CN102029145B - Iron-based composite absorbing agent and preparation method thereof - Google Patents
Iron-based composite absorbing agent and preparation method thereof Download PDFInfo
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- CN102029145B CN102029145B CN 200910177320 CN200910177320A CN102029145B CN 102029145 B CN102029145 B CN 102029145B CN 200910177320 CN200910177320 CN 200910177320 CN 200910177320 A CN200910177320 A CN 200910177320A CN 102029145 B CN102029145 B CN 102029145B
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000002131 composite material Substances 0.000 title abstract description 5
- 239000006096 absorbing agent Substances 0.000 title abstract 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 52
- 239000002184 metal Substances 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 150000002739 metals Chemical class 0.000 claims abstract description 25
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 19
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 19
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003463 adsorbent Substances 0.000 claims description 144
- 239000000243 solution Substances 0.000 claims description 106
- 238000003756 stirring Methods 0.000 claims description 63
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 53
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 53
- 150000001875 compounds Chemical class 0.000 claims description 41
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 25
- 239000012266 salt solution Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 150000002505 iron Chemical class 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims description 8
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 239000013049 sediment Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 239000011737 fluorine Substances 0.000 abstract description 27
- 229910052731 fluorine Inorganic materials 0.000 abstract description 27
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 11
- 239000003651 drinking water Substances 0.000 abstract description 7
- 235000020188 drinking water Nutrition 0.000 abstract description 7
- 150000002910 rare earth metals Chemical class 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 153
- 239000000725 suspension Substances 0.000 description 47
- 238000000151 deposition Methods 0.000 description 27
- 230000008021 deposition Effects 0.000 description 27
- 238000001179 sorption measurement Methods 0.000 description 27
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 26
- 239000000203 mixture Substances 0.000 description 17
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 239000011550 stock solution Substances 0.000 description 15
- 238000001556 precipitation Methods 0.000 description 14
- 239000006228 supernatant Substances 0.000 description 13
- 238000005119 centrifugation Methods 0.000 description 12
- 238000005485 electric heating Methods 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 8
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000002594 sorbent Substances 0.000 description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 230000007246 mechanism Effects 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 206010042674 Swelling Diseases 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- 206010016818 Fluorosis Diseases 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- SLTJEVXIUBGBAY-UHFFFAOYSA-J [Na+].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O Chemical compound [Na+].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O SLTJEVXIUBGBAY-UHFFFAOYSA-J 0.000 description 3
- -1 basic metal salt Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 208000004042 dental fluorosis Diseases 0.000 description 3
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 description 3
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 208000002064 Dental Plaque Diseases 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical group [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052728 basic metal Inorganic materials 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 2
- VZDYWEUILIUIDF-UHFFFAOYSA-J cerium(4+);disulfate Chemical compound [Ce+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VZDYWEUILIUIDF-UHFFFAOYSA-J 0.000 description 2
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 description 2
- 229910000355 cerium(IV) sulfate Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000006115 defluorination reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000004334 fluoridation Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- MPDGHEJMBKOTSU-YKLVYJNSSA-N 18beta-glycyrrhetic acid Chemical compound C([C@H]1C2=CC(=O)[C@H]34)[C@@](C)(C(O)=O)CC[C@]1(C)CC[C@@]2(C)[C@]4(C)CC[C@@H]1[C@]3(C)CC[C@H](O)C1(C)C MPDGHEJMBKOTSU-YKLVYJNSSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 240000004101 Iris pallida Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 206010033799 Paralysis Diseases 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 241000720974 Protium Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000002384 drinking water standard Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229940053652 fluorinse Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 description 1
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- QCAWEPFNJXQPAN-UHFFFAOYSA-N methoxyfenozide Chemical compound COC1=CC=CC(C(=O)NN(C(=O)C=2C=C(C)C=C(C)C=2)C(C)(C)C)=C1C QCAWEPFNJXQPAN-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000006199 nebulizer Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- NIAGBSSWEZDNMT-UHFFFAOYSA-M tetraoxidosulfate(.1-) Chemical compound [O]S([O-])(=O)=O NIAGBSSWEZDNMT-UHFFFAOYSA-M 0.000 description 1
- 208000016261 weight loss Diseases 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 1
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Abstract
The invention discloses an iron-based composite absorbing agent and a preparation method thereof. The iron-based composite absorbing agent comprises iron hydrated oxide, hydrated oxides of other metal and polyving akohol, wherein the other metals are at least one of lanthanide series rare earth metals and zirconium (Zr). The absorbing agent has high absorption capacity on fluorine and can effectively remove fluorinion in water especially in drinking water.
Description
Technical field
The present invention relates to novel absorption material and preparation method thereof, relate to particularly and can effectively remove iron-based compound adsorbent of fluorine ion in the water and preparation method thereof.
Background technology
Drinking water is the main path of human intake's fluorine.Because the fluorine too high levels can cause multiple diseases such as fluorine dental plaque, fluorosis of bone in the drinking water, severe patient can cause the patient to paralyse.Therefore all there are strict requirements to the fluorine content of drinking water for The World Health Organization (WHO) and ministry of Health of China door.The fluorine content of drinking water standard of WHO regulation is 0.6-1.5mg/L, and the highest fluorine content of regulation is 1mg/L in the drinking water sanitary standard of China.
