CN104923164B - 碘吸附剂、水处理用罐、碘吸附系统及碘吸附剂的制造方法 - Google Patents
碘吸附剂、水处理用罐、碘吸附系统及碘吸附剂的制造方法 Download PDFInfo
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- CN104923164B CN104923164B CN201510096493.8A CN201510096493A CN104923164B CN 104923164 B CN104923164 B CN 104923164B CN 201510096493 A CN201510096493 A CN 201510096493A CN 104923164 B CN104923164 B CN 104923164B
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- Prior art keywords
- adsorbent
- iodine
- carrier
- silver
- functional group
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 115
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 239000011630 iodine Substances 0.000 title claims abstract description 111
- 229910052740 iodine Inorganic materials 0.000 title claims abstract description 111
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 62
- 230000008569 process Effects 0.000 title claims abstract description 36
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title abstract description 11
- 125000000962 organic group Chemical group 0.000 claims abstract description 34
- 229910052709 silver Inorganic materials 0.000 claims abstract description 31
- 239000004332 silver Substances 0.000 claims abstract description 31
- 125000000524 functional group Chemical group 0.000 claims abstract description 25
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 15
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000005864 Sulphur Substances 0.000 claims abstract description 15
- 239000010703 silicon Substances 0.000 claims abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 239000002210 silicon-based material Substances 0.000 claims abstract description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 9
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 9
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 9
- 125000001424 substituent group Chemical group 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 42
- 239000000741 silica gel Substances 0.000 claims description 38
- 229910002027 silica gel Inorganic materials 0.000 claims description 38
- 238000010521 absorption reaction Methods 0.000 claims description 33
- 239000007787 solid Substances 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 claims description 8
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 claims description 5
- 150000002497 iodine compounds Chemical class 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 26
- 238000004090 dissolution Methods 0.000 abstract description 6
- 239000007822 coupling agent Substances 0.000 description 21
- 239000002904 solvent Substances 0.000 description 13
- -1 it is neutral Substances 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 8
- 229940006461 iodide ion Drugs 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 5
