範囲にある場合、プリン体に対する吸着性が向上するという知見を見出し、本発明を完成するに至った。 The present inventors conducted many experiments and studied the amount of interlayer water in weak acid-treated clay, and found that when the amount of interlayer water is within a specific range, the adsorption to purines improves. The present invention has now been completed.
本発明によれば、ジオクタヘドラル型スメクタイト系粘土の酸処理物からなり、水蒸気吸着法により測定されるＢＥＴ比表面積（Ａ）と窒素吸着法により測定されるＢＥＴ比表面積（Ｂ）との比、（Ａ）／（Ｂ）が０．９０～５．００の範囲にあり、ジオクタヘドラル型スメクタイト系粘土に特有の層間水の量が、付着水及び層間水を除いた吸着剤１ｇあたり３０ｍｇ以下にあることを特徴とするプリン体用吸着剤が提供される。 According to the present invention, the ratio of the BET specific surface area (A) measured by the water vapor adsorption method to the BET specific surface area (B) measured by the nitrogen adsorption method, which is made of an acid-treated product of dioctahedral type smectite clay, A)/(B) is in the range of 0.90 to 5.00, and the amount of interlayer water characteristic of dioctahedral smectite clay is 30 mg or less per 1 g of adsorbent excluding adhering water and interlayer water. Provided is an adsorbent for purine bodies characterized by the following.
本発明の吸着剤においては、
（１）Ｈｏ≦－３．０の固体酸量が０．１０～０．７０ｍｍｏｌ／ｇ－ｄｒｙ ｃｌａｙの範囲にあること、
（２）窒素吸着法により測定されるＢＥＴ比表面積の値が６５～４００ｍ２／ｇの範囲にあること、
（３）（Ａ）／（Ｂ）が０．９０～２．８０の範囲にあること、
（４）プリン体がキサンチン化合物であること、
（５）キサンチン化合物がカフェインであること、
（６）プリン体がアデニンまたはグアニン化合物であること、
が好適である。
In the adsorbent of the present invention,
(1) The amount of solid acid with Ho≦-3.0 is in the range of 0.10 to 0.70 mmol/g-dry clay,
(2) The value of BET specific surface area measured by nitrogen adsorption method is in the range of 65 to 400 m 2 /g,
(3) (A)/(B) is in the range of 0.90 to 2.80;
(4) Purines are xanthine compounds;
(5) the xanthine compound is caffeine;
(6) Purines are adenine or guanine compounds,
is suitable.
また、本発明によれば、前記吸着剤を、プリン体を含むアルコール溶液に入れて、該プリン体を吸着除去することを特徴とする、アルコール溶液からプリン体を除去する方法が提供される。 Further, according to the present invention, there is provided a method for removing purines from an alcoholic solution, characterized in that the adsorbent is placed in an alcoholic solution containing purines, and the purines are adsorbed and removed.
本発明の吸着剤は、後述する実施例に示されているように、少量での使用により、酸性白土と同等或いはそれ以上にプリン体含有溶液からプリン体を多く除去することができる。 As shown in the Examples described below, the adsorbent of the present invention, when used in a small amount, can remove a large amount of purines from a purine-containing solution as much as or more than acid clay.
また、本発明の吸着剤は、弱酸処理白土から成るため、酸性白土に比して濾過性も高く、吸着処理後の溶液から容易に除去することができる。 Furthermore, since the adsorbent of the present invention is made of clay treated with a weak acid, it has higher filterability than acid clay and can be easily removed from the solution after the adsorption treatment.
そのため、本発明の吸着剤は、プリン体に対する吸着性が高く、お茶やコーヒー等の飲料からカフェインを除去してのカフェインレス飲料の製造に好適に適用され、さらに、ビール等のアルコール飲料からのプリン体の除去にも適用することができる。
そして、本発明の吸着剤は、ジオクタヘドラル型スメクタイト系粘土の酸処理物からなるものであることから、従来公知の酸処理を施していないスメクタイト系粘土に比して、含有する浸出性のＮａイオン、Ｃａイオンが低く抑えられており、シュウ酸Ｃａ等をはじめとする析出物の発生を抑制することができる他、飲料の色や香味への影響を抑制することができる。
Therefore, the adsorbent of the present invention has a high adsorption property for purines, and is suitably applied to the production of decaffeinated beverages by removing caffeine from beverages such as tea and coffee. It can also be applied to the removal of purines from.
Since the adsorbent of the present invention is made of an acid-treated product of dioctahedral-type smectite clay, the leachable Na ions contained in the adsorbent are higher than conventional smectite clays that have not been subjected to acid treatment. , Ca ions are suppressed to a low level, and the generation of precipitates such as Ca oxalate can be suppressed, and the influence on the color and flavor of the beverage can be suppressed.
＜弱酸処理白土＞
本発明の吸着剤は、ジオクタヘドラル型スメクタイト系粘土の酸処理物からなるものであるが、一般的に活性白土と称されるものに比して弱い酸処理によって得られ、弱酸処理白土というべきものである。従って、以下、プリン体用吸着剤として使用される酸処理物を「弱酸処理白土」と呼ぶことがある。
例えば、本出願人による特開２００９－０７２７５９には、ジオクタヘドラル型粘土を酸処理して得られる半活性白土と呼ばれる酸処理物がポリ乳酸解重合用触媒として使用されることが開示されているが、本発明で使用する弱酸処理白土は、この半活性白土よりも更に弱い酸処理によって得られる。
<Weak acid treated white clay>
The adsorbent of the present invention is made of an acid-treated product of dioctahedral-type smectite clay, and it is obtained by a weaker acid treatment than what is generally called activated clay, and is what should be called weak acid-treated clay. It is. Therefore, hereinafter, the acid-treated product used as an adsorbent for purine bodies may be referred to as "weak acid-treated clay."
For example, JP 2009-072759 by the present applicant discloses that an acid-treated product called semi-active clay obtained by acid-treating dioctahedral clay is used as a catalyst for polylactic acid depolymerization. The weakly acid-treated clay used in the present invention is obtained by an even weaker acid treatment than this semi-activated clay.
本発明において吸着剤として使用される弱酸処理白土は、ジオクタヘドラル型スメクタイト系粘土の酸処理レベルが非常に低いため、水蒸気吸着法により測定されるＢＥＴ比表面積（Ａ）と窒素吸着法により測定されるＢＥＴ比表面積（Ｂ）との比（Ａ）／（Ｂ）が０．９０以上であり、吸着性の観点から、好ましくは１．１０以上、特に好ましくは１．２０以上である。また、５．００以下であり、濾過性の観点から、好ましくは４．２０以
下、特に好ましくは３．３０以下、最も好ましくは２．８０以下である。
The weakly acid-treated clay used as an adsorbent in the present invention has a BET specific surface area (A) measured by the water vapor adsorption method and a nitrogen adsorption method, since the acid treatment level of the dioctahedral smectite clay is very low. The ratio (A)/(B) to the BET specific surface area (B) is 0.90 or more, and from the viewpoint of adsorptivity, it is preferably 1.10 or more, particularly preferably 1.20 or more. Further, it is 5.00 or less, and from the viewpoint of filterability, it is preferably 4.20 or less, particularly preferably 3.30 or less, and most preferably 2.80 or less.