Fluorine content of drinking water exceeds standard, and problem is much national in the world extensively to be existed, and this problem is serious to Chinese influence.China removes last overseas, and all there is endemia fluorosis in various degree in all the other each province and city, is distributed in 1187 counties (city, district, flag), and lesion population is about more than 100,000,000, surplus the fluorine dental plaque patient 4,000 ten thousand, surplus the fluorosis of bone patient 260 ten thousand.Since the 1950's, technology of Fluoride Removal has obtained certain progress, and particularly the activated alumina technology of Fluoride Removal is recommended as the optimization process technology by mechanism of U.S. government.But the activated alumina adsorption capacity is lower, and the regeneration period is shorter, makes its use cost and complexity increase; In use there is the aluminium ion stripping in activated alumina in addition, the potential hazard of polluted drinking water.Therefore the research and development that are used for the novel de-fluoridation adsorbent of alternative activated alumina receive in the world to be paid much attention to.
Patent documentation 1 (one Chinese patent application open CN1326900A) has proposed to contain a kind of and the aqueous hydrochloric acid solution of calcium carbonate reaction and the aqueous solution fluoride ion removing agent of a kind of rare earth element such as cerium, lanthanum or its mixture etc., but it also need utilize flocculant when using.Patent documentation 2 (the open CN1954906A of one Chinese patent application) has proposed a kind of composite metal oxide de-fluoridation adsorbent, and it contains transition metal, aluminium and rare earth metal, is still a kind of adsorbent that contains aluminium.
Newest research results in recent years shows that the oxide of iron, rare earth and some transition metal has higher anion adsorption capacity.Huang Xia is called in name in the Chinese patent 99199712.7 (patent documentation 3) of " iron-rare earth element compound water treatment adsorbent and preparation method thereof " and points out; Compare with activated alumina, the adsorbent of being made up of divalence or trivalent iron salt and rare-earth element salt significantly increases the adsorption capacity of phosphorus and arsenic.Huang Xia is called in name among the Chinese patent 03153998.X (patent documentation 4) of " oxide of high activity iron and preparation method thereof " and points out; Compare with activated alumina, the adsorbent that is made by trivalent iron salt and water soluble hydroxy polymer or water-soluble amide based polyalcohol significantly increases the adsorption capacity of phosphorus.
Yet, the adsorption capacity of above-mentioned two kinds of adsorbents, especially the adsorption capacity to fluorine remains further to be improved.And, because costing an arm and a leg, rare earth cause production cost high.Therefore, need the high adsorbent of exploitation fluorine adsorption capacity, particularly under the constant situation of production cost, improve the fluorine adsorption capacity of adsorbent.
The prior art document
The open CN1326900A of patent documentation 1 one Chinese patent application
The open CN1954906A of patent documentation 2 one Chinese patent application
Summary of the invention
The problem that invention will solve
To the little defective of the existing ubiquitous adsorption capacity of adsorbent, the technical problem that the present invention will solve is to improve the adsorption capacity of adsorbent, especially to the adsorption capacity of fluorine ion.
The inventor has carried out research with keen determination to the problems referred to above; And find: through in the aqueous solution of polyvinyl alcohol (PVA) polymer substance, adding iron salt solutions; Add other metal salt solutions again; Can obtain especially the iron-based compound adsorbent that the adsorption capacity to fluorine improves, said other metals are selected from least a in lanthanide rare metal and the zirconium, thus completion the present invention.
The scheme that is used to deal with problems
First aspect of the present invention provides a kind of iron-based compound adsorbent, and it contains molten iron and closes oxide, other hydrous metal oxides and polyvinyl alcohol, and wherein said other metals are selected from least a in lanthanide rare metal and the zirconium (Zr).
Second aspect of the present invention provides the as above described iron-based compound adsorbent of first aspect, and said iron-based compound adsorbent also contains lanthanide rare metal and alkali-metal sulfuric acid double salt.
The third aspect of the invention provides as above first aspect or the described iron-based compound adsorbent of second aspect, and wherein said lanthanide rare metal is at least a in lanthanum (La) and the cerium (Ce).
Fourth aspect present invention provides the as above described iron-based compound adsorbent in the arbitrary aspect of first aspect to the third aspect, the mol ratio of wherein said iron and other metals (iron: other metals) be 40: 1 to 3: 1.
Fifth aspect present invention provides the as above described iron-based compound adsorbent in the arbitrary aspect of first aspect to fourth aspect, and wherein, said polyvinyl alcohol accounts for the 0.5-10% of said adsorbent gross weight.
The 6th aspect of the present invention provides the as above described iron-based compound adsorbent in arbitrary aspect, first aspect to the five aspects, and wherein, said adsorbent is mainly unformed shape.
The 7th aspect of the present invention provides the preparation method of above-mentioned iron-based compound adsorbent, and this method comprises adding molysite or iron salt solutions in the aqueous solution of polyvinyl alcohol, again after wherein adding aqueous slkali; Under agitation add other metal salt solutions, simultaneously probable back adds aqueous slkali, stirs; Separate and obtain sediment, purifying, drying; Obtain the iron-based compound adsorbent, wherein said other metals are selected from least a in lanthanide rare metal and the zirconium (Zr).
The effect of invention
Iron-based compound adsorbent provided by the invention is mainly the unformed shape material, has bigger specific area and fluorine adsorption capacity.The adsorbent that adsorbent of forming with adsorbent of the prior art such as activated alumina, divalence or trivalent iron salt and rare-earth element salt and trivalent iron salt and water soluble hydroxy polymer or water-soluble amide based polyalcohol make etc. is compared, and the fluorine adsorption capacity of iron-based compound adsorbent of the present invention is high relatively.And because the consumption of other metals such as rare earth metal is suitable, the cost of iron-based compound adsorbent of the present invention is not high relatively.
Description of drawings
Fig. 1 is the X-ray diffraction spectrogram (XRD figure) of iron-based compound adsorbent of the present invention among the embodiment 1.
Fig. 2 is the XRD figure of iron-based compound adsorbent of the present invention among the embodiment 2.
Fig. 3 is the XRD figure of iron-based compound adsorbent of the present invention among the embodiment 5.