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- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 229910001961 silver nitrate Inorganic materials 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 150000007522 mineralic acids Chemical group 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 239000013535 sea water Substances 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
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- 150000003839 salts Chemical class 0.000 description 3
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- 238000001228 spectrum Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- NFYLSJDPENHSBT-UHFFFAOYSA-N chromium(3+);lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+3].[La+3] NFYLSJDPENHSBT-UHFFFAOYSA-N 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000005384 cross polarization magic-angle spinning Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- YSZJKUDBYALHQE-UHFFFAOYSA-N rhenium trioxide Chemical compound O=[Re](=O)=O YSZJKUDBYALHQE-UHFFFAOYSA-N 0.000 description 2
- 238000000550 scanning electron microscopy energy dispersive X-ray spectroscopy Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 2
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- NAOLWIGVYRIGTP-UHFFFAOYSA-N 1,3,5-trihydroxyanthracene-9,10-dione Chemical compound C1=CC(O)=C2C(=O)C3=CC(O)=CC(O)=C3C(=O)C2=C1 NAOLWIGVYRIGTP-UHFFFAOYSA-N 0.000 description 1
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 1
- OQXSRALAOPBHPM-UHFFFAOYSA-N 2-hydroxypropanoic acid;silver Chemical compound [Ag].CC(O)C(O)=O OQXSRALAOPBHPM-UHFFFAOYSA-N 0.000 description 1
- BUBVLQDEIIUIQG-UHFFFAOYSA-N 3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-2-one Chemical compound C=1C=CC=CC=1COC1C(OCC=2C=CC=CC=2)C(OCC=2C=CC=CC=2)C(=O)OC1COCC1=CC=CC=C1 BUBVLQDEIIUIQG-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical class CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- RBWNDBNSJFCLBZ-UHFFFAOYSA-N 7-methyl-5,6,7,8-tetrahydro-3h-[1]benzothiolo[2,3-d]pyrimidine-4-thione Chemical compound N1=CNC(=S)C2=C1SC1=C2CCC(C)C1 RBWNDBNSJFCLBZ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
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- 238000004438 BET method Methods 0.000 description 1
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- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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- PHOQVHQSTUBQQK-UHFFFAOYSA-N aldono-1,5-lactone Chemical compound OCC1OC(=O)C(O)C(O)C1O PHOQVHQSTUBQQK-UHFFFAOYSA-N 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
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- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910001423 beryllium ion Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
