JP2014171997A - Anion adsorptive material, method for producing the same, and water treating material - Google Patents
Anion adsorptive material, method for producing the same, and water treating material Download PDFInfo
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- JP2014171997A JP2014171997A JP2013048130A JP2013048130A JP2014171997A JP 2014171997 A JP2014171997 A JP 2014171997A JP 2013048130 A JP2013048130 A JP 2013048130A JP 2013048130 A JP2013048130 A JP 2013048130A JP 2014171997 A JP2014171997 A JP 2014171997A
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- Prior art keywords
- quaternary ammonium
- anion
- cellulose
- anion adsorbent
- ammonium salt
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- 150000001450 anions Chemical class 0.000 title claims abstract description 91
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000000463 material Substances 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 230000000274 adsorptive effect Effects 0.000 title abstract description 7
- 229920000297 Rayon Polymers 0.000 claims abstract description 85
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 50
- 229920002678 cellulose Polymers 0.000 claims abstract description 45
- 239000001913 cellulose Substances 0.000 claims abstract description 45
- 239000004627 regenerated cellulose Substances 0.000 claims abstract description 33
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 12
- 239000003463 adsorbent Substances 0.000 claims description 54
- 238000011282 treatment Methods 0.000 claims description 46
- -1 quaternary ammonium ions Chemical class 0.000 claims description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 238000001179 sorption measurement Methods 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 150000003945 chlorohydrins Chemical class 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000000835 fiber Substances 0.000 abstract description 80
- 239000002964 rayon Substances 0.000 abstract description 31
- 229910052785 arsenic Inorganic materials 0.000 description 49
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 46
- 238000009987 spinning Methods 0.000 description 43
- 239000007788 liquid Substances 0.000 description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 238000000034 method Methods 0.000 description 25
- 238000009991 scouring Methods 0.000 description 19
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- 229920000742 Cotton Polymers 0.000 description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 14
- 238000005406 washing Methods 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 239000011550 stock solution Substances 0.000 description 10
- 206010042674 Swelling Diseases 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 230000008961 swelling Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000004408 titanium dioxide Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- OWTFKEBRIAXSMO-UHFFFAOYSA-N arsenite(3-) Chemical compound [O-][As]([O-])[O-] OWTFKEBRIAXSMO-UHFFFAOYSA-N 0.000 description 6
- 239000004745 nonwoven fabric Substances 0.000 description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 6
- 229960001763 zinc sulfate Drugs 0.000 description 6
- 229910000368 zinc sulfate Inorganic materials 0.000 description 6
- 230000006835 compression Effects 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- 238000006477 desulfuration reaction Methods 0.000 description 5
- 230000023556 desulfurization Effects 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 description 5
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 4
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 4
- 229940000489 arsenate Drugs 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000003651 drinking water Substances 0.000 description 4
- 235000020188 drinking water Nutrition 0.000 description 4
- 239000010842 industrial wastewater Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 4
- 231100000167 toxic agent Toxicity 0.000 description 4
- 239000003440 toxic substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 229940000488 arsenic acid Drugs 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 239000003673 groundwater Substances 0.000 description 3
- 239000008235 industrial water Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000002594 sorbent Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 238000002166 wet spinning Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229940006020 arsenite ion Drugs 0.000 description 2
- FLNKWZNWHZDGRT-UHFFFAOYSA-N azane;dihydrochloride Chemical compound [NH4+].[NH4+].[Cl-].[Cl-] FLNKWZNWHZDGRT-UHFFFAOYSA-N 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012851 eutrophication Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910001410 inorganic ion Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- TXXWBTOATXBWDR-UHFFFAOYSA-N n,n,n',n'-tetramethylhexane-1,6-diamine Chemical compound CN(C)CCCCCCN(C)C TXXWBTOATXBWDR-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- 241001507939 Cormus domestica Species 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- BMSYAGRCQOYYMZ-UHFFFAOYSA-N [As].[As] Chemical compound [As].[As] BMSYAGRCQOYYMZ-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 1
- HAYXDMNJJFVXCI-UHFFFAOYSA-N arsenic(5+) Chemical compound [As+5] HAYXDMNJJFVXCI-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- KTTMEOWBIWLMSE-UHFFFAOYSA-N diarsenic trioxide Chemical compound O1[As](O2)O[As]3O[As]1O[As]2O3 KTTMEOWBIWLMSE-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920000083 poly(allylamine) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- KEAYESYHFKHZAL-BJUDXGSMSA-N sodium-22 Chemical compound [22Na] KEAYESYHFKHZAL-BJUDXGSMSA-N 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Treatment Of Water By Ion Exchange (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
本発明は、陰イオン吸着材、その製造方法及び水処理材に関し、詳細には、水中の砒素など有害な陰イオンの吸着除去、或いはリン酸など富栄養化の陰イオンを吸着回収することができる陰イオン吸着材、その製造方法及び水処理材に関する。 The present invention relates to an anion adsorbent, a method for producing the same, and a water treatment material, and in particular, adsorbs and removes harmful anions such as arsenic in water or eutrophication anions such as phosphoric acid. The present invention relates to an anion adsorbent that can be produced, a production method thereof, and a water treatment material.
砒酸、クロム酸、ほう酸などの無機性陰イオンは人体に対して有害であり、酸化された金属酸化物の陰イオンは、単独でも毒性が強く、除去する技術が必要とされている。中でも砒酸は、銀鉱石などの鉱脈がある土地の水から見られる有毒化合物であり、場所によってはトンネル工事などにより地下水から湧水となって出てくるために、砒酸（砒素）を除去する対策が必要となる。 Inorganic anions such as arsenic acid, chromic acid, and boric acid are harmful to the human body, and the oxidized metal oxide anion is highly toxic by itself, and a technique for removing it is required. In particular, arsenic acid is a toxic compound found in the water of land with veins such as silver ore, and depending on the location, it comes out as spring water from groundwater due to tunnel construction etc., so measures to remove arsenic (arsenic) Is required.
従来、砒素などの有毒物質を含有する水溶液にアルカリ剤を添加して有毒物質を水酸化物として沈殿・除去させる方法が報告されている。例えば、特許文献１には、砒酸イオンなどの有害な無機性イオンを含有する水に、少なくともセリウムの塩を主成分として含有する希土類元素の塩溶液及び水酸化マグネシュウムを添加し、ＰＨ８から１１にて沈澱を生成させ、固液分離することにより、砒素イオンを除去することが記載されている。しかし、このような方法では、ある程度有毒物質の濃度が高い場合は有効であるが、低濃度の場合は凝集物が生成し難いため有毒物質が沈殿せずに流出してしまうとともに排水がアルカリ性であり、もう一度中和する必要があった。 Conventionally, a method has been reported in which an alkaline agent is added to an aqueous solution containing a toxic substance such as arsenic to precipitate and remove the toxic substance as a hydroxide. For example, in Patent Document 1, a salt solution of a rare earth element containing at least a cerium salt as a main component and magnesium hydroxide is added to water containing harmful inorganic ions such as arsenate ions, and PH8 to 11 are added. It is described that arsenic ions are removed by forming a precipitate and performing solid-liquid separation. However, such a method is effective when the concentration of the toxic substance is high to some extent, but when the concentration is low, it is difficult to produce agglomerates. There was a need to neutralize again.
特許文献２には、有機高分子樹脂と、ゼオライト、複合金属酸化物などの無機イオン吸着体を含んでなるフィブリルが三次元網目構造を形成してなり、外表面に開口する連通孔を有する多孔性成形体により砒素を吸着して除去することが記載されている。 In Patent Document 2, a fibril including an organic polymer resin and a fibril containing an inorganic ion adsorbent such as zeolite or composite metal oxide forms a three-dimensional network structure, and has a pore having a communication hole that opens to the outer surface. It describes that arsenic is adsorbed and removed by an adhesive molded body.
特許文献３には、陰イオン吸着ゲルとして、架橋による三次元網目構造を有するとともに、網目を形成する主鎖が、末端に正の電荷を有するイオン性の官能基をもつ側鎖を派生した構造を有する有機高分子ゲルが記載されている。特許文献４には、Ｎ−カルボキシメチル化ポリアミン系高分子をビスコースに混合し、湿式紡糸して得られたＮ−カルボキシメチル化ポリアミン系高分子を含有したセルロース繊維を砒素などの重金属の吸着材として用いることが記載されている。特許文献５には、アミノ基、或いは環状イミノ基、及びカルボキシル基を分子内に有する水溶性の両性イオン性高分子が繊維母材に混合された繊維状吸着材を溶液中の極性化合物や金属の吸着除去に用いることが記載されている。 Patent Document 3 discloses a structure in which an anion-adsorbing gel has a three-dimensional network structure by crosslinking, and the main chain forming the network is derived from a side chain having an ionic functional group having a positive charge at the terminal. Organic polymer gels having the following are described: Patent Document 4 adsorbs heavy metal such as arsenic on cellulose fibers containing N-carboxymethylated polyamine polymer obtained by mixing N-carboxymethylated polyamine polymer with viscose and wet spinning. The use as a material is described. In Patent Document 5, a fibrous adsorbent in which a water-soluble zwitterionic polymer having an amino group or a cyclic imino group and a carboxyl group in the molecule is mixed with a fiber matrix is used as a polar compound or metal in a solution. It is described that it is used for adsorption removal.
一方、生活、畜産、水産、農業、流通などの分野で排出される排水は、大型処理施設で処理して放流される。しかしながら、排水中には除去し切れなかった希薄なリン酸根が含まれ、放流先で藻類の異常増殖を引き起こし、それに伴う環境悪化をもたらしている。特許文献６には、砒酸イオンなどの酸素酸イオンを吸着するカチオン性基を有し、３次元網目構造を有する高分子物からなるアニオン収着部と、このアニオン収着部を支持基材に固定支持させている水処理に使用されるリン酸イオンなどの酸素酸イオンを収着する酸素酸イオン収着材が記載されている。 On the other hand, wastewater discharged in fields such as livelihood, livestock, fisheries, agriculture and distribution is treated and discharged at a large treatment facility. However, dilute phosphate radicals that could not be removed are contained in the wastewater, causing abnormal growth of algae at the discharge destination and resulting environmental deterioration. Patent Document 6 discloses an anion sorption part made of a polymer having a cationic group that adsorbs an oxyacid ion such as an arsenate ion and a three-dimensional network structure, and the anion sorption part as a supporting substrate. An oxyacid ion sorbent is described that sorbs oxygenate ions such as phosphate ions used in fixed and supported water treatment.