Fig. 4 is the XRD figure that compares adsorbent in the comparative example 1.
Fig. 5 is the XRD figure that compares adsorbent in the comparative example 2.
Fig. 6 is the thermogravimetric analysis figure of adsorbent.
Among Fig. 6; 1# is meant the iron-based compound adsorbent of the present invention among the embodiment 1, and 2# is meant the iron-based compound adsorbent of the present invention among the embodiment 2, and 3# is meant the iron-based compound adsorbent of the present invention among the embodiment 5; 4# is meant the comparison adsorbent of comparative example 1, and 5# is meant the comparison adsorbent of comparative example 2.
The specific embodiment
Below in conjunction with the specific embodiment the present invention is elaborated.Characteristics of the present invention and advantage will become more clear, clear and definite along with these explanations.
Used term " hydrous oxide " meaning is meant and contains oxide hydroxy in the literary composition; Comprise metal ion under the alkaline solution effect from the sediment of solution with and in various degree desciccate; For example, common so-called hydroxide such as iron hydroxide, ferrous hydroxide, lanthanide rare metal hydroxides (like lanthanum hydroxide, cerium hydroxide etc.), zirconium hydroxide etc. and desciccate in various degree thereof.
Used term " composite hydrous oxide " meaning is meant the complex oxide one of at least that contains in iron hydroxy and other metals such as lanthanide rare metal (like lanthanum, cerium etc.) and the zirconium in the literary composition.
Used term " molysite " is meant the general name of the salt of metallic elements of ferrum in the literary composition, comprises divalent iron salt and trivalent iron salt.
Used term in the literary composition " lanthanide rare metal and alkali-metal sulfuric acid double salt " is meant the complex vitriolate that lanthanide rare metallic element and alkali metal form as cation.
In iron-based compound adsorbent of the present invention, the degree of polymerization of said polyvinyl alcohol is not special to be limited, and is more than 500 but preferably use the degree of polymerization, particularly 500 to 2400 polyvinyl alcohol.
In an embodiment of iron-based compound adsorbent of the present invention; The mol ratio of said iron and said other metals (iron: other metals) be 40: 1 to 3: 1; Preferred 20: 1 to 3: 1, also more preferably 16: 1 to 8: 1 and 6: 1 to 3: 1, further preferred 12: 1 to 8: 1.The mol ratio of iron and other metals can advantageously make the gained adsorbent have bigger adsorption capacity with low relatively cost in above-mentioned scope.
In an embodiment of iron-based compound adsorbent of the present invention, said polyvinyl alcohol accounts for the 0.5-10% of said adsorbent gross weight, preferred 0.6-8.5%.
The present invention also provides the preparation method of above-mentioned iron-based compound adsorbent, and in a preferred embodiment, this method may further comprise the steps:
(1) aqueous solution of preparation polyvinyl alcohol;
(2) at room temperature in step (1), add molysite or iron salt solutions in the obtained aqueous solution, dissolve and stir, obtain the polyvinyl alcohol water solution of molysite;
(3) under stirring state, the polyvinyl alcohol water solution of the molysite of gained adds aqueous slkali in step (2), and is about 11.0 for about 6.5-until pH value of solution, stirs a period of time again;
(4) under stirring state, continue to add other metal salt solutions, add aqueous slkali then, about 8.0 until pH value of solution for about 5.0-, stir a period of time again, wherein said other metals are selected from least a in lanthanide rare metal and the zirconium (Zr);
(5) sediment is separated, washing, drying obtains the iron-based compound adsorbent.
Wherein, in step (1), can as polyvinyl alcohol is at first added swelling in the cold water, be heated to temperature 80-90 ℃ stirring and dissolving then through the aqueous solution of methods known in the art preparation polyvinyl alcohol to obtain the higher concentration stock solution.The method of preparing above-mentioned stock solution is in those skilled in the art's knowledge and limit of power.Employed polyvinyl alcohol water solution can be obtained by above-mentioned stock solution dilution in the step (1).The polyvinyl alcohol water solution preferred weight concentration of using in the methods of the invention is 0.1%-2.0%, more preferably 0.1%-1.0%.Weight concentration is in this scope, and the ratio of viscosities of solution is suitable for subsequent treatment, strong operability.
In step (2), used molysite is ferrous iron and/or ferric water soluble salt, like nitrate, chloride or sulfate etc., perhaps its mixture.The preferred mixture that uses sulfate or contain sulfate.
In step (3), used aqueous slkali can be NaOH or potassium hydroxide solution etc., uses its regulator solution pH about 11.0 for about 6.5-, preferably about 8.0-about 9.5.In this pH scope, can be fully with suitable form deposition.In addition, evenly carry out fully, preferably to above-mentioned scope, stirring a period of time preferred 10 minutes again with aqueous slkali adjusting pH in order to impel reaction.
In step (4), other used metal salt solutions can be other metals, and promptly the water-soluble salt solution one of at least in lanthanide rare metal and the zirconium like the aqueous solution of nitrate, chloride and sulfate etc., preferably uses the aqueous solution of sulfate.Wherein the lanthanide rare metal is preferably in lanthanum and the cerium at least a.Used aqueous slkali can be NaOH or potassium hydroxide solution etc., and the pH that uses its regulator solution is about 8.0 for about 5.0-, and preferably about 5.0-is about 6.5, also 5.5-about 6.5 more preferably from about.In this pH scope, deposition can be carried out fully, and the adsorption capacity of gained adsorbent is higher.Stir a period of time, preferred 30 minutes purpose is to impel reaction evenly to carry out again, and products therefrom composition and distribution etc. are evenly.