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- 239000004568 cement Substances 0.000 description 1
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- XTEGARKTQYYJKE-UHFFFAOYSA-M chlorate Inorganic materials [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-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
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 1
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- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
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- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
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- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- YACCECLVHQLZQK-UHFFFAOYSA-N methoxyperoxyethane Chemical compound CCOOOC YACCECLVHQLZQK-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
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- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
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- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- NBYLLBXLDOPANK-UHFFFAOYSA-M silver 2-carboxyphenolate hydrate Chemical compound C1=CC=C(C(=C1)C(=O)O)[O-].O.[Ag+] NBYLLBXLDOPANK-UHFFFAOYSA-M 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
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- 238000002798 spectrophotometry method Methods 0.000 description 1
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- 229910052905 tridymite Inorganic materials 0.000 description 1
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- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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Abstract
实施方式涉及碘吸附剂、水处理用罐、碘吸附系统及碘吸附剂的制造方法。实施方式提供银的溶出少的碘吸附剂。实施方式的碘吸附剂是具有作为含硅化合物的载体、与载体键合的有机基团和银的吸附剂,有机基团在末端具有用S-或SR表示的官能团,银与S-或SR的硫键合,R是氢原子或含有烃的取代基,使吸附剂中的硫相对于吸附剂中的硅的元素比为MS/MSi、除以载体的比表面积A(m2/g)得到的值MS/(MSi·A)为2.4×10-4g/m2≤MS/(MSi·A)≤2.7×10-4g/m2。
Description
技术领域
实施方式涉及碘吸附剂、水处理用罐、碘吸附系统及碘吸附剂的制造方法。
背景技术
随着工业的发展和人口的增加,要求水资源的有效利用。因此,废水的再利用非常重要。为了达成这些目标,需要水的净化、即从水中将其他物质分离。作为从液体中将其他物质分离的方法,已知各种方法,例如可举出膜分离、离心分离、活性碳吸附、臭氧处理、利用凝集将浮游物质除去等。通过这种方法,可以将水中含有的碘和氮等对环境影响大的化学物质除去,将分散在水中的油类、粘土等除去。
碘是在X射线造影剂或图像诊断用的标记试剂等医药品领域、激光器和LCD用偏振片等光学领域以及有机导体和色素敏化太阳能电池等电子材料领域等各种领域中起到重要作用的元素。因此,由于其需求的扩大和近年的环境法规的强化,其回收和再利用的重要性提高。
作为选择性回收碘的方法,市场有售添加固定有银的活性碳或硅胶。其利用了银与碘的强键合性。但是,对于这些材料来说,在其制法上认为银仅作为活性炭或硅胶上的盐析出,因此银的担载量少,并且当在水中使用时,由于银的溶出因而有性能下降的顾虑。
另外,当使用硅胶作为基材时,硅胶会溶解在水或水溶性有机溶剂中,因此当在水性介质中长期地使用时,有吸附剂的体积减少、萎缩的吸附剂通过过滤器向使用环境外流出的因空间速度的变化导致的系统性能降低等的顾虑。
现有技术文献
专利文献
专利文献1:日本特开平7-241460号公报
发明内容
发明要解决的课题
实施方式提供载体溶出少的碘吸附剂。
用于解决课题的手段
实施方式的碘吸附剂是具有作为含硅化合物的载体、与载体键合的有机基团和银的吸附剂,有机基团在末端具有用S-或SR表示的官能团,银与S-或SR的硫键合,R是氢原子或含有烃的取代基,使吸附剂中的硫相对于吸附剂中的硅的元素比为MS/MSi、除以载体的比表面积A(m2/g)所得的值MS/(MSi·A)为2.4×10-4g/m2≤MS/(MSi·A)≤2.7×10-4g/m2。