かかる弱酸処理白土は、上記範囲のＢＥＴ比表面積比（Ａ／Ｂ）を有することによって、プリン体に対して優れた吸着性能を発揮できるものと推察される。
即ち、ＢＥＴ比表面積を測定する方法として、窒素を用いた方法（窒素法）が一般的であるが、水蒸気を用いて測定する方法（水蒸気法）も存在する。粘土ハンドブック（第三版）によれば、窒素法では、単位質量当たりの端面を含む全外部表面積が測定され、ジオクタヘドラル型スメクタイト系粘土のように三層構造を有するものでは、窒素分子が液体窒素温度で層間に侵入しないので、外部表面積のみが測定される。一方、水蒸気のような極性の吸着質を用いた水蒸気法においては、かかる吸着質が粘土の層間に十分侵入するので、内部表面が測定される。従って、Ａ／Ｂが上記範囲内にあるということは、非常に弱い酸処理によって微細孔が増大し、且つ、スメクタイト系粘土の基本三層の層間が拡大していることを意味している。微細孔の増大はプリン体（特にカフェインなどのキサンチン化合物）に対する選択吸着性を向上させ、基本三層の層間の拡大は、適度な表面親水性をもたらし、水系およびアルコール溶液でのプリン体の吸着性を高めている。上記Ａ／Ｂの値を有する本発明の吸着剤（弱酸処理白土）は、酸処理工程において基本三層の層間の適度な拡大と層間内での微細孔の形成がバランスよく生じるため、プリン体に対して極めて高い選択吸着性を示すものと信じられる。
例えば、強い酸で処理して得られる従来公知の活性白土や半活性白土では、基本三層の層間の拡がりが大きくなり、しかも層間に形成されている微細孔をつぶしてしまう。そのため、Ａ／Ｂの値は小さくなり、従って、プリン体吸着特性は、極めて低いものとなる。
It is presumed that such weak acid-treated clay can exhibit excellent adsorption performance for purines by having a BET specific surface area ratio (A/B) within the above range.
That is, as a method for measuring the BET specific surface area, a method using nitrogen (nitrogen method) is generally used, but a method using water vapor (water vapor method) also exists. According to the Clay Handbook (3rd edition), in the nitrogen method, the total external surface area including the end surface per unit mass is measured. Only the external surface area is measured since there is no interlayer penetration at temperature. On the other hand, in the steam method using a polar adsorbate such as water vapor, the adsorbate penetrates sufficiently between the layers of the clay so that the internal surface can be measured. Therefore, the fact that A/B is within the above range means that the micropores are increased by the very weak acid treatment and the interlayers between the three basic layers of smectite clay are expanded. The increase in micropores improves the selective adsorption of purines (especially xanthine compounds such as caffeine), and the expansion of the three basic layers provides appropriate surface hydrophilicity, which improves the adsorption of purines in aqueous and alcoholic solutions. Improves adsorption. The adsorbent of the present invention (weak acid-treated clay) having the above A/B value has a well-balanced expansion of the three basic layers and the formation of micropores within the layers in the acid treatment process, so the purine It is believed that it exhibits extremely high selective adsorption against.
For example, in the conventionally known activated clay and semi-activated clay obtained by treatment with a strong acid, the spread between the three basic layers increases, and furthermore, the micropores formed between the layers are crushed. Therefore, the value of A/B becomes small, and therefore, the purine adsorption properties become extremely low.
さらに、かかる弱酸処理白土は、酸処理を施されているために優れた濾過性を有すると推察される。
酸処理を施していないスメクタイト系粘土（酸性白土）は、基本層の間にＮａ等のカチオンを含む大きな層間を有しているために、水に対して高い膨潤性を示し、膨潤による微分散化によって濾過性が悪いと考えられている。かかる弱酸処理白土の場合、スメクタイト系粘土中の塩基成分の一部が酸と反応し、ある種、水やアルコールなどに対して不溶性のバインダーとなって粒子間を結合するために、溶液中での微分散化が抑制され、優れた濾過性を示すものと考えられる。
よって、酸処理の程度が弱いほどＡ／Ｂが大きくなり、濾過性が損なわれる虞がある。
Furthermore, it is presumed that such weak acid-treated clay has excellent filterability because it has been acid-treated.
Smectite clay (acid clay) that has not been acid-treated has large interlayers containing cations such as Na between the basic layers, so it exhibits high swelling properties with water and is finely dispersed by swelling. It is thought that filtration performance is poor due to oxidation. In the case of such weak acid-treated clay, some of the base components in the smectite clay react with the acid and become a kind of binder that is insoluble in water and alcohol, binding particles together. It is thought that fine dispersion of the particles is suppressed and excellent filterability is exhibited.
Therefore, the weaker the acid treatment, the larger the A/B ratio, which may impair filterability.
粘土鉱物に保有される水は、粒子表面に吸着する吸着水、層間域に存在する層間水、結晶構造内部の水酸基を指す構造水などに分類される。本発明者等は、弱酸処理白土の層間水についての検討の結果、層間水の量が特定の範囲にある際に、プリン体に対する吸着性が向上するという知見を見出した。
ここで、吸着水は６０～８０℃、層間水は９０～１５０℃で粘土鉱物から脱離することが知られている。そこで、本発明者は、後述する実施例の通り、８０℃における乾燥減量（吸着水の量を示す）と１５０℃における乾燥減量（吸着水＋層間水の量を示す）をそれぞれ測定し、それらの差分を層間水の量とした。層間水の量は、付着水及び層間水を除いた吸着剤１ｇあたりの量（ｍｇ／ｇ）として示す。
Water retained in clay minerals is classified into adsorbed water that adsorbs on particle surfaces, interlayer water that exists in interlayer regions, and structural water that refers to hydroxyl groups within the crystal structure. As a result of studies on interlayer water in weak acid-treated clay, the present inventors have found that adsorption to purines improves when the amount of interlayer water is within a specific range.
Here, it is known that adsorbed water is desorbed from clay minerals at 60 to 80°C and interlayer water is desorbed from clay minerals at 90 to 150°C. Therefore, the present inventor measured the loss on drying at 80°C (indicating the amount of adsorbed water) and the loss on drying at 150°C (indicating the amount of adsorbed water + interlayer water), respectively, as described in the Examples below. The difference was taken as the amount of interlayer water. The amount of interlayer water is expressed as the amount (mg/g) per gram of adsorbent excluding adhering water and interlayer water.