しかし、特許文献２に記載の多孔性成形体は、平均粒径が１００〜２５００μｍの球状粒子として用いられており、取扱いが煩雑であるという問題がある。同様に、特許文献３に記載の有機高分子ゲルも、取扱いが煩雑であるという問題がある。また、特許文献４及び５に記載の金属の吸着材は、両性官能基が共存しているため、処理対象中の共存イオンの影響を受け易く、結果として砒素などの陰イオンに対する吸着性能が劣る恐れがある。 However, the porous molded body described in Patent Document 2 is used as spherical particles having an average particle diameter of 100 to 2500 μm, and there is a problem that handling is complicated. Similarly, the organic polymer gel described in Patent Document 3 also has a problem that it is complicated to handle. Moreover, since the amphoteric functional groups coexist in the metal adsorbents described in Patent Documents 4 and 5, they are easily affected by coexisting ions in the treatment target, and as a result, the adsorption performance for anions such as arsenic is inferior. There is a fear.
一方、特許文献６に記載の酸素酸イオン収着材は、カチオン性基を有する三次元網目構造を有する高分子物（具体的にはポリアリルアミンが網状化されたジエポキシ化合物）を介して繊維などの支持基材に固定した収着材であるため、カチオン化性基がリン酸を含む被処理物に接触しにくい構造であり、また、三次元網目構造を有する高分子の状態では、実上の強度が十分ではない可能性がある。 On the other hand, the oxyacid ion sorbent described in Patent Document 6 is a fiber or the like via a polymer having a three-dimensional network structure having a cationic group (specifically, a diepoxy compound in which polyallylamine is networked). Since the sorbent is fixed to the support substrate, the cationizable group has a structure that makes it difficult to contact the object to be treated containing phosphoric acid, and in the state of a polymer having a three-dimensional network structure, May not be strong enough.
本発明は、上記従来の問題を鑑み、取扱い性が良好であり、陰イオン特に砒素に対する吸着性が高い陰イオン吸着材、その製造方法及び水処理材を提供する。 In view of the above conventional problems, the present invention provides an anion adsorbent having good handleability and high adsorptivity to anions, particularly arsenic, a method for producing the anion adsorbent, and a water treatment material.
本発明は、第４級アンモニウムイオンを含む再生セルロース成形体で構成される陰イオン吸着材であって、セルロースと第４級アンモニウムイオンが化学結合していることを特徴とする陰イオン吸着材に関する。 The present invention relates to an anion adsorbent composed of a regenerated cellulose molded article containing quaternary ammonium ions, wherein the cellulose and quaternary ammonium ions are chemically bonded. .
本発明は、また、上記の陰イオン吸着材の製造方法であって、ビスコース成形体を第４級アンモニウム塩で処理して、セルロースに第４級アンモニウムイオンを化学結合する工程を含むことを特徴とする陰イオン吸着材の製造方法に関する。 The present invention is also a method for producing the anion adsorbent described above, comprising a step of treating a viscose molded body with a quaternary ammonium salt to chemically bond quaternary ammonium ions to cellulose. It is related with the manufacturing method of the characteristic anion adsorbent.
本発明は、また、上記の陰イオン吸着材を含む水処理材に関する。 The present invention also relates to a water treatment material including the anion adsorbent described above.
本発明は、再生セルロース成形体において、セルロースに第４級アンモニウムイオン（第４級アンモニウム基）を化学結合することにより、砒酸イオン、亜砒酸イオン、リン酸イオンなどの陰イオンに対して高い吸着性を有する陰イオン吸着材を提供することができる。また、本発明の陰イオン吸着材は、濡れ性が高いため、液体の被処理対象（水中）から陰イオンを吸着して除去・回収する際に取扱いが簡便である。また、再生セルロース成形体は、生分解性に優れるため、砒素などを吸着した後の陰イオン吸着材の処理も簡便であるとともに、有害金属や富栄養化のリンなどの回収も可能になる。また、本発明の水処理材は、上記の陰イオン吸着材を含むことにより、液体の被処理対象から砒素（砒酸イオン、亜砒酸イオン）、リン（リン酸イオン）などの陰イオンを効果的に除去・回収することができる。 In the regenerated cellulose molded article, the present invention has a high adsorptivity to anions such as arsenate ions, arsenite ions, phosphate ions by chemically bonding quaternary ammonium ions (quaternary ammonium groups) to cellulose. It is possible to provide an anion adsorbent having the following. Moreover, since the anion adsorbent of the present invention has high wettability, it is easy to handle when anion is adsorbed and removed / recovered from a liquid target (in water). In addition, since the regenerated cellulose molded article is excellent in biodegradability, it is easy to treat the anion adsorbent after adsorbing arsenic and the like, and it is possible to recover harmful metals and eutrophic phosphorus. In addition, the water treatment material of the present invention includes the anion adsorbent described above, thereby effectively removing anions such as arsenic (arsenate ions, arsenite ions) and phosphorus (phosphate ions) from the liquid treatment target. Can be removed and recovered.
本発明の製造方法によると、ビスコース成形体を第４級アンモニウム塩で処理することで、セルロースと第４級アンモニウム塩を反応させて、セルロースに第４級アンモニウムイオンを化学結合させ、砒酸イオン、亜砒酸イオン、リン酸イオンなどの陰イオンに対する吸着性が高い陰イオン吸着材を提供することができる。 According to the production method of the present invention, by treating a viscose molded body with a quaternary ammonium salt, cellulose and a quaternary ammonium salt are reacted to chemically bond a quaternary ammonium ion to cellulose, thereby forming an arsenate ion. An anion adsorbent having high adsorptivity to anions such as arsenite ions and phosphate ions can be provided.
本発明者は、再生セルロース成形体において、水に対して半透膜性を有するセルロースに第４級アンモニウムイオンを化学結合、具体的には共有結合（配位）させ、陰イオンとの反応部位（結合部位）となるカチオン部位を再生セルロース成形体に付与することで、水中の砒素イオンなどの陰イオンに対する吸着性が格段に向上することを見出し本発明に至った。本発明において、セルロースに第４級アンモニウムイオンが化学結合するということは、当然ながら、セルロースに第４級アンモニウムイオンが直接化学結合していることを意味する。すなわち、本発明において、第４級アンモニウムイオンは、再生セルロース成形体の表面にも内部にも結合している。本発明では、セルロース素材の中でもより非晶質を多く含む再生セルロースを基材として使用しているため、セルロースに第４級アンモニウムイオンを化学結合することにより、セルロース成形体の表面に加えてセルロース成形体の内部にも第４級アンモニウムイオンが結合することになり、セルロースの半透膜効果により処理液中のイオンが成形体内部まで入り、イオン交換能が向上し、水中の砒素を含むイオンなどの陰イオンに対する吸着性が格段に向上すると推測される。本発明の陰イオン吸着材は、再生セルロース成形体であるため、処理液との接触面積がより広く、水に対して半透膜性を有するセルロースにより処理液中のイオンが成形体内部まで入る。加えて、上述したとおり、陰イオンとの反応部位となる第４級アンモニウムイオンに由来するカチオン部位が成形体内部にも存在するため、陰イオンの吸着が効率的に行われ、有害陰イオンを高い効率で除去し、或いは、有用な陰イオンを高い効率で回収することができる。本発明の陰イオン吸着材は、飲料水、工業用水、工業用排水、汚染土壌の溶出液などの液体の被処理対象と接触し、これらの水中の砒素、リン酸イオンなどの陰イオンを吸着保持して、液体の被処理対象から砒素などの有害陰イオンを除去し、或いは、リン酸イオンなどの有用な陰イオンを回収することができる。また、再生セルロース成形体は生分解性であるため、排水中の富栄養化の元となるリン酸などを除去回収した後、それを農地に還元することができる。更に使用後は、再生セルロース成形体自体を酵素分解や灰化させて吸着固定化された金属種を回収することもできる。本発明の陰イオン吸着材は、水処理材、好ましくは砒素吸着用水処理材として用いることができる。 The present inventor made a reaction site with an anion by chemically bonding, specifically covalently bonding (coordinating) a quaternary ammonium ion to cellulose having a semipermeable membrane with respect to water in the regenerated cellulose molded body. The present inventors have found that the adsorption property to anions such as arsenic ions in water is remarkably improved by providing a regenerated cellulose molded article with a cation site to be a (binding site). In the present invention, the fact that quaternary ammonium ions are chemically bonded to cellulose naturally means that quaternary ammonium ions are directly chemically bonded to cellulose. That is, in the present invention, the quaternary ammonium ions are bonded to the surface and the inside of the regenerated cellulose molded body. In the present invention, regenerated cellulose containing a larger amount of amorphous material is used as a base material among cellulose materials. Therefore, cellulose is added to the surface of the cellulose molded body by chemically bonding quaternary ammonium ions to cellulose. Quaternary ammonium ions are also bonded inside the molded body, and ions in the treatment liquid enter the molded body due to the semipermeable membrane effect of cellulose, improving the ion exchange ability, and ions containing arsenic in water. It is presumed that the adsorptivity to anions, such as Since the anion adsorbent of the present invention is a regenerated cellulose molded article, the contact area with the treatment liquid is larger, and ions in the treatment liquid enter the molded article by cellulose having a semipermeable membrane with respect to water. . In addition, as described above, since a cation portion derived from a quaternary ammonium ion that becomes a reaction site with an anion is also present in the molded body, the anion is efficiently adsorbed and harmful anions are removed. It can be removed with high efficiency, or useful anions can be recovered with high efficiency. The anion adsorbent of the present invention is in contact with a liquid treatment target such as drinking water, industrial water, industrial wastewater, or an eluate of contaminated soil, and adsorbs anions such as arsenic and phosphate ions in the water. The harmful anions such as arsenic can be removed from the liquid treatment target, or useful anions such as phosphate ions can be recovered. In addition, since the regenerated cellulose molded body is biodegradable, after removing and recovering phosphoric acid and the like, which are the source of eutrophication in the wastewater, it can be returned to farmland. Furthermore, after use, the regenerated cellulose molded body itself can be enzymatically decomposed or ashed to recover the metal species adsorbed and immobilized. The anion adsorbent of the present invention can be used as a water treatment material, preferably a water treatment material for arsenic adsorption.