附图说明
图1是使用了实施方式的碘吸附剂的水处理系统的概念图。
图2是与配管连接的水处理罐的截面示意图。
图3是实施例的固体C13NMR光谱。
图4是表示实施例的碘吸附量的时间依赖性的曲线。
图5是表示实施例的碘吸附量的时间依赖性的曲线。
具体实施方式
实施方式的碘吸附剂是具有作为含硅化合物的载体、与载体键合的有机基团和银的吸附剂,有机基团在末端具有用S-或SR表示的官能团,银与S-或SR的硫键合,R是氢原子或含有烃的取代基,使吸附剂中的硫相对于吸附剂中的硅的元素比为MS/MSi、除以载体的比表面积A(m2/g)得到的值MS/(MSi·A)为2.4×10-4g/m2≤MS/(MSi·A)≤2.7×10-4g/m2。
实施方式的水处理用罐是收容有碘吸附剂的水处理用罐,碘吸附剂是具有作为含硅化合物的载体、与载体键合的有机基团和银的吸附剂,有机基团在末端具有用S-或SR表示的官能团,银与S-或SR的硫键合,R是氢原子或含有烃的取代基,使吸附剂中的硫相对于吸附剂中的硅的元素比为MS/MSi、除以载体的比表面积A(m2/g)得到的值MS/(MSi·A)为2.4×10-4g/m2≤MS/(MSi·A)≤2.7×10-4g/m2。
实施方式的碘吸附系统具有:收容有碘吸附剂的吸附手段;向吸附手段供给含有碘化合物的被处理介质的供给手段;将被处理介质从吸附手段中排出的排出手段;用于对吸附手段的供给侧或排出侧的至少一者上设置的被处理介质中的碘化合物的含量进行测定的测定手段;以及用于在基于来自测定手段的信息求得的值达到预先设定的值时减少自供给手段向吸附手段供给的被处理介质的供给量的控制手段,其中,碘吸附剂是具有作为含硅化合物的载体、与载体键合的有机基团和银的吸附剂,有机基团在末端具有用S-或SR表示的官能团,银与S-或SR的硫键合,R是氢原子或含有烃的取代基,使吸附剂中的硫相对于吸附剂中的硅的元素比为MS/MSi、除以载体的比表面积A(m2/g)得到的值MS/(MSi·A)为2.4×10-4g/m2≤MS/(MSi·A)≤2.7×10-4g/m2。
实施方式的碘吸附剂的制造方法具有以下工序:使含水率u为10质量%≤u≤35质量%的含硅化合物的载体与含有在末端具有用S-或SR表示的官能团的有机基团的偶联剂发生偶联反应的工序;和使进行了偶联反应的反应物与含银的有机酸或无机酸接触的工序。
(碘吸附剂)
实施方式的碘吸附剂具有载体、与载体键合的在末端具有用S-或SR表示的官能团的有机基团和与S-或SR的硫键合的银。R是氢原子或含有烃的取代基。优选使吸附剂中的硫相对于吸附剂中的硅的元素比为MS/MSi、除以载体的比表面积A(m2/g)得到的值MS/(MSi·A)为2.4×10-4g/m2以上且2.7×10-4g/m2以下(2.4×10-4g/m2≤MS/(MSi·A)≤2.7×10-4g/m2)。
作为实施方式的载体,优选是能够对碘吸附剂赋予可供于实用的强度的构件。对于导入有机基团的载体来说,优选:表面具有很多羟基、从而通过以下说明的制造方法、载体的修饰比例的提高的载体。其中,载体可以使用酸性载体或者酸性载体预先经中性化处理的中性载体等。其中,中性化处理可举出例如在钙离子等添加物中对载体进行处理。作为这种载体,具体地说可以使用硅胶(SiO2、中性、酸性)和铝硅酸盐及氧化硅氧化铝中的至少任一种含硅化合物。
另外,金属氧化物也可作为单体与上述硅胶等同样地使用。作为金属氧化物,可举出形成氧化钛(TiO2)、氧化铝(Al2O3)及氧化锆(ZrO2)、三氧化钴(CoO3)、氧化钴(CoO)、氧化钨(WO3)、氧化钼(MoO3)、氧化铟锡(ITO)、氧化铟(In2O3)、氧化铅(PbO2)、钛酸锆酸铅(PZT)、氧化铌(Nb2O5)、氧化钍(ThO2)、氧化钽(Ta2O5)、钛酸钙(CaTiO3)、钴酸镧(LaCoO3)、三氧化铼(ReO3)、氧化铬(Cr2O3)、氧化铁(Fe2O3)、铬酸镧(LaCrO3)、钛酸钡(BaTiO3)等的烷氧基金属或卤化物等。
本实施方式的载体的大小优选平均粒径d为100μm以上且5mm以下(100μm≤d≤5mm)。当使载体的平均粒径为100μm以上且5mm以下(100μm≤d≤5mm)时,例如在进行碘吸附时,能够兼顾碘吸附剂在色谱柱、滤筒或罐中的高充填率与通水的容易性。当平均粒径小于100μm时,碘吸附剂在色谱柱等中的填充率变得过高、空隙的比例减少,因此通水变难。另一方面,当平均粒径超过5mm时,碘吸附剂在色谱柱等中的填充率变得过低、空隙增大、通水变得容易,但由于碘吸附剂与含碘的排水的接触面积减少,因此利用碘吸附剂的碘的吸附比例减少。优选的载体的平均粒径d为100μm以上且2mm以下(100μm≤d≤2mm)、更优选300μm以上且1mm以下(300μm≤d≤1mm)。
平均粒径可通过筛分法进行测定。具体地说,根据JISZ8901:2006“试验用粉体及试验用粒子”、使用数个网眼为100μm~5mm之间的筛子进行筛分从而可以测定。
另外,本实施方式的碘吸附剂可以仅通过变化载体的大小来调节吸附剂本身的大小,为了获得处理容易的吸附剂,将载体的大小设定为所需大小即可。即,不进行造粒等操作即可获得处理容易的碘吸附剂。另外,由于不需要进行造粒等,因此可以简化为了获得处理容易的碘吸附剂所需的制造工序,可以实现成本降低。
实施方式的有机基团与载体键合,且在末端具有用S-或SR表示的官能团。S-是指硫醇盐部位。末端的SR是指硫醇、硫化物、硫酯多元醇等官能团。当SR的R为大的官能团时,由于立体障碍等因而有阻碍金属或金属离子的配位或碘的吸附的可能性。因此,作为取代基的R的碳数优选为6以下。通过使具有上述官能团的偶联剂与载体发生反应,向载体导入有机基团。作为偶联剂,例如可举出硅烷偶联剂、钛酸酯系偶联剂、铝酸盐系偶联剂等。利用偶联剂导入有机基团时,与载体键合的氧和末端的硫之间优选用碳数为1~6的碳链键合。与载体键合的氧和末端的硫之间更优选用直链的碳数为1~6的碳链键合。具有碳数为1~6的碳链的有机基团例如可举出具有烷基链或烷氧基链的有机基团。该具有烷基链或烷氧基链的有机基团也可具有侧链。
银与实施方式的硫键合而作为碘吸附剂发挥功能。银为离子时,优选1价的银离子。有碘吸附剂含有0价的银的情况。银为0价时,0价的银例如可举出银离子被有机基团的硫还原的银。有银离子与成对的阴离子进行离子性键合的情况。
