JP5435708B2 - Metal adsorbent sintered porous body and method for producing the same - Google Patents
Metal adsorbent sintered porous body and method for producing the same Download PDFInfo
- Publication number
- JP5435708B2 JP5435708B2 JP2009107818A JP2009107818A JP5435708B2 JP 5435708 B2 JP5435708 B2 JP 5435708B2 JP 2009107818 A JP2009107818 A JP 2009107818A JP 2009107818 A JP2009107818 A JP 2009107818A JP 5435708 B2 JP5435708 B2 JP 5435708B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- metal
- porous body
- sintered porous
- resin particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910052751 metal Inorganic materials 0.000 title claims description 83
- 239000002184 metal Substances 0.000 title claims description 82
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 239000003463 adsorbent Substances 0.000 title description 45
- 239000002245 particle Substances 0.000 claims description 163
- 229920005989 resin Polymers 0.000 claims description 86
- 239000011347 resin Substances 0.000 claims description 86
- 239000000178 monomer Substances 0.000 claims description 70
- 239000011148 porous material Substances 0.000 claims description 50
- 125000000524 functional group Chemical group 0.000 claims description 49
- 229920006037 cross link polymer Polymers 0.000 claims description 48
- 229920005992 thermoplastic resin Polymers 0.000 claims description 43
- 239000000843 powder Substances 0.000 claims description 42
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 32
- 125000003277 amino group Chemical group 0.000 claims description 27
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 25
- -1 polyethylene Polymers 0.000 claims description 25
- 229920002554 vinyl polymer Polymers 0.000 claims description 24
- 229920002873 Polyethylenimine Polymers 0.000 claims description 22
- 239000003957 anion exchange resin Substances 0.000 claims description 22
- 239000004698 Polyethylene Substances 0.000 claims description 14
- 238000007334 copolymerization reaction Methods 0.000 claims description 14
- 229920000573 polyethylene Polymers 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- 150000001412 amines Chemical class 0.000 claims description 10
- 239000004743 Polypropylene Substances 0.000 claims description 9
- 229920001155 polypropylene Polymers 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 238000005349 anion exchange Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000007900 aqueous suspension Substances 0.000 claims description 5
- 238000004132 cross linking Methods 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- 238000012662 bulk polymerization Methods 0.000 claims description 4
- 238000010558 suspension polymerization method Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 125000000218 acetic acid group Chemical class C(C)(=O)* 0.000 claims 2
- 238000001179 sorption measurement Methods 0.000 description 92
- 239000013522 chelant Substances 0.000 description 55
- 239000010949 copper Substances 0.000 description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 21
- 229910052802 copper Inorganic materials 0.000 description 21
- 238000000034 method Methods 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 229910001385 heavy metal Inorganic materials 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 17
- 238000002156 mixing Methods 0.000 description 15
- 239000011651 chromium Substances 0.000 description 14
- 230000008961 swelling Effects 0.000 description 13
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 12
- 229910052785 arsenic Inorganic materials 0.000 description 12
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 12
- 239000011572 manganese Substances 0.000 description 12
- 229910052750 molybdenum Inorganic materials 0.000 description 12
- 239000011733 molybdenum Substances 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 229910052720 vanadium Inorganic materials 0.000 description 12
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 12
- 239000011701 zinc Substances 0.000 description 12
- 150000002739 metals Chemical class 0.000 description 11
- 238000011084 recovery Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 229910052793 cadmium Inorganic materials 0.000 description 10
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 10
- 239000003456 ion exchange resin Substances 0.000 description 10
- 229920003303 ion-exchange polymer Polymers 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000835 fiber Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 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 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 7
- 150000001242 acetic acid derivatives Chemical class 0.000 description 7
- 229910052804 chromium Inorganic materials 0.000 description 7
- 125000003700 epoxy group Chemical group 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 125000004018 acid anhydride group Chemical group 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 230000004927 fusion Effects 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 150000004715 keto acids Chemical class 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 238000010517 secondary reaction Methods 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 230000000274 adsorptive effect Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 4
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 4
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-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
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- DDKMFQGAZVMXQV-UHFFFAOYSA-N (3-chloro-2-hydroxypropyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)CCl DDKMFQGAZVMXQV-UHFFFAOYSA-N 0.000 description 2
- POTYORUTRLSAGZ-UHFFFAOYSA-N (3-chloro-2-hydroxypropyl) prop-2-enoate Chemical compound ClCC(O)COC(=O)C=C POTYORUTRLSAGZ-UHFFFAOYSA-N 0.000 description 2
- ONMLAAZEQUPQSE-UHFFFAOYSA-N (3-hydroxy-2,2-dimethylpropyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)CO ONMLAAZEQUPQSE-UHFFFAOYSA-N 0.000 description 2
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 2
- QLLUAUADIMPKIH-UHFFFAOYSA-N 1,2-bis(ethenyl)naphthalene Chemical compound C1=CC=CC2=C(C=C)C(C=C)=CC=C21 QLLUAUADIMPKIH-UHFFFAOYSA-N 0.000 description 2
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 2
- HGOUNPXIJSDIKV-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butyl 2-methylprop-2-enoate Chemical compound CCC(CO)(CO)COC(=O)C(C)=C HGOUNPXIJSDIKV-UHFFFAOYSA-N 0.000 description 2
- LAPSWRILDMAOMS-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol 2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O.CC(=C)C(O)=O.CC(C)(CO)CO LAPSWRILDMAOMS-UHFFFAOYSA-N 0.000 description 2
- FDUFQLNPPGRIKX-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CC(C)(CO)CO FDUFQLNPPGRIKX-UHFFFAOYSA-N 0.000 description 2
- GWCJNVUIVCCXER-UHFFFAOYSA-N 2-(1-phenylprop-2-enoxymethyl)oxirane Chemical compound C=1C=CC=CC=1C(C=C)OCC1CO1 GWCJNVUIVCCXER-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- GPOGMJLHWQHEGF-UHFFFAOYSA-N 2-chloroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCl GPOGMJLHWQHEGF-UHFFFAOYSA-N 0.000 description 2
- WHBAYNMEIXUTJV-UHFFFAOYSA-N 2-chloroethyl prop-2-enoate Chemical compound ClCCOC(=O)C=C WHBAYNMEIXUTJV-UHFFFAOYSA-N 0.000 description 2
- RKOOOVKGLHCLTP-UHFFFAOYSA-N 2-methylprop-2-enoic acid;propane-1,2,3-triol Chemical compound CC(=C)C(O)=O.OCC(O)CO RKOOOVKGLHCLTP-UHFFFAOYSA-N 0.000 description 2
- UPTHZKIDNHJFKQ-UHFFFAOYSA-N 2-methylprop-2-enoic acid;propane-1,2,3-triol Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O.OCC(O)CO UPTHZKIDNHJFKQ-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- 239000005695 Ammonium acetate Substances 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- DJEQZVQFEPKLOY-UHFFFAOYSA-N N,N-dimethylbutylamine Chemical compound CCCCN(C)C DJEQZVQFEPKLOY-UHFFFAOYSA-N 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 2
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001408 amides Chemical group 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 2
- 229940106681 chloroacetic acid Drugs 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000003621 irrigation water Substances 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 description 2
- ZUHZZVMEUAUWHY-UHFFFAOYSA-N n,n-dimethylpropan-1-amine Chemical compound CCCN(C)C ZUHZZVMEUAUWHY-UHFFFAOYSA-N 0.000 description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- FAIDIRVMPHBRLT-UHFFFAOYSA-N propane-1,2,3-triol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OCC(O)CO FAIDIRVMPHBRLT-UHFFFAOYSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- BZVJOYBTLHNRDW-UHFFFAOYSA-N triphenylmethanamine Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(N)C1=CC=CC=C1 BZVJOYBTLHNRDW-UHFFFAOYSA-N 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- MPJPKEMZYOAIRN-UHFFFAOYSA-N 1,3,5-tris(2-methylprop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound CC(=C)CN1C(=O)N(CC(C)=C)C(=O)N(CC(C)=C)C1=O MPJPKEMZYOAIRN-UHFFFAOYSA-N 0.000 description 1
- LXQMHOKEXZETKB-UHFFFAOYSA-N 1-amino-2-methylpropan-2-ol Chemical compound CC(C)(O)CN LXQMHOKEXZETKB-UHFFFAOYSA-N 0.000 description 1
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- YXCGQNYTCLWIIL-UHFFFAOYSA-N CCC(CO)(CO)CO.Cl.Cl.Cl Chemical compound CCC(CO)(CO)CO.Cl.Cl.Cl YXCGQNYTCLWIIL-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002521 alkyl halide group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 230000006675 polyamination Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Water Treatment By Sorption (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Description
この発明は、熱可塑性樹脂粉体の融着により形成される連続気孔をもつ焼結多孔体内部にキレート樹脂粒子あるいはイオン交換樹脂粒子からなる機能性吸着材粒子を固定した金属吸着性焼結多孔体およびその製造方法に関するものである。 This invention relates to a metal-adsorptive sintered porous material in which functional adsorbent particles made of chelate resin particles or ion-exchange resin particles are fixed inside a sintered porous material having continuous pores formed by fusing thermoplastic resin powders. The present invention relates to a body and a manufacturing method thereof.
重金属には高い有害性を示すものが多いところから、環境中への排出に関しては厳しい規制が行われている。そのため、環境中に排出される工場排水や、各種の製品の製造に使用される用水、さらには飲料水等の中から有害重金属を取り除くことが必要である。また、廃棄電子機器中には希少金属が大量に含まれており、これらは都市鉱山とも呼ばれる貴重な資源であるため、これらに含まれる有価金属の回収も必要とされている。 Because many heavy metals are highly hazardous, there are strict regulations on their release into the environment. For this reason, it is necessary to remove harmful heavy metals from industrial wastewater discharged into the environment, water used for manufacturing various products, and drinking water. In addition, waste electronic devices contain a large amount of rare metals, which are valuable resources called urban mines, and therefore, it is necessary to recover valuable metals contained in these metals.
被処理溶液から重金属を除去するための材料として、イオン交換樹脂やキレート樹脂が用いられている。しかし、イオン交換樹脂を使用してこれらの重金属を除去しようとすると、これらの被処理溶液中に含まれる高濃度の塩類や有機物のために重金属の除去が困難な場合が多い。このために、特許文献１および特許文献２に開示されているようにキレート樹脂を利用した重金属の除去の技術が提案されている。また、特許文献３ないし６に開示されているように有価金属の回収にも金属選択性の高いキレート樹脂の使用が提案されている。 As a material for removing heavy metals from the solution to be treated, ion exchange resins and chelate resins are used. However, when these heavy metals are to be removed using an ion exchange resin, removal of heavy metals is often difficult due to the high concentration of salts and organic substances contained in these solutions. For this reason, as disclosed in Patent Document 1 and Patent Document 2, a technique for removing heavy metals using a chelate resin has been proposed. In addition, as disclosed in Patent Documents 3 to 6, the use of a chelate resin having a high metal selectivity for the recovery of valuable metals has been proposed.
キレート樹脂は、重金属の除去回収について有効な吸着材であると思われるが、これらの先行文献に提案されているキレート樹脂の形態は粒子・粉体状であるため、何らかの管体に充てんして使用しなければならないなどキレート樹脂の粒状・粉体状という形状に伴う問題や不便さがある。さらに、粒状・粉体状という形状であるため、重金属を吸着させた後、再生しようとする場合、まず粒状・粉体状のキレート樹脂を管体から抜き取り、キレート樹脂を再生し、再度管体へ充てんしなければならないなどの煩雑な作業が必要となる。 The chelate resin is considered to be an effective adsorbent for heavy metal removal and recovery. However, the chelate resin proposed in these prior documents is in the form of particles / powder. There are problems and inconveniences associated with the shape of granular and powdered chelate resins, such as having to use them. Furthermore, because it is in the form of particles / powder, if you want to regenerate it after adsorbing heavy metals, first remove the chelate resin in the form of particles / powder from the tube, regenerate the chelate resin, and then again the tube Complicated work such as having to fill in is required.
このような問題に対し、キレート能を有する繊維が提案されている。特許文献７には化学的なグラフト法によりキレート性官能基が導入された繊維が、また特許文献８および特許文献９には放射線照射グラフト重合法により合成繊維にキレート性官能基が導入された繊維が開示されている。 In response to such problems, fibers having chelating ability have been proposed. Patent Document 7 discloses a fiber in which a chelating functional group is introduced by a chemical grafting method, and Patent Document 8 and Patent Document 9 describe a fiber in which a chelating functional group is introduced into a synthetic fiber by a radiation irradiation graft polymerization method. Is disclosed.
しかしながら、これらのキレート性官能基が導入された繊維を製造しようとすると、放射線照射装置が必要であったり、繊維にキレート性官能基をグラフトするなど製造工程は煩雑かつ複雑であるという問題がある。しかもキレート性官能基は、繊維の表面のみに導入されるので、繊維では比表面積が少なく、繊維の単位重量あるいは単位面積当たりの重金属の吸着量を多くすることができない。これらの点から重金属の吸着量の大きいイオン交換樹脂やキレート樹脂等の粒子状の形態の吸着材に注意がはらわれることになる。 However, when it is intended to produce fibers having these chelating functional groups introduced, there is a problem that a radiation irradiation apparatus is required, and the production process is complicated and complicated, such as grafting chelating functional groups onto the fibers. . In addition, since the chelating functional group is introduced only on the surface of the fiber, the specific surface area of the fiber is small, and the amount of heavy metal adsorbed per unit weight or unit area of the fiber cannot be increased. From these points, attention is paid to adsorbents in the form of particles such as ion exchange resins and chelate resins that have a large amount of heavy metal adsorption.
一方、粒子状の吸着材を取り扱いの容易な成型品を得る方法として、熱可塑性樹脂の焼結多孔体（一般に、プラスチック焼結フィルタとよばれる）内部に、活性炭をはじめとする無機系の粒子状吸着材を保持させるという方法が提案されている。たとえば、特許文献１０には、熱可塑性樹脂としてポリエチレンを用いて活性炭の粒状物などを保持させたフィルタが開示されている。また、特許文献１１に、ポリエチレンやポリプロピレン等の熱可塑性樹脂粉体と市販のイオン交換樹脂の粒子との混合物を焼結して、熱可塑性樹脂の多孔質焼結体のマトリックス中にイオン交換樹脂粒子が一体化された結合製品が開示されている。 On the other hand, as a method of obtaining a molded article that is easy to handle the particulate adsorbent, inorganic particles such as activated carbon are placed inside a sintered porous body of a thermoplastic resin (generally called a plastic sintered filter). A method of holding the adsorbent adsorbent has been proposed. For example, Patent Document 10 discloses a filter using polyethylene as a thermoplastic resin to hold activated carbon particles and the like. Further, in Patent Document 11, a mixture of thermoplastic resin powders such as polyethylene and polypropylene and commercially available ion exchange resin particles is sintered, and the ion exchange resin is placed in a matrix of a porous sintered body of the thermoplastic resin. A bonded product with integrated particles is disclosed.