本発明において、成形体とは、繊維、スポンジなどの形態を示すものをいう。特に、繊維であることが好ましい。再生セルロース成形体が繊維状であると、濡れ性が高いため、液体の被処理対象から陰イオンを吸着して除去する際に取扱いが簡便である。また、繊維状であると、処理対象との接触面積も大きく、陰イオンの吸着効率が高くなる。 In the present invention, a molded product refers to a material that exhibits a form such as fiber or sponge. In particular, a fiber is preferable. When the regenerated cellulose molded body is fibrous, the wettability is high, and therefore handling is easy when adsorbing and removing anions from the liquid target. Moreover, when it is fibrous, the contact area with the process target is large, and the adsorption efficiency of anions is increased.
本発明において、再生セルロース成形体は、ビスコース法、銅アンモニア法、溶剤紡糸法などのいずれかの方法で、セルロースを凝固再生させて得ることができる。セルロース内部（成形体内部）に第４級アンモニウムイオンを化学結合させやすい観点から、セルロースは半透膜性が高い非晶質構造を採ることが好ましい。セルロースの非晶質性を示す指標として、一次膨潤度が挙げられる。一次膨潤度は、７０％以上であることが好ましく、８０〜１２０％であることがより好ましい。特に、ビスコース法又は銅アンモニア法によって得られるレーヨンは、一次膨潤度が上記範囲を満たし、好ましい。なお、一次膨潤度は、湿式紡糸法などの湿式で製造した再生セルロース成形体において、乾燥工程を経ない状態で測定した膨潤度をいい、乾燥工程を経たのちに測定される二次膨潤度とは区別される。この膨潤度は、ＪＩＳ Ｌ １０１５ ８．２６（水膨潤度）に準じて求められる。 In the present invention, the regenerated cellulose molded product can be obtained by coagulating and regenerating cellulose by any method such as a viscose method, a copper ammonia method, or a solvent spinning method. From the viewpoint of easy chemical bonding of quaternary ammonium ions to the inside of the cellulose (inside the molded body), the cellulose preferably has an amorphous structure with high semipermeable membrane properties. As an index showing the amorphous nature of cellulose, the primary swelling degree can be mentioned. The primary swelling degree is preferably 70% or more, and more preferably 80 to 120%. In particular, rayon obtained by the viscose method or the copper ammonia method is preferable because the primary swelling degree satisfies the above range. The primary swelling degree refers to the degree of swelling measured after the drying process in the regenerated cellulose molded body produced by a wet method such as a wet spinning method, and the secondary swelling degree measured after the drying process. Are distinguished. This swelling degree is determined according to JIS L 1015 8.26 (water swelling degree).
上記陰イオン吸着材（陰イオン吸着材を構成する再生セルロース成形体）は、特に限定されないが、窒素含有率が、０．００５〜０．１質量％であることが好ましく、０．０２〜０．０８質量％であることがより好ましい。上記陰イオン吸着材（陰イオン吸着材を構成する再生セルロース成形体）における窒素含有率は、第４級アンモニウムイオンを構成する窒素成分が陰イオン吸着材（陰イオン吸着材を構成する再生セルロース成形体）に占める割合を示すものである。窒素含有率が０．００５質量％未満であると、陰イオン吸着性が低くなりすぎる恐れがあり、０．１質量％を超えると、成形体の脆化の恐れがある。陰イオン吸着材を構成する再生セルロース成形体が繊維の場合、窒素含有率は、以下のようにして測定することができる。なお、上記陰イオン吸着材を構成する再生セルロース成形体がスポンジの場合、原綿サンプル０．５ｇの代わりに、スポンジサンプル０．５ｇを用いる以外は、繊維の場合と同様にして、窒素含有率を測定することができる。 The anion adsorbent (the regenerated cellulose molded body constituting the anion adsorbent) is not particularly limited, but the nitrogen content is preferably 0.005 to 0.1% by mass, and 0.02 to 0 More preferably, the content is 0.08% by mass. The nitrogen content in the anion adsorbent (regenerated cellulose molded body constituting the anion adsorbent) is such that the nitrogen component constituting the quaternary ammonium ion is an anion adsorbent (regenerated cellulose molding constituting the anion adsorbent). It shows the ratio to the body). If the nitrogen content is less than 0.005% by mass, the anion adsorptivity may be too low, and if it exceeds 0.1% by mass, the molded article may be brittle. When the regenerated cellulose molded article constituting the anion adsorbent is a fiber, the nitrogen content can be measured as follows. When the regenerated cellulose molded body constituting the anion adsorbent is a sponge, the nitrogen content is set in the same manner as in the case of the fiber except that 0.5 g of the sponge sample is used instead of 0.5 g of the raw cotton sample. Can be measured.
＜成形体（繊維の場合）の窒素含有率の測定＞
（１）原綿サンプル（採集試料）を０．５ｇ（絶乾量）精秤し、１００ｍＬのケルダールフラスコに入れ、硫酸８ｍL、過塩素酸１ｍＬを加え電熱器上で加熱し、綿を分解する。
（２）４Ｎ−水酸化ナトリウムで中和する。
（３）これを蒸留フラスコ５００ｍＬに入れ、純水を加え３５０ｍＬにし、酸化マグネシウム０．２５ｇを加え、アンモニア測定用蒸留装置（ＪＩＳ）により蒸留する。
（４）蒸留液を純水で２００ｍＬとしたものを検水とし、検水を適量（検水分取量）とり、ＥＤＴＡ１ｍＬ、ナトリウムフェノラート１０ｍＬ及び次亜塩素酸ナトリウム５ｍＬを加え撹拌し、波長６３０ｎｍの吸光度を吸光光度計（Ｕ−３９００型分光光度計；株式会社日立ハイテクノロジーズ製）を用いて測定する。
（４）別に同じ試薬のなど容量を用い、同様の方法により空試験を行い必要な補正をする。
（５）計算式は下記のとおりである。
窒素含有率（質量％）＝（Ａ−Ｂ）×０．７６２×１０-3×（２００／Ｖ）×（１００／Ｓ）
Ａ：検量線から求めたＮＨ4（ｍｇ）
Ｂ：空試験値（ｍｇ）
Ｖ：検水の分取量（ｍＬ）
Ｓ：採取試料の絶乾量（ｇ）
<Measurement of nitrogen content of molded body (in the case of fibers)>
(1) 0.5 g (absolute amount) of a raw cotton sample (collected sample) is precisely weighed, placed in a 100 mL Kjeldahl flask, added with 8 mL of sulfuric acid and 1 mL of perchloric acid, and heated on an electric heater to decompose the cotton.
(2) Neutralize with 4N sodium hydroxide.
(3) Put this into a 500 mL distillation flask, add pure water to 350 mL, add 0.25 g of magnesium oxide, and distill with a distillation apparatus for ammonia measurement (JIS).
(4) Distilled solution with 200 mL of pure water is used as test water, an appropriate amount of test water (sample water content) is taken, 1 mL of EDTA, 10 mL of sodium phenolate and 5 mL of sodium hypochlorite are added and stirred, and the wavelength is 630 nm. Is measured using an absorptiometer (U-3900 type spectrophotometer; manufactured by Hitachi High-Technologies Corporation).
(4) Separately, use the same volume of the same reagent, perform a blank test by the same method, and make necessary corrections.
(5) The calculation formula is as follows.
Nitrogen content (% by mass) = (A−B) × 0.762 × 10 −3 × (200 / V) × (100 / S)
A: NH 4 (mg) determined from a calibration curve
B: Blank test value (mg)
V: Amount of sample water (mL)
S: Absolutely dry amount of collected sample (g)
上記陰イオン吸着材（陰イオン吸着材を構成する再生セルロース成形体）は、特に限定されないが、第４級アンモニウムイオンを窒素換算して０．０１〜０．１質量％含むことが好ましく、０．０５〜０．０８質量％含むことがより好ましい。窒素換算した第４級アンモニウムイオンの含有率が０．０１質量％未満であると、陰イオン吸着性が低くなりすぎる恐れがあり、０．１質量％を超えると、成形体の脆化の恐れがある。 The anion adsorbent (the regenerated cellulose molded body constituting the anion adsorbent) is not particularly limited, but preferably contains 0.01 to 0.1% by mass of quaternary ammonium ions in terms of nitrogen. It is more preferable to contain 0.05-0.08 mass%. If the content of quaternary ammonium ions in terms of nitrogen is less than 0.01% by mass, the anion adsorptivity may be too low, and if it exceeds 0.1% by mass, the molded article may be embrittled. There is.