实施方式的有机基团的硫相对于吸附剂整体的硅的原子比MS/MSi(-)可利用扫描型电子显微镜能量分散型X射线分光法(SEM-EDX:Scanning Electron Microscope/EnergyDispersive X-ray Spectroscopy)进行测定。
SEM-EDX的测定方法在以下的条件下进行。测定区域是以10,000倍倍率观察到的整个视野。
·试样制备:在碳带上适量地分散试样,进行碳蒸镀。
·装置:Carl ZEISS制ULTRA55(SEM)、Thermo Fisher制NSS312E(EDX)
·电子束条件(加速电压):6kV
·观察倍率:10000倍
·观察模式:反射电子图像
实施方式中,从碘的吸附性能和抑制载体溶出的观点出发,优选MS/MSi(-)除以载体比表面积A(m2/g)得到的值MS/(MSi·A)(g/m2)为2.4×10-4(g/m2)以上且2.7×10-4(g/m2)以下。当MS/(MSi·A)(g/m2)少于2.4×10-4(g/m2)时,吸附剂表面的被覆率低,因而裸露至表面的硅烷醇基(SiOH)多,因此作为载体的硅胶的溶出量增多(由于硅胶的溶出是以硅烷醇基为起点而开始)。另一方面认为:当MS/(MSi·A)(g/m2)多于2.7×10-4(g/m2)时,表面被覆率高,因此细孔部分堵塞,通水性降低,吸附剂无法利用至内部;或者表面的疏水性提高,吸附剂的亲水性降低,吸附能力下降。
与银离子成对的阴离子是有机酸离子或无机酸离子。作为与银离子成对的有机酸离子,可举出醋酸离子、乳酸离子、柠檬酸离子、水杨酸离子等。另外,作为与银离子成对的无机酸离子,可举出硝酸离子、硫酸离子、碳酸离子、氯酸离子、亚硝酸离子、高氯酸离子、亚硫酸离子等。有这些阴离子含有在碘吸附剂中的情况。
认为:对于实施方式的碘吸附剂来说,与碘吸附剂的有机基团所含的、用S-或SR表示的官能团的硫键合的银将被处理水中含有的碘吸附。即认为:在被处理水中,碘以碘化物离子(I-)或碘酸离子(IO3 -)等阴离子的形态存在,但通过这种阴离子与银键合,从而将被处理水中的碘吸附。
(碘吸附剂的制造方法)
接着,对本实施方式的碘吸附剂的制造方法进行说明。但以下说明的制造方法为一个例子,只要可获得本实施方式的碘吸附剂,则无特别限定。另外,优选:进行各处理之后进行过滤,用反应溶剂或者甲苯、纯水或醇等适当的溶剂进行洗涤、将其干燥,然后进行接下来的处理。实施方式的碘吸附剂的制造方法具有:使含水率u为10质量%以上且30质量%以下(10质量%≤u≤30质量%)的含硅化合物的载体与含有在末端具有用S-或SR表示的官能团的有机基团的偶联剂发生偶联反应的工序;和使发生了偶联反应的反应物与含银的有机酸或无机酸接触的工序。
首先准备上述载体,利用在末端具有用S-或SR表示的官能团的偶联剂对该载体的表面进行处理,向载体导入硫醇部位或硫化物部位等。载体优选在偶联剂反应前作为前处理实施了含水处理的载体。载体的含水率优选为10质量%以上且35质量%以下(10质量%≤u≤35质量%)。更优选的载体的含水率为10质量%以上且30质量%以下(10质量%≤u≤30质量%)。进一步优选的载体的含水率为20质量%以上且30质量%以下(20质量%≤u≤30质量%)。作为偶联剂,例如可举出例如γ-硫烷基丙基三甲氧基硅烷或γ-硫烷基丙基三乙氧基硅烷、3-巯基丙基三乙氧基硅烷、3-巯基丙基三甲氧基硅烷、3-巯基丙基甲基二甲氧基硅烷等硫醇系偶联剂,双(三乙氧基甲硅烷基丙基)四硫化物等硫化物系偶联剂、硫烷基钛酸酯、硫烷基铝螯合物、硫烷基铝锆酸盐等偶联剂。
偶联剂与载体的反应有下述方法:使偶联剂汽化、与载体反应的方法;在溶剂中混合偶联剂、与载体进行混合,从而使其反应的方法;不使用溶剂、与载体直接接触进行反应的方法。在使各反应进行时,通过进行加热或减压等,可以调节导入至碘吸附剂的硫的量(比例)。
关于反应溶剂,更优选芳香族性溶剂,但醇类及醇类与水的混合溶剂等只要能够溶解硫醇部位或具有硫醇盐部位的偶联剂即可。关于反应温度,特别是使用芳香族性溶剂时,从偶联剂的水解难以发生、偶联剂之间的缩合反应难以发生的方面出发是优选的。进而,从能够在高温下进行处理、可提高配位基的修饰率的方面出发更为优选。另一方面,在水溶性溶剂中,由于偶联剂的水解易于发生、偶联剂之间的缩合反应易于发生,因此优选在更低温下进行。
通过偶联反应导入了有机基团的载体例如可在洗涤干燥后直接用于银的担载反应,也可在银的担载之前进行在含有葡萄糖酸-1,5-内酯的醇性溶剂中加热的处理。洗涤干燥优选例如在利用有机基团导入反应的溶剂进行洗涤后进行常温(25℃)风干或热风干燥。热风干燥的温度只要是使其干燥的温度则无特别限定,例如优选为200℃以下。作为醇性溶剂,可以使用甲醇、乙醇、丙醇或丁醇等。根据载体或有机基团,还可使用丙酮、THF、DMSO、DMF等有机溶剂。其中,加热温度随溶剂的不同、优选的范围不同,但优选为室温(25℃)以上且沸点以下。该处理的原理虽然还不清楚,但碘吸附剂的碘吸附能力提高。优选在醇性溶剂中的加热处理后也可利用醇性溶剂和纯水进行洗涤、再进行与上述同样的干燥处理。
接着,对如上获得的载体担载银离子。例如可举出在制备银的无机酸或有机酸的盐的水溶液之后,在该水溶液中浸渍上述载体实施搅拌的手法;或在色谱柱中填充上述载体,在该色谱柱中流过上述水溶液的手法等。
作为上述的银的无机酸或有机酸的盐,可举出硝酸银、硫酸银、碳酸银、氯酸银、亚硝酸银、高氯酸银、亚硫酸银、醋酸银、乳酸银、柠檬酸银、水杨酸银等,从对水的溶解性的观点出发,优选硝酸银。
(碘吸附系统及碘吸附剂的使用方法)
接着,对使用了上述碘吸附剂的吸附系统及其使用方法进行说明。碘吸附系统具有:具备碘吸附剂的吸附手段;向吸附手段供给含有碘化合物的被处理介质的供给手段;将被处理介质从吸附手段中排出的排出手段;用于对吸附手段的供给侧或排出侧的至少一者设置的被处理介质中的碘化合物的含量进行测定的测定手段;以及用于在基于来自测定手段的信息求得的值达到预先设定的值时减少自所述供给手段向吸附手段供给的被处理介质的供给量的控制手段。
图1是表示本实施方式的碘吸附中使用的装置的概略构成和处理系统的概念图。
如图1所示,在本装置中并列地配置填充有上述碘吸附剂的水处理用罐(吸附手段)T1及T2的同时,在水处理用罐T1及T2的外侧设置有接触效率促进手段X1及X2。接触效率促进手段X1及X2可以为机械搅拌装置或非接触的磁力搅拌装置,但并非必须的构成要素、可以省略。