In step (5), can use that the conventional method in this area is separated, purifying and drying, separation can through as centrifugation, isolated by filtration etc. carry out, purifying can through as washing etc. carry out, drying can be through carrying out like air dry or heat drying etc.Yet, for fear of deteriorations such as the composition of final adsorbent product, forms, baking temperature preferred more than 20 ℃ to being lower than 200 ℃, more preferably more than 40 ℃ to being lower than 110 ℃.Certainly, also can the adsorbent of drying pulverized or grind be particulate or powder.
In addition; In order further to control iron and the mol ratio of other metals and the weight content of PVA in the final adsorbent product; Can easily control through the used amount of substance of control in the preparation method, these are all in those skilled in the art's knowledge and limit of power.
Iron-based compound adsorbent provided by the invention has the fluorine adsorption capacity of raising; Its efficient adsorption mechanism still imperfectly understands; Analyze according to sorbing material rerum natura testing result; Infer that its possibility mechanism is following: polyvinyl alcohol has peptizaiton in water, promptly polyvinyl alcohol increases solution viscosity, and surface tension reduces; When the polyvinyl alcohol water solution of molysite during in aqueous slkali effect settle; Less surface tension helps the formation of new deposition core; In addition; Higher solution viscosity, PVA chain structure and the hydroxyl on the PVA chain in the aqueous solution is to the factors such as affinity interaction of metal oxide deposition; All the reunion between new deposition core tendency is played interception, cause forming the compound that molten iron that unformed shape or glassy state deposition separate out closes oxide and polyvinyl alcohol thus, make the specific area that precipitates improve greatly.When other metal salt solutions during in aqueous slkali effect settle, the compound precipitation of formation is distributed in the surface of above-mentioned gained unformed shape or glassy state hydrated ferric oxide deposition, finally obtains the iron-based compound adsorbent of unformed shape or glassy state.Because above-mentioned iron-based deposition has big specific area, and other metallic compounds depositions that are in the surface have stronger adsorption effect to fluorine ion, because the synergy of these factors significantly improves the adsorption capacity to fluorine.
Further Analysis on Mechanism shows, when other metal salt solutions during in aqueous slkali effect settle, the pH of precipitation reaction is comparatively remarkable to the active influence of adsorbent surface.When pH＞9, the adsorbent surface active component is hydrous metal oxides and a small amount of insoluble basic metal salt of unformed shape; And when pH＜6, it is complicated that the adsorbent surface active component becomes, and possibly exist with insoluble basic metal salt in a large number.
Especially; When other slaines that adopted are the lanthanide rare slaine; And when having a large amount of sulfate ion in the solution; It will form the insoluble double salt of lanthanide rare metal sulfate and alkali metal sulfates, for example cerous sulfate sodium, lanthanum sulfate sodium etc. at particle surface in aqueous slkali effect settle.The ion exchange process of sulfate radical and fluorine ion takes place in above-mentioned lanthanide rare metal and alkali-metal sulfuric acid double salt in fluorine-containing solution, therefore can cause adsorbent that bigger defluorination capacity is arranged.
Yet just to the reasonable supposition of mechanism of the present invention, its efficient mechanism is not limited only to above-mentioned explanation in above-mentioned explanation, and mechanism of the present invention and protection domain are not limited.
Embodiment
Come more specifically to describe the present invention below in conjunction with specific embodiment.
Used material and instrument among the embodiment
PVA-1750 polyvinyl alcohol, average degree of polymerization are 1700, Chemical Reagent Co., Ltd., Sinopharm Group
PVA-124 polyvinyl alcohol, average degree of polymerization are 2400, Beijing chemical reagents corporation
PVA-0588 polyvinyl alcohol, average degree of polymerization are 500, the Sichuan vinylon plant
Inorganic medicaments such as molysite, other slaines and NaOH are chemical pure, can be obtained by each chemical reagents corporation or chemical industry factory and office
The accurate reinforcement electric mixer of JJ-1, Jintan, Jiangsu Fuhua Instr Ltd.
PHS-3C numeral shows pH meter, last Haikang appearance Instr Ltd.
The TDL-40B centrifuge, Wuxi Rui Jiang centrifuge factory
DH-101 electric heating constant temperature air dry oven, Beijing Li Kangdasheng Science and Technology Ltd.
HZQ-X100 air constant temperature oscillator, Taicang, Jiangsu experimental facilities factory
Take by weighing 50 gram PVA-1750, added 600 ml deionized water swellings 6 hours, under mechanical agitation, heat then, and keep 90 ℃ of constant temperature, after 3 hours, PVA all dissolves.With the cooling of PVA solution, be settled to 1000 milliliters, obtain 5% PVA-1750 stock solution.Under the room temperature 1M ferric chloride solution 64ml is mixed with 1M copperas solution 32ml, adding PVA stock solution 4ml also stirs, and preparation contains the 0.96M molysite mixed solution 100ml of 0.2% (wt/v) PVA-1750; Under stirring state, in solution, add the 5M sodium hydroxide solution, show pH meter The real time measure pH value of solution value through numeral, along with addition amount of sodium hydroxide increases; Begin to occur deposition; Continue to add sodium hydroxide solution, pH rises, and is 9.0 up to the deposition pH of mixed; Stop to add sodium hydroxide solution, continue to stir suspension 10 minutes; In suspension, add the lanthanum sulfate solution 50ml of 0.5M then, under stirring condition, add small amounts of sodium hydroxide solution, suspension pH value is adjusted to 6.0, continue to stir suspension 30 minutes; With above-mentioned suspension with centrifuge centrifugal 5 minutes, reject supernatant under 4000rpm; Add the appropriate amount of deionized water washing precipitation; Precipitate dispersion with electric mixer, and then centrifugation, secondary so washed; Finally be deposited under 105 ℃ in the electric heating constant temperature air dry oven dry 12 hours, obtain adsorbent 1.