本発明において吸着剤として用いられる弱酸処理白土は、層間水の量が３０ｍｇ／ｇ以下であり、好ましくは２０ｍｇ／ｇ以下であり、より好ましくは１５／ｍｇ／ｇ以下である。
また、層間水の量は５ｍｇ／ｇ以上であることが好ましい。なぜなら、層間水の量が５ｍｇ／ｇを下回るようにするためには必然的に高温での処理を行わなければならなくなり、そうすると層間に形成されている微細孔がつぶれてしまい、プリン体に対する吸着性が損なわれてしまうためである。
The amount of interlayer water in the weakly acid-treated clay used as an adsorbent in the present invention is 30 mg/g or less, preferably 20 mg/g or less, and more preferably 15 mg/g or less.
Moreover, it is preferable that the amount of interlayer water is 5 mg/g or more. This is because in order to keep the amount of interlayer water below 5 mg/g, treatment must be carried out at high temperatures, which collapses the micropores formed between the layers, causing adsorption to the purine body. This is because the sex will be lost.
層間水の量が特定の範囲にある際に吸着性が向上するメカニズムについては未だ明らかではないが、層間や層間内の微細孔からプリン体吸着サイトを覆っていた水分子が取り除かれることで、プリン体が吸着し易くなったものと考えられる。 Although the mechanism by which adsorption improves when the amount of interlayer water is within a certain range is still unclear, water molecules covering purine adsorption sites are removed from the interlayers and micropores within the interlayers. This is thought to be due to the fact that purines were more easily adsorbed.
また、吸着水の量が低減された本発明の吸着剤は、再度吸湿したとしても、吸湿した水は吸着水として保有されるので、層間水は新たに保有されず、吸着性能は損なわれない。 In addition, even if the adsorbent of the present invention, which has a reduced amount of adsorbed water, absorbs moisture again, the absorbed water will be retained as adsorbed water, so interlayer water will not be newly retained and the adsorption performance will not be impaired. .
本発明において吸着剤として用いる弱酸処理白土は、一般的に活性白土と称されるものに比して弱い酸処理によって得られるため、固体酸点として働くＡｌやＭｇを覆っているＮａ分やＣａ分が取り除かれ、さらには、酸処理の進行に伴ってＡｌ分やＭｇ分が溶出することに起因する固体酸量の減少が抑えられている。その結果、従来の酸処理で得られる一般的に活性白土と称されるもの、或いは、酸処理を行っていない酸性白土に比して同等以上の固体酸量を示す。弱酸処理白土は、好適にはＨｏ≦－３．０の固体酸量が０．１０～０．７０ｍｍｏｌ／ｇ－ｄｒｙ ｃｌａｙの範囲にあり、比較的強い固体酸を多く含んでいることを意味している。即ち、プリン体に対して固体酸による化学的吸着性能が高められており、後述する実施例にも示されているように、少量での使用により、従来公知の活性白土や酸性白土と同等或いはそれ以上にプリン体含有溶液からプリン体を多く除去することができる。 The weakly acid-treated clay used as an adsorbent in the present invention is obtained by a weaker acid treatment compared to what is generally called activated clay, so it contains Na and Ca that cover Al and Mg, which act as solid acid sites. Furthermore, the decrease in the amount of solid acid caused by the elution of Al and Mg as the acid treatment progresses is suppressed. As a result, it exhibits an amount of solid acid equal to or higher than that of what is generally called activated clay obtained by conventional acid treatment or acid clay that has not been subjected to acid treatment. The weak acid-treated clay preferably has a solid acid amount of Ho≦-3.0 in the range of 0.10 to 0.70 mmol/g-dry clay, which means that it contains a large amount of relatively strong solid acids. ing. In other words, the chemical adsorption performance of solid acids on purines has been improved, and as shown in the examples below, when used in small amounts, it can be as good as or equal to conventionally known activated clay or acid clay. Even more purines can be removed from the purine-containing solution.
また、本発明において吸着剤として用いる弱酸処理白土は、弱いながらも酸処理されているため、窒素法によるＢＥＴ比表面積が、酸処理を施していないスメクタイト系粘土に比して向上しており、好適には６５～４００ｍ２／ｇ、特に好適には１００～４００ｍ２／ｇの範囲にある。しかるに、かかる弱酸処理白土は、酸処理を施していないスメクタイト系粘土に比して、ＢＥＴ比表面積比（Ａ／Ｂ）は低いが、高い吸着性を示すと考えられる。 In addition, since the weakly acid-treated clay used as an adsorbent in the present invention has been acid-treated, although weakly, the BET specific surface area measured by the nitrogen method is improved compared to smectite clay that has not been acid-treated. It is preferably in the range of 65 to 400 m 2 /g, particularly preferably 100 to 400 m 2 /g. However, although such weak acid-treated clay has a lower BET specific surface area ratio (A/B) than smectite clay that has not been acid-treated, it is considered to exhibit high adsorption.
さらにまた、上記の弱酸処理白土は、ジオクタヘドラル型スメクタイト系粘土の結晶構造に由来する特有のＸ線回折ピークを示し、例えば、Ｘ線回折測定において、面指数（０６）に由来する回折ピークを２θ＝６２度（ｄ＝１．４９～１．５０Å）付近に有している。 Furthermore, the above-mentioned weak acid-treated clay exhibits a unique X-ray diffraction peak derived from the crystal structure of dioctahedral-type smectite clay. For example, in X-ray diffraction measurement, the diffraction peak derived from the plane index (06) is =62 degrees (d=1.49 to 1.50 Å).
＜弱酸処理白土の製造＞
上記のような特性を有する弱酸処理白土は、ジオクタヘドラル型スメクタイト系粘土を粗砕、混練して所定濃度の酸水溶液を用いて、所定の条件で酸処理することにより製造される。即ち、この弱酸処理白土は、半活性白土と同様にして得られるが、半活性白土に比してマイルドな条件での酸処理によって得られるものである。
<Production of weak acid treated clay>
Weak acid-treated clay having the above characteristics is produced by roughly crushing and kneading dioctahedral smectite clay, and then acid-treating the clay under predetermined conditions using an acid aqueous solution of a predetermined concentration. That is, this weakly acid-treated clay is obtained in the same manner as semi-activated clay, but is obtained by acid treatment under milder conditions than semi-activated clay.