上記陰イオン吸着材（陰イオン吸着材を構成する再生セルロース成形体）は、特に限定されないが、カチオン化度が０．００３〜０．１ｍｍｏｌ/ｇであることが好ましく、より好ましくは０．０１〜０．０５ｍｍｏｌ/ｇである。カチオン化度が０．００３ｍｍｏｌ/ｇ未満であると、陰イオン吸着性が低くなりすぎる恐れがあり、０．１ｍｍｏｌ/ｇを超えると、成形体の脆化の恐れがある。本発明において、上記陰イオン吸着材を構成する再生セルロース成形体が繊維の場合、カチオン化度は、以下のように測定する。なお、上記陰イオン吸着材を構成する再生セルロース成形体がスポンジの場合、原綿サンプル１．０ｇの代わりに、スポンジサンプル１．０ｇを用いる以外は、繊維の場合と同様にして、カチオン化度を測定することができる。 The anion adsorbent (regenerated cellulose molded body constituting the anion adsorbent) is not particularly limited, but the cationization degree is preferably 0.003 to 0.1 mmol / g, more preferably 0.01. ~ 0.05 mmol / g. If the degree of cationization is less than 0.003 mmol / g, the anion adsorptivity may be too low, and if it exceeds 0.1 mmol / g, the molded article may be brittle. In the present invention, when the regenerated cellulose molded body constituting the anion adsorbent is a fiber, the degree of cationization is measured as follows. In the case where the regenerated cellulose molded body constituting the anion adsorbent is a sponge, the degree of cationization is set in the same manner as in the fiber except that 1.0 g of the sponge sample is used instead of 1.0 g of the raw cotton sample. Can be measured.
＜成形体（繊維の場合）のカチオン化度の測定＞
（１）原綿サンプルを１．０ｇ精秤し、２００ｍＬのメスフラスコに入れ、水４０ｍＬ及び緩衝液（酢酸ナトリウム２５ｇと酢酸２２ｍＬに純水を加え１００ｍＬとしたもの）８ｍＬを加える。
（２）フラスコを振り混ぜながら、Ｍ／２０（０．０５Ｍ）フェリシアン化カリウム５０ｍＬをピペットで加えた後、水を加えて２００ｍＬとし１時間放置する。
（３）これを乾燥したガラスフィルターを用いて吸引ろ過し最初のろ液約２０ｍＬを捨てて、次のろ液１００ｍＬを正確にはかり、１０％ヨウ化カリウム溶液１０ｍＬ、１０％硫酸亜鉛を１０ｍＬ加え、遊離したヨウ素を指示薬としてデンプン溶液を用いＮ／１０（０．１Ｎ）チオ硫酸ナトリウム（Ｎａ2Ｓ2Ｏ3）溶液で測定する。
（４）別に同じ試薬のなど容量を用い、同様の方法により空試験を行い必要な補正をする。
（５）計算式は下記のとおりである。下記計算式において、カチオン化活性剤有効成分が、カチオン化度（ｍｍｏｌ／ｇ）になる。
(1) 1.0 g of a raw cotton sample is precisely weighed and placed in a 200 mL volumetric flask, and 40 mL of water and 8 mL of a buffer solution (25 mL of sodium acetate and 22 mL of acetic acid to make 100 mL) are added.
(2) While shaking the flask, add 50 mL of M / 20 (0.05 M) potassium ferricyanide with a pipette, add water to make 200 mL, and let stand for 1 hour.
(3) Suction-filter this with a dry glass filter, discard about 20 mL of the first filtrate, accurately measure the next 100 mL of filtrate and add 10 mL of 10% potassium iodide solution and 10 mL of 10% zinc sulfate. Measured with a N / 10 (0.1 N) sodium thiosulfate (Na 2 S 2 O 3 ) solution using a starch solution with free iodine as an indicator.
(4) Separately, use the same volume of the same reagent, perform a blank test by the same method, and make necessary corrections.
(5) The calculation formula is as follows. In the following calculation formula, the cationization activator active ingredient is the degree of cationization (mmol / g).
上記第４級アンモニウムイオンは、特に限定されないが、例えば、第４級アンモニウム塩型クロルヒドリン誘導体、第４級アンモニウム塩型高分子などの第４級アンモニウム塩由来であることが好ましく、より好ましくは、第４級アンモニウム塩型クロルヒドリン誘導体由来である。上記第４級アンモニウム塩型クロルヒドリン誘導体としては、例えば、Ｎ−Ｎ’−ジ−（３−クロロ−２−ヒドロキシ−プロピル）−Ｎ−Ｎ’−テトラメチル−ｎ−ヘキサン−１，６−ジアンモニウムジクロライド（テトラメチルヘキサメチレンジアミン４級塩ともいう。）などが挙げられる。具体的には、カチオノンＫＣＮ（一方社油脂工業製商品名）などの市販のものを用いることができる。 The quaternary ammonium ion is not particularly limited, but is preferably derived from a quaternary ammonium salt such as a quaternary ammonium salt type chlorohydrin derivative or a quaternary ammonium salt type polymer, more preferably, It is derived from a quaternary ammonium salt type chlorohydrin derivative. Examples of the quaternary ammonium salt type chlorohydrin derivative include NN′-di- (3-chloro-2-hydroxy-propyl) -NN′-tetramethyl-n-hexane-1,6-di. And ammonium dichloride (also referred to as tetramethylhexamethylenediamine quaternary salt). Specifically, commercially available products such as Kathionone KCN (trade name, manufactured by Yushi Kogyo Co., Ltd.) can be used.
本発明の陰イオン吸着材は、ビスコース成形体を第４級アンモニウム塩で処理することで、セルロースと第４級アンモニウム塩を反応させて、セルロースに第４級アンモニウムイオンを化学結合させることで製造することができる。例えば、繊維状の再生セルロース成形体で構成された陰イオン吸着材（以下、陰イオン吸着性レーヨン繊維ともいう。）は、原料ビスコースを湿式紡糸して得られたビスコースレーヨン糸条を第４級アンモニウム塩で処理することで製造することができる。 The anion adsorbent of the present invention is obtained by treating a viscose molded body with a quaternary ammonium salt to react cellulose and a quaternary ammonium salt to chemically bond quaternary ammonium ions to the cellulose. Can be manufactured. For example, an anion adsorbent (hereinafter also referred to as anion-adsorbing rayon fiber) composed of a fibrous regenerated cellulose molded product is obtained by using a viscose rayon yarn obtained by wet spinning raw material viscose. It can be produced by treatment with a quaternary ammonium salt.
原料ビスコースとしては、セルロースを７〜１０質量％、水酸化ナトリウムを５〜８質量％、二硫化炭素を２〜３．５質量％含むビスコース原液を調製して用いるとよい。このとき、必要に応じて、エチレンジアミン四酢酸（ＥＤＴＡ）などの添加剤を使用することもできる。原料ビスコースの温度は１８〜２３℃に保持するのが好ましい。原料ビスコースをそのまま紡糸用ビスコース液として用いる。 As the raw material viscose, a viscose stock solution containing 7 to 10% by mass of cellulose, 5 to 8% by mass of sodium hydroxide, and 2 to 3.5% by mass of carbon disulfide may be prepared and used. At this time, additives such as ethylenediaminetetraacetic acid (EDTA) can be used as necessary. The temperature of the raw material viscose is preferably maintained at 18 to 23 ° C. The raw material viscose is used as it is as a viscose liquid for spinning.
紡糸浴（ミューラー浴）としては、硫酸を９５〜１３０ｇ／Ｌ、硫酸亜鉛を１０〜１７ｇ／Ｌ、硫酸ナトリウム（芒硝）を２９０〜３７０ｇ／Ｌ含む強酸性浴を用いることが好ましい。より好ましい硫酸濃度は、１００〜１２０ｇ／Ｌである。 As the spinning bath (Mueller bath), it is preferable to use a strongly acidic bath containing 95 to 130 g / L of sulfuric acid, 10 to 17 g / L of zinc sulfate, and 290 to 370 g / L of sodium sulfate (sodium salt). A more preferable sulfuric acid concentration is 100 to 120 g / L.
上記陰イオン吸着性レーヨン繊維は、例えば通常の円形ノズルを用いて製造することができる。紡糸ノズルとしては、目的とする生産量にもよるが、直径０．０５〜０．１２ｍｍのホールを１０００〜２００００個有する円形ノズルを用いることが好ましい。上記紡糸ノズルを用い、紡糸用ビスコース液を紡糸浴中に押し出して紡糸し、凝固再生させる。紡糸速度は３０〜８０ｍ／分の範囲が好ましい。また、延伸率は３９〜５５％が好ましい。ここで延伸率とは、延伸前のスライバー速度を１００としたとき、延伸後のスライバー速度をどこまで速くしたかを示すものである。倍率で示すと、延伸前が１、延伸後は１．３９〜１．５５倍となる。 The anion-adsorptive rayon fiber can be produced using, for example, a normal circular nozzle. As the spinning nozzle, it is preferable to use a circular nozzle having 1000 to 20000 holes having a diameter of 0.05 to 0.12 mm, depending on the target production amount. Using the spinning nozzle, the spinning viscose liquid is extruded into a spinning bath, spun, and coagulated and regenerated. The spinning speed is preferably in the range of 30 to 80 m / min. The stretching ratio is preferably 39 to 55%. Here, the stretching ratio indicates how much the sliver speed after stretching is increased when the sliver speed before stretching is 100. In terms of magnification, it is 1 before stretching and 1.39 to 1.55 times after stretching.
得られたレーヨン繊維糸条を所定の長さにカットし、精練処理を行う。精練工程は、通常の方法で、熱水処理、水硫化処理、漂白、酸洗い及び油剤付与の順で行うとよい。その後、必要に応じて圧縮ローラーや真空吸引などの方法で余分な油剤、水分を繊維から除去し、乾燥処理を施す。 The obtained rayon fiber yarn is cut into a predetermined length and scoured. The scouring step is preferably performed in the order of hot water treatment, hydrosulfurization treatment, bleaching, pickling, and oil application. Then, if necessary, excess oil agent and moisture are removed from the fiber by a method such as a compression roller or vacuum suction, and a drying treatment is performed.
