JP4519665B2 - 重金属成分の回収方法 - Google Patents
重金属成分の回収方法 Download PDFInfo
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- JP4519665B2 JP4519665B2 JP2005019778A JP2005019778A JP4519665B2 JP 4519665 B2 JP4519665 B2 JP 4519665B2 JP 2005019778 A JP2005019778 A JP 2005019778A JP 2005019778 A JP2005019778 A JP 2005019778A JP 4519665 B2 JP4519665 B2 JP 4519665B2
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- 229910001385 heavy metal Inorganic materials 0.000 title claims description 114
- 238000000034 method Methods 0.000 title claims description 45
- 238000011084 recovery Methods 0.000 title claims description 10
- 239000002245 particle Substances 0.000 claims description 102
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 98
- 239000007788 liquid Substances 0.000 claims description 24
- 230000005291 magnetic effect Effects 0.000 claims description 20
- 239000002351 wastewater Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 230000002378 acidificating effect Effects 0.000 claims description 9
- 230000005415 magnetization Effects 0.000 claims description 9
- 238000004065 wastewater treatment Methods 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 description 32
- 239000007864 aqueous solution Substances 0.000 description 26
- 150000002500 ions Chemical class 0.000 description 22
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 19
- 239000003513 alkali Substances 0.000 description 16
- 239000010949 copper Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 150000003839 salts Chemical class 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 229910000859 α-Fe Inorganic materials 0.000 description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 9
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000011651 chromium Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- -1 aluminum ions Chemical class 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 239000000084 colloidal system Substances 0.000 description 5
- 229960004887 ferric hydroxide Drugs 0.000 description 5
- 229960002089 ferrous chloride Drugs 0.000 description 5
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 5
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003456 ion exchange resin Substances 0.000 description 4
- 229920003303 ion-exchange polymer Polymers 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N iron (II) ion Substances [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 239000010802 sludge Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- 239000004277 Ferrous carbonate Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 230000005294 ferromagnetic effect Effects 0.000 description 3
- 235000019268 ferrous carbonate Nutrition 0.000 description 3
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 3
- 229960004652 ferrous carbonate Drugs 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910000015 iron(II) carbonate Inorganic materials 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 2
- 238000007885 magnetic separation Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- JZQOJFLIJNRDHK-CMDGGOBGSA-N alpha-irone Chemical compound CC1CC=C(C)C(\C=C\C(C)=O)C1(C)C JZQOJFLIJNRDHK-CMDGGOBGSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 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
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 230000005307 ferromagnetism Effects 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052598 goethite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 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