ところで、汎用のイオン交換樹脂やキレート樹脂は、水中で高度に膨潤して細孔を生じるという特性を有する。乾燥体積を基準とすると、水中での膨潤体積は数倍以上にもなる。膨潤しなければ細孔は生まれず、非膨潤状態での比表面積は数十ｍ２／ｇ以下と非常に小さい。このため、イオン交換樹脂やキレート樹脂の粒子を十分に水中で膨潤させた後、管体等に充てんして使用する。しかし、細孔を生じていない非膨潤状態の粒子を熱可塑性樹脂粉体に混合して焼結多孔体を作製しても、その粒子のもつ機能を十分に発揮することができない。そして、水中で使用しても、イオン交換樹脂やキレート樹脂の粒子の周囲は、熱可塑性樹脂との融着によって固定されていて十分に膨潤することができないため、機能性樹脂本来の機能を十分に発揮させることは不可能である。一部が膨潤して細孔を広げたとしても、焼結多孔体が形成する細孔の閉塞を引き起こしてしまう。さらに、膨潤・収縮が繰り返されると、熱可塑性樹脂との融着状態が崩れて、焼結多孔体から脱離・漏出が生じるおそれもある。 By the way, general-purpose ion exchange resins and chelate resins have the property that they are highly swollen in water to form pores. Based on the dry volume, the swollen volume in water is several times or more. If it does not swell, pores are not produced, and the specific surface area in the non-swelled state is as small as several tens m 2 / g or less. For this reason, after ion-exchange resin or chelate resin particles are sufficiently swollen in water, they are filled into a tube or the like for use. However, even when non-swelled particles having no pores are mixed with a thermoplastic resin powder to produce a sintered porous body, the functions of the particles cannot be fully exhibited. And even when used in water, the surroundings of the ion exchange resin and chelate resin particles are fixed by fusion with the thermoplastic resin and cannot sufficiently swell, so that the original function of the functional resin is sufficient. It is impossible to make it appear. Even if a part swells and widens the pores, the pores formed by the sintered porous body are blocked. Furthermore, if the swelling / shrinking is repeated, the fused state with the thermoplastic resin may be lost, and detachment / leakage may occur from the sintered porous body.
本発明は、これらの点にかんがみてなされたもので、単位重量ないし単位面積当たりの金属の吸収量が高く、しかも共存する塩類や有機物の影響を受けることがなく、取扱いが容易で、製造が簡便でしかも各種の要求を満たしやすい金属吸着性の焼結多孔体およびその製造方法を提供しようとするものである。 The present invention has been made in view of these points, has a high metal absorption amount per unit weight or unit area, is not affected by coexisting salts and organic substances, is easy to handle, and can be manufactured. An object of the present invention is to provide a metal adsorbing sintered porous body that is simple and easily meets various requirements, and a method for producing the same.
本発明は、鋭意研究を行った結果、特定の機能性樹脂粒子１０〜７０重量％および熱可塑性樹脂粉体９０〜３０重量％からなる粒子と粉体との混合物を熱可塑性樹脂の融点付近の温度で加熱・焼結することにより製造された焼結多孔体が、単位重量ないし単位表面積あたりの金属吸着量が高く、しかも共存する塩類や有機物の影響を受けることなく、取扱いが容易で、製造方法が簡便で、しかも各種の要求を満たしやすい金属吸着性の焼結多孔体となるという知見に基づいてなされたものである。 In the present invention, as a result of intensive studies, a mixture of particles and powders consisting of 10 to 70% by weight of specific functional resin particles and 90 to 30% by weight of thermoplastic resin powder is placed near the melting point of the thermoplastic resin. Sintered porous body manufactured by heating and sintering at high temperature has a high metal adsorption per unit weight or unit surface area, and is easy to handle without being affected by coexisting salts and organic substances. This is based on the knowledge that the method is simple and the metal-adsorbing sintered porous body easily meets various requirements.
より詳しくは、本発明は、
以下の（ｉ）または（ｉｉ）から選ばれる機能性樹脂粒子１０〜７０重量％および熱可塑性樹脂粉体９０〜３０重量％からなる粒子と粉体との混合物を熱可塑性樹脂の融点付近の温度で加熱・焼結することを特徴とする金属吸着性の焼結多孔体を製造する方法とこのようにして製造された金属吸着性の焼結多孔体に関するものである。
（ｉ）アミノ基ないしイミノ基と反応する官能基を有するビニルモノマー１０〜７０重量％とビニル基を２個以上有する架橋性モノマー３０〜９０重量％とよりなるモノマー混合物１００重量部を細孔調節剤となる溶媒５０〜２００重量部の存在下に共重合させて得られた多孔質の架橋高分子担体粒子を、平均分子量が２００〜６００のポリエチレンイミンと反応させ、ついでハロゲン化酢酸と反応させてカルボキシメチル化した機能性樹脂粒子。または
（ｉｉ）アミノ基ないしイミノ基と反応する官能基を有しないビニルモノマー０〜７０重量％とビニル基を２個以上有する架橋性モノマー１００〜３０重量％とよりなるモノマー混合物１００重量部を、細孔調節剤となる溶媒５０〜２００重量部の存在下に共重合させて得られる多孔質の架橋高分子担体粒子にさらにアミノ基ないしイミノ基と反応する官能基を導入して多孔質の架橋高分子担体粒子を製造し、この架橋高分子担体粒子を平均分子量が２００〜６００のポリエチレンイミンと反応させ、ついでハロゲン化酢酸と反応させてカルボキシメチル化した機能性樹脂粒子。
More specifically, the present invention
A mixture of particles and powder consisting of 10 to 70% by weight of functional resin particles selected from the following (i) or (ii) and 90 to 30% by weight of thermoplastic resin powder is heated to a temperature near the melting point of the thermoplastic resin. The present invention relates to a method for producing a metal-adsorptive sintered porous body characterized by heating and sintering in step 1 and a metal-adsorptive sintered porous body thus produced.
(I) Pore adjustment of 100 parts by weight of a monomer mixture comprising 10 to 70% by weight of a vinyl monomer having a functional group that reacts with an amino group or imino group and 30 to 90% by weight of a crosslinkable monomer having two or more vinyl groups Porous crosslinked polymer carrier particles obtained by copolymerization in the presence of 50 to 200 parts by weight of a solvent serving as an agent are reacted with polyethyleneimine having an average molecular weight of 200 to 600, and then reacted with halogenated acetic acid. Carboxymethylated functional resin particles. Or (ii) 100 parts by weight of a monomer mixture composed of 0 to 70% by weight of a vinyl monomer having no functional group that reacts with an amino group or imino group and 100 to 30% by weight of a crosslinkable monomer having two or more vinyl groups. A functional group that reacts with an amino group or an imino group is further introduced into porous crosslinked polymer carrier particles obtained by copolymerization in the presence of 50 to 200 parts by weight of a solvent serving as a pore regulator, and porous crosslinking is performed. Functional resin particles produced by producing polymer carrier particles, reacting the crosslinked polymer carrier particles with polyethyleneimine having an average molecular weight of 200 to 600, and then reacting with halogenated acetic acid.
さらに、（ｉ）および（ｉｉ）の多孔質の架橋高分子担体粒子は、水系懸濁重合方法により製造されたものであるか、あるいは塊状重合により製造された多孔質の架橋高分子を粉砕・分級して製造されたものである。
機能性樹脂粒子と混合する熱可塑性樹脂粉体の樹脂としては、ポリエチレン、ポリプロピレン、ポリエチレンとポリプロピレンの混合物、およびこれらの樹脂を主成分とする熱可塑性樹脂混合物が使用される。ポリエチレンやポリプロピレンと混合して使用することができる樹脂としては、たとえばエチレン−酢酸ビニル共重合体あるいはエチレン−ビニルアルコール共重合体があげられる。この混合使用される熱可塑性樹脂の使用割合は、ポリエチレン、ポリプロピレンまたはポリエチレンとポリプロピレンの混合物と同じ重量まで添加混合して使用してもよい。
Further, the porous crosslinked polymer carrier particles (i) and (ii) are produced by an aqueous suspension polymerization method, or the porous crosslinked polymer produced by bulk polymerization is pulverized. It is manufactured by classification.
As the resin of the thermoplastic resin powder to be mixed with the functional resin particles, polyethylene, polypropylene, a mixture of polyethylene and polypropylene, and a thermoplastic resin mixture mainly composed of these resins are used. Examples of the resin that can be used by mixing with polyethylene or polypropylene include an ethylene-vinyl acetate copolymer and an ethylene-vinyl alcohol copolymer. The thermoplastic resin used for mixing may be added to and mixed with polyethylene, polypropylene, or a mixture of polyethylene and polypropylene up to the same weight.
さらに、機能性樹脂粒子の重量の３０重量％まで、以下の（ａ）または（ｂ）の陰イオン交換樹脂粒子で置換することができる。
（ａ）アミノ基ないしイミノ基と反応する官能基を有するビニルモノマー１０〜７０重量％とビニル基を２個以上有する架橋性モノマー９０〜３０重量％とよりなるモノマー混合物１００重量部を細孔調節剤となる溶媒５０〜２００重量部の存在下に共重合させて得られた多孔質の架橋高分子担体粒子をアミンと反応させて陰イオン交換基とした陰イオン交換樹脂粒子。
（ｂ）アミノ基ないしイミノ基と反応する官能基を有しないビニルモノマー０〜７０重量％とビニル基を２個以上有する架橋性モノマー１００〜３０重量％とよりなるモノマー混合物１００重量部を、細孔調節剤となる溶媒５０〜２００重量部の存在下に共重合させて得られる多孔質の架橋高分子担体粒子にさらにアミノ基ないしイミノ基と反応する官能基を導入して多孔質の架橋高分子担体粒子をアミンと反応させて陰イオン交換基とした陰イオン交換樹脂粒子。
すなわち、機能性樹脂粒子と陰イオン交換樹脂粒子の混合割合は、１００〜７０重量％：０〜３０重量％の範囲である。
陰イオン交換樹脂粒子は、金属オキソ酸類の吸着特性の改善のために混合されるものであり、混合しても混合しなくてもよい。ただし、大量に混合した場合には、キレート樹脂粒子の金属吸着特性が極度に減少してしまうおそれがあるため、３０重量％以下、好ましくは２０重量％以下で混合される。
陰イオン交換樹脂を製造する場合に使用されるアミンは、どのようなものであってもよいが、低分子アミンを用いることが好ましく、たとえば、メチルアミン、エチルアミン、プロピルアミン、ブチルアミン、２−アミノエタノール等の一級アミン、ジメチルアミン、ジエチルアミン、ジプロピルアミン、ジブチルアミン、Ｎ−メチル−２−アミノエタノール等の二級アミン、トリチルアミン、トリエチルアミン、ジメチルエチルアミン、ジメチルプロピルアミン、ジメチルブチルアミン、Ｎ,Ｎ−ジメチル−２−アミノエタノール等の三級アミンがあげられる。
Furthermore, up to 30% by weight of the functional resin particles can be substituted with the following anion exchange resin particles (a) or (b).
(A) Pore control of 100 parts by weight of a monomer mixture composed of 10 to 70% by weight of a vinyl monomer having a functional group that reacts with an amino group or imino group and 90 to 30% by weight of a crosslinkable monomer having two or more vinyl groups Anion exchange resin particles obtained by reacting porous crosslinked polymer carrier particles obtained by copolymerization in the presence of 50 to 200 parts by weight of a solvent serving as an agent with amines to form anion exchange groups.
(B) 100 parts by weight of a monomer mixture composed of 0 to 70% by weight of a vinyl monomer having no functional group that reacts with an amino group or imino group and 100 to 30% by weight of a crosslinkable monomer having two or more vinyl groups is finely divided. A functional group that reacts with an amino group or an imino group is further introduced into the porous crosslinked polymer carrier particles obtained by copolymerization in the presence of 50 to 200 parts by weight of a solvent serving as a pore regulator, thereby increasing the degree of porous crosslinking. Anion exchange resin particles obtained by reacting molecular carrier particles with amines to form anion exchange groups.
That is, the mixing ratio of the functional resin particles and the anion exchange resin particles is in the range of 100 to 70% by weight: 0 to 30% by weight.
The anion exchange resin particles are mixed for improving the adsorption property of the metal oxo acids, and may be mixed or not mixed. However, when mixed in a large amount, the metal adsorption property of the chelate resin particles may be extremely reduced, so that the mixing is performed at 30% by weight or less, preferably 20% by weight or less.
Any amine can be used in the production of the anion exchange resin, but it is preferable to use a low molecular weight amine such as methylamine, ethylamine, propylamine, butylamine, 2-amino. Primary amines such as ethanol, secondary amines such as dimethylamine, diethylamine, dipropylamine, dibutylamine, N-methyl-2-aminoethanol, tritylamine, triethylamine, dimethylethylamine, dimethylpropylamine, dimethylbutylamine, N, N -Tertiary amines such as dimethyl-2-aminoethanol.
機能性樹脂粒子と熱可塑性樹脂粉体との粒子と粉体との混合物を熱可塑性樹脂の融点付近の温度で加熱・焼結すると、混合物中の熱可塑性樹脂粉体は、その表層付近が融着して相互に結合し、多孔質で三次元網目状の構造を形成するが、この際機能性樹脂粒子がこの網目状の構造中に固定された焼結体となるので、機能性樹脂粒子の機能を損なうことなく、取り扱いが容易で各種要求に対応しやすい金属吸着性の焼結多孔体を製造することができる。この際、機能性樹脂粒子の表面と熱可塑性樹脂粉体の表面とが融着により結合して一体的になることも予想される。 When a mixture of functional resin particles and thermoplastic resin powder and powder is heated and sintered at a temperature near the melting point of the thermoplastic resin, the surface of the thermoplastic resin powder in the mixture melts. Are bonded to each other to form a porous, three-dimensional network structure. In this case, the functional resin particles become a sintered body fixed in the network structure. Without impairing the function, it is possible to manufacture a metal-adsorbing sintered porous body that is easy to handle and easily meets various requirements. At this time, the surface of the functional resin particles and the surface of the thermoplastic resin powder are also expected to be integrated by fusion.