また、再生セルロース成形体としてビスコーススポンジを用いることも可能である。ビスコーススポンジの製造方法の一例としては、汎用的なビスコース原液１００質量部に対し、補強繊維としてレーヨンのカット綿(例えば、ダイワボウレーヨン社製「ＳＢ」、繊度３．３ｄｔｅｘ、繊維長１０ｍｍ)を６．５質量部、結晶芒硝を６．５質量部入れ、混練機を使用して十分に混練を行い、得られた混合物を適当に孔の開いたステンレス製容器に入れ、９０℃以上の温水に入れ５時間放置する。このようにして得られたビスコーススポンジは、ビスコースに含まれる副生成物も含有しているため、脱硫や晒を行い、副生性物が除去される。 It is also possible to use a viscose sponge as a regenerated cellulose molded body. As an example of a method for producing a viscose sponge, rayon cut cotton (for example, “SB” manufactured by Daiwabo Rayon Co., Ltd., fineness 3.3 dtex, fiber length 10 mm) is used as a reinforcing fiber with respect to 100 parts by mass of a general-purpose viscose stock solution. 6.5 parts by mass and 6.5 parts by mass of crystal mirabilite, kneaded thoroughly using a kneader, and the resulting mixture was placed in a stainless steel container with a suitable hole and heated to 90 ° C or higher. Put in warm water and leave for 5 hours. Since the viscose sponge obtained in this way also contains by-products contained in the viscose, desulfurization and bleaching are performed to remove by-products.
次に、繊維状又はスポンジ状の再生セルロース成形体を第４級アンモニウム塩で処理し、セルロースに第４級アンモニウムイオンを化学結合、具体的には共有結合させる。繊維状の再生セルロース成形体の場合、第４級アンモニウム塩による処理は、精練工程中で行ってもよく、精練工程後に後加工として行ってもよい。例えば、精練処理時に、レーヨン繊維を連続した糸状のまま第４級アンモニウム塩の浴中を通過させて第４級アンモニウム塩を付着させてもよいし、精練工程でレーヨン繊維に第４級アンモニウム塩の水溶液をシャワーして付着させてもよい。或いは、乾燥後のレーヨン繊維（原綿）を、第４級アンモニウム塩の浴中に浸漬し、その後絞ることにより第４級アンモニウム塩を付着させてもよく、レーヨン繊維（原綿）を不織布などに加工した状態で第４級アンモニウム塩の浴中を通過させて第４級アンモニウム塩を付着させてもよい。スポンジ状の再生セルロース成形体の場合、第４級アンモニウム塩の水溶液に含浸させてセルロースに第４級アンモニウムイオンを化学結合させる。 Next, the fibrous or sponge-like regenerated cellulose molded body is treated with a quaternary ammonium salt, and quaternary ammonium ions are chemically bonded to the cellulose, specifically, covalently bonded. In the case of a fibrous regenerated cellulose molded body, the treatment with the quaternary ammonium salt may be performed during the scouring step, or may be performed as a post-processing after the scouring step. For example, at the time of scouring treatment, the rayon fiber may be passed through a quaternary ammonium salt bath in the form of a continuous thread to adhere the quaternary ammonium salt, or the quaternary ammonium salt may be attached to the rayon fiber in the scouring step. The aqueous solution may be attached by showering. Alternatively, the dried rayon fiber (raw cotton) may be immersed in a quaternary ammonium salt bath and then squeezed to attach the quaternary ammonium salt, and the rayon fiber (raw cotton) is processed into a nonwoven fabric or the like. In this state, the quaternary ammonium salt may be attached by passing through a quaternary ammonium salt bath. In the case of a sponge-like regenerated cellulose molded article, an aqueous solution of a quaternary ammonium salt is impregnated to chemically bond quaternary ammonium ions to cellulose.
第４級アンモニウム塩による処理は、アルカリ雰囲気中、第４級アンモニウム塩の水溶液を用いて行うことができる。第４級アンモニウム塩としては、例えば、第４級アンモニウム塩型クロルヒドリン誘導体、第４級アンモニウム塩型高分子などを用いることが好ましく、より好ましくは、第４級アンモニウム塩型クロルヒドリン誘導体を用いる。上記第４級アンモニウム塩型クロルヒドリン誘導体としては、例えば、Ｎ−Ｎ’−ジ−（３−クロロ−２−ヒドロキシ−プロピル）−Ｎ−Ｎ’−テトラメチル−ｎ−ヘキサン−１，６−ジアンモニウムジクロライド（テトラメチルヘキサメチレンジアミン４級塩ともいう。）などが挙げられる。上記第４級アンモニウム塩型クロルヒドリン誘導体としては、具体的には、カチオノンＫＣＮ（一方社製商品名）などの市販のものを用いることができる。 The treatment with a quaternary ammonium salt can be performed using an aqueous solution of a quaternary ammonium salt in an alkaline atmosphere. As the quaternary ammonium salt, for example, a quaternary ammonium salt type chlorohydrin derivative, a quaternary ammonium salt type polymer or the like is preferably used, and more preferably a quaternary ammonium salt type chlorohydrin derivative is used. Examples of the quaternary ammonium salt type chlorohydrin derivative include NN′-di- (3-chloro-2-hydroxy-propyl) -NN′-tetramethyl-n-hexane-1,6-di. And ammonium dichloride (also referred to as tetramethylhexamethylenediamine quaternary salt). As the quaternary ammonium salt type chlorohydrin derivative, specifically, commercially available products such as cationone KCN (trade name, manufactured by one company) can be used.
第４級アンモニウム塩は、カチオン化度が１．０〜８．０ｍｍｏｌ／ｇであることが好ましく、より好ましくは、２．５〜６．０ｍｍｏｌ／ｇである。カチオン化度が上記範囲であると、再生セルロース成形体のセルロースに化学結合した後、陰イオンに対する吸着効果を発揮できる。本発明において、第４級アンモニウムのカチオン化度は、フェリシアンカリ法によって評価測定する。原理は、第４級アンモニウム塩水溶液をＫ3｛Ｆｅ（ＣＮ）6｝と反応させて黄色反応物（沈澱）を生成させ、黄色沈澱を濾別し過剰のフェリシアンカリをＫＩにより還元して遊離したヨードをチオ硫酸で逆滴定してカチオン量に換算する。 The quaternary ammonium salt preferably has a cationization degree of 1.0 to 8.0 mmol / g, more preferably 2.5 to 6.0 mmol / g. When the degree of cationization is in the above range, an anion adsorption effect can be exhibited after chemically bonding to cellulose of the regenerated cellulose molded article. In the present invention, the degree of cationization of quaternary ammonium is evaluated and measured by the Felician Cali method. The principle is that a quaternary ammonium salt aqueous solution is reacted with K 3 {Fe (CN) 6 } to form a yellow reactant (precipitate), the yellow precipitate is filtered off, and excess ferricyankali is reduced with KI. The liberated iodo is titrated back with thiosulfuric acid and converted to the amount of cation.
上記第４級アンモニウム塩の水溶液は、ｐＨが９〜１４であることが好ましく、より好ましくはｐＨが１１〜１４である。上記第４級アンモニウム塩の水溶液のｐＨは、水酸化アルカリ化合物、例えば水酸化ナトリウムを添加することで調整できる。上記第４級アンモニウム塩の水溶液中の水酸化ナトリウムなどの水酸化アルカリ化合物の濃度は０．１〜４０ｇ／Ｌであることが望ましい。第４級アンモニウム塩の水溶液中の水酸化アルカリ化合物の濃度が低すぎると、セルロースと第４級アンモニウム塩の反応が進まない恐れがあり、水酸化アルカリ化合物の濃度が高すぎると、セルロースが膨潤し、成形体が溶着した状態になる恐れがある。第４級アンモニウム塩の水溶液は、特に限定されないが、第４級アンモニウム塩の濃度が０．１〜５０ｇ/Ｌであることが好ましく、より好ましくは、１．０〜４０ｇ/Ｌである。処理温度については、セルロースに第４級アンモニウムイオンが化学結合できればよく、特に限定されないが、１０〜１００℃程度の温度範囲で行うことが好ましい。なお、室温（２０±５℃）において、浸漬などにより再生セルロース成形体を第４級アンモニウム塩の水溶液と接触させた後、７０〜１００℃程度の温度範囲で熱処理することで、セルロースと第４級アンモニウム塩を反応させて、セルロースに第４級アンモニウムイオンを化学結合してもよい。 The aqueous solution of the quaternary ammonium salt preferably has a pH of 9 to 14, more preferably 11 to 14. The pH of the aqueous solution of the quaternary ammonium salt can be adjusted by adding an alkali hydroxide compound such as sodium hydroxide. The concentration of the alkali hydroxide compound such as sodium hydroxide in the aqueous solution of the quaternary ammonium salt is preferably 0.1 to 40 g / L. If the concentration of the alkali hydroxide compound in the aqueous solution of the quaternary ammonium salt is too low, the reaction between the cellulose and the quaternary ammonium salt may not proceed. If the concentration of the alkali hydroxide compound is too high, the cellulose swells. However, the molded body may be in a welded state. The aqueous solution of the quaternary ammonium salt is not particularly limited, but the concentration of the quaternary ammonium salt is preferably 0.1 to 50 g / L, more preferably 1.0 to 40 g / L. The treatment temperature is not particularly limited as long as quaternary ammonium ions can be chemically bonded to cellulose, but it is preferably performed in a temperature range of about 10 to 100 ° C. In addition, after making a regenerated cellulose molded object contact with the aqueous solution of a quaternary ammonium salt by immersion etc. at room temperature (20 +/- 5 degreeC), it heat-processes in the temperature range of about 70-100 degreeC, and a cellulose and 4th. A quaternary ammonium ion may be chemically bonded to cellulose by reacting a quaternary ammonium salt.
上記陰イオン吸着性レーヨン繊維は、繊度が０．３〜１７ｄｔｅｘ（デシテックス）であることが好ましい。より好ましくは１．１〜８ｄｔｅｘであり、さらに好ましくは１．７〜６ｄｔｅｘである。さらにより好ましくは２．２〜６ｄｔｅｘである。繊度が０．３ｄｔｅｘ未満であると、延伸時に単繊維切れが発生しやすい傾向にある。繊度が１７ｄｔｅｘを超えると、繊維の再生状態が不良になりやすく、繊維自体の強伸度に影響があり、加工性が悪くなる場合がある。 The anion-adsorbing rayon fiber preferably has a fineness of 0.3 to 17 dtex (decitex). More preferably, it is 1.1-8 dtex, More preferably, it is 1.7-6 dtex. Even more preferably, it is 2.2 to 6 dtex. When the fineness is less than 0.3 dtex, the single fiber tends to be broken during stretching. If the fineness exceeds 17 dtex, the regenerated state of the fiber tends to be poor, the strength and elongation of the fiber itself are affected, and workability may be deteriorated.