原料粘土として用いるジオクタヘドラル型スメクタイト系粘土は、火山岩や溶岩等が海水の影響下で変成したものと考えられており、主要成分であるジオクタヘドラル型スメクタイトはＳｉＯ４四面体層－ＡｌＯ６八面体層－ＳｉＯ４四面体層からなり、且つこれらの四面体層と八面体層が部分的に異種金属で同形置換された三層構造を基本構造（単位層）としており、このような三層構造の積層層間には、Ｃａ，Ｋ，Ｎａ等の陽イオンや水素イオンとそれに配位している水分子が存在している。また、基本三層構造の八面体層中のＡｌの一部にＭｇやＦｅ（ＩＩ）が置換し、四面体層中のＳｉの一部にＡｌが置換しているため、結晶格子はマイナスの電荷を有しており、このマイナスの電荷が基本層間に存在する金属陽イオンや水素イオンにより中和されている。このようなスメクタイト系粘土には、酸性白土、ベントナイト、フラーズアース等があり、基本層間に存在する金属陽イオンの種類や量、及び水素イオン量等によってそれぞれ異なる特性を示す。例えば、ベントナイトでは、基本層間に存在するＮａイオン量が多く、このため、水に懸濁分散させた分散液のｐＨが高く、一般に高アルカリサイドにあり、また、水に対して高い膨潤性を示し、さらにはゲル化して固結するという性質を示す。一方、酸性白土では、基本層間に存在する水素イオン量が多く、このため、水に懸濁分散させた分散液のｐＨが低く、一般に酸性サイドにあり、また、水に対して膨潤性を示すものの、ベントナイトと比較すると、その膨潤性は総じて低く、ゲル化には至らない。 The dioctahedral smectite clay used as raw material clay is thought to be metamorphosed from volcanic rock or lava under the influence of seawater, and the main component, dioctahedral smectite, consists of a SiO 4 tetrahedral layer - an AlO 6 octahedral layer. The basic structure (unit layer) is a three-layer structure (unit layer) consisting of SiO 4 tetrahedral layers, and these tetrahedral layers and octahedral layers are partially isomorphically substituted with different metals. Between the layers, cations such as Ca, K, Na, etc., hydrogen ions, and water molecules coordinated therewith exist. In addition, Mg and Fe(II) are substituted for part of the Al in the octahedral layer of the basic three-layer structure, and Al is substituted for part of the Si in the tetrahedral layer, so the crystal lattice is negative. It has an electric charge, and this negative charge is neutralized by metal cations and hydrogen ions that exist between the basic layers. Such smectite clays include acid clay, bentonite, fuller's earth, etc., and each exhibits different characteristics depending on the type and amount of metal cations present between the basic layers, the amount of hydrogen ions, etc. For example, bentonite has a large amount of Na ions existing between the basic layers, and therefore the pH of the dispersion suspended in water is high, generally on the high alkaline side, and it also has high swelling properties in water. It also exhibits the property of gelling and solidifying. On the other hand, acid clay has a large amount of hydrogen ions existing between the basic layers, so the pH of the dispersion suspended in water is low, generally on the acidic side, and also exhibits swelling properties in water. However, compared to bentonite, its swelling property is generally low and does not result in gelation.
本発明において、弱酸処理白土の製造に用いるジオクタヘドラル型スメクタイト系粘土は、特に限定されるものではなく、上述した各種の何れをも使用することができる。また、かかる原料粘土は、粘土の成因、産地及び同じ産地でも埋蔵場所（切羽）等によっても相違するが、一般的には、酸化物換算で以下のような組成を有している。
ＳｉＯ２；５０～７５質量％
Ａｌ２Ｏ３；１１～２５質量％
Ｆｅ２Ｏ３；２～２０質量％
ＭｇＯ；２～７質量％
ＣａＯ；０．１～３質量％
Ｎａ２Ｏ；０．１～３質量％
Ｋ２Ｏ；０．１～３質量％
その他の酸化物（ＴｉＯ２等）；２質量％以下
Ｉｇ－ｌｏｓｓ（１０５０℃）；５～１１質量％
In the present invention, the dioctahedral type smectite clay used for producing the weak acid-treated clay is not particularly limited, and any of the above-mentioned types can be used. In addition, such raw material clay differs depending on the origin of the clay, the place of production, and the place of burial (face) even in the same place of production, but generally it has the following composition in terms of oxides.
SiO 2 ; 50 to 75% by mass
Al 2 O 3 ; 11-25% by mass
Fe 2 O 3 ; 2 to 20% by mass
MgO; 2-7% by mass
CaO; 0.1 to 3% by mass
Na 2 O; 0.1 to 3% by mass
K 2 O; 0.1 to 3% by mass
Other oxides (TiO 2 etc.); 2% by mass or less Ig-loss (1050°C); 5-11% by mass
また、原料粘土は、産地等によっては、石英等の不純物を多く含んでいることもある。従って、上記のジオクタヘドラル型スメクタイト系粘土を、必要により石砂分離、浮力選鉱、磁力選鉱、水簸、風簸等の精製操作に賦して不純物をできるだけ除去した後に酸処理を行うのがよい。このような処理を行った後に、以下に述べるマイルドな条件での酸処理を行うことにより、Ａ／Ｂが上記範囲内にある弱酸処理白土を得ることができる。 Furthermore, depending on the region of production, the raw clay may contain a large amount of impurities such as quartz. Therefore, it is preferable to subject the above-mentioned dioctahedral type smectite clay to purification operations such as rock and sand separation, buoyancy beneficiation, magnetic beneficiation, water elutriation, elutriation, etc. as necessary to remove as many impurities as possible, and then perform acid treatment. After performing such treatment, by performing acid treatment under mild conditions described below, it is possible to obtain weakly acid-treated clay having A/B within the above range.
酸処理は、酸水溶液中に原料粘土を投入し、混合攪拌することにより行われる。酸処理に用いる酸水溶液は、特に限定されるものではないが、コスト、環境への影響等の観点から硫酸水溶液が一般に使用される。 The acid treatment is performed by adding raw clay to an acid aqueous solution and mixing and stirring. The acid aqueous solution used in the acid treatment is not particularly limited, but a sulfuric acid aqueous solution is generally used from the viewpoint of cost, environmental impact, and the like.
また、かかる酸処理は、既に述べたように、従来公知の活性白土や半活性白土を製造する際の酸処理に比してマイルドな条件下で行われ、例えば硫酸水溶液を使用する場合には、原料粘土中に含まれる水分も硫酸水溶液を構成するものとして算出した硫酸水溶液量が、原料粘土１００質量部（１１０℃乾燥物として）当り２５０～８００質量部、その時の硫酸水溶液の濃度が１～１５質量％程度になるような条件で酸処理を行えばよい。酸処理にあたっては、必要により２５～９５℃程度に加熱することもできる。このようにして、原料の組成、用いる酸水溶液の酸濃度、処理温度等によって、比表面積比（Ａ／Ｂ）が所定の範囲となる程度の時間（０．５～１２時間程度、好ましくは０．５～８時間程度、特に好ましくは０．５～４時間程度）、酸処理を行えばよい。 In addition, as mentioned above, this acid treatment is performed under milder conditions than the acid treatment used to produce conventionally known activated clay or semi-activated clay. For example, when using an aqueous sulfuric acid solution, , the amount of sulfuric acid aqueous solution calculated assuming that the water contained in the raw clay also constitutes the sulfuric acid aqueous solution is 250 to 800 parts by mass per 100 parts by mass of raw clay (as a dry product at 110°C), and the concentration of the sulfuric acid aqueous solution at that time is 1 The acid treatment may be performed under conditions such that the concentration is about 15% by mass. In the acid treatment, heating can be carried out to about 25 to 95°C if necessary. In this way, depending on the composition of the raw materials, the acid concentration of the acid aqueous solution used, the treatment temperature, etc., the specific surface area ratio (A/B) is kept within a predetermined range (about 0.5 to 12 hours, preferably 0. The acid treatment may be carried out for about .5 to 8 hours, particularly preferably for about 0.5 to 4 hours).