細孔調節剤となる溶媒は、ビニルモノマーと相溶性をもちかつ重合反応に寄与しない溶媒を意味し、生成した高分子を多孔質にするとともに、比表面積を大きくするために必要なものであり、溶媒（細孔調節剤）の種類と量により細孔径および比表面積を調節する。細孔調節剤は、使用するモノマーの物性により適宜選択される。これら溶媒（細孔調節剤）の使用量が少なすぎると十分な細孔径および比表面積を得るとことはできない。一方、細孔調節剤の量が多すぎる場合には、軟質になって膨潤度合いが大きくなるとともに、細孔径が大きくなり過ぎて比表面積が小さくなるとともに機械的強度が低下する、さらには、水系懸濁重合を用いる場合には粒子が形成されないなどの問題が生じる。したがって、重合させるモノマー総量１００重量部に対して５０〜２００重量部、好ましくは１００〜２００重量部の範囲で使用する。 The solvent used as a pore regulator means a solvent that is compatible with the vinyl monomer and does not contribute to the polymerization reaction, and is necessary for making the produced polymer porous and increasing the specific surface area. The pore diameter and specific surface area are adjusted according to the type and amount of the solvent (pore regulator). The pore regulator is appropriately selected depending on the physical properties of the monomer used. If the amount of these solvents (pore regulators) used is too small, sufficient pore diameter and specific surface area cannot be obtained. On the other hand, when the amount of the pore regulator is too large, the degree of swelling becomes soft and the degree of swelling increases, the pore diameter becomes too large and the specific surface area decreases and the mechanical strength decreases. When suspension polymerization is used, there arises a problem that particles are not formed. Therefore, it is used in the range of 50 to 200 parts by weight, preferably 100 to 200 parts by weight, based on 100 parts by weight of the total amount of monomers to be polymerized.
アミノ基ないしイミノ基と反応する官能基を有するビニルモノマーの官能基としては、ハロゲン化アルキル基、エポキシ基、酸無水物基などがあげられる。
ハロゲン化アルキル基を有するビニルモノマーとしては、たとえばクロロメチルスチレン、３−クロロ−２−ヒドロキシプロピルメタクリレート、３−クロロ−２−ヒドロキシプロピルアクリレート、２−クロロエチルメタクリレート、２−クロロエチルアクリレート等があげられる。
エポキシ基を有する官能性モノマーとしては、たとえばグリシジルメタクリレート、グリシジルアクリレート、ビニルベンジルグリシジルエーテル等があげられる。
酸無水物基を有するビニルモノマーとしては、たとえば無水マレイン酸があげられる。
アミノ基ないしイミノ基と反応する官能基を有しないビニルモノマーとしては、二次反応によりハロゲン化アルキル基あるいはエポキシ基を導入しやすいビニルモノマーが好ましく、たとえばスチレン、エチルビニルベンゼン、ビニルナフタレン、２−ヒドロキシエチルメタクリレート、グリセリンメタクリレート、ネオペンチルグリコールメタクリレート、トリメチロールプロパンメタクリレート、Ｎ，Ｎ−ジエチルアミノエチルメタクリレートなどがあげられる。
Examples of the functional group of the vinyl monomer having a functional group that reacts with an amino group or an imino group include a halogenated alkyl group, an epoxy group, and an acid anhydride group.
Examples of the vinyl monomer having a halogenated alkyl group include chloromethylstyrene, 3-chloro-2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 2-chloroethyl methacrylate, 2-chloroethyl acrylate and the like. It is done.
Examples of the functional monomer having an epoxy group include glycidyl methacrylate, glycidyl acrylate, vinylbenzyl glycidyl ether and the like.
Examples of the vinyl monomer having an acid anhydride group include maleic anhydride.
As the vinyl monomer having no functional group that reacts with an amino group or imino group, a vinyl monomer that can easily introduce a halogenated alkyl group or an epoxy group by a secondary reaction is preferable. For example, styrene, ethyl vinyl benzene, vinyl naphthalene, 2- Examples thereof include hydroxyethyl methacrylate, glycerin methacrylate, neopentyl glycol methacrylate, trimethylol propane methacrylate, N, N-diethylaminoethyl methacrylate and the like.
２個以上のビニル基を有する架橋性モノマーとしては、ジビニルベンゼン、ジビニルナフタレン等の芳香族架橋性モノマー、エチレンジメタクリレート、ジエチレングリコールジメタクリレート、グリセリンジメタクリレート、トリメチロールプロパントリメタクリレート、ネオペンチルグリコールトリメタクリレート等の多官能メタクリレート系モノマー、エチレンジアクリレート、ジエチレングリコールジアクリレート、グリセリンジアクリレート、トリメチロールプロパントリアクリレート、ネオペンチルグリコールトリアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート等の多官能アクリレート系モノマー、この他、トリアリルイソシアヌレート、トリメタアリルイソシアヌレート等のシアヌル酸骨格を有する架橋性モノマーなどがあげられる。 Examples of the crosslinkable monomer having two or more vinyl groups include aromatic crosslinkable monomers such as divinylbenzene and divinylnaphthalene, ethylene dimethacrylate, diethylene glycol dimethacrylate, glycerin dimethacrylate, trimethylolpropane trimethacrylate, neopentyl glycol trimethacrylate. Polyfunctional methacrylate monomers such as ethylene diacrylate, diethylene glycol diacrylate, glycerin diacrylate, trimethylolpropane triacrylate, neopentyl glycol triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, etc., this Others, triallyl isocyanurate, trimethallyl isocyanurate, etc. Such as crosslinking monomer having a cyanuric acid structure and the like.
多孔質の架橋高分子担体粒子とポリエチレンイミンとを反応させて、ポリエチレンイミンを導入するが、このポリエチレンイミンの導入反応は、公知のとおりである。たとえば、ポリエチレンイミンを、水、アルコール、ジメチルホルムアミド等あるいはそれらの混合溶媒中に溶解し、その溶液中に反応性官能基を有する多孔質の架橋性高分子担体を分散させ、撹拌しながら、室温〜８０℃で、３〜２４時間の反応を行う。ただし、アミド構造で導入されたものを還元する必要がある場合には、ＬｉＡＬＨ４、ＢＨ３−ＴＨＦを用いた公知の方法で還元する。 Porous crosslinked polymer carrier particles and polyethyleneimine are reacted to introduce polyethyleneimine, and this polyethyleneimine introduction reaction is known. For example, polyethyleneimine is dissolved in water, alcohol, dimethylformamide or the like or a mixed solvent thereof, and a porous crosslinkable polymer carrier having a reactive functional group is dispersed in the solution. The reaction is carried out at -80 ° C for 3-24 hours. However, when it is necessary to reduce the amide structure introduced, it is reduced by a known method using LiALH 4 or BH 3 -THF.
ポリエチレンイミンを多孔質の架橋高分子担体に導入後、公知の方法により、アルカリ条件下でハロゲン化酢酸を用いてカルボキシメチル化を行う。ハロゲン化酢酸としては、クロロ酢酸、ブロモ酢酸等が用いられる。アルカリ濃度に関しては特に規定はしないが、一般には０．５〜３ｍｏｌ／Ｌの水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム等を用いる。カルボキシメチル化して得られたキレート樹脂粒子は、水、酸、水の順に洗浄し、目的に応じて対イオン交換を行った後、乾燥して、金属吸着性焼結多孔体製造に供せられる。
本発明で使用する樹脂などについては、発明を実施するための形態のところでさらに説明する。
After introducing polyethyleneimine into the porous crosslinked polymer carrier, carboxymethylation is carried out using a halogenated acetic acid under alkaline conditions by a known method. As the halogenated acetic acid, chloroacetic acid, bromoacetic acid or the like is used. The alkali concentration is not particularly specified, but generally 0.5 to 3 mol / L sodium hydroxide, potassium hydroxide, sodium carbonate or the like is used. The chelate resin particles obtained by carboxymethylation are washed in the order of water, acid, and water, and after performing counterion exchange according to the purpose, they are dried and used for the production of a metal-adsorptive sintered porous body. .
The resin used in the present invention will be further described in the form for carrying out the invention.
本発明によれば、多孔質の架橋高分子担体を基材とする機能性吸着材粒子と熱可塑性樹脂粉体とを混合し、熱融着法を用いて焼結多孔体を製造することにより、機能性吸着材粒子のもつ金属吸着性を損なうことなく、工場排水、用水、環境水等の中の重金属除去回収に適した金属吸着性の焼結多孔体を得ることができる。本発明の金属吸着性の焼結多孔体は、使用目的に適した金型を用いることにより、多彩な形状を有する金属吸着性の焼結多孔体を得ることが可能である。すなわち、金型の変更により、平板状や円盤状、円柱状や角柱状、中空の円筒状や角筒状、さらには、これらの一端を閉塞させたカップ状等の多彩な成形体とすることが可能である。この金属吸着性焼結多孔体の使用に当たっては、粒子状の吸着材のように管体に充てんして使用するということも可能ではあるが、本発明の金属吸着性の焼結多孔体を流路に差し込む、あるいは槽内に投入するだけでよく、作業性が大幅に改善される。 According to the present invention, by mixing functional adsorbent particles based on a porous cross-linked polymer carrier and a thermoplastic resin powder, a sintered porous body is produced using a thermal fusion method. Thus, it is possible to obtain a metal-adsorbing sintered porous body suitable for heavy metal removal and recovery in industrial wastewater, irrigation water, environmental water, etc. without impairing the metal-adsorbing property of the functional adsorbent particles. The metal-adsorbing sintered porous body of the present invention can be obtained in various shapes by using a mold suitable for the intended purpose. That is, by changing the mold, it is possible to obtain various molded bodies such as flat plate shape, disk shape, columnar shape, prismatic shape, hollow cylindrical shape, rectangular tube shape, and cup shape with one end closed. Is possible. When using this metal-adsorbing sintered porous body, it is possible to fill it with a tube like a particulate adsorbent, but the metal-adsorbing sintered porous body of the present invention is flown. It only needs to be inserted into the road or put into the tank, and the workability is greatly improved.
本発明において用いる機能性吸着材粒子の基材となる多孔質の架橋高分子担体は、アミノ基ないしイミノ基と反応する官能基を有するビニルモノマーとビニル基を２個以上有する架橋性モノマーとをこれらビニルモノマーと相溶性を持ちかつ重合反応に寄与しない細孔調節剤となる溶媒の存在下で共重合させて得られる多孔質の架橋高分子担体粒子、あるいは、アミノ基ないしイミノ基と反応する官能基を有しないビニルモノマーとビニル基を２個以上有する架橋性モノマーとを細孔調節剤となる溶媒の存在下で共重合させて得られる多孔質の架橋高分子に二次的な反応によりアミノ基ないしイミノ基と反応する官能基を導入したものである。 The porous cross-linked polymer carrier used as a base material for the functional adsorbent particles used in the present invention comprises a vinyl monomer having a functional group that reacts with an amino group or an imino group and a cross-linkable monomer having two or more vinyl groups. It reacts with porous cross-linked polymer carrier particles obtained by copolymerization in the presence of a solvent that is compatible with these vinyl monomers and does not contribute to the polymerization reaction, or with amino groups or imino groups. By a secondary reaction to a porous cross-linked polymer obtained by copolymerizing a vinyl monomer having no functional group and a cross-linkable monomer having two or more vinyl groups in the presence of a solvent serving as a pore regulator. A functional group that reacts with an amino group or imino group is introduced.
機能性吸着材粒子の焼結多孔体内での膨潤による問題を解消させるため、本発明の多孔質の架橋高分子担体におけるビニル基を２個以上有する架橋性モノマーの量は、全モノマーの重量に対して３０％以上である。アミノ基ないしイミノ基と反応する官能基を有するビニルモノマーとの共重合により多孔質の架橋高分子担体を得る場合には、金属吸着性を示すアミン系化合物を反応させる官能基が１０重量％未満では金属吸着量が低くなりすぎるため、架橋性モノマーの量は３０〜９０重量％の範囲である必要がある。アミノ基ないしイミノ基と反応する官能基を有しないビニルモノマーとの共重合により多孔質の架橋高分子担体を得る場合には、アミノ基ないしイミノ基と反応する官能基は二次反応により導入するため、架橋性モノマーの量は３０〜１００重量％の範囲でよい。 In order to eliminate the problem due to swelling of the functional adsorbent particles in the sintered porous body, the amount of the crosslinkable monomer having two or more vinyl groups in the porous crosslinked polymer carrier of the present invention is equal to the weight of all monomers. On the other hand, it is 30% or more. When a porous cross-linked polymer carrier is obtained by copolymerization with a vinyl monomer having a functional group that reacts with an amino group or imino group, the functional group that reacts with an amine compound exhibiting metal adsorption is less than 10% by weight. Then, since the amount of metal adsorption becomes too low, the amount of the crosslinkable monomer needs to be in the range of 30 to 90% by weight. When a porous crosslinked polymer carrier is obtained by copolymerization with a vinyl monomer having no functional group that reacts with an amino group or imino group, the functional group that reacts with an amino group or imino group is introduced by a secondary reaction. Therefore, the amount of the crosslinkable monomer may be in the range of 30 to 100% by weight.
アミノ基ないしイミノ基と反応する官能基を有するビニルモノマーの官能基としては、ハロゲン化アルキル基、エポキシ基、酸無水物基などがあげられる。ハロゲン化アルキル基を有する反応性モノマーとしては、例えば、クロロメチルスチレン、３−クロロ−２−ヒドロキシプロピルメタクリレート、３−クロロ−２−ヒドロキシプロピルアクリレート、２−クロロエチルメタクリレート、２−クロロエチルアクリレート等があげられる。エポキシ基を有する官能性モノマーとしては、例えば、グリシジルメタクリレート、グリシジルアクリレート、ビニルベンジルグリシジルエーテル等があげられる。酸無水物基を有するビニルモノマーとしては、例えば、無水マレイン酸があげられる。 Examples of the functional group of the vinyl monomer having a functional group that reacts with an amino group or an imino group include a halogenated alkyl group, an epoxy group, and an acid anhydride group. Examples of the reactive monomer having a halogenated alkyl group include chloromethylstyrene, 3-chloro-2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 2-chloroethyl methacrylate, and 2-chloroethyl acrylate. Can be given. Examples of the functional monomer having an epoxy group include glycidyl methacrylate, glycidyl acrylate, vinylbenzyl glycidyl ether, and the like. Examples of the vinyl monomer having an acid anhydride group include maleic anhydride.