上記陰イオン吸着性レーヨン繊維は、長繊維状及び短繊維状のいずれの形態でもよい。上記長繊維状としては、例えば、トウ、フィラメント、不織布などが挙げられ、上記短繊維状としては、例えば、湿式抄紙用原綿、エアレイド不織布用原綿、カード用原綿などが挙げられる。 The anion-adsorbing rayon fiber may be in the form of either a long fiber or a short fiber. Examples of the long fiber shape include tow, filament, and non-woven fabric, and examples of the short fiber shape include wet papermaking raw cotton, airlaid non-woven raw cotton, and card raw cotton.
上記陰イオン吸着性レーヨン繊維は、繊維構造物を形成して用いることができる。上記陰イオン吸着性レーヨン繊維を含む繊維構造物であると、砒素を含む液体の被処理対象の条件により、繊度や繊維空隙を容易に調整することができ、液体の被処理対象から砒素を効果的に除去することができ、好ましい。上記繊維構造物は、特に限定されないが、例えば、トウ、フィラメント、紡績糸、詰め綿、紙、不織布、織物、編物などが挙げられる。上記陰イオン吸着性レーヨン繊維は、単独又はその他のレーヨン繊維、コットン、麻、ウール、アクリル、ポリエステル、ポリアミド、ポリオレフィン、ポリウレタンなどの他の繊維と混綿して用いることができる。他の繊維と混綿して繊維構造物を形成する場合、特に限定されないが、上記陰イオン吸着性レーヨン繊維は、繊維構造物１００質量％に対して、５０質量％以上含まれることが好ましく、より好ましくは７０質量％以上含まれる。 The anion-adsorptive rayon fiber can be used after forming a fiber structure. The fiber structure containing the anion-adsorptive rayon fiber can easily adjust the fineness and the fiber gap depending on the condition of the liquid treatment target containing arsenic, and the arsenic is effective from the liquid treatment target. This is preferable. Although the said fiber structure is not specifically limited, For example, a tow | toe, a filament, spun yarn, stuffed cotton, paper, a nonwoven fabric, a textile fabric, a knitted fabric etc. are mentioned. The anion-adsorptive rayon fibers can be used alone or mixed with other fibers such as other rayon fibers, cotton, hemp, wool, acrylic, polyester, polyamide, polyolefin, polyurethane and the like. When forming a fiber structure by blending with other fibers, the anion-adsorbing rayon fiber is preferably contained in an amount of 50% by mass or more with respect to 100% by mass of the fiber structure. Preferably 70 mass% or more is contained.
上記陰イオン吸着材を構成する再生セルロース成形体が繊維の場合は、繊維及びそれを含む繊維構造物は、液体の被処理対象と接触させて水中の陰イオンを吸着除去する陰イオン吸着材及び水処理材として使用するのに適している。特に、上記陰イオン吸着性レーヨン繊維及び繊維構造物は、液体の被処理対象と接触させて水中の砒素を吸着除去する砒素吸着材及び砒素吸着性水処理材として使用するのに適している。液体の被処理対象としては、特に限定されないが、飲料水、河川水、海水、地下水、下水、工業用水、工業用排水、汚染土壌の溶出液などが挙げられる。吸着除去する陰イオンとしては、例えば、リン（リン酸イオン）、砒素（砒酸イオン、亜砒酸イオン）などが挙げられる。本発明の陰イオン吸着材は、低濃度の陰イオンでも吸着可能であり、吸着除去効率が高い。例えば、陰イオンの濃度が０．０１〜１００ｐｐｍの広範囲について処理可能である。 In the case where the regenerated cellulose molded body constituting the anion adsorbent is a fiber, the fiber and the fiber structure including the same are brought into contact with a liquid target to be treated, and an anion adsorbent that adsorbs and removes an anion in water. Suitable for use as water treatment material. In particular, the anion adsorptive rayon fiber and the fiber structure are suitable for use as an arsenic adsorbent and an arsenic adsorbent water treatment material that adsorb and remove arsenic in water by making contact with a liquid target. Although it does not specifically limit as a liquid to-be-processed object, Drinking water, river water, seawater, groundwater, sewage, industrial water, industrial wastewater, the eluate of contaminated soil, etc. are mentioned. Examples of the anion to be removed by adsorption include phosphorus (phosphate ion), arsenic (arsenate ion, arsenite ion) and the like. The anion adsorbent of the present invention can adsorb even a low concentration of anions and has high adsorption removal efficiency. For example, a wide range of anion concentration of 0.01 to 100 ppm can be processed.
上記陰イオン吸着性レーヨン繊維を開繊しカラムに詰め、或いは再生セルローススポンジで構成された陰イオン吸着材をカラムに詰め、詰め綿又は詰め材料として使用して飲料水などの液体処理対象の濾過にも使用可能であるし、原綿に対して各種加工を行い、使用環境に合わせた仕様にすることもできる。例えば、紡毛用紡績を行い太い紡績糸に加工後、糸巻き用カートリッジフィルターに加工して、水処理材として用いてもよい。ニードルパンチ不織布のような不織布状態に加工した濾過布でもよく、水流交絡不織布としてワイパーやウェットシートに使用してもよい。湿紙として生産した物を抄紙し、コーヒーのドリッパーのような形態で濾過材として使用することも可能である。 The anion-adsorptive rayon fiber is opened and packed in a column, or an anion adsorbent composed of regenerated cellulose sponge is packed in a column, and is used as padding cotton or a filling material to filter liquid treatment targets such as drinking water Can also be used, and various processing can be applied to the raw cotton to make it suitable for the usage environment. For example, after spinning into a spun yarn and processing it into a thick spun yarn, it may be processed into a thread-wound cartridge filter and used as a water treatment material. A filter cloth processed into a nonwoven fabric state such as a needle punched nonwoven fabric may be used, or a hydroentangled nonwoven fabric may be used for a wiper or a wet sheet. A product produced as a wet paper can be made and used as a filter medium in the form of a coffee dripper.
以下、実施例により本発明をさらに具体的に説明する。本発明は、下記の実施例に限定されるものではない。なお、下記の実施例において添加量を単に％と表記した場合は、質量％を意味する。 Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to the following examples. In the following examples, when the addition amount is simply expressed as%, it means mass%.
（実施例１）
［紡糸用ビスコース液の調製］
紡糸用ビスコース液として、セルロース８．５質量％、水酸化ナトリウム５．７質量％、二硫化炭素２．８質量％を含むビスコース原液を用いた。紡糸用ビスコース液の温度は２０℃に保った。
［紡糸条件］
上記紡糸用ビスコース液を、２浴緊張紡糸法により、紡糸速度５０ｍ／分、延伸率４５％で紡糸して、繊度３．３ｄｔｅｘのレギュラーレーヨン繊維の糸条を得た。第１浴（紡糸浴）としては、硫酸１００ｇ／Ｌ、硫酸亜鉛１５ｇ／Ｌ、硫酸ナトリウム３５０ｇ／Ｌを含むミューラー浴（５０℃）を用いた。また、ビスコースを吐出する紡糸口金には、孔径０．０９ｍｍのホールを４０００個有する円形ノズルを用いた。
［精練条件］
上記で得られたレギュラーレーヨン繊維の糸条を、繊維長５１ｍｍにカットし、精練処理を行った。精練工程では、熱水処理後に水洗を行い、水硫化ソーダをシャワーして脱硫を実施した。次いで、十分水洗し、油剤を付与した後、圧縮ローラーで余分な水分と油剤を繊維から落とし、乾燥処理（６０℃、７時間）を施した。
［処理条件］
第４級アンモニウム塩（「カチオノンＫＣＮ」、一方社油脂工業社製）を４０ｇ／Ｌ、水酸化ナトリウムを１０ｇ／Ｌ含む第４級アンモニウム塩の水溶液を調製した。精練処理後のレギュラーレーヨン繊維を、第４級アンモニウム塩の水溶液の浴中に、浴比が１：２０となるように浸漬し、８０℃で４０分間処理した。その後、イオン交換水で水洗を４回行い、次いで硫酸（ｐＨ３．０）で２回洗浄し、さらにイオン交換水で水洗を２回行い、水洗液のｐＨ５．９となったところで、２槽式洗濯機による脱水を１分間行い、その後乾燥処理（６０℃、７時間）を施し繊維Ａを得た。なお、上記第４級アンモニウム塩は、上述したように評価測定したカチオン化度が、２．２７ｍｍｏｌ／ｇであった。
Example 1
[Preparation of viscose liquid for spinning]
As the spinning viscose solution, a viscose stock solution containing 8.5% by mass of cellulose, 5.7% by mass of sodium hydroxide, and 2.8% by mass of carbon disulfide was used. The temperature of the spinning viscose liquid was kept at 20 ° C.
[Spinning conditions]
The spinning viscose liquid was spun at a spinning speed of 50 m / min and a draw ratio of 45% by a two-bath tension spinning method to obtain a regular rayon fiber yarn having a fineness of 3.3 dtex. As the first bath (spinning bath), a Mueller bath (50 ° C.) containing 100 g / L of sulfuric acid, 15 g / L of zinc sulfate, and 350 g / L of sodium sulfate was used. In addition, a circular nozzle having 4000 holes having a hole diameter of 0.09 mm was used as a spinneret for discharging viscose.
[Scouring conditions]
The regular rayon fiber yarn obtained above was cut into a fiber length of 51 mm and subjected to a scouring treatment. In the scouring process, water washing was performed after the hot water treatment, and desulfurization was performed by showering sodium hydrosulfide. Then, after sufficiently washing with water and applying an oil agent, excess moisture and the oil agent were dropped from the fiber with a compression roller, and a drying treatment (60 ° C., 7 hours) was performed.