上記のような酸処理により、窒素法によるＢＥＴ比表面積と水蒸気法によるＢＥＴ比表面積の比Ａ／Ｂや固体酸量、窒素法によるＢＥＴ比表面積の値が上述の範囲にあり、プリン体に対する吸着性能に優れた本発明の吸着剤（弱酸処理白土）が得られる。 By the above acid treatment, the ratio A/B of the BET specific surface area by the nitrogen method and the BET specific surface area by the water vapor method, the amount of solid acid, and the value of the BET specific surface area by the nitrogen method are within the above range, and the adsorption to purine is The adsorbent of the present invention (weak acid treated clay) with excellent performance can be obtained.
また、上述した酸処理によって得られる弱酸処理白土は、一般に、酸化物換算で、下記の化学組成を有している。
ＳｉＯ２；５０～８５質量％
Ａｌ２Ｏ３；８～２３質量％
Ｆｅ２Ｏ３；１～１０質量％以下
ＭｇＯ；１～５質量％以下
ＣａＯ；０．１～２質量％以下
Ｎａ２Ｏ；０．１～１質量％
Ｋ２Ｏ；０．１～１質量％
その他の酸化物（ＴｉＯ２等）；２質量％以下
Ｉｇ－ｌｏｓｓ（１０５０℃）；４～９質量％
Furthermore, the weakly acid-treated clay obtained by the acid treatment described above generally has the following chemical composition in terms of oxides.
SiO 2 ; 50-85% by mass
Al 2 O 3 ; 8-23% by mass
Fe 2 O 3 ; 1 to 10% by mass or less MgO; 1 to 5% by mass or less CaO; 0.1 to 2% by mass or less Na 2 O; 0.1 to 1% by mass
K 2 O; 0.1 to 1% by mass
Other oxides (TiO2, etc.): 2% by mass or less Ig-loss (1050°C): 4-9% by mass
酸処理後は水でろ過洗浄し、その後、層間水の量を調整するために乾燥処理を行う。乾燥処理は、層間水の量が所定の範囲となればよく、オーブンでの熱乾燥、風乾、マイクロ波照射など任意の方法で行うことができる。
乾燥温度は、乾燥処理の方法によっても異なるが、例えばオーブンにて静置乾燥させる場合、層間水を粘土鉱物から脱離させるために、オーブン温度を１２０℃以上にするのが好ましく、１４０℃以上にするのがより好ましい。また、層間に形成されている微細孔がつぶれてしまわないように、オーブン温度を２００℃未満にするのが好ましく、１７０℃未満にするのがより好ましい。
乾燥時間は、層間水の量が所定の範囲となればよく特に限定されないが、オーブンにて静置乾燥させる場合、概ね２時間以上行えば十分である。
After the acid treatment, it is filtered and washed with water, and then a drying process is performed to adjust the amount of interlayer water. The drying process can be performed by any method such as heat drying in an oven, air drying, microwave irradiation, etc. as long as the amount of interlayer water is within a predetermined range.
The drying temperature varies depending on the drying method, but for example, when drying in an oven, the oven temperature is preferably 120°C or higher, and 140°C or higher in order to remove interlayer water from the clay mineral. It is more preferable to Further, in order to prevent the micropores formed between the layers from being crushed, the oven temperature is preferably lower than 200°C, and more preferably lower than 170°C.
The drying time is not particularly limited as long as the amount of interlayer water is within a predetermined range, but in the case of standing to dry in an oven, it is sufficient to dry for about 2 hours or more.
＜プリン体＞
本発明において、前述した弱酸処理白土は、プリン体、即ち、プリン骨格を有する化合物に対して優れた選択吸着性を示す。
<Purine>
In the present invention, the above-mentioned weak acid-treated clay exhibits excellent selective adsorption to purines, that is, compounds having a purine skeleton.
プリン骨格は、下記式：
プリン体の１つとしては、下記式：
さらに、キサンチンから派生する化合物としては、下記式：
カフェイン以外のキサンチン誘導体としては、これに限定されるものではないが、テオフィリン、テオブロミン、パラキサンチン等を挙げることができる。
キサンチン、ヒポキサンチンおよびキサンチンから派生する化合物を、本明細書では、総じてキサンチン化合物とする。本発明の吸着剤は、キサンチン化合物に対して優れた選択吸着性を示し、キサンチン化合物用吸着剤として好適であり、カフェイン用吸着剤として特に好適である。
Furthermore, as a compound derived from xanthine, the following formula:
Examples of xanthine derivatives other than caffeine include, but are not limited to, theophylline, theobromine, paraxanthine, and the like.
Xanthine, hypoxanthine and compounds derived from xanthine are collectively referred to herein as xanthine compounds. The adsorbent of the present invention exhibits excellent selective adsorption properties for xanthine compounds, is suitable as an adsorbent for xanthine compounds, and is particularly suitable as an adsorbent for caffeine.
また、プリン体として、アデニン、グアニンもある。アデニンまたはグアニンから派生する化合物としては、アデニンまたはグアニンとリボースから構成されるプリンヌクレオシド（アデノシン、グアノシン）や、さらにリン酸を構成成分に含むプリンヌクレオチド（アデニル酸、グアニル酸）等が挙げられる。また、アデニンまたはグアニンから派生する他の有機化合物としては、これに限定されるものではないが、デオキシグアノシン、デオキシグアノシン三リン酸、ニコチンアミドアデニンジヌクレオチド（ＮＡＤ）、フラビンアデニンジヌクレオチド（ＦＡＤ）、イノシン、イノシン酸等を挙げることができる。本明細書では、上記のアデニンまたはグアニン、および、アデニンまたはグアニンから派生する化合物を、アデニンまたはグアニン化合物と総称する。本発明の吸着剤は、アデニンおよびグアニンに対する選択的吸着性を示し、それ故、アデニンまたはグアニン化合物に対しても優れた選択的吸着性を示し、かかる化合物用の吸着剤として好適である。後述する実施例においては、本発明の吸着剤はグアニンにリボース環がβ－Ｎ９－グリコシド結合で構成されたヌクレオシドであるグアノシンに対して優れた選択的吸着性を示す。 There are also adenine and guanine as purines. Examples of compounds derived from adenine or guanine include purine nucleosides (adenosine, guanosine) composed of adenine or guanine and ribose, and purine nucleotides (adenylic acid, guanylic acid) that further contain phosphoric acid as a constituent. Other organic compounds derived from adenine or guanine include, but are not limited to, deoxyguanosine, deoxyguanosine triphosphate, nicotinamide adenine dinucleotide (NAD), and flavin adenine dinucleotide (FAD). , inosine, inosinic acid, and the like. In this specification, the above adenine or guanine and compounds derived from adenine or guanine are collectively referred to as adenine or guanine compounds. The adsorbent of the present invention exhibits selective adsorption for adenine and guanine, and therefore also exhibits excellent selective adsorption for adenine or guanine compounds, and is suitable as an adsorbent for such compounds. In the Examples described below, the adsorbent of the present invention exhibits excellent selective adsorption to guanosine, which is a nucleoside in which the ribose ring of guanine is composed of a β-N 9 -glycosidic bond.