Similar with embodiment 1, at room temperature 1M ferrum sulfuricum oxydatum solutum 64ml is mixed with 1M copperas solution 32ml, adding PVA-1750 stock solution 4ml also stirs, and preparation contains the 0.96M molysite mixed solution 100ml of 0.2% (wt/v) PVA; Under stirring state, in solution, add the 5M sodium hydroxide solution, show pH meter The real time measure pH value of solution value through numeral, along with addition amount of sodium hydroxide increases; Begin to occur deposition; Continue to add sodium hydroxide solution, pH rises, and is 9.0 up to the deposition pH of mixed; Stop to add sodium hydroxide solution, continue to stir suspension 10 minutes; In suspension, add the ceric sulfate solution 50ml of 0.5M then, under stirring condition, add small amounts of sodium hydroxide solution, suspension pH value is adjusted to 5.9, continue to stir suspension 30 minutes; With above-mentioned suspension with centrifuge centrifugal 5 minutes, reject supernatant under 4000rpm; Add the appropriate amount of deionized water washing precipitation; Precipitate dispersion with electric mixer, and then centrifugation, secondary so washed; Finally be deposited under 80 ℃ in the electric heating constant temperature air dry oven dry 12 hours, obtain adsorbent 2.
Similar with embodiment 1, at room temperature 1M iron nitrate solution 64ml is mixed with 1M copperas solution 32ml, adding PVA-1750 stock solution 4ml also stirs, and preparation contains the 0.96M molysite mixed solution 100ml of 0.2% (wt/v) PVA; Under stirring state, in solution, add the 5M sodium hydroxide solution, show pH meter The real time measure pH value of solution value through numeral, along with addition amount of sodium hydroxide increases; Begin to occur deposition; Continue to add sodium hydroxide solution, pH rises, and is 8.5 up to the deposition pH of mixed; Stop to add sodium hydroxide solution, continue to stir suspension 10 minutes; In suspension, add the zirconyl chloride solution 100ml of 0.5M then, under stirring condition, add small amounts of sodium hydroxide solution, suspension pH value is adjusted to 6.1, continue to stir suspension 30 minutes; With above-mentioned suspension with centrifuge centrifugal 5 minutes, reject supernatant under 4000rpm; Add the appropriate amount of deionized water washing precipitation; Precipitate dispersion with electric mixer, and then centrifugation, secondary so washed; Finally be deposited under 80 ℃ in the electric heating constant temperature air dry oven dry 12 hours, obtain adsorbent 3.
Take by weighing 50 gram PVA-124, added 600 ml deionized water swellings 6 hours, under mechanical agitation, heat then, and keep 90 ℃ of constant temperature of temperature, after 3 hours, PVA all dissolves.With the cooling of PVA solution, be settled to 1000 milliliters, obtain 5% PVA-124 stock solution.At room temperature 1M ferric chloride solution 64ml is mixed with 1M copperas solution 32ml, adding PVA-124 stock solution 4ml also stirs, and preparation contains the 0.96M molysite mixed solution 100ml of 0.2% (wt/v) PVA; Under stirring state, in solution, add the 5M sodium hydroxide solution, show pH meter The real time measure pH value of solution value through numeral, along with addition amount of sodium hydroxide increases; Begin to occur deposition; Continue to add sodium hydroxide solution, pH rises, and is 9.2 up to the deposition pH of mixed; Stop to add sodium hydroxide solution, continue to stir suspension 10 minutes; In suspension, add the lanthanum sulfate solution 50ml of 0.1M then, under stirring condition, add small amounts of sodium hydroxide solution, suspension pH value is adjusted to 6.5, continue to stir suspension 30 minutes; With above-mentioned suspension with centrifuge centrifugal 5 minutes, reject supernatant under 4000rpm; Add the appropriate amount of deionized water washing precipitation; Precipitate dispersion with electric mixer, and then centrifugation, secondary so washed; Finally be deposited under 105 ℃ in the electric heating constant temperature air dry oven dry 12 hours, obtain adsorbent 4.
Similar with embodiment 1, at room temperature get 1M ferric chloride solution 64ml and 1M copperas solution 32ml, adding PVA-1750 stock solution 4ml also stirs, and preparation contains the 0.96M iron chloride mixed solution 100ml of 0.2% (wt/v) PVA; Under stirring state, in solution, add the 5M sodium hydroxide solution, show pH meter The real time measure pH value of solution value through numeral, along with addition amount of sodium hydroxide increases; Begin to occur deposition; Continue to add sodium hydroxide solution, pH rises, and is 9.0 up to the deposition pH of mixed; Stop to add sodium hydroxide solution, continue to stir suspension 10 minutes; In suspension, add the lanthanum chloride solution 50ml of 0.2M then, under stirring condition, add small amounts of sodium hydroxide solution, suspension pH value is adjusted to 6.0, continue to stir suspension 30 minutes; With above-mentioned suspension with centrifuge centrifugal 5 minutes, reject supernatant under 4000rpm; Add the appropriate amount of deionized water washing precipitation; Precipitate dispersion with electric mixer, and then centrifugation, secondary so washed; Finally be deposited under 105 ℃ in the electric heating constant temperature air dry oven dry 12 hours, obtain adsorbent 5.