[Processing conditions]
An aqueous solution of a quaternary ammonium salt containing 40 g / L of a quaternary ammonium salt (“Cathionone KCN”, manufactured by Yushi Kogyo Co., Ltd.) and 10 g / L of sodium hydroxide was prepared. The regular rayon fiber after the scouring treatment was immersed in a bath of an aqueous solution of a quaternary ammonium salt so that the bath ratio was 1:20 and treated at 80 ° C. for 40 minutes. Thereafter, washing with ion-exchanged water 4 times, followed by washing with sulfuric acid (pH 3.0) twice, followed by washing with ion-exchanged water twice, and when the pH of the washing solution reached 5.9, a two-tank type Dehydration with a washing machine was performed for 1 minute, and then a drying process (60 ° C., 7 hours) was performed to obtain fiber A. The quaternary ammonium salt had a degree of cationization evaluated and measured as described above of 2.27 mmol / g.
（比較例１）
［紡糸用ビスコース液の調製］
酸化ジルコニウムの微粒子（平均粒子径１．５μｍ、株式会社三井金属製）１００質量部と、分散剤（「デモールＴ」、花王ケミカル製）５質量部の混合物に、純水を添加混合して酸化ジルコニウムの濃度が１５質量％の分散液を調製した。酸化ジルコニウムの添加量がセルロースに対して１１質量％となるように、得られた酸化ジルコニウムの分散液を原料ビスコースへ添加し、混合機にて攪拌混合を行い、紡糸用ビスコース液を調製した。温度は２０℃に保った。原料ビスコースとしては、セルロース８．５質量％、水酸化ナトリウム５．７質量％、二硫化炭素２．８質量％を含むビスコース原液を用いた。
［紡糸条件］
得られた紡糸用ビスコース液を、２浴緊張紡糸法により、紡糸速度５０ｍ／分、延伸率４５％で紡糸して、繊度１．７ｄｔｅｘの酸化ジルコニウムを含有するレーヨン繊維の糸条を得た。第一浴（紡糸浴）としては、硫酸１００ｇ／Ｌ、硫酸亜鉛１５ｇ／Ｌ、硫酸ナトリウム３５０ｇ／Ｌ含むミューラー浴（５０℃）を用いた。また、ビスコースを吐出する紡糸口金には、孔径０．０７ｍｍのホールを４０００個有する円形ノズルを用いた。紡糸中、単糸切れなどの不都合は生じず、混合ビスコースの紡糸性は良好であった。
［精練条件］
上記で得られた酸化ジルコニウム含有レーヨン繊維の糸条を、繊維長５１ｍｍにカットし、精練処理を行った。精練工程では、熱水処理後に水洗を行い、水硫化ソーダをシャワーして脱硫を実施した。次いで、十分水洗し、油剤を付与した後、圧縮ローラーで余分な水分と油剤を繊維から落とし、乾燥処理（６０℃、７時間）を施し繊維Ｂを得た。
(Comparative Example 1)
[Preparation of viscose liquid for spinning]
Oxidized by adding pure water to a mixture of 100 parts by mass of zirconium oxide fine particles (average particle size 1.5 μm, Mitsui Kinzoku Co., Ltd.) and 5 parts by mass of a dispersant (“Demol T”, manufactured by Kao Chemical Co., Ltd.) A dispersion having a zirconium concentration of 15% by mass was prepared. The resulting zirconium oxide dispersion is added to the raw material viscose so that the added amount of zirconium oxide is 11% by mass with respect to cellulose, and the mixture is stirred and mixed to prepare a spinning viscose liquid. did. The temperature was kept at 20 ° C. As the raw material viscose, a viscose stock solution containing 8.5% by mass of cellulose, 5.7% by mass of sodium hydroxide, and 2.8% by mass of carbon disulfide was used.
[Spinning conditions]
The obtained viscose liquid for spinning was spun at a spinning speed of 50 m / min and a draw rate of 45% by a two-bath tension spinning method to obtain a rayon fiber yarn containing zirconium oxide having a fineness of 1.7 dtex. . As the first bath (spinning bath), a Mueller bath (50 ° C.) containing 100 g / L of sulfuric acid, 15 g / L of zinc sulfate and 350 g / L of sodium sulfate was used. In addition, a circular nozzle having 4000 holes having a hole diameter of 0.07 mm was used as a spinneret for discharging viscose. During spinning, inconveniences such as single yarn breakage did not occur, and the spinnability of the mixed viscose was good.
[Scouring conditions]
The yarn of the rayon fiber containing zirconium oxide obtained above was cut into a fiber length of 51 mm and scoured. In the scouring process, water washing was performed after the hot water treatment, and desulfurization was performed by showering sodium hydrosulfide. Then, after sufficiently washing with water and applying an oil agent, excess water and an oil agent were dropped from the fiber with a compression roller, followed by drying treatment (60 ° C., 7 hours) to obtain a fiber B.
（比較例２）
［紡糸用ビスコース液の調製］
二酸化チタン（平均粒子径０．５μｍ）１００質量部と、分散剤ヘキサメタリン酸ナトリウム１質量部の混合物に、純水を添加混合して二酸化チタンの濃度が１５質量％の分散液を調製した。二酸化チタンの添加量がセルロースに対して１０質量％となるように、得られた二酸化チタンの分散液を原料ビスコースへ添加し、混合機にて攪拌混合を行い、紡糸用ビスコース液を調製した。温度は２０℃に保った。原料ビスコースとしては、セルロース８．５質量％、水酸化ナトリウム５．７質量％、二硫化炭素２．８質量％を含むビスコース原液を用いた。
［紡糸条件］
得られた紡糸用ビスコース液を、２浴緊張紡糸法により、紡糸速度５０ｍ／分、延伸率４５％で紡糸して、繊度１．７ｄｔｅｘの二酸化チタンを含有するレーヨン繊維の糸条を得た。第一浴（紡糸浴）としては、硫酸１００ｇ／Ｌ、硫酸亜鉛１５ｇ／Ｌ、硫酸ナトリウム３５０ｇ／Ｌ含むミューラー浴（５０℃）を用いた。また、ビスコースを吐出する紡糸口金には、孔径０．０７ｍｍのホールを４０００個有する円形ノズルを用いた。紡糸中、単糸切れなどの不都合は生じず、混合ビスコースの紡糸性は良好であった。
［精練条件］
上記で得られた二酸化チタン含有レーヨン繊維の糸条を、繊維長５１ｍｍにカットし、精練処理を行った。精練工程では、熱水処理後に水洗を行い、水硫化ソーダをシャワーして脱硫を実施した。次いで、十分水洗し、油剤を付与した後、圧縮ローラーで余分な水分と油剤を繊維から落とし、乾燥処理（６０℃、７時間）を施し繊維Ｃを得た。
(Comparative Example 2)
[Preparation of viscose liquid for spinning]
Pure water was added to and mixed with a mixture of 100 parts by mass of titanium dioxide (average particle diameter 0.5 μm) and 1 part by mass of sodium hexametaphosphate to prepare a dispersion having a titanium dioxide concentration of 15% by mass. The resulting titanium dioxide dispersion is added to the raw material viscose so that the amount of titanium dioxide added is 10% by mass with respect to the cellulose, and the mixture is stirred and mixed to prepare a spinning viscose liquid. did. The temperature was kept at 20 ° C. As the raw material viscose, a viscose stock solution containing 8.5% by mass of cellulose, 5.7% by mass of sodium hydroxide, and 2.8% by mass of carbon disulfide was used.
[Spinning conditions]
The obtained viscose solution for spinning was spun at a spinning speed of 50 m / min and a draw rate of 45% by a two-bath tension spinning method to obtain a rayon fiber yarn containing titanium dioxide having a fineness of 1.7 dtex. . As the first bath (spinning bath), a Mueller bath (50 ° C.) containing 100 g / L of sulfuric acid, 15 g / L of zinc sulfate and 350 g / L of sodium sulfate was used. In addition, a circular nozzle having 4000 holes having a hole diameter of 0.07 mm was used as a spinneret for discharging viscose. During spinning, inconveniences such as single yarn breakage did not occur, and the spinnability of the mixed viscose was good.
[Scouring conditions]
The yarn of the titanium dioxide-containing rayon fiber obtained above was cut into a fiber length of 51 mm and subjected to a scouring treatment. In the scouring process, water washing was performed after the hot water treatment, and desulfurization was performed by showering sodium hydrosulfide. Next, after sufficiently washing with water and applying an oil agent, excess moisture and the oil agent were dropped from the fiber with a compression roller, and drying treatment (60 ° C., 7 hours) was performed to obtain a fiber C.