＜用途＞
本発明において吸着剤として使用する弱酸処理白土は、プリン体に対する選択吸着性に優れているばかりか、少量の使用で済むので飲料の風味に影響し得る金属類の溶出も少なく、そのため、お茶やコーヒー等の飲料からカフェインを除去してカフェインレスとするために好適に使用され、また、ビール等のアルコール飲料からプリン体を除去するための
吸着剤として使用される。例えば、上述のプリン体が溶解している溶液に０．００１～１０質量部の量で添加して使用される。
これら飲料からカフェイン等を除去するには、前述した弱酸処理白土を、適度な平均粒径（例えば、１０～３００μｍ程度）の粉末状に粒度調整し、これを飲料と混合すればよい。
本発明のプリン体用吸着剤は、上記飲料のほか、各種調味料やサプリメントなどを含めた食品、あるいは、工業や農業に用いられる各種薬品などの製造工程中の固液分離（濾過）において用いることができ、用いられる工程において適する粒度に適宜調整を行うことで、飲料に何ら制限されることなく適用できる。
また、本発明の吸着剤は、アデニンまたはグアニン化合物選択吸着性や濾過性を活かし、創薬や製薬など医薬の分野に適用することもできる。
本発明の吸着剤は、特に飲料や食品の分野に適用することが好ましい。
<Application>
The weak acid-treated clay used as an adsorbent in the present invention not only has excellent selective adsorption properties for purines, but because only a small amount is needed, metals that can affect the flavor of beverages are less likely to elute. It is suitably used to remove caffeine from drinks such as coffee to make them decaffeinated, and is also used as an adsorbent to remove purines from alcoholic drinks such as beer. For example, it is used by adding it in an amount of 0.001 to 10 parts by mass to a solution in which the above-mentioned purine is dissolved.
In order to remove caffeine and the like from these beverages, it is sufficient to adjust the particle size of the aforementioned weak acid-treated clay into a powder with an appropriate average particle size (for example, about 10 to 300 μm) and mix this with the beverage.
The adsorbent for purines of the present invention is used in solid-liquid separation (filtration) during the manufacturing process of not only the above-mentioned beverages but also foods including various seasonings and supplements, and various chemicals used in industry and agriculture. By adjusting the particle size appropriately in the process used, it can be applied to beverages without any restrictions.
Further, the adsorbent of the present invention can also be applied to the medical fields such as drug discovery and pharmaceuticals by taking advantage of its selective adsorption ability and filterability for adenine or guanine compounds.
The adsorbent of the present invention is preferably applied particularly to the fields of beverages and foods.
本発明の吸着剤は、後述する実施例に示したように、プリン体を含むアルコール溶液に入れてプリン体を吸着除去することができるので、例えば、ビールや発泡酒をはじめとしたプリン体を含むアルコール飲料等から好適にプリン体を除去することができる。
アルコール溶液とは、アルコールが含まれている液体を意味し、アルコール以外に例えば水等が含まれていてもよい。具体的には、ビールや発泡酒等の発酵麦芽飲料、ビールテイスト飲料、酒、ワイン、醸造アルコール、焼酎、スピリッツ類、リキュール類、ウイスキー、ブランデー、清酒、果実酒、酎ハイ、カクテル等の飲料用として提供されるものに加え、食品用、工業用、農業用、医療用として提供される各種アルコール含有製品及びその製造工程で用いる原料等が挙げられる。アルコールは特に制限はなく、例えば、メタノール、エタノール、低級アルコール（例えば、２－プロパノール、エチレングリコール、グリセリン等）、高級アルコール（炭素数８～２２以上の脂肪族アルコール、例えば、カプリルアルコール、ラウリルアルコール、ミリスチルアルコール、セチルアルコール、ステアリルアルコール、オレイルアルコール、リノリルアルコール等）、フェノール、芳香族アルコール等が挙げられ、好ましくは、エタノールが挙げられる。また、アルコールの濃度は特に制限がなく、上記アルコールを少なくとも１種以上含む溶液に適用できる。上述の本発明の吸着剤をアルコール溶液に適用する方法により、上記アルコール含有製品及びその製造工程で用いる原料等から、好適にプリン体を除去することができる。
As shown in the examples below, the adsorbent of the present invention can adsorb and remove purines when placed in an alcoholic solution containing purines. Purine bodies can be suitably removed from alcoholic beverages, etc.
The alcohol solution means a liquid containing alcohol, and may also contain, for example, water in addition to alcohol. Specifically, beverages such as fermented malt beverages such as beer and low-malt beer, beer-taste beverages, alcohol, wine, brewed alcohol, shochu, spirits, liqueurs, whisky, brandy, sake, fruit liquor, chuhai, cocktails, etc. In addition to alcohol-containing products provided for commercial use, alcohol-containing products provided for food, industrial, agricultural, and medical uses, as well as raw materials used in the manufacturing process thereof, are included. Alcohols are not particularly limited, and include, for example, methanol, ethanol, lower alcohols (e.g., 2-propanol, ethylene glycol, glycerin, etc.), higher alcohols (aliphatic alcohols having 8 to 22 or more carbon atoms, e.g., caprylic alcohol, lauryl alcohol). , myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, linolyl alcohol, etc.), phenol, aromatic alcohols, and preferably ethanol. Further, the concentration of alcohol is not particularly limited, and the solution can be applied to a solution containing at least one of the above-mentioned alcohols. By applying the above-described adsorbent of the present invention to an alcohol solution, purines can be suitably removed from the above-mentioned alcohol-containing products and raw materials used in the manufacturing process thereof.
本発明において吸着剤として使用する弱酸処理白土は、酸処理によりＢＥＴ比表面積が増大し、比較的強い固体酸を多く含んでいるという特徴を有している。そのため、本発明の吸着剤は、従来の活性白土と同様に、油脂類や鉱物油類の脱色、触媒又は触媒担体に何ら制限なく使用することができる。 The weak acid-treated clay used as an adsorbent in the present invention has a BET specific surface area increased by acid treatment and is characterized by containing a large amount of relatively strong solid acids. Therefore, the adsorbent of the present invention, like conventional activated clay, can be used for decolorizing oils and fats and mineral oils, and for catalysts and catalyst carriers without any restrictions.
本発明の優れた効果を、次の実験例により説明する。 The excellent effects of the present invention will be explained by the following experimental examples.
（１）窒素吸着法によるＢＥＴ比表面積（Ｂ）
マイクロメリティクス社製ＴｒｉＳｔａｒ ３０００を用いて窒素吸着法により測定を行ない、ＢＥＴ法により算出した。なお、前処理は１５０℃で２時間行った。
(1) BET specific surface area (B) by nitrogen adsorption method
Measurement was performed by the nitrogen adsorption method using TriStar 3000 manufactured by Micromeritics, and calculation was performed by the BET method. Note that the pretreatment was performed at 150° C. for 2 hours.