Embodiment 6 preparation of adsorbent
Take by weighing 50 gram PVA-588, added 300 ml deionized water swellings 6 hours, under mechanical agitation, heat then, and keep 90 ℃ of constant temperature of temperature, after 3 hours, PVA all dissolves.With the cooling of PVA solution, be settled to 500 milliliters, obtain 10% PVA-588 stock solution.At room temperature 1M ferric chloride solution 60ml is mixed with 1M copperas solution 30ml, adding PVA-588 stock solution 10ml also stirs, and preparation contains the 0.9M molysite mixed solution 100ml of 1.0% (wt/v) PVA; Under stirring state, in solution, add the 5M sodium hydroxide solution, show pH meter The real time measure pH value of solution value through numeral, along with addition amount of sodium hydroxide increases; Begin to occur deposition; Continue to add sodium hydroxide solution, pH rises, and is 9.5 up to the deposition pH of mixed; Stop to add sodium hydroxide solution, continue to stir suspension 10 minutes; In suspension, add the lanthanum sulfate solution 50ml of 0.1M then, under stirring condition, add small amounts of sodium hydroxide solution, suspension pH value is adjusted to 6.2, continue to stir suspension 30 minutes; With above-mentioned suspension with centrifuge centrifugal 5 minutes, reject supernatant under 4000rpm; Add the appropriate amount of deionized water washing precipitation; Precipitate dispersion with electric mixer, and then centrifugation, secondary so washed; Finally be deposited under 105 ℃ in the electric heating constant temperature air dry oven dry 12 hours, obtain adsorbent 6.
Embodiment 7 preparation of adsorbent
Similar with embodiment 1, at room temperature get 1M ferrum sulfuricum oxydatum solutum 90ml, adding PVA-1750 stock solution 10ml also stirs, and preparation contains the 0.90M ferric sulfate mixed solution 100ml of 0.5% (wt/v) PVA; Under stirring state, in solution, add the 5M sodium hydroxide solution, show pH meter The real time measure pH value of solution value through numeral, along with addition amount of sodium hydroxide increases; Begin to occur deposition; Continue to add sodium hydroxide solution, pH rises, and is 8.5 up to the deposition pH of mixed; Stop to add sodium hydroxide solution, continue to stir suspension 10 minutes; In suspension, add the lanthanum chloride solution 50ml of 0.2M then, under stirring condition, add small amounts of sodium hydroxide solution, suspension pH value is adjusted to 5.9, continue to stir suspension 30 minutes; With above-mentioned suspension with centrifuge centrifugal 5 minutes, reject supernatant under 4000rpm; Add the appropriate amount of deionized water washing precipitation; Precipitate dispersion with electric mixer, and then centrifugation, secondary so washed; Finally be deposited under 80 ℃ in the electric heating constant temperature air dry oven dry 12 hours, obtain adsorbent 7.
Similar with embodiment 1, at room temperature 1M ferrum sulfuricum oxydatum solutum 64ml is mixed with 1M copperas solution 32ml, adding PVA-1750 stock solution 4ml also stirs, and preparation contains the 0.96M molysite mixed solution 100ml of 0.2% (wt/v) PVA; Under stirring state, in solution, add the 5M sodium hydroxide solution, show pH meter The real time measure pH value of solution value through numeral, along with addition amount of sodium hydroxide increases; Begin to occur deposition; Continue to add sodium hydroxide solution, pH rises, and is 9.0 up to the deposition pH of mixed; Stop to add sodium hydroxide solution, continue to stir suspension 10 minutes; In suspension, add the cerous nitrate solution 50ml of 0.25M then, under stirring condition, add small amounts of sodium hydroxide solution, suspension pH value is adjusted to 6.1, continue to stir suspension 30 minutes; With above-mentioned suspension with centrifuge centrifugal 5 minutes, reject supernatant under 4000rpm; Add the appropriate amount of deionized water washing precipitation; Precipitate dispersion with electric mixer, and then centrifugation, secondary so washed; Finally be deposited under 105 ℃ in the electric heating constant temperature air dry oven dry 12 hours, obtain adsorbent 8.
Similar with embodiment 1, at room temperature get 1M ferric chloride solution 96ml, adding PVA-1750 stock solution 4ml also stirs, and preparation contains the 0.96M iron chloride mixed solution 100ml of 0.2% (wt/v) PVA; Under stirring state, in solution, add the 5M sodium hydroxide solution, show pH meter The real time measure pH value of solution value through numeral, along with addition amount of sodium hydroxide increases; Begin to occur deposition; Continue to add sodium hydroxide solution, pH rises, and is 9.0 up to the deposition pH of mixed; Stop to add sodium hydroxide solution, continue to stir suspension 10 minutes; In suspension, add the lanthanum chloride solution 50ml of 0.2M then, under stirring condition, add small amounts of sodium hydroxide solution, suspension pH value is adjusted to 6.0, continue to stir suspension 30 minutes; With above-mentioned suspension with centrifuge centrifugal 5 minutes, reject supernatant under 4000rpm; Add the appropriate amount of deionized water washing precipitation; Precipitate dispersion with electric mixer, and then centrifugation, secondary so washed; Finally be deposited under 105 ℃ in the electric heating constant temperature air dry oven dry 12 hours, obtain adsorbent 9.
Comparative example 1 preparation of adsorbent
Method according to 1 record of embodiment in the patent documentation 3 (Chinese patent 99199712.7); At normal temperatures 0.5M iron chloride 40ml, 0.5M copperas solution 20ml, 0.5M ceric sulfate solution 16ml are mixed; And be settled to 100ml, obtain containing the mixing salt solution of iron chloride 0.2M, ferrous iron 0.1M, quadrivalent cerium 0.08M.Under agitation in mixed solution, add the 1M sodium hydroxide solution, and, when pH reaches 9.5, stop NaOH and add, continue to stir to make in 30 minutes to react and carry out fully through the digital pH value that shows the pH meter monitoring reaction.With above-mentioned suspension with centrifuge centrifugal 5 minutes, reject supernatant under 4000rpm; Add the appropriate amount of deionized water washing precipitation; Precipitate dispersion with electric mixer, and then centrifugation, secondary so washed; Finally be deposited under 105 ℃ in the electric heating constant temperature air dry oven dry 12 hours, must compare adsorbent 1.