- 239000006247 magnetic powder Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910001172 neodymium magnet Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Water Treatment By Sorption (AREA)
- Compounds Of Iron (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Manufacture And Refinement Of Metals (AREA)
Description
また吸着法としては、水中の重金属イオンを樹脂中の官能基で交換吸着するイオン交換法、水中の重金属イオンを活性炭、亜炭、ゼオライト、活性アルミナ等の吸着剤で吸着する方法が提唱され、実用化されている。
公害と対策Vol13,No.1 p37〜p41 水処理技術Vol.22,No.6 p475〜p491
本発明では、まず、重金属成分含有液にマグネタイト粒子を分散させる。
上記マグネタイト粒子の平均粒子径が150nmより大きく、比表面積が10m2 /gより小さい場合、重金属成分含有液中でマグネタイト粒子が沈降してしまい均一な分散が困難になる他、マグネタイト粒子表面の吸着サイトが減少し、目的とする重金属吸着の十分な効果が得られない。即ち、平均粒子径が150nmより大きく、比表面積が10m2 /gより小さいマグネタイト粒子で十分な吸着効果を得ようとすると、マグネタイト粒子が多量に必要になる他、機器及び攪拌機が大型化してしまう等の問題が生じる。また、平均粒子径が10nmより小さく、比表面積が100m2 /gを超えるようなマグネタイト粒子では、重金属吸着の効果は大きいが、負荷磁場398kA/mにおける飽和磁化量が50Am2 /kgより小さくなるため、磁気的な力での回収が困難になる。
本発明の回収方法の対象となる好適な重金属成分としては、銅、鉛、カドミウム、クロム、マンガン、白金、パラジウム、ロジウム等があげられる。
本発明のマグネタイト粒子の製造法の一例を45nmのマグネタイト粒子(マグネタイト2)を例に説明する。
80リットルの反応器に10リットル/minの窒素ガスを吹き込みながら、0.6mol/minの塩化第一鉄水溶液40リットルと該塩化第一鉄に対し4.8molの塩化第二鉄を添加し、水溶液を良く混合した。次いで、該塩化第一鉄と塩化第二鉄を含む水溶液中の塩化第一鉄及び塩化第二鉄に対し0.6当量の水酸化アルカリ及び0.6当量の炭酸アルカリを含む水溶液20リットルを混合し、水酸化第一鉄と水酸化第二鉄コロイド及び炭酸第一鉄と水酸化第二鉄コロイドを含む懸濁液を得た。次いで、この懸濁液(第一鉄塩反応水溶液)を60℃に加熱し、60℃の反応温度を維持しながら,窒素ガスの流通を停止し、空気を20リットル/min通気して酸化反応を行った。得られたマグネタイト粒子をろ過し、60℃の脱イオン水200リットルで水洗した。水洗したマグネタイト粒子の一部を窒素気流下、120℃で乾燥した。得られたマグネタイト粒子(マグネタイト2)の平均粒子径は45nmであり、比表面積は25.5m2 /gであり、保磁力は13.30kA/mであり、負荷磁場398kA/mにおける飽和磁化量は78.1Am2 /kgであった。
下記表1に示す製造条件とした以外はマグネタイト2の製造法と同様にしてマグネタイト1及び3〜5をそれぞれ製造した。マグネタイト1、2及び3が本発明のマグネタイト粒子(実施例)であり、マグネタイト4及び5は比較例である。
得られたマグネタイト1〜5の諸特性を下記表2に示す。
〔平均粒子径〕
マグネタイト粒子の平均粒子径は「透過型電子顕微鏡 H−7600」(日立製作所(株)社製)で撮影された写真より測定した。
〔比表面積〕
マグネタイト粒子の比表面積は「マルチソーブ−12」(ユアサアイオニックス)を使用し、BET法にて測定した。
〔pH〕
JIS(Z−8802)に準じて測定を行った。マグネタイト粒子試料5gに純水105mlを入れ、5分間煮沸し、ろ過後、溶液のpHを「pHメーターHM−30G」(東亜DKK(株)社製)で測定を行った。
〔磁気特性〕
マグネタイト粒子の磁気特性は「振動試料磁力計VSM−3S」(東英工業(株)社製)を使用し、外部磁場398kA/m(5kOe)で測定した。
各種重金属イオンを1×10-5moldm-3含む水溶液100ml中に含水率50%のマグネタイト粒子を0.1〜2g加え、リン酸塩でpHを7に調整し、30分間攪拌した。マグネタイト粒子をネオジ鉄ボロン磁石で沈降させた。このときの液温は20℃であった。上澄み液をシリンジフィルターでろ過後、「偏光ゼーマン原子吸光分光光度計 Z-6100」(日立製作所(株)社製)を用い重金属イオンを測定した(測定結果A)。また、回収したマグネタイト粒子を0.1Nの硝酸100mlで30分間水洗後、ネオジ鉄ボロン磁石でマグネタイト粒子を沈降させた。上澄み液のpHは1.2であった。この上澄み液をシリンジフィルターでろ過後、「偏光ゼーマン原子吸光分光光度計 Z-6100」(日立製作所(株)社製)を用い重金属イオンを測定した(測定結果B)。
<Cu2+>
重金属イオンとしてCu2+を用い各マグネタイトについて試験を行った。各マグネタイトの吸着挙動並びに回収挙動を表3〜表7に示す。
また、0.1N硝酸で洗浄した場合、マグネタイトの粒子径にかかわらずCu2+イオンを効率よく回収できることがわかる。
図3に示す結果より、本発明のマグネタイト粒子は、NaClが共存する場合でも溶液中のCu2+イオンを効率よく吸着していることがわかる。
次にマグネタイト2を使用した各重金属の吸着挙動を表9〜表11に示す。
〔pHによる影響〕
マグネタイト2を0.5g添加し、30分間攪拌したときのCu2+、Pb2+、Cd2+、Cr6+の吸着挙動に対するpHの影響を図4〜図7にそれぞれ示す。
図7に示されるように、Cr6+は弱酸性即ちpH4.5〜6.5の範囲で効率よく吸着されている。これは弱酸性でマグネタイト成分中のFe2+が還元剤として作用し、Cr6+がCr3+に還元されるためと考えられる。
Claims (5)
- 重金属成分含有液から重金属成分を回収するにあたり、該重金属成分含有液に平均粒子径10〜150nm、比表面積10〜100m2 /g及び負荷磁場398kA/mにおける飽和磁化量50〜90Am2 /kgのマグネタイト粒子を分散させ、該重金属成分含有液を弱酸性からアルカリ性にして、重金属成分を該マグネタイト粒子の表面に吸着させた後、磁気的な力でマグネタイト粒子を回収し、重金属成分をマグネタイト粒子と共に液中から分離し、更に分離したマグネタイト粒子を水に分散させ、該分散液を酸性に調整することにより、重金属成分を液中に再溶出し、重金属成分を回収することを特徴とする重金属成分の回収方法。
- 重金属成分含有排水から重金属成分を除去するにあたり、該重金属成分含有排水に平均粒子径10〜150nm、比表面積10〜100m2 /g及び負荷磁場398kA/mにおける飽和磁化量50〜90Am2 /kgのマグネタイト粒子を分散させ、該重金属成分含有排水を弱酸性からアルカリ性にして、重金属成分を該マグネタイト粒子の表面に吸着させた後、磁気的な力でマグネタイト粒子を回収し、重金属成分を排水から除去することを特徴とする排水処理方法。
- 請求項1記載の重金属成分の回収方法又は請求項2記載の排水処理方法に用いられる、平均粒子径10〜150nm、比表面積10〜100m2 /g及び負荷磁場398kA/mにおける飽和磁化量50〜90Am2 /kgの重金属回収用又は排水処理用のマグネタイト粒子。
- 重金属成分をマグネタイト粒子の表面に吸着させるときの重金属成分含有液のpHが4.5〜12であり、重金属成分を液中に再溶出するときの分散液のpHが1〜4.5である請求項1記載の重金属成分の回収方法。
- 重金属成分をマグネタイト粒子の表面に吸着させるときの重金属成分含有排水のpHが4.5〜12である請求項2記載の排水処理方法。
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