（２）水蒸気吸着法によるＢＥＴ比表面積（Ａ）
日本ベル株式会社製ＢＥＬＳＯＲＰ ＭＡＸを用いて水蒸気吸着法により測定を行ない、ＢＥＴ法により算出した。なお、前処理は１５０℃で２時間行った。
(2) BET specific surface area (A) by water vapor adsorption method
Measurement was carried out by the water vapor adsorption method using BELSORP MAX manufactured by Nippon Bell Co., Ltd., and calculation was performed by the BET method. Note that the pretreatment was performed at 150° C. for 2 hours.
（３）層間水の量
吸着剤粉末約２ｇを秤量し、８０℃のオーブンで２時間静置乾燥した。その後再度秤量し、湿量基準の８０℃乾燥減量Ｗ８０（％）を求めた。
吸着剤粉末約２ｇを秤量し、１５０℃のオーブンで２時間静置乾燥した。その後再度秤量し、湿量基準の１５０℃乾燥減量Ｗ１５０（％）を求めた。
下記式：
ＷＬ＝（Ｗ１５０－Ｗ８０）／（１００－Ｗ１５０）×１０００
により、付着水及び層間水を除いた吸着剤１ｇあたりの層間水の量ＷＬ（ｍｇ／ｇ）を求めた。
(3) Amount of interlayer water Approximately 2 g of adsorbent powder was weighed and left to dry in an oven at 80° C. for 2 hours. Thereafter, it was weighed again to determine the weight loss W 80 (%) on drying at 80° C. on a wet basis.
Approximately 2 g of adsorbent powder was weighed and left to dry in an oven at 150° C. for 2 hours. Thereafter, it was weighed again to determine the weight loss W 150 (%) on drying at 150° C. on a wet basis.
The following formula:
W L = (W 150 - W 80 )/(100 - W 150 ) x 1000
Accordingly, the amount W L (mg/g) of interlayer water per 1 g of adsorbent excluding adhering water and interlayer water was determined.
（４）固体酸量
ｎ－ブチルアミン滴定法にてＨｏ≦－３．０の固体酸量を測定した。試料は、予め、１５０℃で３時間乾燥したものについて測定を行った｛参考文献：「触媒」Ｖｏｌ．１１，Ｎｏ６，Ｐ２１０－２１６（１９６９）｝。
(4) Amount of solid acid The amount of solid acid, Ho≦-3.0, was measured by n-butylamine titration method. The sample was previously dried at 150°C for 3 hours before measurement {Reference: "Catalyst" Vol. 11, No. 6, P210-216 (1969)}.
（５）カフェイン吸着試験
本実施例におけるカフェイン吸着能は、０．２ｇ／Ｌ濃度のカフェイン水溶液から、１ｇの吸着剤（無水）が吸着できるカフェイン量（ｍｇ）とし、下記の方法により測定し、算出した。
先ず、無水カフェイン（試薬特級、和光純薬工業（株）製）をイオン交換水に溶かし、０．２ｇ／Ｌ濃度のカフェイン水溶液を得た。
この０．２ｇ／Ｌ濃度のカフェイン水溶液３０ｇを５０ｍｌ容量の遠沈管に秤取し、吸着剤０．０９ｇ（対液０．３質量％）を加えて振とう機（ヤマト科学（株）製ＳＡ３００、振とうスピード５）により０．５時間振とうした。
次に遠心分離機（（株）クボタ製 ５２００）により遠心加速度３０００ｒｐｍで１５分処理した液の上澄みをイオン交換水により１０倍に希釈して液（試料液）を得た。試料液の２７３ｎｍ波長光の吸光度を分光光度計（日本分光（株）製Ｖ－６３０）により測定した。そして、予め作成したカフェイン濃度と２７３ｎｍ波長光の吸光度の関係を示す検量線を用いて試料液のカフェイン残存量を算出し、吸着剤添加前のカフェイン量から差し引いた値を吸着剤のカフェイン吸着量とした。
(5) Caffeine adsorption test The caffeine adsorption capacity in this example is the amount of caffeine (mg) that can be adsorbed by 1 g of adsorbent (anhydrous) from a caffeine aqueous solution with a concentration of 0.2 g/L, and the following method is used. It was measured and calculated by.
First, anhydrous caffeine (special grade reagent, manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in ion-exchanged water to obtain an aqueous caffeine solution with a concentration of 0.2 g/L.
Weigh out 30 g of this 0.2 g/L caffeine aqueous solution into a 50 ml centrifuge tube, add 0.09 g of adsorbent (0.3% by mass to the liquid), and shake it using a shaker (Yamato Scientific Co., Ltd.). It was shaken for 0.5 hour at SA300 and shaking speed 5).
Next, the supernatant of the liquid was treated with a centrifugal separator (5200 manufactured by Kubota Corporation) at a centrifugal acceleration of 3000 rpm for 15 minutes and diluted 10 times with ion-exchanged water to obtain a liquid (sample liquid). The absorbance of the sample solution at a wavelength of 273 nm was measured using a spectrophotometer (V-630, manufactured by JASCO Corporation). Then, the residual amount of caffeine in the sample solution was calculated using a pre-prepared calibration curve showing the relationship between the caffeine concentration and the absorbance of 273 nm wavelength light, and the value subtracted from the amount of caffeine before adding the adsorbent was calculated. It was defined as the amount of caffeine adsorbed.
（６）グアノシン吸着試験
本実施例におけるグアノシン吸着能は、０．２ｇ／Ｌ濃度のグアノシン水溶液から、１ｇの試料（無水）が吸着できるグアノシン量（ｍｇ）とし、下記の方法により測定し、算出した。
先ず、グアノシン（Ａｌｆａ Ａｅｓａｒ製）を５体積％エタノール水溶液１Ｌに溶解し、０．２ｇ／Ｌ濃度のグアノシン溶液を得た。
この０．２ｇ／Ｌ濃度のグアノシン溶液３０ｇを５０ｍｌ容量の遠沈管に秤取し、０．２５８ｇ（対液０．８６質量％）の試験粉末を加えて振とう機（ヤマト科学（株）製ＳＡ３００、振とうスピード５）により０．５時間振とうした。
次に遠心分離機（（株）クボタ製 ５２００）により回転数３０００ｒｐｍで３０分処理し、液の上澄みをイオン交換水により１０倍に希釈した液（試料液）を得た。試料液の
２５５ｎｍ波長光の吸光度を分光光度計（日本分光（株）製Ｖ－６３０）により測定した。そして、あらかじめ作成したグアノシン濃度と２５５ｎｍ波長光の吸光度の関係を示す検量線を用いて、試料液のグアノシン濃度を算出した。この値から試料単位量あたりのグアノシン吸着量を計算した。
(6) Guanosine adsorption test The guanosine adsorption capacity in this example was calculated by measuring the amount (mg) of guanosine that can be adsorbed by 1 g of sample (anhydrous) from a guanosine aqueous solution with a concentration of 0.2 g/L using the following method. did.