Comparative example 2 preparation of adsorbent
Method according to 1 record of embodiment in the patent documentation 4 (Chinese patent 03153998.X); Get 1M ferric chloride solution 96ml at normal temperatures; Add above-mentioned PVA-1750 storing solution 4ml and mix, obtain the mixed solution of PVA content 0.2%, ferric chloride concn 0.96M.NaOH solution with 5M under stirring carries out precipitation reaction to mixed solution, and control reaction final states pH value is 2.5, continues to stir to make in 30 minutes to react and carries out fully.With above-mentioned suspension with centrifuge centrifugal 5 minutes, reject supernatant under 4000rpm; Add the appropriate amount of deionized water washing precipitation; Precipitate dispersion with electric mixer, and then centrifugation, secondary so washed; Finally be deposited under 105 ℃ in the electric heating constant temperature air dry oven dry 12 hours, must compare adsorbent 2.
The correlated performance evaluation of adsorbent
The chemical composition of adsorbent and the analytical calculation of composition
With the sample of sorbent grinding of drying and through 150 mesh sieve branches, obtain powder sorbent.Adopt the U.S. IRIS Intrepid II XSP of Thermo Fisher company plasma emission spectrometer; At RF Power=1150W; Nebulizer Flow=26.0PSI; Under the conditions of work such as Auxiliary gas=1.0LPM, metallic element in the powder sorbent and element sulphur are directly measured, obtained the wherein quality percentage composition of Fe, La, Na, S etc.
Under nitrogen protection, adopt the U.S. Q5000 of TA company thermogravimetric analyzer, with the programming rate of 10 ℃/min, powder sorbent is carried out the thermogravimetric analysis of 25～550 ℃ of scopes and measure.Owing to nitrogen protection is arranged, can think that the interior non-oxidation reaction of adsorbent takes place with the inorganic salts decomposition reaction, and the dehydration reaction only takes place.This ceiling temperature can be similar to the hydroxyl of thinking in the hydrous metal oxides and all remove and be converted into metal oxide, and then can be through the weight percentage of protium in the former adsorbent of fluid loss approximate calculation.
For confirming PVA content in the adsorbent, all centrifuged supernatant in the adsorbent building-up process are collected, adopt Shanghai essence JH-721 visible spectrophotometer, under the 640nm wavelength, through PVA content in IKI-boric acid spectrophotometry supernatant; Because it is known to add the amount of PVA in the synthetic reaction, therefore can calculate the PVA content in the adsorbent through mass balance, and then calculate the weight percentage of carbon in the adsorbent through the content of carbon among the PVA.
At last be 100% character, calculate the weight content of oxygen element in the adsorbent according to all elements percentage composition sum in the adsorbent.
Mensuration and result of calculation are seen table 1.
The chemical composition of table 1 adsorbent and composition
Except that above-mentioned composition analysis result, from adsorbent 1,2 and 5 and relatively the thermogravimetric analysis figure of 2 four samples of adsorbent can find out that the adsorbent weight-loss curve does not exist between saltation zone, so do not have free water to exist in the adsorbent.
Sorbent structure is analyzed
With the sample of sorbent grinding of drying and through 150 mesh sieve branches, obtain powder sorbent.Get above-mentioned powder sorbent, adopt the D 8 type powder x-ray diffractions of German Bruker company, adopt the copper target to make negative electrode; 25 ℃ of room temperatures; Operating voltage 40KV, electric current 40mA produce the X ray of wavelength 1.5406A down, in 10～70 degree angle of diffraction scopes, carry out diffractometry, and adsorbent diffracting spectrum and standard substance collection of illustrative plates are compared; The result shows; Most of ferric hydrous oxide exists with unformed shape, and other metals exist with unformed shape under the higher synthesis condition of pH, and rare earth element is lower at pH and the synthesis condition that has sulfate radical to exist under can form insoluble complex salt crystal.The X-ray diffraction spectrogram (XRD figure) that adsorbent 1,2 and 5 compares adsorbent 1 and 2 is seen accompanying drawing 1 to 5 respectively.
Get above-mentioned absorbent powder; The degassing is after 2 hours under 200 ℃ and 0.001psi condition; Adopt the U.S. QuadraSorb Station of Quantacrome company 3 specific surface area measuring instruments; With nitrogen is that adsorbate carries out isothermal absorption measurement under temperature 77.3K, and calculates the specific area of adsorbent through the BET equation.
The structured testing result of part adsorbent sees table 2.
The structured testing result of table 2 adsorbent
| The adsorbent numbering | The XRD type feature | |
| Adsorbent | ||
| 1 | The unformed shape thing, XRD diffraction maximum visible part lanthanum element forms the lanthanum sulfate sodium crystal | 112.9 |
| |
The unformed shape thing, XRD diffraction maximum visible part Ce elements forms the cerous sulfate sodium crystal | 119.9 |
| |
The unformed shape thing, XRD diffraction maximum visible part ferro element forms the magnetic iron ore crystal, and the part lanthanum element forms the lanthanum sulfate sodium crystal | 109.0 |
| Compare adsorbent 1 | XRD spectra does not have obvious diffraction maximum, does not have the crystal structure material, and promptly adsorbent is the unformed shape material | 215.6 |
| Compare adsorbent 2 | XRD spectra does not have obvious diffraction maximum, does not have the crystal structure material, and promptly adsorbent is the unformed shape material | 165.6 |
The adsorption capacity evaluation method of adsorbent
Estimate the defluorination adsorption capacity of each embodiment and comparative example adsorbent through following method: fully soak with the polypropylene conical flask of rare nitric acid, use running water, deionized water washes clean then successively to 250ml; In conical flask, add the about 20mg of adsorbent that accurately weighs, and add 10mg/L Fluorinse 100ml, put into the air constant temperature oscillator at 25 ℃ after conical flask is added a cover, adsorption reaction is 24 hours under the 180rpm; To adsorb back solution and filter, and with fluoride ion selective electrode filter liquor carried out the residual fluorine measurement of concetration, and calculate the Unit Weight adsorbance of adsorbent according to following formula.
q＝V(c
i-c
e)/m
Wherein V is the fluorine liquor capacity, c
iBe initial fluorine concentration, c
eBe absorption back fluorine concentration, q is the Unit Weight adsorbance.