上記モノマーと共重合が可能なビニル基を２個以上有する架橋性モノマーとしては、ジビニルベンゼン、ジビニルナフタレン等の芳香族架橋性モノマー、エチレンジメタクリレート、ジエチレングリコールジメタクリレート、グリセリンジメタクリレート、トリメチロールプロパントリメタクリレート、ネオペンチルグリコールトリメタクリレート等の多官能メタクリレート系モノマー、エチレンジアクリレート、ジエチレングリコールジアクリレート、グリセリンジアクリレート、トリメチロールプロパントリアクリレート、ネオペンチルグリコールトリアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート等の多官能アクリレート系モノマー、この他、トリアリルイソシアヌレート、トリメタアリルイソシアヌレート等のシアヌル酸骨格をもつ架橋性モノマー等があげられる。 Examples of the crosslinkable monomer having two or more vinyl groups copolymerizable with the above monomers include aromatic crosslinkable monomers such as divinylbenzene and divinylnaphthalene, ethylene dimethacrylate, diethylene glycol dimethacrylate, glycerin dimethacrylate, trimethylolpropane trichloride. Polyfunctional methacrylate monomers such as methacrylate, neopentyl glycol trimethacrylate, ethylene diacrylate, diethylene glycol diacrylate, glycerin diacrylate, trimethylolpropane triacrylate, neopentyl glycol triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, etc. Multifunctional acrylate monomer, triallyl isocyanurate, trimer Crosslinking monomers with cyanuric acid skeleton such as triallyl isocyanurate and the like.
本発明では、アミノ基ないしイミノ基と反応する官能基を有しないビニルモノマーとビニル基を２個以上有する架橋性モノマーとの共重合により得られる多孔質の架橋高分子に二次反応によりアミノ基ないしイミノ基と反応する官能基を導入した多孔質の架橋高分子担体粒子を使用することが可能である。二次反応によりアミノ基ないしイミノ基と反応する官能基を導入する場合、酸無水物基を導入することも可能ではあるが、導入反応が煩雑であるため、本発明においては、ハロゲン化アルキル基あるいはエポキシ基を導入する。二次反応によりハロゲン化アルキル基あるいはエポキシ基を導入しやすいモノマーとしては、フェニル基、水酸基、アミノ基などをもつモノマーが用いられる。このようなモノマーとしては、例えば、スチレン、エチルビニルベンゼン、ビニルナフタレン、２−ヒドロキシエチルメタクリレート、グリセリンメタクリレート、ネオペンチルグリコールメタクリレート、トリメチロールプロパンメタクリレート、Ｎ，Ｎ−ジエチルアミノエチルメタクリレートなどがあげられる。 In the present invention, a porous cross-linked polymer obtained by copolymerization of a vinyl monomer having no functional group that reacts with an amino group or imino group and a cross-linkable monomer having two or more vinyl groups is subjected to an amino group by a secondary reaction. It is also possible to use porous crosslinked polymer carrier particles into which functional groups that react with imino groups are introduced. When a functional group that reacts with an amino group or imino group is introduced by a secondary reaction, it is possible to introduce an acid anhydride group, but since the introduction reaction is complicated, an alkyl halide group is used in the present invention. Alternatively, an epoxy group is introduced. As a monomer that can easily introduce a halogenated alkyl group or an epoxy group by a secondary reaction, a monomer having a phenyl group, a hydroxyl group, an amino group, or the like is used. Examples of such monomers include styrene, ethyl vinyl benzene, vinyl naphthalene, 2-hydroxyethyl methacrylate, glycerin methacrylate, neopentyl glycol methacrylate, trimethylol propane methacrylate, N, N-diethylaminoethyl methacrylate, and the like.
本発明においては、非膨潤状態においても十分な比表面積を有する多孔質の高分子担体粒子である必要があるため、ビニルモノマーの共重合時に、ビニルモノマーと相溶性を持ちかつ重合反応に寄与しない細孔調節剤となる溶媒を存在させて共重合を行う。細孔調節剤は生成した高分子を多孔質にするとともに、比表面積を大きくするために必要なものであり、細孔調節剤の種類と量により細孔径および比表面積を調節する。細孔調節剤は、使用するモノマーの物性により適宜選択されるものであるが、一般的に、トルエン、キシレンなどの芳香族炭化水素、酢酸ブチル、フタル酸ジメチルなどのエステル類、アミルアルコール、オクチルアルコールなどの難溶性アルコール類、オクタン、ドデカンなどのパラフィン類が使用される。これら細孔調節剤の使用量が少なすぎると十分な細孔径および比表面積を得るとことはできない。一方、細孔調節剤の量が多すぎる場合には、軟質になって膨潤度合いが大きくなる、細孔径が大きくなり過ぎて比表面積が小さくなるとともに機械的強度が低下する、さらには、水系懸濁重合を用いる場合には粒子が形成されないなどの問題が生じる。したがって、重合させるモノマー総量１００重量部に対して５０〜２００重量部、好ましくは１００〜２００重量部の範囲で使用する。多孔質の架橋高分子担体の細孔径、比表面積は吸着対象成分や共存成分の特性にも依存するが、本発明においては、非膨潤時の細孔物性として、平均細孔径４〜５０ｎｍ、比表面積１００〜１０００ｍ２／ｇのものを用いるのが好ましい。 In the present invention, since it is necessary to be a porous polymer carrier particle having a sufficient specific surface area even in a non-swelled state, it has compatibility with the vinyl monomer and does not contribute to the polymerization reaction when copolymerizing the vinyl monomer. Copolymerization is carried out in the presence of a solvent serving as a pore regulator. The pore regulator is necessary for making the produced polymer porous and increasing the specific surface area, and the pore diameter and the specific surface area are adjusted by the kind and amount of the pore regulator. The pore regulator is appropriately selected depending on the physical properties of the monomer used, but in general, aromatic hydrocarbons such as toluene and xylene, esters such as butyl acetate and dimethyl phthalate, amyl alcohol, octyl Slightly soluble alcohols such as alcohol and paraffins such as octane and dodecane are used. If the amount of these pore regulators used is too small, sufficient pore diameter and specific surface area cannot be obtained. On the other hand, when the amount of the pore regulator is too large, the degree of swelling becomes soft and the degree of swelling increases, the pore diameter becomes too large and the specific surface area decreases and the mechanical strength decreases. When turbid polymerization is used, there arises a problem that particles are not formed. Therefore, it is used in the range of 50 to 200 parts by weight, preferably 100 to 200 parts by weight, based on 100 parts by weight of the total amount of monomers to be polymerized. Although the pore diameter and specific surface area of the porous crosslinked polymer carrier depend on the properties of the adsorption target component and the coexisting component, in the present invention, the average pore diameter of 4 to 50 nm, the ratio of the pore properties when not swollen It is preferable to use one having a surface area of 100 to 1000 m 2 / g.
多孔質の架橋高分子担体を製造する場合の共重合反応としては、水系懸濁重合法、塊状重合法などの公知の重合方法を用いることが可能である。ただし、無水マレイン酸などの酸無水物基を有するモノマーを使用する場合は、水系懸濁重合で重合することはできない。水系懸濁重合で多孔質の高分子粒子を得る場合、ポリビニルアルコールや水溶性セルロースなどの水溶液中に重合性モノマー、細孔調節剤、重合開始剤の混合溶液を入れ、撹拌羽根、ホモミキサー、スターティックミキサー等を用いて適切な油滴径に分散した後、加温により重合反応を開始させて粒子状の高分子を得る。塊状重合法を用いる場合には、重合性モノマー、細孔調節剤、重合開始剤の混合溶液を加温して重合反応を開始させて塊状の高分子を得る。その後、ハンマーミル、ロールクラッシャー、ボールミル等を用いて粉砕後、目的の粒子径に分級して使用する。 As a copolymerization reaction for producing a porous crosslinked polymer carrier, a known polymerization method such as an aqueous suspension polymerization method or a bulk polymerization method can be used. However, when a monomer having an acid anhydride group such as maleic anhydride is used, it cannot be polymerized by aqueous suspension polymerization. When obtaining porous polymer particles by aqueous suspension polymerization, a mixed solution of a polymerizable monomer, a pore regulator, and a polymerization initiator is placed in an aqueous solution such as polyvinyl alcohol or water-soluble cellulose, and a stirring blade, a homomixer, After dispersing to an appropriate oil droplet size using a static mixer or the like, the polymerization reaction is started by heating to obtain a particulate polymer. When the bulk polymerization method is used, a mixed polymer of a polymerizable monomer, a pore regulator, and a polymerization initiator is heated to initiate a polymerization reaction, thereby obtaining a bulk polymer. Thereafter, the mixture is pulverized using a hammer mill, roll crusher, ball mill or the like, and then classified into a desired particle size for use.
高度に膨潤する機能性吸着材粒子を用いて焼結多孔体を成形した場合には、焼結多孔体の細孔の閉塞や機能性吸着材粒子の脱離などの問題が生じるため、本発明においては機能性吸着材粒子の膨潤度を押さえるため、膨潤度の低い多孔質の架橋高分子担体を用いる。膨潤度は、一般に乾燥時のベッド体積とメタノール等の極性溶媒に膨潤させた時のベッド体積から、式１により求められる。本発明においては１．０〜２．０、好ましくは１．０〜１．８の膨潤度を示す架橋高分子担体が用いられる。 When a sintered porous body is formed using functional adsorbent particles that swell highly, problems such as blockage of pores of the porous porous body and desorption of functional adsorbent particles occur. In order to suppress the swelling degree of the functional adsorbent particles, a porous crosslinked polymer carrier having a low swelling degree is used. The degree of swelling is generally obtained by Equation 1 from the bed volume when dried and the bed volume when swollen in a polar solvent such as methanol. In the present invention, a crosslinked polymer carrier having a degree of swelling of 1.0 to 2.0, preferably 1.0 to 1.8 is used.
本発明の機能性吸着材粒子は、多孔質の架橋高分子担体にポリエチレンイミンを導入後、ハロゲン化酢酸によりカルボシキメチル化されたものである。ポリエチレンイミンそのものもキレート性官能基として機能するが、多くの重金属を一斉に吸着するためには、カルボキシメチル化を行ったアミノ化カルボン酸型官能基が優れている。 The functional adsorbent particles of the present invention are those obtained by introducing polyethyleneimine into a porous crosslinked polymer carrier and then carboxylmethylated with a halogenated acetic acid. Polyethyleneimine itself functions as a chelating functional group, but an aminated carboxylic acid type functional group subjected to carboxymethylation is excellent for adsorbing many heavy metals simultaneously.
一般に、ポリエチレンイミンは鎖長の異なる化合物の混合物であるとともに、直鎖状構造の他に分岐構造の化合物も混在している。つまり、ポリエチレンイミンに含まれるアミノ基構造は、一級、二級、三級のアミノ基が存在しうるが、本発明において使用されるポリエチレンイミンの構造や一級〜三級アミンの比率はどのようなものであってもよく、本発明ではそれらを総合してポリエチレンイミン骨格の化合物という。 In general, polyethyleneimine is a mixture of compounds having different chain lengths, and also has a branched structure compound in addition to a linear structure. That is, the amino group structure contained in polyethyleneimine may include primary, secondary, and tertiary amino groups, but what is the structure of polyethyleneimine used in the present invention and the ratio of primary to tertiary amines? In the present invention, these are collectively referred to as a compound having a polyethyleneimine skeleton.
アミノカルボン酸型キレート剤においては、ポリエチレンイミン骨格の鎖長が長いほど強い金属錯体を形成することが知られている。また、鎖長が長い官能基を担体に固定した場合には、スペーサ効果によって官能基の自由度も高くなり、吸脱着が迅速になるという利点がある。しかし、鎖長が長すぎる（平均分子量６００以上、特に１,０００以上） 場合には、高分子担体の細孔内部まで官能基を高密度に導入することができない。したがって、本発明の製造法において高分子担体に導入されるポリエチレンイミンは、至適な鎖長を有していなければならず、その平均分子量は２００ないし６００である。 In aminocarboxylic acid type chelating agents, it is known that the longer the chain length of the polyethyleneimine skeleton, the stronger the metal complex formed. In addition, when a functional group having a long chain length is fixed to a carrier, there is an advantage that the degree of freedom of the functional group is increased due to the spacer effect, and adsorption / desorption is quick. However, when the chain length is too long (average molecular weight of 600 or more, particularly 1,000 or more), functional groups cannot be introduced at high density into the pores of the polymer carrier. Therefore, the polyethyleneimine introduced into the polymer carrier in the production method of the present invention must have an optimum chain length, and the average molecular weight is 200 to 600.
ポリエチレンイミンの導入反応は、公知のとおりである。すなわち、ポリエチレンイミンを、水、アルコール、ジメチルホルムアミド等あるいはそれらの混合溶媒中に溶解し、その溶液中に反応性官能基を有する多孔質の架橋高分子担体を分散させ、攪拌しながら、室温〜８０℃で、３〜２４時間の反応を行う。ただし、アミド構造で導入されたものを還元する必要がある場合には、ＬｉＡＬＨ４、ＢＨ３−ＴＨＦを用いた公知の方法で還元する。 The introduction reaction of polyethyleneimine is as known. That is, polyethyleneimine is dissolved in water, alcohol, dimethylformamide or the like or a mixed solvent thereof, and a porous crosslinked polymer carrier having a reactive functional group is dispersed in the solution. The reaction is carried out at 80 ° C. for 3 to 24 hours. However, when it is necessary to reduce the amide structure introduced, it is reduced by a known method using LiALH 4 or BH 3 -THF.