（比較例３）
［紡糸用ビスコース液の調製］
針葉樹活性炭（平均粒子径１．２μｍ）１００質量部と、分散剤（「デモールＴ」、花王ケミカル製）５質量部の混合物に、純水を添加混合して活性炭の濃度が１５質量の％分散液を調製した。活性炭の添加量をセルロースに対して１７．６質量％となるように、得られた活性炭の分散液を原料ビスコースへ添加し、混合機にて攪拌混合を行い、紡糸用ビスコース液を調製した。温度は２０℃に保った。原料ビスコースとしては、セルロース８．５質量％、水酸化ナトリウム５．７質量％、二硫化炭素２．８質量％を含むビスコース原液を用いた。
［紡糸条件］
得られた紡糸用ビスコース液を、２浴緊張紡糸法により、紡糸速度５０ｍ／分、延伸率４５％で紡糸して、繊度３．３ｄｔｅｘの活性炭を含有するレーヨン繊維の糸条を得た。第一浴（紡糸浴）としては、硫酸１００ｇ／Ｌ、硫酸亜鉛１５ｇ／Ｌ、硫酸ナトリウム３５０ｇ／Ｌ含むミューラー浴（５０℃）を用いた。また、ビスコースを吐出する紡糸口金には、孔径０．０９ｍｍのホールを４０００個有する円形ノズルを用いた。紡糸中、単糸切れなどの不都合は生じず、混合ビスコースの紡糸性は良好であった。
［精練条件］
上記で得られた活性炭含有レーヨン繊維の糸条を、繊維長５１ｍｍにカットし、精練処理を行った。精練工程では、熱水処理後に水洗を行い、水硫化ソーダをシャワーして脱硫を実施した。次いで、十分水洗し、油剤を付与した後圧縮ローラーで余分な水分と油剤を繊維から落とし、乾燥処理（６０℃、７時間）を施し繊維Ｄを得た。
(Comparative Example 3)
[Preparation of viscose liquid for spinning]
Pure water is added and mixed in a mixture of 100 parts by weight of softwood activated carbon (average particle size 1.2 μm) and 5 parts by weight of a dispersant (“Demol T”, manufactured by Kao Chemical Co., Ltd.). A liquid was prepared. The obtained activated carbon dispersion is added to the raw material viscose so that the amount of activated carbon added is 17.6% by mass with respect to cellulose, and the mixture is stirred and mixed to prepare a spinning viscose liquid. did. The temperature was kept at 20 ° C. As the raw material viscose, a viscose stock solution containing 8.5% by mass of cellulose, 5.7% by mass of sodium hydroxide, and 2.8% by mass of carbon disulfide was used.
[Spinning conditions]
The obtained spinning viscose liquid was spun at a spinning speed of 50 m / min and a draw rate of 45% by a two-bath tension spinning method to obtain a rayon fiber yarn containing activated carbon having a fineness of 3.3 dtex. As the first bath (spinning bath), a Mueller bath (50 ° C.) containing 100 g / L of sulfuric acid, 15 g / L of zinc sulfate and 350 g / L of sodium sulfate was used. In addition, a circular nozzle having 4000 holes having a hole diameter of 0.09 mm was used as a spinneret for discharging viscose. During spinning, inconveniences such as single yarn breakage did not occur, and the spinnability of the mixed viscose was good.
[Scouring conditions]
The yarn of the activated carbon-containing rayon fiber obtained above was cut into a fiber length of 51 mm and subjected to a scouring treatment. In the scouring process, water washing was performed after the hot water treatment, and desulfurization was performed by showering sodium hydrosulfide. Then, after sufficiently washing with water and applying the oil agent, excess moisture and oil agent were dropped from the fiber with a compression roller, and drying treatment (60 ° C., 7 hours) was performed to obtain fiber D.
（比較例４）
紡糸用ビスコース液として、セルロース８．５質量％、水酸化ナトリウム５．７質量％、二硫化炭素２．８質量％を含むビスコース原液をそのまま使用し、実施例１と同様の紡糸条件及び精練条件で紡糸、精練し、セルロース１００％のレギュラーレーヨン繊維（繊維Ｅ）を得た。
(Comparative Example 4)
As a viscose solution for spinning, a viscose stock solution containing 8.5% by mass of cellulose, 5.7% by mass of sodium hydroxide, and 2.8% by mass of carbon disulfide was used as it was. Spinning and scouring were performed under scouring conditions to obtain 100% cellulose regular rayon fiber (fiber E).
実施例の繊維のカチオン化度を上述したとおり評価測定し、その結果を下記表１に示した。また、実施例の繊維における窒素含有率を上述したとおり測定し、下記表１に示した。また、実施例の繊維における窒素換算した第４級アンモニウムイオンの含有率も下記表１に示した。また、実施例及び比較例の繊維の砒素に対する吸着性を下記のように測定・評価し、その結果を下記表１に示した。 The degree of cationization of the fibers of the examples was evaluated and measured as described above, and the results are shown in Table 1 below. Moreover, the nitrogen content in the fibers of the examples was measured as described above and is shown in Table 1 below. The content of quaternary ammonium ions in terms of nitrogen in the fibers of the examples is also shown in Table 1 below. Further, the adsorptivity of the fibers of Examples and Comparative Examples to arsenic was measured and evaluated as follows, and the results are shown in Table 1 below.
（砒素の吸着試験１）
（ａ）砒素として換算した濃度が０．９７９ｐｐｍの砒酸（砒酸イオン）の水溶液を原液として用いた。原液における砒素濃度を初期砒素濃度とした。
（ｂ）原液１００ｍＬと試料１．０ｇをポリプロピレン容器に入れ、２４時間振とうした後、試料を取り除き、誘導結合プラズマ質量分析装置（ＩＣＰ−ＭＳ、島津製作所製、「ＩＣＰＭ−８５００」）を使用して残液中の砒素濃度を測定した。残液中の砒素濃度を吸着後砒素濃度とした。
（ｃ）下記式により、砒素除去率を算出した。
砒素除去率（％） ＝ １００−｛（吸着後砒素濃度／初期砒素濃度）×１００｝
(Arsenic adsorption test 1)
(A) An aqueous solution of arsenic acid (arsenate ion) having a concentration converted to arsenic of 0.979 ppm was used as a stock solution. The arsenic concentration in the stock solution was defined as the initial arsenic concentration.
(B) Put 100 mL of the stock solution and 1.0 g of the sample in a polypropylene container, shake for 24 hours, remove the sample, and use an inductively coupled plasma mass spectrometer (ICP-MS, manufactured by Shimadzu Corporation, “ICPM-8500”) Then, the arsenic concentration in the residual liquid was measured. The arsenic concentration in the residual liquid was defined as the arsenic concentration after adsorption.
(C) The arsenic removal rate was calculated by the following formula.
Arsenic removal rate (%) = 100 − {(arsenic concentration after adsorption / initial arsenic concentration) × 100}
（砒素の吸着試験２）
（ａ）砒素として換算した濃度が１ｍｇ／Ｌの三酸化二砒酸（亜砒酸イオン）を含む塩酸溶液を対象砒素溶液として用いた。対象砒素溶液における砒素濃度を対象砒素溶液濃度とした。
（ｂ）対象砒素溶液２００ｍＬと繊維試料２．０ｇをポリプロピレン容器に入れ、緩やかに５時間振とうした後、試料を取り除き、工業排水試験法ＪＩＳ Ｋ ０１０２ ６１．３に従い、残液中の砒素濃度を測定した。残液中の砒素濃度を吸着後砒素溶液濃度とした。
（ｃ）下記式により、砒素除去率を算出した。
砒素除去率（％）＝１００−｛（吸着後砒素溶液濃度／対象砒素溶液濃度）×１００｝
(Arsenic adsorption test 2)
(A) A hydrochloric acid solution containing diarsenic trioxide (arsenite ion) having a concentration converted to arsenic of 1 mg / L was used as the target arsenic solution. The arsenic concentration in the target arsenic solution was defined as the target arsenic solution concentration.
(B) Put 200 mL of the target arsenic solution and 2.0 g of the fiber sample into a polypropylene container, gently shake for 5 hours, remove the sample, and observe the arsenic concentration in the remaining liquid according to the industrial wastewater test method JIS K 0102 61.3 Was measured. The arsenic concentration in the residual liquid was defined as the arsenic solution concentration after adsorption.
(C) The arsenic removal rate was calculated by the following formula.
Arsenic removal rate (%) = 100 − {(Arsenic solution concentration after adsorption / Target arsenic solution concentration) × 100}
上記表１の結果から分かるように、セルロースに第４級アンモニウムイオンが化学結合している実施例１のレーヨン繊維は、液体被処理対象（水中）の砒素を９０％以上除去していた。一方、第４級アンモニウムイオンを含まない比較例４のレギュラーレーヨン繊維は、陰イオン吸着性能を有しておらず、水中から砒素を除去することができなかった。また、カチオン吸着特性を有する酸化ジルコニウム又は二酸化チタンをセルロース内に有する比較例１〜２の繊維も、陰イオン吸着性能が格段に低く、砒素イオンの除去率が３０％未満であった。同様に、物理吸着特性を有する活性炭をセルロース内に有する比較例３の繊維は、陰イオン吸着性能を有しておらず、水中から砒素イオンを除去することができなかった。 As can be seen from the results of Table 1 above, the rayon fiber of Example 1 in which quaternary ammonium ions are chemically bonded to cellulose has removed 90% or more of arsenic from the liquid treatment target (in water). On the other hand, the regular rayon fiber of Comparative Example 4 containing no quaternary ammonium ions did not have anion adsorption capability and could not remove arsenic from water. Further, the fibers of Comparative Examples 1 and 2 having zirconium oxide or titanium dioxide having cation adsorption characteristics in the cellulose also had a remarkably low anion adsorption performance and an arsenic ion removal rate of less than 30%. Similarly, the fiber of Comparative Example 3 having activated carbon having physical adsorption characteristics in cellulose did not have anion adsorption performance and could not remove arsenic ions from water.
本発明の陰イオン吸着材及び水処理材は、飲料水、河川水、海水、地下水、下水、工業用水、工業用排水、汚染土壌の溶出液などの水中の砒酸イオン、亜砒酸イオンなどの陰イオンを除去するのに用いることができる。 The anion adsorbent and water treatment material of the present invention include drinking water, river water, seawater, groundwater, sewage, industrial water, industrial wastewater, anions such as arsenate ions in water such as effluent of contaminated soil, and arsenite ions. Can be used to remove
Claims (8)
セルロースと第４級アンモニウムイオンが化学結合していることを特徴とする陰イオン吸着材。 An anion adsorbent composed of a regenerated cellulose molded article containing quaternary ammonium ions,
An anion adsorbent characterized in that cellulose and quaternary ammonium ions are chemically bonded.
ビスコース成形体を第４級アンモニウム塩で処理して、第４級アンモニウムイオンをセルロースに化学結合する工程を含む陰イオン吸着材の製造方法。 A method for producing the anion adsorbent according to any one of claims 1 to 4,
A method for producing an anion adsorbent comprising a step of treating a viscose molded product with a quaternary ammonium salt to chemically bond quaternary ammonium ions to cellulose.
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