另外,介由排水供给线路(供给手段)L1、L2及L4将储存有含碘的排水的排水储存罐W1与水处理用罐T1及T2连接,介由排水排出线路(排出手段)L3、L5及L6连接于外部。
其中,在供给线路L1、L2及L4上分别设有阀(控制手段)V1、V2及V4,在排出线路L3及L5上分别设有阀V3及V5。另外,在供给线路L1上设有泵P1。进而,在排水储存罐W1、供给线路L1及排出线路L6上分别设有浓度测定手段(测定手段)M1、M2及M3。
另外,上述阀、泵的控制及测定装置中的测定值的监测由控制部C1进行统一集中管理。
图2表示与配管4(L2-L4)连接的、填充有碘吸附剂的水处理用罐T1、T2的截面示意图。图中的箭头表示处理水的流动方向。水处理用罐T1、T2由碘吸附剂1、收容碘吸附剂的罐2和用于使碘吸附剂不漏出至罐2外的隔板3构成。作为水处理用罐T1、T2,可以是罐2其本身可交换的滤筒型的形态、也可以是能够交换罐2内的碘吸附剂的形态。当除了碘以外还有吸附使其回收的物质时,可以将其他的吸附剂收容在罐2中。
接着,对使用了图1所示的装置的碘的吸附操作进行说明。
首先,对于水处理用罐T1及T2利用泵P1将排水从罐W1通过排水供给线路L1、L2及L4供给至水处理用罐T1及T2。此时,排水中的碘被吸附在水处理用罐T1及T2、吸附后的排水通过排水排出线路L3、L5排出至外部。
此时,可以根据需要驱动接触效率促进手段X1及X2,增大填充于水处理用罐T1及T2内的碘吸附剂与排水的接触面积,提高利用水处理用罐T1及T2的碘的吸附效率。
在此,通过水处理用罐T1及T2的设于供给侧的浓度测定手段M2和设于排出侧的浓度测定手段M3,观测水处理用罐T1及T2的吸附状态。当吸附顺利地进行时,利用浓度测定手段M3测定的碘的浓度显示低于利用浓度测定手段M2测定的碘的浓度的值。但是,随着水处理用罐T1及T2中的碘的吸附逐渐地进行,在供给侧及排出侧上配置的浓度测定手段M2及M3的所述碘的浓度差减少。
因此,在浓度测定手段M3判断达到预先设定的规定的值、利用水处理用罐T1及T2进行的碘的吸附能力达到饱和时,基于来自浓度测定手段M2、M3的信息,控制部C1暂时地停止泵P1,关闭阀V2、V3及V4,停止排水向水处理用罐T1及T2的供给。
其中,虽然图1中未图示出,但当排水的pH发生变动时或pH为强酸性或强碱性、脱离适于本实施方式的吸附材料的pH区域时,也可利用浓度测定手段M1或/及M2对排水的pH进行测定,通过控制部C1调节排水的pH。
当水处理用罐T1及T2达到饱和时,与适当的填充有新型的碘吸附剂的水处理用罐进行交换,碘吸附达到饱和的水处理用罐T1及T2被供至适当的必要的后处理。例如,当水处理用罐T1及T2含有放射性碘时,例如将水处理用罐T1及T2粉碎之后进行水泥固化,作为放射性废弃物保管在地下设施等中。
其中,上述例中对使用了水处理用罐的排水中的碘的吸附系统及操作进行了说明,但通过上述的向色谱柱中通气含有碘的排气,也可以将排气中的碘吸附除去。
以下通过实施例具体地说明发明。
(实施例1)
利用筛分法将硅胶(FUJI SILYSIA制QRiACT-Q6)分级成粒径300-500μm,将含水率调节至30质量%。在可分离式烧瓶(5L)中投入3-巯基丙基三甲氧基硅烷(833.34g)及甲苯(1680.05g)充分地搅拌。向其中投入利用前述的方法制备的硅胶(500g),设置搅拌翼。将烧瓶设置在覆套加热器中,开始加热搅拌。一边保持溶剂的回流状态,一边从回流开始加热搅拌9小时。将烧瓶冷却至室温,通过吸引过滤将硅胶和溶液分离。利用与溶剂同量的甲苯洗涤所得的硅胶,使其风干至固体成分量达到90wt%以上,从而获得了具有有机基团的硅胶粒子。
在可分离式烧瓶(5L)中投入之前获得的具有有机基团的硅胶粒子(580.00g)、葡萄糖酸-1,5-内酯(573.42g)及甲醇(9471.37g),设置搅拌翼。将该烧瓶设置在覆套加热器中,一边将反应体系中的温度保持在60℃、一边加热搅拌6小时。将烧瓶冷却至室温,通过吸引过滤将硅胶和溶液分离。首先利用与反应溶剂同量的甲醇洗涤所得的硅胶,接着利用反应溶剂的1.5倍体积的纯水进行洗涤。使其风干至固体成分量达到90wt%以上,从而获得了反应物。
在塑料容器(20L)中投入硝酸银(365.29g),向其中投入纯水(11811.11g),充分地搅拌使硝酸银完全地溶解。向其中投入2-3-2中获得的反应生成物(690.00g),设置搅拌翼,在室温下搅拌1小时。通过吸引过滤将硅胶和溶液分离,利用纯水对所得的硅胶进行洗涤直至滤液变成中性。洗涤后将硅胶返回至塑料容器,添加纯水(硅胶的20倍左右体积)搅拌1小时。通过吸引过滤将硅胶和溶液分离,利用纯水(硅胶的25倍左右体积)进行洗涤,从而获得了标题所示的化合物。
(实施例2)
在上述实施例1中使硅烷偶联反应后的干燥条件不是风干、而是进行130℃加热干燥,除此之外同样地进行,获得了实施例2的吸附剂。
(实施例3)
在上述实施例1中使硅胶的含水率为20质量%,除此之外同样地进行,获得了实施例3的吸附剂。
(实施例4)
在上述实施例1中使硅胶的含水率为20质量%、使硅烷偶联反应后的干燥条件为不是风干、而是进行130℃加热干燥,除此之外同样地进行,获得了实施例4的吸附剂。
(实施例5)
在上述实施例1中作为硅胶使用关东化学制的硅胶60N(粒径为100-210μm)、并使硅胶的含水率为25质量%,除此之外同样地进行,获得了实施例5的吸附剂。
(比较例1)
在上述实施例1中使硅胶的含水率为5质量%,除此之外同样地进行,获得了比较例1的吸附剂。
(比较例2)
在上述实施例2中使硅胶的含水率为40质量%,除此之外同样地进行,获得了比较例2的吸附剂。
(比较例3)
在上述实施例1中作为硅胶使用关东化学制的硅胶60N(粒径为100-210μm)、并使硅胶的含水率为5质量%,除此之外同样地进行,获得了比较例3的吸附剂。
对于实施例1~5及比较例1~3的碘吸附性能试验进行说明。在塑料制螺旋瓶(10ml)中投入上述获得的吸附剂(20mg)和分别以500mg/L的浓度含有碘化钾和氯化钠的试验溶液(10ml),使用卧式混合转子在室温下、60rpm的条件下搅拌1小时。之后,利用孔径0.2μm的纤维素膜滤器(MinisartRC-15)进行过滤,定量测定了所得水溶液中的碘化物离子浓度。
碘化物离子浓度使用离子色谱法算出。作为离子色谱法装置,使用日本Waters制Alliance HPLC系统,在以下的条件下进行了测定。
·色谱柱Shodex IC SI-904E
·洗脱液1.8mM Na2CO3+1.7mM NaHCO3aq.