ポリエチレンイミンを多孔質の架橋高分子担体に導入後、公知の方法により、アルカリ条件下でハロゲン化酢酸を用いてカルボキシメチル化を行う。ハロゲン化酢酸としては、クロロ酢酸、ブロモ酢酸等が用いられる。アルカリ濃度に関しては特に規定はしないが、一般には０．５〜３ｍｏｌ／Ｌの水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム等を用いる。このようにして得られたキレート樹脂粒子は、水、酸、水の順に洗浄し、目的に応じて対イオン交換を行った後、乾燥して、金属吸着性焼結多孔体の製造に供せられる。 After introducing polyethyleneimine into the porous crosslinked polymer carrier, carboxymethylation is carried out using a halogenated acetic acid under alkaline conditions by a known method. As the halogenated acetic acid, chloroacetic acid, bromoacetic acid or the like is used. The alkali concentration is not particularly specified, but generally 0.5 to 3 mol / L sodium hydroxide, potassium hydroxide, sodium carbonate or the like is used. The chelate resin particles thus obtained are washed in order of water, acid, and water, and after performing counterion exchange according to the purpose, they are dried and used for the production of a metal-adsorptive sintered porous body. It is done.
アミノカルボン酸型官能基は、ヒ素、モリブデン、バナジウム等のように水溶液中で陰イオン（金属オキソ酸と呼ばれる） として存在する金属元素の吸着性が必ずしも高いとはいえない。本発明においては、この問題を解消するため、キレート樹脂と同様の多孔質の架橋高分子担体に陰イオン交換基を導入した陰イオン交換樹脂粒子をキレート樹脂粒子に適宜混合して、これら金属オキソ酸に対する吸着性を改善する。前記反応性官能基を有する多孔質の架橋高分子担体への陰イオン交換基の導入は、ポリエチレンイミンの導入方法と同様である。すなわち、導入目的のアミンを、水、アルコール、ジメチルホルムアミド等あるいはそれらの混合溶媒中に溶解し、反応性官能基を有する多孔質の架橋高分子担体を分散させて、攪拌しながら、室温〜８０℃で、３〜２４時間の反応により多孔質高架橋性陰イオン交換樹脂を得る。 The aminocarboxylic acid type functional group does not necessarily have a high adsorptivity of a metal element present as an anion (called a metal oxo acid) in an aqueous solution such as arsenic, molybdenum, vanadium and the like. In the present invention, in order to solve this problem, anion exchange resin particles having an anion exchange group introduced into a porous crosslinked polymer carrier similar to the chelate resin are appropriately mixed with the chelate resin particles, and these metal oxo Improve acid adsorption. The introduction of an anion exchange group into the porous crosslinked polymer carrier having a reactive functional group is the same as the method for introducing polyethyleneimine. That is, an amine to be introduced is dissolved in water, alcohol, dimethylformamide or the like or a mixed solvent thereof, and a porous crosslinked polymer carrier having a reactive functional group is dispersed and stirred at room temperature to 80 A porous highly crosslinkable anion exchange resin is obtained by reaction at 3 ° C. for 3 to 24 hours.
陰イオン交換樹脂を製造する場合、導入するアミンに関しては特に規定しないが、キレート性官能基を立体的に阻害しない低分子アミンを用いることが好ましい。例えば、メチルアミン、エチルアミン、プロピルアミン、ブチルアミン、２−アミノエタノール等の一級アミン、ジメチルアミン、ジエチルアミン、ジプロピルアミン、ジブチルアミン、Ｎ−メチル−２−アミノエタノール等の二級アミン、トリチルアミン、トリエチルアミン、ジメチルエチルアミン、ジメチルプロピルアミン、ジメチルブチルアミン、Ｎ,Ｎ−ジメチル−２−アミノエタノール等の三級アミンが用いられる。 When producing an anion exchange resin, the amine to be introduced is not particularly defined, but it is preferable to use a low molecular amine that does not sterically hinder the chelating functional group. For example, primary amines such as methylamine, ethylamine, propylamine, butylamine, 2-aminoethanol, secondary amines such as dimethylamine, diethylamine, dipropylamine, dibutylamine, N-methyl-2-aminoethanol, tritylamine, Tertiary amines such as triethylamine, dimethylethylamine, dimethylpropylamine, dimethylbutylamine, N, N-dimethyl-2-aminoethanol are used.
本発明において、陰イオン交換樹脂粒子は金属オキソ酸類の吸着特性の改善のために混合されるものであり、混合しても混合しなくてもよい。ただし、大量に混合した場合には、キレート樹脂粒子の金属吸着特性が極度に減少してしまう恐れがあるため、３０重量％以下、好ましくは２０重量％以下で混合される。 In the present invention, the anion exchange resin particles are mixed in order to improve the adsorption property of the metal oxo acids, and may be mixed or not mixed. However, when mixed in a large amount, the metal adsorption property of the chelate resin particles may be extremely reduced, and therefore, the mixing is performed at 30% by weight or less, preferably 20% by weight or less.
本発明の金属吸着性焼結多孔体は、機能性吸着材粒子と熱可塑性樹脂粉体とを混合後に加熱成形するため、機能性吸着材粒子の熱変性が問題となる。そのため、融点が比較的低いポリエチレンやポリプロピレンが用いられる。これら熱可塑性樹脂粉体を単独あるいは混合して用いることができる。これらの材質は撥水性の強い材質であるが、濡れ性を改善させるため、さらには柔軟性を改善するために、エチレン−酢酸ビニル共重合体やエチレン−ビニルアルコール共重合体の粉体を混合することができる。 Since the metal-adsorbing sintered porous body of the present invention is heat-molded after mixing the functional adsorbent particles and the thermoplastic resin powder, thermal denaturation of the functional adsorbent particles becomes a problem. For this reason, polyethylene or polypropylene having a relatively low melting point is used. These thermoplastic resin powders can be used alone or in combination. These materials have strong water repellency, but in order to improve wettability and further improve flexibility, powders of ethylene-vinyl acetate copolymer and ethylene-vinyl alcohol copolymer are mixed. can do.
本発明において使用される機能性吸着材粒子と熱可塑性樹脂粉体の粒子径は、任意に設定することができるが、一般に、機能性吸着材粒子の平均粒子径は５〜３００μｍ、熱可塑性樹脂粉体の平均粒子径は２０〜８００μｍのものが用いられる。機能性吸着材粒子の平均粒子径が小さい場合には焼結多孔体からの漏出が起きてしまう可能性がある。このような場合、熱可塑性樹脂の溶融度合いを高めることで機能性吸着材粒子の脱落を防ぐことが可能であるが、得られた焼結多孔体の開孔率が低下し、透過性の悪い焼結多孔体となってしまう。そのため、通常は、混合する機能性吸着材粒子の平均径に対して０．５〜４倍の平均径を有する熱可塑性樹脂粉体が使用される。一方、機能性吸着材粒子の粒子径が大きすぎる場合には熱可塑性樹脂粉体との融着度が低くなり、強度、柔軟性ともに不十分な焼結多孔体となってしまう。なお、熱可塑性樹脂粉体の形状に関しては、不定形の破砕型であっても、球形であってもかまわない。 The particle diameters of the functional adsorbent particles and the thermoplastic resin powder used in the present invention can be arbitrarily set. Generally, the average particle diameter of the functional adsorbent particles is 5 to 300 μm, and the thermoplastic resin. A powder having an average particle diameter of 20 to 800 μm is used. When the average particle diameter of the functional adsorbent particles is small, leakage from the sintered porous body may occur. In such a case, it is possible to prevent the functional adsorbent particles from falling off by increasing the degree of melting of the thermoplastic resin, but the porosity of the obtained sintered porous body is reduced and the permeability is poor. It becomes a sintered porous body. Therefore, usually, a thermoplastic resin powder having an average diameter of 0.5 to 4 times the average diameter of the functional adsorbent particles to be mixed is used. On the other hand, when the functional adsorbent particles have an excessively large particle size, the degree of fusion with the thermoplastic resin powder becomes low, resulting in a sintered porous body having insufficient strength and flexibility. The shape of the thermoplastic resin powder may be an irregular crush type or a spherical shape.
本発明において、熱可塑性樹脂粉体に混合される機能性吸着材粒子の量は１０〜７０重量％であり、好ましくは１０〜６０重量％である。添加量が１０重量％未満では焼結多孔体中に固定される機能性吸着材粒子量が少なくなり、十分な金属吸着機能を発揮することができなくなる。また、機能性吸着材粒子の添加量が７０重量％を超えると、焼結多孔体の成形性が低下したり、強度や柔軟性等の物性が低下したりする。 In the present invention, the amount of the functional adsorbent particles mixed with the thermoplastic resin powder is 10 to 70% by weight, preferably 10 to 60% by weight. When the addition amount is less than 10% by weight, the amount of the functional adsorbent particles fixed in the sintered porous body decreases, and a sufficient metal adsorption function cannot be exhibited. On the other hand, when the amount of the functional adsorbent particles added exceeds 70% by weight, the moldability of the sintered porous body is lowered, and physical properties such as strength and flexibility are lowered.
本発明の金属吸着性の焼結多孔体の製造は、つぎの工程によって製造することができる。すなわち、ａ）反応性官能基を有する多孔質の架橋高分子担体を合成する工程、ｂ）前記多孔質の架橋高分子担体にキレート性官能基を導入したキレート樹脂粒子、あるいは、前記多孔質の架橋高分子担体にキレート性官能基を導入したキレート樹脂粒子と前記多孔質の架橋高分子担体にイオン交換性官能基を導入したイオン交換樹脂粒子からなる機能性吸着材粒子を合成する工程、ｃ）機能性吸着材粒子と熱可塑性樹脂粉体とを混合する工程、ｄ）前記機能性吸着材粒子と熱可塑性樹脂粉体との混合物を金型のキャビティに振動させながら充てんする工程、ｅ）前記粒子と粉体との混合物が充てんされた金型を熱可塑性樹脂の融点付近の温度に設定された恒温炉に入れて所定時間加熱して焼結多孔体を成形する工程、および、ｆ）金型を冷却して成形された焼結多孔体を取り出す工程、により製造される。金型の代わりに、金属板あるいは耐熱性のあるプラスチックシート上に、粒子と粉体との混合物を均一にまき、所定の温度に設定した恒温炉中で所定時間加熱するという方法によっても焼結多孔体を得ることが可能である。 The metal adsorbent sintered porous body of the present invention can be manufactured by the following steps. That is, a) a step of synthesizing a porous crosslinked polymer carrier having a reactive functional group, b) a chelate resin particle having a chelating functional group introduced into the porous crosslinked polymer carrier, or the porous A step of synthesizing functional adsorbent particles comprising chelate resin particles having chelating functional groups introduced into a crosslinked polymer carrier and ion exchange resin particles having ion-exchange functional groups introduced into the porous crosslinked polymer carrier; c ) A step of mixing the functional adsorbent particles and the thermoplastic resin powder; d) a step of filling the mixture of the functional adsorbent particles and the thermoplastic resin powder into the mold cavity while vibrating; e) A step in which a mold filled with the mixture of particles and powder is placed in a constant temperature oven set to a temperature near the melting point of the thermoplastic resin and heated for a predetermined time to form a sintered porous body, and f) Cold mold Step of taking a sintered porous body which is formed by, manufactured by. Sintering is also performed by a method in which a mixture of particles and powder is evenly spread on a metal plate or a heat-resistant plastic sheet instead of a mold and heated in a constant temperature oven set at a predetermined temperature for a predetermined time. It is possible to obtain a porous body.
本発明の金属吸着性の焼結多孔体の製造方法によれば、得られる焼結多孔体の細孔径は、使用する熱可塑性樹脂粉体の平均粒子径および粒度分布により決定されると考えてよい。焼結多孔体の濾過精度や通液精度を調節するために、特許文献１２に示されるような多層式焼結体とすることも可能である。すなわち、金型下部に、目的濾過精度を達成しうる粒子径を有する熱可塑性樹脂粉体を、目的の厚さが得られる量だけ充てんして恒温炉中で加熱融着により焼結多孔体を成形後、いったん金型を開け、本発明の粒子と粉体との混合物の一定量を充てんし、再度恒温炉中で所定時間加熱して焼結多孔体を成形するという方法を用いる。この方法により、下面（あるいは上面） に細孔径の異なる焼結多孔体層と一体となった焼結多孔体を得ることができる。焼結多孔体と一体となる熱可塑性樹脂の多孔体層の細孔径は、金属吸着性焼結多孔体がもつ細孔径より大きくても、あるいは小さくてもかまわない。 According to the method for producing a metal-adsorbing sintered porous body of the present invention, it is considered that the pore diameter of the obtained sintered porous body is determined by the average particle diameter and particle size distribution of the thermoplastic resin powder used. Good. In order to adjust the filtration accuracy and liquid passing accuracy of the sintered porous body, a multilayer sintered body as shown in Patent Document 12 can be used. That is, the lower part of the mold is filled with a thermoplastic resin powder having a particle size that can achieve the target filtration accuracy in an amount that can achieve the target thickness, and the sintered porous body is formed by heat fusion in a constant temperature furnace. After molding, a method is used in which the mold is once opened, filled with a certain amount of the mixture of particles and powder of the present invention, and heated again in a constant temperature furnace for a predetermined time to form a sintered porous body. By this method, a sintered porous body integrated with a sintered porous body layer having different pore diameters on the lower surface (or upper surface) can be obtained. The pore diameter of the porous layer of the thermoplastic resin integrated with the sintered porous body may be larger or smaller than the pore diameter of the metal-adsorbing sintered porous body.
本発明により提供される金属吸着性の焼結多孔体は、排水や用水中の重金属除去、環境水や金属処理溶液中からの有価金属の回収、さらには食品や飲料水中からの有害金属の除去などに用いられる。本発明の金属吸着性の焼結多孔体を用いて水溶液中の重金属を吸着・除去する条件は、本発明の記載により限定されるものではないが、例えば、銅、鉛、カドミウム等の吸着に主眼をおく場合は、被処理溶液のｐＨを３〜７、好ましくは４〜６に調整することにより、それら金属を効率よく吸着することができる。この吸着最適ｐＨ域は金属により異なるため、吸着・除去目的金属の吸着特性に合わせて調整すれば種々の金属の吸着に適用することができる。更に、上記のようにして重金属を吸着した金属吸着性の焼結多孔体を、例えば硝酸や塩酸等の酸性水溶液で処理すると、キレートを形成して吸着された重金属は速やかに脱離するので、吸着した重金属を高効率で回収できるとともに、金属吸着性の焼結多孔体の再生を行うことができる。 The metal-adsorbing sintered porous material provided by the present invention is capable of removing heavy metals from wastewater and irrigation water, recovering valuable metals from environmental water and metal treatment solutions, and removing harmful metals from food and drinking water. Used for etc. The conditions for adsorbing and removing heavy metals in an aqueous solution using the metal-adsorbing sintered porous body of the present invention are not limited by the description of the present invention. For example, for adsorption of copper, lead, cadmium, etc. When the main focus is placed, these metals can be adsorbed efficiently by adjusting the pH of the solution to be treated to 3 to 7, preferably 4 to 6. Since the optimum pH range for adsorption differs depending on the metal, it can be applied to adsorption of various metals if it is adjusted according to the adsorption characteristics of the adsorption / removal target metal. Furthermore, when the metal-adsorbing sintered porous body adsorbing heavy metals as described above is treated with an acidic aqueous solution such as nitric acid or hydrochloric acid, chelate is formed and the adsorbed heavy metals are rapidly desorbed. The adsorbed heavy metal can be recovered with high efficiency and the metal adsorbing sintered porous body can be regenerated.