First, guanosine (manufactured by Alfa Aesar) was dissolved in 1 L of a 5% by volume ethanol aqueous solution to obtain a guanosine solution with a concentration of 0.2 g/L.
Weigh out 30 g of this 0.2 g/L concentration guanosine solution into a 50 ml centrifuge tube, add 0.258 g (0.86% by mass of the liquid) of the test powder, and use a shaker (Yamato Scientific Co., Ltd.). It was shaken for 0.5 hour at SA300 and shaking speed 5).
Next, the mixture was treated with a centrifuge (manufactured by Kubota Corporation, 5200) for 30 minutes at a rotational speed of 3000 rpm, and the supernatant of the liquid was diluted 10 times with ion-exchanged water to obtain a liquid (sample liquid). The absorbance of the sample solution at a wavelength of 255 nm was measured using a spectrophotometer (V-630, manufactured by JASCO Corporation). Then, the guanosine concentration of the sample solution was calculated using a calibration curve prepared in advance showing the relationship between the guanosine concentration and the absorbance of light at a wavelength of 255 nm. From this value, the amount of guanosine adsorbed per unit amount of sample was calculated.
下記の実施例および比較例に示す吸着剤粉末について、物性および各種吸着試験結果を表１及び２に示す。 Tables 1 and 2 show the physical properties and various adsorption test results for the adsorbent powders shown in the Examples and Comparative Examples below.
（実施例１）
新潟県胎内市産のジオクタヘドラル型スメクタイト系粘土を粗砕、オーブンにて１１０℃で１２時間乾燥、粉砕、分級して粘土粉末を得た。
ビーカーに１０質量％硫酸水溶液２２０ｍｌを採り、９０℃に加熱した。そこへ前記粘土粉末３０ｇを添加し、液温を９０℃に維持した状態で撹拌し、３０分間酸処理を行った。酸処理終了後、酸処理物を水でろ過洗浄し、洗浄後のろ過ケーキを１５０℃のオーブンで１２時間静置乾燥し、粉砕、分級して吸着剤粉末を得た。
(Example 1)
Dioctahedral-type smectite clay produced in Tainai City, Niigata Prefecture was roughly crushed, dried in an oven at 110°C for 12 hours, crushed, and classified to obtain clay powder.
220 ml of a 10% by mass sulfuric acid aqueous solution was placed in a beaker and heated to 90°C. 30 g of the clay powder was added thereto, stirred while maintaining the liquid temperature at 90° C., and acid-treated for 30 minutes. After the acid treatment, the acid-treated product was filtered and washed with water, and the washed filter cake was left to dry in an oven at 150° C. for 12 hours, crushed, and classified to obtain an adsorbent powder.
（実施例２）
洗浄後のろ過ケーキを１５０℃のオーブンで１２時間静置乾燥した後、相対湿度７５％にて吸湿した以外は実施例１と同様にして吸着剤粉末を得た。
(Example 2)
After leaving the washed filter cake to dry in an oven at 150° C. for 12 hours, an adsorbent powder was obtained in the same manner as in Example 1, except that the cake was subjected to moisture absorption at a relative humidity of 75%.
（実施例３）
洗浄後のろ過ケーキをロータリーキルンにてキルン出口が２３０℃になるような条件で４０分間乾燥した以外は実施例１と同様にして吸着剤粉末を得た。
(Example 3)
An adsorbent powder was obtained in the same manner as in Example 1, except that the washed filter cake was dried in a rotary kiln for 40 minutes under conditions such that the temperature at the kiln outlet was 230°C.
（実施例４）
洗浄後のろ過ケーキを８０℃のオーブンで２時間静置乾燥し、粉砕、分級した後、さらにオーブンにて１５０℃で２時間静置乾燥した以外は実施例１と同様にして吸着剤粉末を得た。
(Example 4)
Adsorbent powder was prepared in the same manner as in Example 1, except that the washed filter cake was left to dry in an oven at 80°C for 2 hours, crushed and classified, and then left to dry in an oven at 150°C for 2 hours. Obtained.
（比較例１）
山形県鶴岡市産のジオクタヘドラル型スメクタイト系粘土を粗砕、オーブンにて１５０℃で１２時間静置乾燥し、粉砕、分級して吸着剤粉末を得た。
(Comparative example 1)
Dioctahedral-type smectite clay produced in Tsuruoka City, Yamagata Prefecture was crushed, left to dry in an oven at 150°C for 12 hours, crushed, and classified to obtain an adsorbent powder.
（比較例２）
洗浄後のろ過ケーキを８０℃のオーブンで１２時間静置乾燥した以外は実施例１と同様にして酸処理物から成る粉末を得た。
(Comparative example 2)
A powder consisting of the acid-treated product was obtained in the same manner as in Example 1, except that the filter cake after washing was left to dry in an oven at 80° C. for 12 hours.
（比較例３）
粗砕した粘土を８０℃のオーブンで１２時間静置乾燥した以外は比較例１と同様にして吸着剤粉末を得た。
(Comparative example 3)
An adsorbent powder was obtained in the same manner as in Comparative Example 1, except that the coarsely crushed clay was left to dry in an oven at 80° C. for 12 hours.
（実験例１）
実施例１と同様にして酸処理物から成る吸着剤粉末を得た後、さらに２００℃のオーブンで２時間乾燥して吸着剤粉末を得た。
(Experiment example 1)
An adsorbent powder made of an acid-treated product was obtained in the same manner as in Example 1, and then dried in an oven at 200° C. for 2 hours to obtain an adsorbent powder.
（比較例４）
粗砕した粘土を２００℃のオーブンで１２時間静置乾燥した以外は比較例１と同様にして吸着剤粉末を得た。
(Comparative example 4)
An adsorbent powder was obtained in the same manner as in Comparative Example 1, except that the coarsely crushed clay was left to dry in an oven at 200° C. for 12 hours.
Claims (4)
水蒸気吸着法により測定されるＢＥＴ比表面積（Ａ）と窒素吸着法により測定されるＢＥＴ比表面積（Ｂ）との比、（Ａ）／（Ｂ）が０．９０～１．４０の範囲にあり、
ジオクタヘドラル型スメクタイト系粘土に特有の層間水の量が、付着水及び層間水を除いた吸着剤１ｇあたり３０ｍｇ以下にあるプリン体用吸着剤であって、
該プリン体がカフェインまたはグアノシンであることを特徴とするプリン体用吸着剤。 Consists of acid-treated dioctahedral smectite clay,
The ratio of BET specific surface area (A) measured by water vapor adsorption method to BET specific surface area (B) measured by nitrogen adsorption method, (A)/(B), is in the range of 0.90 to 1.40 . ,
An adsorbent for purine bodies in which the amount of interlayer water characteristic of dioctahedral type smectite clay is 30 mg or less per gram of adsorbent excluding adhering water and interlayer water,
An adsorbent for purines, characterized in that the purines are caffeine or guanosine .
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