·流速1.2mL/分钟
·检测器Shodex CD Suppressor module
·色谱柱温度30℃
作为碘化物离子的吸附能力的指标,使用了每单位质量的碘化物离子吸附量(以下记载为mg-I/g)。
对实施例1~4及比较例1~3的硅胶溶出量试验进行说明。在塑料制螺旋瓶(10ml)中投入如上获得的吸附剂(20mg)和纯水(20ml),使用卧式混合转子在室温下、60rpm的条件下搅拌1小时。之后,利用孔径为0.2μm的纤维素膜滤器(Minisart RC-15)进行过滤,定量测定了所得水溶液中的Si浓度。
Si浓度使用ICP发射分光光度法算出。作为装置使用SII NanoTechnology株式会社制SPS-4000。
硫与硅的原子比(MS/MSi)在上述条件下利用EDX分析算出。
作为硅胶溶出量的指标,使用了每单位质量的Si溶出量(以下记载为mg-Si/g)。
为了在粒径不同的材料之间也进行比较,算出所述MS/MSi除以载体的比表面积A(m2/g)得到的值。比表面积与QARiACT-Q6有关,使用岛津制作所-Micromeritics TriStar-II3020利用BET法算出。对于硅胶60N,使用关东化学发行的制品数据表的值。
对实施例1及2、比较例1的长期通水试验进行说明。利用离子交换水稀释MARINEART(大阪药研株式会社制、人工海水的配制物(日文原文为“人工海水の素”)),制作了34%的海水。在其中投入吸附剂,在减压下进行浸渍,从而进行了脱气。将利用前述方法进行了脱气的10ml的吸附剂填充在直径为18mm、高为80cm的色谱柱中。使循环流量为SV10,使利用前述方法制作的34%的人工海水通水20~36日。将吸附剂从色谱柱中取出,测定粒度分布。
作为粒度分布测定装置,使用SHIMADZU制、SALD-3100,不进行超声波照射,二氧化硅的折射率使用说明书记载的1.55进行了测定。
作为吸附剂的体积减少的指标,使用了由下式导出的通水结束后的吸附剂的中间粒径相对于通水开始前的吸附剂的中间粒径的减少率。作为中间粒径(直径)测定装置,使用了SHIMADZU制、SALD-3100。
粒径减少率=100×(通水前的吸附剂的中间粒径-通水后的吸附剂的中间粒径)/(通水前的吸附剂的中间粒径)
实施例与比较例的各种性能评价结果
表1
实施例与比较例的各种性能评价结果
表2A
表2B
由表1和表2可知,实施例中获得的吸附剂具有碘吸附能力,与比较例相比,Si溶出量低。另外,实施例1及2的长期通水试验中的体积减少率与比较例1相比小。由以上可认为,Si溶出量低者,在长期通水中的体积减少率也低,因此实施例3及4的长期通水中的体积减少率与实施例1及2一样地低。
对实施例1~4的碘吸附性能的时间依赖性试验进行说明。在塑料制螺旋瓶(500ml)中投入上述获得的吸附剂(50mg)和分别以50mg/L及17.6mg/L的浓度含有碘化钾和氯化钠的试验溶液(500ml),使用恒温振荡槽,在25℃、60rpm的条件下搅拌24小时。在此期间,将吸附剂添加至试验液之后,在1小时、3小时、6小时、9小时及24小时后分别采集各3ml的上清,利用孔径为0.2μm的纤维素膜滤器(Minisart RC-15)进行过滤,定量测定了所得水溶液中的碘化物离子浓度。
碘化物离子浓度使用离子色谱法算出。作为离子色谱法装置,使用日本Waters制Alliance HPLC系统,在以下的条件下进行了测定。
·色谱柱Shodex IC SI-904E
·洗脱液1.8mM Na2CO3+1.7mM NaHCO3aq.