つぎに、実施例によって本発明を説明するが、この実施例によって本発明をなんら限定するものではない。 Next, the present invention will be described with reference to examples, but the present invention is not limited to the examples.
金属吸着性の焼結多孔体Ａの作製
（１）キレート樹脂粒子ａの合成
まず、多孔質の架橋高分子担体の合成は、懸濁重合法により行った。グリシジルメタクリレート６０ｇ、エチレンジメタクリレート１４０ｇ、酢酸ブチル２００ｇおよび２,２’−アゾビスイソブチロニトリル２ｇの混合物を、０．１％ポリビニルアルコール水溶液２，０００ｍＬ中に加え、油滴径が６０μｍになるようにプロペラ式の撹拌機により撹拌した。その後、７０℃で６時間重合反応を行った。生成した共重合体粒子を濾取し、水、メタノール、水の順で洗浄した。一日風乾後、分級を行い、３２〜９０μｍの多孔質の架橋高分子担体８５ｇを得た。この架橋高分子担体７０ｇを、イソプロピルアルコール２００ｍＬ、水８００ｍＬにポリエチレンイミン３００（日本触媒製エポミンＳＰ−００３、平均分子量：３００、アミン比：一級４５％、二級３５％、三級２０％）１５０ｇを溶解した溶液中に加え、５０℃で６時間反応させてポリアミノ化を行った。生成したポリアミノ化樹脂を濾取後、水、メタノール、水の順で洗浄した。このポリアミノ化樹脂の全量を、１Ｍ ＮａＯＨ１，０００ｍＬにクロロ酢酸ナトリウム２５０ｇを溶解した溶液中に加え、４０℃で６時間反応させ、カルボキシメチル化を行った。この反応物を濾過して十分に水で洗浄後、メタノールに置換し、乾燥させ、キレート樹脂粒子ａを得た。
Preparation of metal adsorbing porous porous body A (1) Synthesis of chelate resin particles a First, a porous crosslinked polymer carrier was synthesized by a suspension polymerization method. A mixture of 60 g of glycidyl methacrylate, 140 g of ethylene dimethacrylate, 200 g of butyl acetate and 2 g of 2,2′-azobisisobutyronitrile is added to 2,000 mL of a 0.1% aqueous polyvinyl alcohol solution, resulting in an oil droplet diameter of 60 μm. The mixture was stirred with a propeller type stirrer. Thereafter, a polymerization reaction was carried out at 70 ° C. for 6 hours. The produced copolymer particles were collected by filtration and washed with water, methanol and water in this order. After air drying for one day, classification was performed to obtain 85 g of a porous crosslinked polymer carrier having a size of 32 to 90 μm. 70 g of this crosslinked polymer carrier was added to 200 mL of isopropyl alcohol, 800 mL of water, and polyethyleneimine 300 (Epomin SP-003, Nippon Shokubai, average molecular weight: 300, amine ratio: 45% primary, 35% secondary, 20% tertiary) 150 g Was added to the dissolved solution and reacted at 50 ° C. for 6 hours for polyamination. The produced polyaminated resin was collected by filtration and washed with water, methanol, and water in this order. The total amount of this polyaminated resin was added to a solution obtained by dissolving 250 g of sodium chloroacetate in 1,000 mL of 1M NaOH, and reacted at 40 ° C. for 6 hours to carry out carboxymethylation. The reaction product was filtered and sufficiently washed with water, then replaced with methanol and dried to obtain chelate resin particles a.
（２）キレート樹脂粒子ａの特性評価
前記（１）で得られたキレート樹脂粒子ａの２５０ｍｇをとり、下部に孔径２０μｍのフィルタを挿入した注射筒型リザーバーに充てんし、充てんベッド上部にも同様のフィルタを挿入した。この充てん済みリザーバーに、アセトニトリル、水、３Ｍ硝酸、水および０．１Ｍ酢酸アンモニウム緩衝液（ｐＨ５） の順で、それぞれ１０ｍＬずつ通液してコンディショニングを行った。その後、０．０５Ｍ酢酸アンモニウム緩衝液（ｐＨ５） で調整された０．５Ｍ硫酸銅溶液３ｍＬを通液し、キレート性官能基を銅で飽和させた後、水１０ｍＬ、０．００５Ｍ硝酸５ｍＬで洗浄した。吸着された銅を３Ｍ硝酸３ｍＬで溶出させあるいは溶出し、溶出液を１０ｍＬに定容後、吸光光度計で８０５ｎｍにおける銅の吸光度を測定し、銅吸着量を求めた。その結果、銅の吸着量は、０．３３ｍｍｏｌＣｕ／ｇであり、十分な金属吸着能を示した。また、架橋高分子担体とキレート樹脂粒子ａについて、平均粒子径と分散度 （ＢｅｃｋｍａｎＣｏｕｌｔｅｒ Ｍｕｌｔｉｓｉｚｅｒ３ ＣｏｕｌｔｅｒＣｏｕｎｔｅｒで測定）、比表面積と平均細孔径（Ｂｅｃｋｍａｎ Ｃｏｕｌｔｅｒ ＳＡ３１００ Ｓｕｒｆａｃｅ ＡｒｅａＡｎａｌｙｚｅｒで測定）、乾燥状態のベッド体積とメタノール膨潤ベッド体積から求めた膨潤度を測定した。その結果を表１に示す。キレート樹脂粒子ａは、分級精度も良く、十分な細孔径および比表面積を有し、膨潤度も低いことが分かる。
(2) Characteristic evaluation of chelate resin particles a 250 mg of the chelate resin particles a obtained in the above (1) are taken and filled into a syringe-type reservoir in which a filter having a pore diameter of 20 μm is inserted in the lower part, and the same is applied to the upper part of the packed bed. Inserted a filter. Conditioning was performed by passing 10 mL each of acetonitrile, water, 3M nitric acid, water and 0.1M ammonium acetate buffer (pH 5) in this filled reservoir. Thereafter, 3 mL of 0.5 M copper sulfate solution adjusted with 0.05 M ammonium acetate buffer (pH 5) was passed through to saturate the chelating functional group with copper, and then washed with 10 mL of water and 5 mL of 0.005 M nitric acid. did. The adsorbed copper was eluted or eluted with 3 mL of 3M nitric acid, and the volume of the eluate was adjusted to 10 mL, and the absorbance of copper at 805 nm was measured with an absorptiometer to determine the amount of adsorbed copper. As a result, the adsorption amount of copper was 0.33 mmol Cu / g, indicating a sufficient metal adsorption ability. Further, for the crosslinked polymer carrier and the chelate resin particles a, the average particle size and dispersity (measured by Beckman Coulter Multisizer 3 Coulter Counter), specific surface area and average pore size (measured by Beckman Coulter SA 3100 Surface Area Analyzer), dry bed volume and methanol The degree of swelling determined from the swollen bed volume was measured. The results are shown in Table 1. It can be seen that the chelate resin particles a have good classification accuracy, a sufficient pore diameter and specific surface area, and a low degree of swelling.
（３）金属吸着性の焼結多孔体Ａの作製
前記（１） で得られたキレート樹脂粒子ａの２０ｇとポリエチレン粉体（平均粒子径１２５μｍ）３０ｇを混合して混合物とした、この混合物の一部を直径４７ｍｍ、厚さ３ｍｍの円盤が得られる金型のキャビティに振動させながら充てんをした。その後、金型に蓋をし、１３０℃の恒温炉中で２０分間加熱した。加熱終了後、金型を空冷し、成型品を取り出し、円盤状の直径４７ｍｍ、厚さ３ｍｍの金属吸着性焼結多孔体Ａのフイルターを得た。
(3) Production of metal adsorbing porous porous body A 20 g of the chelate resin particles a obtained in the above (1) and 30 g of polyethylene powder (average particle size 125 μm) were mixed to form a mixture. A portion was filled while vibrating in a mold cavity where a disk having a diameter of 47 mm and a thickness of 3 mm was obtained. Thereafter, the mold was covered and heated in a constant temperature oven at 130 ° C. for 20 minutes. After the heating, the mold was air-cooled, and the molded product was taken out to obtain a filter of metal adsorbing sintered porous body A having a disk-like diameter of 47 mm and a thickness of 3 mm.
（４）金属吸着性焼結多孔体Ａの特性評価
前記（３）で得られた金属吸着性の焼結多孔体Ａのフイルターを直径１３ｍｍに打ち抜き、フィルタホルダに挟み込み、前記（２）と同様の方法で銅の吸着量を調べた。銅吸着量は０．１１ｍｍｏｌ Ｃｕ／ｇであり、十分な金属吸着能を示した。この金属吸着性の焼結多孔体Ａのフイルター中のキレート樹脂粒子の混合量は４０％であるので、キレート樹脂粒子ａ単独で測定した銅の吸着能力の８３．３％を維持していることとなり、ポリエチレン粉体との融着による大きな機能低下はなく十分な金属吸着能を示した。このときの各流出液をＢｅｃｋｍａｎ ＣｏｕｌｔｅｒＭｕｌｔｉｓｉｚｅｒ ３ Ｃｏｕｌｔｅｒ Ｃｏｕｎｔｅｒを用いて測定したが、焼結多孔体Ａのフイルターからのキレート樹脂粒子の漏出は観察されなかった。
(4) Characteristic Evaluation of Metal Adsorbent Sintered Porous Material A The filter of the metal adsorbent sintered porous material A obtained in (3) above is punched out to a diameter of 13 mm and sandwiched between filter holders, as in (2) above. The amount of copper adsorbed was examined by the method described above. The amount of copper adsorption was 0.11 mmol Cu / g, indicating a sufficient metal adsorption capacity. Since the mixing amount of the chelate resin particles in the filter of the metal adsorbing porous porous body A is 40%, 83.3% of the adsorption capacity of copper measured by the chelate resin particles a alone is maintained. Thus, there was no significant functional deterioration due to fusion with polyethylene powder, and sufficient metal adsorption capacity was exhibited. Each effluent at this time was measured using a Beckman Coulter Multisizer 3 Coulter Counter, but leakage of chelate resin particles from the filter of the sintered porous body A was not observed.
（５）評価試験１
金属吸着性焼結多孔体Ａの各種金属の吸着特性評価
（３）で得られた金属吸着性焼結多孔体Ａのフイルターを直径１３ｍｍの円盤状に打ち抜き、フィルタホルダに挟み込み、前記 （２）と同様のコンディショニングを行った。その後、種々のｐＨに調整した金属混合標準液 （五価ヒ素Ａｓ（５価）、カドミウムＣｄ、コバルトＣｏ、三価クロムＣｒ（ＩＩＩ）、銅Ｃｕ、鉄Ｆｅ、マンガンＭｎ、モリブデンＭｏ、ニッケルＮｉ、鉛Ｐｂ、バナジウムＶ、亜鉛Ｚｎ、各０．１ｍｇ／Ｌ）を通液し、金属を吸着させた。吸着させた金属は、前記 （２）と同様に３Ｍ硝酸３ｍＬで溶出させ、溶出液中の金属濃度を測定して、回収率を求めた。金属濃度の測定には、ＰｅｒｋｉｎＥｌｍｅｒＯｐｔｉｍａ ３０００ＤＶ ＩＣＰ発光分光分析装置を用いた。また、前記（２）で作製したキレート樹脂ａのカートリッジを用いて、同様の測定を行った。これらの測定した結果を図１に示す。金属吸着性焼結多孔体Ａの各種金属の吸着特性は、混合した実施例１のキレート樹脂粒子ａの吸着特性とほとんど同じであり、本発明による金属吸着性の焼結多孔体は、焼結多孔体内に固定されたキレート樹脂粒子の吸着特性を変化させていないことが分かる。金属吸着性の焼結多孔体Ａでは、多くの金属についてｐＨ４以上で高い回収率が得られた。アミノカルボン酸型キレート樹脂で錯形成が遅いといわれる三価クロムＣｒ（ＩＩＩ）は中性以上のｐＨでほぼ１００％の回収率が得られた。金属オキソ酸は、汎用のアミノカルボン酸型キレート樹脂と同様に五価ヒ素の回収率が低かったが、モリブデン、バナジウムは、それぞれｐＨ５以下およびｐＨ７以下でほぼ１００％の回収率が得られた。
(5) Evaluation test 1
The metal adsorptive sintered porous body A was obtained by punching the filter of the metal adsorptive sintered porous body A obtained in (3) into a disk shape having a diameter of 13 mm, and sandwiching it in a filter holder. (2) The same conditioning was performed. After that, mixed metal standard solutions adjusted to various pH (pentavalent arsenic As (pentavalent), cadmium Cd, cobalt Co, trivalent chromium Cr (III), copper Cu, iron Fe, manganese Mn, molybdenum Mo, nickel Ni , Lead Pb, vanadium V, zinc Zn, 0.1 mg / L each), and the metal was adsorbed. The adsorbed metal was eluted with 3 mL of 3M nitric acid in the same manner as in (2) above, and the metal concentration in the eluate was measured to determine the recovery rate. A PerkinElmerOptima 3000DV ICP emission spectroscopic analyzer was used to measure the metal concentration. The same measurement was performed using the chelate resin a cartridge prepared in (2) above. The results of these measurements are shown in FIG. The adsorption characteristics of various metals of the metal-adsorbing sintered porous body A are almost the same as the adsorption characteristics of the mixed chelate resin particles a of Example 1, and the metal-adsorbing sintered porous body according to the present invention is sintered. It can be seen that the adsorption characteristics of the chelate resin particles fixed in the porous body are not changed. In the metal-adsorbing sintered porous body A, a high recovery rate was obtained at a pH of 4 or more for many metals. Trivalent chromium Cr (III), which is said to be slow in complex formation with an aminocarboxylic acid type chelate resin, has a recovery rate of almost 100% at a pH of neutral or higher. The metal oxo acid had a low recovery rate of pentavalent arsenic as with the general-purpose aminocarboxylic acid type chelate resin, but the recovery rates of molybdenum and vanadium were almost 100% at pH 5 or less and pH 7 or less, respectively.