The fluorine adsorbance result of calculation of each adsorbent is shown in table 3.
The fluorine adsorption capacity of table 3 adsorbent
| The adsorbent numbering | Absorption back fluorine concentration | Adsorption capacity (mg/g) |
| Adsorbent 1 | 1.26 | 41.42 |
| |
1.36 | 43.31 |
| |
4.05 | 27.75 |
| |
6.41 | 16.98 |
| |
3.89 | 30.17 |
| Adsorbent 6 | 6.12 | 18.26 |
| Adsorbent 7 | 2.82 | 32.61 |
| |
2.50 | 33.83 |
| |
5.82 | 20.64 |
| Compare adsorbent 1 | 5.82 | 20.24 |
| Compare adsorbent 2 | 7.12 | 13.68 |
Result by last table 3 can find out that adsorbent 1-9 of the present invention all has higher fluorine adsorption capacity, therefore can be used for effectively removing the fluorine ion that anhydrates.And because the rare earth metal consumption is low, the production cost of adsorbent 1-9 is not high.
Though preparation condition is similar, yet compare with the comparison adsorbent 1 in the comparative example 1, adsorbent 1 among the embodiment 1 and 2 and 2 fluorine adsorption capacity are obviously high.
Through concrete embodiment and preferred embodiment the present invention has been carried out clear, detailed ground explain; Yet; Embodiment that these are concrete and embodiment only are some exemplary instances of technical scheme of the present invention, protection scope of the present invention are not constituted any restriction.It should be understood that; Under the situation that does not depart from design of the present invention and claims scope required for protection; Those skilled in the art can carry out various modifications or replacement to the each side and the details of technical scheme of the present invention and embodiment thereof, and these modifications or replacement all should be in protection scope of the present invention.
Claims (6)
1. iron-based compound adsorbent; It contains molten iron and closes oxide, other hydrous metal oxides and polyvinyl alcohol; Wherein said other metals are selected from least a in lanthanide rare metal and the zirconium (Zr), and said iron-based compound adsorbent also contains lanthanide rare metal and alkali-metal sulfuric acid double salt, and said lanthanide rare metal is at least a in lanthanum (La) and the cerium (Ce); Said alkali metal is at least a in sodium and the potassium; The mol ratio of said iron and other metals is an iron: other metals are 40: 1 to 3: 1, and said polyvinyl alcohol accounts for the 0.5-10% of said adsorbent gross weight, and said adsorbent is mainly unformed shape.
2. according to the said iron-based compound adsorbent of claim 1, the mol ratio of wherein said iron and other metals is an iron: other metals are 20: 1 to 3: 1.
3. according to the said iron-based compound adsorbent of claim 1, the mol ratio of wherein said iron and other metals is an iron: other metals are 16: 1 to 8: 1 or 6: 1 to 3: 1.
4. according to the said iron-based compound adsorbent of claim 1, the mol ratio of wherein said iron and other metals is an iron: other metals are 12: 1 to 8: 1.
5. iron-based compound adsorbent according to claim 1, wherein said polyvinyl alcohol accounts for the 0.6-8.5% of said adsorbent gross weight.
6. method for preparing the said iron-based compound adsorbent of claim 1, this method comprise and in the aqueous solution of polyvinyl alcohol, add molysite or iron salt solutions, again after wherein adding aqueous slkali; Under agitation add other metal salt solutions, simultaneously probable back adds aqueous slkali, stirs; Separate and obtain sediment, purifying, drying; Obtain the iron-based compound adsorbent, wherein said other metals are selected from least a in lanthanum (La), cerium (Ce) and the zirconium (Zr), and this method may further comprise the steps:
(1) aqueous solution of preparation polyvinyl alcohol;
(2) at room temperature in step (1), add molysite or iron salt solutions in the obtained aqueous solution, stirring and dissolving obtains the polyvinyl alcohol water solution of molysite;
(3) under stirring state, the polyvinyl alcohol water solution of the molysite of gained adds aqueous slkali in step (2), is 6.5-11.0 until pH value of solution, stirs a period of time again;
(4) under stirring state, continue to add other metal salt solutions, add aqueous slkali then, be 5.0-8.0 until pH value of solution, stir a period of time again;
(5) sediment is separated, washing, drying obtains the iron-based compound adsorbent.
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| CN107198934A (en) * | 2017-07-18 | 2017-09-26 | 西安鼎研科技股份有限公司 | A kind of VOCs administering method of water using crystalline state as adsorbent |
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| US4284726A (en) * | 1978-05-13 | 1981-08-18 | Yasumasa Shigetomi | Composite anion adsorbent and method for making same |
| CN1486783A (en) * | 2003-08-22 | 2004-04-07 | 清华大学 | High-activity ferric oxide adsorbant and its prepn |
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| US4284726A (en) * | 1978-05-13 | 1981-08-18 | Yasumasa Shigetomi | Composite anion adsorbent and method for making same |
| CN1486783A (en) * | 2003-08-22 | 2004-04-07 | 清华大学 | High-activity ferric oxide adsorbant and its prepn |
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