·流速1.2mL/分钟
·检测器Shodex CD Suppressor module
·色谱柱温度30℃
对图3所示的固体13CNMR光谱的测定进行说明。实施例1~4的固体13CNMR光谱使用日本电子制JNM-ECX400/SH40T6/VT(固体探针),在以下的条件下进行了测定。
观测核(观测频率):13C(100.5MHz)
标准物质:TMS(外部标准/0ppm)
测定模式:CPMAS(Cross Polarization-Magic Angle Spinning,交叉极化魔角旋转)法
试样管转速:约5kHz
接触时间:3ms
脉冲延迟时间:1s
实施例1~4的碘吸附能力的时间依赖性评价结果和固体13CNMR光谱测定结果
表3A
表3B
将以四甲基硅烷为标准时的烷基的固体13C-NMR光谱示于表2。这里“以四甲基硅烷为标准”是指“使四甲基硅烷的共振频率为0(0ppm)”。另外,化学位移可基于下式求得。
化学位移δ(ppm)=(与TMS的频率差/共振频率)×106
例如当共振频率为300MHz时,与TMS的频率之差为300Hz的峰的化学位移达到1。
由表3可知,在实施例中,在固体13C NMR光谱中,在30ppm~40ppm之间的区域(30ppm≤δ≤40ppm)具有峰的实施例1及3与在30ppm~40ppm之间的区域没有峰的实施例2及4相比,与24小时时的碘吸附量低。另外,由图4及图5所示的碘吸附量的时间依赖性的曲线可知,在30ppm~40ppm之间的区域具有峰的实施例1及3与在30ppm~40ppm之间的区域没有峰的实施例2及4相比,碘吸附量相对于吸附试验时间的变化更为直线。由以上的结果可知,实施例1及3特别是可以长期地保持碘吸附量。
以上,对本发明的数个实施方式进行了说明,但这些实施方式作为例子进行公开,并非是为了限定发明的范围。这些新型的实施方式可以用其他各种方式进行实施,在不脱离发明主旨的范围内可进行各种省略、替换、变更。这些实施方式或其变形在包含在发明范围或要旨的同时,包含在权利要求书所记载的发明和与其均等的范围内。
Claims (15)
1.一种碘吸附剂,其是具有作为含硅化合物的载体、与所述载体键合的有机基团和银的吸附剂,其特征在于,
所述有机基团在末端具有用S-或SR表示的官能团,
所述银与S-或SR的硫键合,
所述R是氢原子或含有烃的取代基,
使所述吸附剂中的硫相对于所述吸附剂中的硅的元素比为MS/MSi、除以所述载体的比表面积A(m2/g)得到的值MS/(MSi·A)为2.4×10-4g/m2≤MS/(MSi·A)≤2.7×10-4g/m2。
2.根据权利要求1所述的碘吸附剂,其特征在于,
所述载体与所述官能团通过烷基连结,
在所述烷基的固体13C-NMR光谱测定中,以四甲基硅烷为标准时,以化学位移δ计在30ppm≤δ≤40ppm的范围内具有峰。
3.根据权利要求1所述的碘吸附剂,其特征在于,所述SR表示的官能团为硫醇。
4.根据权利要求1所述的碘吸附剂,其特征在于,所述SR表示的官能团为硫化物。
5.根据权利要求1~4中任一项所述的碘吸附剂,其特征在于,所述载体为硅胶。
6.一种水处理用罐,其是以收容有碘吸附剂为特征的水处理用罐,其特征在于,
碘吸附剂是具有作为含硅化合物的载体、与所述载体键合的有机基团和银的吸附剂,
所述有机基团在末端具有用S-或SR表示的官能团,
所述银与S-或SR的硫键合,
所述R是氢原子或含有烃的取代基,
使所述吸附剂中的硫相对于所述吸附剂中的硅的元素比为MS/MSi、除以所述载体的比表面积A(m2/g)得到的值MS/(MSi·A)为2.4×10-4g/m2≤MS/(MSi·A)≤2.7×10-4g/m2。
7.根据权利要求6所述的水处理用罐,其特征在于,
所述载体与所述官能团通过烷基连结,
在所述烷基的固体13C-NMR光谱测定中,以四甲基硅烷为标准时,以化学位移δ计在30ppm≤δ≤40ppm的范围内具有峰。
8.根据权利要求6所述的水处理用罐,其特征在于,所述SR表示的官能团为硫醇。
9.根据权利要求6所述的水处理用罐,其特征在于,所述SR表示的官能团为硫化物。
10.根据权利要求6~9中任一项所述的水处理用罐,其特征在于,所述载体为硅胶。
11.一种碘吸附系统,其具有:
收容有碘吸附剂的吸附手段;
向所述吸附手段供给含有碘化合物的被处理介质的供给手段;
将所述被处理介质从所述吸附手段中排出的排出手段;
用于对所述吸附手段的供给侧或排出侧的至少一者上设置的所述被处理介质中的碘化合物的含量进行测定的测定手段;以及
用于在基于来自所述测定手段的信息求得的值达到预先设定的值时减少所述被处理介质自所述供给手段向所述吸附手段供给的供给量的控制手段,
其特征在于,
所述碘吸附剂是具有作为含硅化合物的载体、与所述载体键合的有机基团和银的吸附剂,
所述有机基团在末端具有用S-或SR表示的官能团,
所述银与S-或SR的硫键合,
所述R是氢原子或含有烃的取代基,
使所述吸附剂中的硫相对于所述吸附剂中的硅的元素比为MS/MSi、除以所述载体的比表面积A(m2/g)得到的值MS/(MSi·A)为2.4×10-4g/m2≤MS/(MSi·A)≤2.7×10-4g/m2。
12.根据权利要求11所述的碘吸附系统,其特征在于,
所述载体与所述官能团通过烷基连结,
在所述烷基的固体13C-NMR光谱测定中,以四甲基硅烷为标准时,以化学位移δ计在30ppm≤δ≤40ppm的范围内具有峰。
13.根据权利要求11所述的碘吸附系统,其特征在于,所述SR表示的官能团为硫醇。
14.根据权利要求11所述的碘吸附系统,其特征在于,所述SR表示的官能团为硫化物。
15.根据权利要求11~14中任一项所述的碘吸附系统,其特征在于,所述载体为硅胶。
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