金属吸着性の焼結多孔体Ｂの製造
実施例１で得られたキレート樹脂粒子ａの１０ｇ、ポリエチレン粉体 （平均粒子径１２５μｍ） ２０ｇおよびエチレン−酢酸ビニル共重合体粉体 （平均粒子径１２０μｍ） ２０ｇを混合後、実施例１（３） と同様の条件で成形し、直径４７ｍｍ、厚さ３ｍｍの円盤状の金属吸着性焼結多孔体Ｂのフイルターを得た。この金属吸着性の焼結多孔体Ｂの金属吸着量を実施例１（４） と同様に測定した。銅吸着量は、０．０５ｍｍｏｌ Ｃｕ／ｇであった。この金属吸着性の焼結多孔体Ｂのフイルター中のキレート樹脂粒子の混合量は２０％であるので、キレート樹脂粒子ａ単独で測定した銅の吸着能力の７５．８％を維持していた。吸着能力の維持率は金属吸着性の焼結多孔体Ａのものよりも若干低かったが、使用可能な範囲の吸着能力を示した。なお、エチレン−酢酸ビニル共重合体粉体を混合した金属吸着性焼結多孔体Ｂは、金属吸着性の焼結多孔体Ａよりも濡れ性が改善されており、乾燥状態であっても速やかに水が浸透した。また、柔軟性も金属吸着性の焼結多孔体Ａよりも高かった。
Production of metal adsorbing sintered porous body B 10 g of chelate resin particles a obtained in Example 1, 20 g of polyethylene powder (average particle size 125 μm) and ethylene-vinyl acetate copolymer powder (average particle size 120 μm) ) After mixing 20 g, it was molded under the same conditions as in Example 1 (3) to obtain a disk-shaped metal-adsorptive sintered porous body B filter having a diameter of 47 mm and a thickness of 3 mm. The metal adsorption amount of this metal adsorbent sintered porous body B was measured in the same manner as in Example 1 (4). The amount of copper adsorbed was 0.05 mmol Cu / g. Since the mixing amount of the chelate resin particles in the filter of the metal adsorbing porous porous body B is 20%, 75.8% of the copper adsorption capacity measured by the chelate resin particles a alone was maintained. The retention rate of the adsorption capacity was slightly lower than that of the metal-adsorbing sintered porous body A, but the adsorption capacity was in a usable range. The metal-adsorbing sintered porous body B mixed with ethylene-vinyl acetate copolymer powder has improved wettability compared to the metal-adsorbing sintered porous body A, and even in a dry state, Water penetrated into the water. Further, the flexibility was higher than that of the metal adsorbing sintered porous body A.
評価試験２
金属吸着性焼結多孔体Ｂの吸着特性評価
前記評価試験１と同様の方法で、実施例２で作製した金属吸着性の焼結多孔体Ｂの吸着特性評価を行った。実施例１で作製した金属吸着性の焼結多孔体Ａとの比較の結果（五価ヒ素Ａｓ（５価）、カドミウムＣｄ、コバルトＣｏ、三価クロムＣｒ（ＩＩＩ）、銅Ｃｕ、鉄Ｆｅ、マンガンＭｎ、モリブデンＭｏ、ニッケルＮｉ、鉛Ｐｂ、バナジウムＶ、亜鉛Ｚｎの各金属）を図２に示す。図から明らかなように、金属吸着性の焼結多孔体ＡおよびＢの吸着特性はほぼ同じであり、熱可塑性樹脂の材質に大きく依存されることがないことが判明した。
Evaluation test 2
Adsorption characteristic evaluation of metal adsorbing sintered porous body B By the same method as the evaluation test 1, the adsorption characteristic evaluation of the metal adsorbing sintered porous body B produced in Example 2 was performed. As a result of comparison with the metal-adsorbing sintered porous body A produced in Example 1 (pentavalent arsenic As (pentavalent), cadmium Cd, cobalt Co, trivalent chromium Cr (III), copper Cu, iron Fe, FIG. 2 shows manganese Mn, molybdenum Mo, nickel Ni, lead Pb, vanadium V, and zinc Zn. As is apparent from the figure, the adsorption characteristics of the metal-adsorbing sintered porous bodies A and B are almost the same, and it has been found that they are not greatly dependent on the material of the thermoplastic resin.
金属吸着性の焼結多孔体Ｃの作製
（１）キレート樹脂粒子ｂの合成
グリシジルメタクリレート８０ｇ、エチレンジメタクリレート１２０ｇとした他は、実施例１（１）と同様の条件で多孔質の架橋高分子担体をまず合成し、得られた架橋高分子担体を２０〜４５μｍに分級した。この分級した架橋高分子担体を用いて、実施例１（１）と同様の条件でキレート樹脂粒子ｂを合成した。得られたキレート樹脂粒子ｂの平均粒子径は３２μｍ、比表面積は２２４ｍ２／ｇ、平均細孔径は１２．１ｎｍ、および膨潤度は１．１８であった。また、実施例１（２）と同様の方法で銅の吸着量を求めたところ、０．５１ｍｍｏｌ Ｃｕ／ｇであった。
Production of metal adsorbing porous porous body C (1) Synthesis of chelate resin particles b Porous crosslinked polymer under the same conditions as in Example 1 (1) except that 80 g of glycidyl methacrylate and 120 g of ethylene dimethacrylate were used. The carrier was first synthesized, and the obtained crosslinked polymer carrier was classified to 20 to 45 μm. Using this classified crosslinked polymer carrier, chelate resin particles b were synthesized under the same conditions as in Example 1 (1). The resulting chelate resin particles b had an average particle size of 32 μm, a specific surface area of 224 m 2 / g, an average pore size of 12.1 nm, and a degree of swelling of 1.18. Moreover, when the adsorption amount of copper was calculated | required by the method similar to Example 1 (2), it was 0.51 mmol Cu / g.
（２）陰イオン交換樹脂ｃの合成
前記（１）の途中工程で得られたと同一の架橋高分子担体２０ｇをイソプロピルアルコール１００ｍＬに分散し、ついで水４００ｍＬにジエチルアミン２００ｇを溶解した溶液を加え、５０℃で６時間反応させた。反応終了後、反応物を濾過し、十分に水で洗浄後、メタノールに置換し、乾燥し、陰イオン交換樹脂粒子ｃを得た。陰イオン交換樹脂粒子ｃの陰イオン交換容量を逆滴定法により求めたところ、１．１ｍｅｑ／ｇであった。
(2) Synthesis of anion exchange resin c 20 g of the same crosslinked polymer carrier obtained in the intermediate step of (1) above was dispersed in 100 mL of isopropyl alcohol, and then a solution of 200 g of diethylamine dissolved in 400 mL of water was added. The reaction was carried out at 6 ° C. for 6 hours. After completion of the reaction, the reaction product was filtered, sufficiently washed with water, substituted with methanol, and dried to obtain anion exchange resin particles c. When the anion exchange capacity of the anion exchange resin particles c was determined by a back titration method, it was 1.1 meq / g.
（３）金属吸着性の焼結多孔体Ｃの作製
前記（１）のキレート樹脂粒子ｂ １８ｇと 前記（２）の陰イオン交換樹脂粒子２ｇを混合し、混合樹脂粒子ｄを得た。この混合樹脂粒子ｄを実施例１（２）と同様の方法で銅吸着量を求めたところ、０．４５ｍｍｏｌＣｕ／ｇであり、ほぼ混合比率に見合った銅吸着量を示した。この混合樹脂粒子ｄの２０ｇとポリエチレン粉体 （平均粒子径１２５μｍ）２０ｇを混合して混合物とした。この混合物を実施例１（３）と同様の方法により加熱焼結して円盤状の金属吸着性焼結多孔体Ｃを得た。実施例１（４）と同様の方法で測定した銅吸着量は０．２１ｍｍｏｌ Ｃｕ／ｇであった。金属吸着性焼結多孔体Ｃ中のキレート樹脂粒子の混合量は５０％であるので、混合樹脂粒子ｄの吸着能力の９３．３％を維持していた。
(3) Preparation of metal adsorbing porous porous body C 18 g of the chelate resin particles b of (1) and 2 g of anion exchange resin particles of (2) were mixed to obtain mixed resin particles d. When the mixed resin particles d were subjected to a copper adsorption amount in the same manner as in Example 1 (2), it was 0.45 mmol Cu / g, indicating a copper adsorption amount substantially commensurate with the mixing ratio. 20 g of the mixed resin particles d and 20 g of polyethylene powder (average particle size 125 μm) were mixed to obtain a mixture. This mixture was heated and sintered in the same manner as in Example 1 (3) to obtain a disk-shaped metal-adsorptive sintered porous body C. The amount of copper adsorbed measured by the same method as in Example 1 (4) was 0.21 mmol Cu / g. Since the mixing amount of the chelate resin particles in the metal adsorptive sintered porous body C is 50%, 93.3% of the adsorption capacity of the mixed resin particles d was maintained.
評価試験３
金属吸着性焼結多孔体Ｃの吸着特性評価
実施例１の評価試験１と同様の方法で、金属吸着性焼結多孔体Ｃの吸着特性評価を行った。焼結多孔体Ｃと混合樹脂粒子ｄとの吸着特性比較の結果（五価ヒ素Ａｓ（５価）、カドミウムＣｄ、コバルトＣｏ、三価クロムＣｒ（ＩＩＩ）、銅Ｃｕ、鉄Ｆｅ、マンガンＭｎ、モリブデンＭｏ、ニッケルＮｉ、鉛Ｐｂ、バナジウムＶ、亜鉛Ｚｎの各金属）を図３に示す。図３から明らかなように、金属吸着性の焼結多孔体Ｃの吸着特性は、混合樹脂粒子ｄと同じであり、焼結多孔体内に固定された混合樹脂粒子ｄの吸着特性を変化させていないことが分かる。
Evaluation test 3
Evaluation of Adsorption Characteristics of Metal Adsorbent Sintered Porous Body C The adsorption characteristics of metal adsorbent sintered porous body C were evaluated in the same manner as in Evaluation Test 1 of Example 1. Results of comparison of adsorption characteristics between sintered porous body C and mixed resin particles d (pentavalent arsenic As (pentavalent), cadmium Cd, cobalt Co, trivalent chromium Cr (III), copper Cu, iron Fe, manganese Mn, FIG. 3 shows molybdenum Mo, nickel Ni, lead Pb, vanadium V, and zinc Zn. As apparent from FIG. 3, the adsorption characteristics of the metal adsorbing sintered porous body C are the same as the mixed resin particles d, and the adsorption characteristics of the mixed resin particles d fixed in the sintered porous body are changed. I understand that there is no.
評価試験４
金属吸着性焼結多孔体Ｃにおける吸着特性改善効果の確認
この実施例３の金属吸着性の焼結多孔体Ｃは、金属捕捉特性を改善させるためにキレート樹脂粒子ｂに陰イオン交換樹脂粒子ｃが１０％混合されている。そこで、金属吸着性の焼結多孔体Ｃにおける、陰イオン交換樹脂粒子の添加効果を確認した。評価試験１と同様の方法で、金属吸着性の焼結多孔体Ｃとキレート樹脂粒子ｂの吸着特性評価を行った。ただし、測定金属元素は、カドミウムＣｄ、ニッケルＮｉ、鉛Ｐｂ、五価ヒ素Ａｓ（５価）、モリブデンＭｏ、バナジウムＶの６種類の金属とした。測定した結果（カドミウムＣｄ、ニッケルＮｉ、鉛Ｐｂ、五価ヒ素Ａｓ（５価）、モリブデンＭｏ、バナジウムＶの各金属）を図４に示す。陰イオン交換樹脂粒子ｃを混合した金属吸着性の焼結多孔体Ｃにおける重金属元素の吸着特性は、元のキレート樹脂粒子ｂに比べて、酸性度の高いｐＨ２での回収率が低かったが、ｐＨ３以上では元のキレート樹脂粒子ｂの吸着特性を反映していた。一方、金属オキソ酸である五価ヒ素は全領域で元のキレート樹脂粒子ｂより高い回収率を示した。また、同じ金属オキソ酸であるモリブデン、バナジウムでは、中性付近の回収率が大幅に改善されており、陰イオン交換樹脂粒子の混合によるイオン交換相互作用が加味されたためと判断された。
Evaluation test 4
Confirmation of Effect of Improving Adsorption Characteristics in Metal Adsorbent Sintered Porous C The metal adsorbent sintered porous C of Example 3 was prepared by adding anion exchange resin particles c to chelate resin particles b in order to improve metal capture properties. 10% is mixed. Therefore, the effect of adding anion exchange resin particles in the metal adsorbing sintered porous body C was confirmed. In the same manner as in the evaluation test 1, the adsorption characteristics of the metal-adsorbing sintered porous body C and the chelate resin particles b were evaluated. However, the measurement metal elements were six kinds of metals of cadmium Cd, nickel Ni, lead Pb, pentavalent arsenic As (pentavalent), molybdenum Mo, and vanadium V. The measurement results (cadmium Cd, nickel Ni, lead Pb, pentavalent arsenic As (pentavalent), molybdenum Mo, and vanadium V) are shown in FIG. The adsorption characteristics of heavy metal elements in the metal-adsorbing sintered porous body C mixed with the anion exchange resin particles c were lower in the recovery rate at pH 2 where the acidity is higher than the original chelate resin particles b. At pH 3 or higher, the adsorption characteristics of the original chelate resin particles b were reflected. On the other hand, pentavalent arsenic, which is a metal oxo acid, showed a higher recovery rate than the original chelate resin particles b in the entire region. In addition, in the same metal oxo acids such as molybdenum and vanadium, the recovery rate in the vicinity of neutrality was greatly improved, and it was judged that the ion exchange interaction due to the mixing of the anion exchange resin particles was taken into account.
本発明によれば、アミノ基ないしイミノ基と反応する官能基を有する多孔質の架橋性高分子担体に金属吸着性を示すアミン系化合物を反応させてなる金属吸着性の機能性吸着材粒子と熱可塑性樹脂の粉体との混合物を熱可塑性樹脂の融点付近の温度に加熱・焼結して、熱可塑性樹脂の融着により成形される焼結体内部に金属吸着性の機能性吸着材粒子を固定させることにより、単位重量ないし単位表面積当たりの金属吸着量が高く、しかも共存する塩類や有機物の影響を受けることなく、取扱いが容易で、製造が簡便で、しかも各種の要求を満たしやすい金属吸着性の焼結多孔体を製造することが可能となる。本発明の金属吸着性の焼結多孔体は、金型の変更により、平板状や円盤状、円柱状や角柱状、中空の円筒状や角筒状、さらには、これらの一端を閉塞させたカップ状等の多彩な成形体とすることが可能である。この金属吸着性焼結多孔体の使用に当たっては、粒子状の吸着材のように管体に充てんして使用するということも可能ではあるが、本発明の金属吸着性の焼結多孔体を流路に差し込む、あるいは槽内に投入するだけでよく、作業性が大幅に改善される。 According to the present invention, metal adsorbent functional adsorbent particles obtained by reacting a porous cross-linkable polymer carrier having a functional group that reacts with an amino group or imino group with an amine compound exhibiting metal adsorbability, and Metal adsorbent functional adsorbent particles inside a sintered body formed by heating and sintering a mixture of thermoplastic resin powder to a temperature close to the melting point of the thermoplastic resin and fusion of the thermoplastic resin By fixing the metal, the metal adsorption amount per unit weight or unit surface area is high, and the metal is easy to handle, easy to manufacture, and easily meets various requirements without being affected by coexisting salts and organic substances. An adsorptive sintered porous body can be produced. The metal adsorptive sintered porous body of the present invention has a flat plate shape, a disk shape, a columnar shape, a prismatic shape, a hollow cylindrical shape, a rectangular tube shape, and one end thereof closed by changing the mold. Various molded bodies such as cups can be formed. When using this metal-adsorbing sintered porous body, it is possible to fill it with a tube like a particulate adsorbent, but the metal-adsorbing sintered porous body of the present invention is flown. It only needs to be inserted into the road or put into the tank, and the workability is greatly improved.
●：実施例１の金属吸着性焼結多孔体Ａ
△：実施例２の金属吸着性焼結多孔体Ｂ
◆：実施例３の金属吸着性焼結多孔体Ｃ
○：実施例１のキレート樹脂粒子ａ
◇：実施例３のキレート樹脂粒子ｂと陰イオン交換樹脂粒子ｃを混合した混合機能性樹脂粒子ｄ
＋：実施例３のキレート樹脂粒子ｂ
●: Metal-adsorbing sintered porous body A of Example 1
Δ: Metal-adsorptive sintered porous body B of Example 2
◆: Metal-adsorptive sintered porous body C of Example 3
○: Chelate resin particles a of Example 1
◇: Mixed functional resin particle d obtained by mixing chelate resin particle b and anion exchange resin particle c of Example 3
+: Chelate resin particle b of Example 3
Claims (5)
（ｉ）アミノ基ないしイミノ基と反応する官能基を有するビニルモノマー１０〜７０重量％とビニル基を２個以上有する架橋性モノマー９０〜３０重量％とよりなるモノマー混合物１００重量部を溶媒５０〜２００重量部の存在下に共重合させて得られた多孔質の架橋高分子担体粒子を、平均分子量が２００〜６００のポリエチレンイミンと反応させ、ついでハロゲン化酢酸と反応させてカルボキシメチル化した機能性樹脂粒子。
（ｉｉ）アミノ基ないしイミノ基と反応する官能基を有しないビニルモノマー０〜７０重量％とビニル基を２個以上有する架橋性モノマー１００〜３０重量％とよりなるモノマー混合物１００重量部を、溶媒５０〜２００重量部の存在下に共重合させて得られる多孔質の架橋高分子担体粒子にさらにアミノ基ないしイミノ基と反応する官能基を導入して多孔質の架橋高分子担体粒子を製造し、この架橋高分子担体粒子を平均分子量が２００〜６００のポリエチレンミンと反応させ、ついでハロゲン化酢酸と反応させてカルボキシメチル化した機能性樹脂粒子。 A mixture of particles and powder consisting of 10 to 70% by weight of functional resin particles selected from the following (i) or (ii) and 90 to 30% by weight of thermoplastic resin powder is heated to a temperature near the melting point of the thermoplastic resin. A method for producing a metal-adsorptive sintered porous body characterized by heating and sintering with a metal.
(I) 100 parts by weight of a monomer mixture composed of 10 to 70% by weight of a vinyl monomer having a functional group that reacts with an amino group or imino group and 90 to 30% by weight of a crosslinkable monomer having two or more vinyl groups, A function in which porous crosslinked polymer carrier particles obtained by copolymerization in the presence of 200 parts by weight are reacted with polyethyleneimine having an average molecular weight of 200 to 600 and then reacted with halogenated acetic acid to be carboxymethylated Resin particles.
(Ii) 100 parts by weight of a monomer mixture composed of 0 to 70% by weight of a vinyl monomer having no functional group that reacts with an amino group or imino group and 100 to 30% by weight of a crosslinkable monomer having two or more vinyl groups, A porous crosslinked polymer carrier particle is produced by introducing a functional group that reacts with an amino group or imino group into the porous crosslinked polymer carrier particle obtained by copolymerization in the presence of 50 to 200 parts by weight. Functional resin particles obtained by reacting the crosslinked polymer carrier particles with polyethyleneamine having an average molecular weight of 200 to 600 and then reacting with halogenated acetic acid to carboxymethylate.
（ａ）アミノ基ないしイミノ基と反応する官能基を有するビニルモノマー１０〜７０重量％とビニル基を２個以上有する架橋性モノマー９０〜３０重量％とよりなるモノマー混合物１００重量部を細孔調節剤となる溶媒５０〜２００重量部の存在下に共重合させて得られた多孔質の架橋高分子担体粒子をアミンと反応させて陰イオン交換基とした陰イオン交換樹脂粒子。
（ｂ）アミノ基ないしイミノ基と反応する官能基を有しないビニルモノマー０〜７０重量％とビニル基を２個以上有する架橋性モノマー１００〜３０重量％とよりなるモノマー混合物１００重量部を、細孔調節剤となる溶媒５０〜２００重量部の存在下に共重合させて得られる多孔質の架橋高分子担体粒子にさらにアミノ基ないしイミノ基と反応する官能基を導入して多孔質の架橋高分子担体粒子をアミンと反応させて陰イオン交換基とした陰イオン交換樹脂粒子。 4. The functional resin particles comprising a mixture of up to 30% by weight of the functional resin particles replaced with the following anion exchange resin particles (a) or (b): A method for producing a metal-adsorbing sintered porous body described in 1.
(A) Pore control of 100 parts by weight of a monomer mixture composed of 10 to 70% by weight of a vinyl monomer having a functional group that reacts with an amino group or imino group and 90 to 30% by weight of a crosslinkable monomer having two or more vinyl groups Anion exchange resin particles obtained by reacting porous crosslinked polymer carrier particles obtained by copolymerization in the presence of 50 to 200 parts by weight of a solvent serving as an agent with amines to form anion exchange groups.
(B) 100 parts by weight of a monomer mixture composed of 0 to 70% by weight of a vinyl monomer having no functional group that reacts with an amino group or imino group and 100 to 30% by weight of a crosslinkable monomer having two or more vinyl groups is finely divided. A functional group that reacts with an amino group or an imino group is further introduced into the porous crosslinked polymer carrier particles obtained by copolymerization in the presence of 50 to 200 parts by weight of a solvent serving as a pore regulator, thereby increasing the degree of porous crosslinking. Anion exchange resin particles obtained by reacting molecular carrier particles with amines to form anion exchange groups.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009107818A JP5435708B2 (en) | 2009-04-27 | 2009-04-27 | Metal adsorbent sintered porous body and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009107818A JP5435708B2 (en) | 2009-04-27 | 2009-04-27 | Metal adsorbent sintered porous body and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2010254841A JP2010254841A (en) | 2010-11-11 |
| JP5435708B2 true JP5435708B2 (en) | 2014-03-05 |
Family
ID=43316130
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2009107818A Active JP5435708B2 (en) | 2009-04-27 | 2009-04-27 | Metal adsorbent sintered porous body and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5435708B2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5940313B2 (en) | 2012-01-27 | 2016-06-29 | 日本フイルコン株式会社 | Polymer adsorbent |
| JP6522970B2 (en) * | 2015-02-03 | 2019-05-29 | スリーエム イノベイティブ プロパティズ カンパニー | Porous compact, gel-like compact and filter |
| JP7213023B2 (en) * | 2018-04-23 | 2023-01-26 | オルガノ株式会社 | METHOD FOR REMOVING METAL IN LIQUID AND H-TYPE CHELATE RESIN MIXED WITH ANION EXCHANGE RESIN |
| JP7153471B2 (en) | 2018-05-31 | 2022-10-14 | スリーエム イノベイティブ プロパティズ カンパニー | Filters and metal ion removers |
| CN113423500A (en) * | 2018-12-05 | 2021-09-21 | 味之素株式会社 | Sintered body for adsorption, method for producing same, and adsorption apparatus |
| DE102019106646A1 (en) * | 2019-03-15 | 2020-09-17 | Instraction Gmbh | Particles with a biocidal coating |
| JP7329205B2 (en) * | 2019-08-26 | 2023-08-18 | 学校法人 名古屋電気学園 | POROUS ADSORPTION MEDIA, SOLID PHASE EXTRACTION CARTRIDGE WITH POROUS ADSORPTION MEDIA AND METHOD FOR MANUFACTURING POROUS ADSORPTION MEDIA |
| JP7373836B2 (en) * | 2019-08-26 | 2023-11-06 | 学校法人 名古屋電気学園 | Porous adsorption medium, solid phase extraction cartridge equipped with porous adsorption medium, and method for producing porous adsorption medium |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1087701A (en) * | 1996-09-12 | 1998-04-07 | Bio Material:Kk | Porous cellulose support and selective separation of metal using the support |
| JP2003112060A (en) * | 2001-08-02 | 2003-04-15 | Asahi Kasei Corp | Ion adsorbing resin and ion adsorbing porous material |
| JP2005021883A (en) * | 2003-06-12 | 2005-01-27 | Nippon Kayaku Co Ltd | Chelate resin and method for removing trace metallic ion |
| JP4605432B2 (en) * | 2004-02-02 | 2011-01-05 | 日立化成工業株式会社 | Chelate resin and process for producing the same |
| RU2008128863A (en) * | 2005-12-15 | 2010-01-20 | Тонен Кемикал Корпорейшн (Jp) | HYDROPHILIC, COMPOSITE MICROPOROUS MEMBRANE AND METHOD FOR ITS MANUFACTURE |
| JP5290603B2 (en) * | 2007-05-28 | 2013-09-18 | オルガノ株式会社 | Particle aggregation type monolithic organic porous body, method for producing the same, particle aggregation type monolithic organic porous ion exchanger, and chemical filter |
-
2009
- 2009-04-27 JP JP2009107818A patent/JP5435708B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2010254841A (en) | 2010-11-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5435708B2 (en) | Metal adsorbent sintered porous body and method for producing the same | |
| Liu et al. | Review on preparation and adsorption properties of chitosan and chitosan composites | |
| Wang et al. | Removal of various pollutants from water and wastewater by modified chitosan adsorbents | |
| Pour et al. | Removal of dyes and heavy metal ions from water by magnetic hydrogel beads based on poly (vinyl alcohol)/carboxymethyl starch-g-poly (vinyl imidazole) | |
| Sun et al. | Polyethylenimine-functionalized poly (vinyl alcohol) magnetic microspheres as a novel adsorbent for rapid removal of Cr (VI) from aqueous solution | |
| US8110289B2 (en) | Sintered body, resin particles and method for producing the same | |
| Pu et al. | Novel highly porous magnetic hydrogel beads composed of chitosan and sodium citrate: an effective adsorbent for the removal of heavy metals from aqueous solutions | |
| Bayramoglu et al. | Polyethylenimine and tris (2-aminoethyl) amine modified p (GA–EGMA) microbeads for sorption of uranium ions: equilibrium, kinetic and thermodynamic studies | |
| JP5590594B2 (en) | Chelating polymer compound-containing metal adsorbent | |
| JP2014510626A (en) | Filter media | |
| KR20140142347A (en) | Composite ion exchange media for liquid filtration systems | |
| Wang et al. | Adsorption of copper ions by ion-imprinted simultaneous interpenetrating network hydrogel: thermodynamics, morphology and mechanism | |
| El-saied et al. | A promising superabsorbent nanocomposite based on grafting biopolymer/nanomagnetite for capture of 134 Cs, 85 Sr and 60 Co radionuclides | |
| JP2006527078A (en) | Arsenic adsorption ion exchanger | |
| Zhu et al. | A facile ion imprinted synthesis of selective biosorbent for Cu2+ via microfluidic technology | |
| Jia et al. | Novel magnetically separable anhydride-functionalized Fe 3 O 4@ SiO 2@ PEI-NTDA nanoparticles as effective adsorbents: Synthesis, stability and recyclable adsorption performance for heavy metal ions | |
| Anirudhan et al. | Arsenic adsorption from contaminated water on Fe (III)‐coordinated amino‐functionalized poly (glycidylmethacrylate)‐grafted TiO2‐densified cellulose | |
| JP6951335B2 (en) | Porous polymer material for binding metal-containing ions or purifying organic molecules | |
| JP5796867B2 (en) | Chelating resin | |
| JP2011088047A (en) | Polymer fixed type metal adsorbent and method of manufacturing the same | |
| Özeroğlu et al. | Adsorption of uranium ions by crosslinked polyester resin functionalized with acrylic acid from aqueous solutions | |
| Li et al. | Sustainably closed loop recycling of hierarchically porous polymer microbeads for efficient removal of cationic dyes | |
| Zhang et al. | Fabrication of sodium alginate-melamine@ ZIF-67 composite hydrogel and its adsorption application for Pb (II) in wastewater | |
| JP2014114436A (en) | Graft copolymer of ethylene-vinyl alcohol copolymer, manufacturing method thereof, and metal adsorbent with use of the same | |
| JP7053167B2 (en) | Adsorbent aggregate and its manufacturing method and adsorption method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20120323 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20130607 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20130614 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20131205 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20131206 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5435708 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |