CN104302378A - 包含含金属颗粒的过滤介质 - Google Patents
包含含金属颗粒的过滤介质 Download PDFInfo
- Publication number
- CN104302378A CN104302378A CN201280063328.7A CN201280063328A CN104302378A CN 104302378 A CN104302378 A CN 104302378A CN 201280063328 A CN201280063328 A CN 201280063328A CN 104302378 A CN104302378 A CN 104302378A
- Authority
- CN
- China
- Prior art keywords
- metal particle
- containing metal
- chloramines
- thermal decomposition
- decomposition product
- 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.)
- Granted
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 23
- 239000002184 metal Substances 0.000 title claims abstract description 23
- 238000001914 filtration Methods 0.000 title claims abstract description 12
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical class ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 claims abstract description 69
- 238000000034 method Methods 0.000 claims abstract description 56
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 46
- 150000001450 anions Chemical class 0.000 claims abstract description 27
- 150000003839 salts Chemical class 0.000 claims abstract description 27
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 27
- 239000011593 sulfur Substances 0.000 claims abstract description 27
- 239000007864 aqueous solution Substances 0.000 claims abstract description 26
- 239000012530 fluid Substances 0.000 claims abstract description 22
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 88
- 229910052799 carbon Inorganic materials 0.000 claims description 84
- 239000002923 metal particle Substances 0.000 claims description 68
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 51
- -1 nitrogenous oxygen anion Chemical class 0.000 claims description 39
- 239000001301 oxygen Substances 0.000 claims description 23
- 229910052760 oxygen Inorganic materials 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 20
- 239000010452 phosphate Substances 0.000 claims description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 12
- 230000005291 magnetic effect Effects 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 20
- 150000001805 chlorine compounds Chemical class 0.000 abstract 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract 1
- 235000021317 phosphate Nutrition 0.000 abstract 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 abstract 1
- 238000001149 thermolysis Methods 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 description 53
- 238000012360 testing method Methods 0.000 description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 239000000463 material Substances 0.000 description 23
- 229910052809 inorganic oxide Inorganic materials 0.000 description 15
- 239000002245 particle Substances 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 239000000460 chlorine Substances 0.000 description 10
- 229910052801 chlorine Inorganic materials 0.000 description 10
- 238000000197 pyrolysis Methods 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 238000007598 dipping method Methods 0.000 description 9
- 239000011572 manganese Substances 0.000 description 9
- 239000005864 Sulphur Substances 0.000 description 7
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 229940099596 manganese sulfate Drugs 0.000 description 3
- 239000011702 manganese sulphate Substances 0.000 description 3
- 235000007079 manganese sulphate Nutrition 0.000 description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007423 decrease Effects 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
- 239000003302 ferromagnetic material Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 235000019988 mead Nutrition 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000010079 rubber tapping Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 2
- 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 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- 229910019093 NaOCl Inorganic materials 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- QRXDDLFGCDQOTA-UHFFFAOYSA-N cobalt(2+) iron(2+) oxygen(2-) Chemical compound [O-2].[Fe+2].[Co+2].[O-2] QRXDDLFGCDQOTA-UHFFFAOYSA-N 0.000 description 1
- 239000004567 concrete Substances 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
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 238000007416 differential thermogravimetric analysis Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- VFNGKCDDZUSWLR-UHFFFAOYSA-L disulfate(2-) Chemical compound [O-]S(=O)(=O)OS([O-])(=O)=O VFNGKCDDZUSWLR-UHFFFAOYSA-L 0.000 description 1
- 238000004710 electron pair approximation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 230000005307 ferromagnetism Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 150000002737 metalloid compounds Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 229940005654 nitrite ion Drugs 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0222—Compounds of Mn, Re
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0233—Compounds of Cu, Ag, Au
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0233—Compounds of Cu, Ag, Au
- B01J20/0237—Compounds of Cu
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0281—Sulfates of compounds other than those provided for in B01J20/045
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0285—Sulfides of compounds other than those provided for in B01J20/045
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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Abstract
本文描述的是一种液体过滤装置,所述液体过滤装置包括将流体入口流体地连接至流体出口的流体导管;和设置在所述流体导管中的水过滤介质;所述水过滤介质包含含金属颗粒,其中所述含金属颗粒包含金属盐的热解产物,其中所述盐选自含氮氧阴离子、含硫阴离子、氯化物、磷酸盐以及它们的组合;以及从水性溶液中除去氯胺的方法。
Description
技术领域
本公开描述了包含含金属颗粒的过滤介质,其中所述含金属颗粒包含金属盐的热解产物,其中所述盐选自含氮氧阴离子、含硫阴离子、氯化物、磷酸盐以及它们的组合。
背景技术
氯胺常常作为游离氯的氯化的替代形式以低浓度用作城市配水系统中的次级消毒剂。对氯胺处理过的水的味道和气味的关注导致对具有氯胺除去能力的水过滤器的需求增加。
已使用碳粒子(例如活性炭粒子)从水流中除去氯胺。通过减小碳的平均粒径和通过增加碳床接触时间可实现氯胺除去的改善。虽然已知参数诸如接触时间和平均粒径影响氯胺除去效率,但是需要更显著的改善而不显著增加过滤介质的压降。
美国专利号5,338,458(Carrubba等人)公开一种用于通过使该介质与具有催化活性的碳质炭接触来从气体或液体介质中除去氯胺的改善方法。
美国专利号6,699,393(Baker等人)示出了从流体流中除去氯胺的改善方法,与具有催化活性的碳质炭相比较,当流体流与活性炭接触时,其已在含氮分子的存在下热解。
发明内容
期望提供一种过滤介质,其比目前可用过滤介质便宜和/或除去氯胺更有效。在一些情况下,还期望提供实心块的碳以除去氯胺。在其他情况下,期望具有一种可以用于填充床的颗粒状材料。在其他情况下,期望提供一种可以幅材形式使用的材料。
在一方面,公开了一种液体过滤装置,其包括将流体入口流体地连接至流体出口的流体导管;以及设置在所述流体导管中的液体过滤介质;所述液体过滤介质包含含金属颗粒,其中所述含金属颗粒包含金属盐的热解产物,其中所述盐选自含氮氧阴离子、含硫阴离子、氯化物、磷酸盐以及它们的组合。
在另一方面,公开了用于从水性溶液中除去氯胺的方法,包括:提供包含氯胺的水性溶液和使所述水性溶液与包含含金属颗粒的组合物接触,其中所述含金属颗粒包含金属盐的热解产物,其中所述盐选自含氮氧阴离子、含硫阴离子、氯化物、磷酸盐以及它们的组合。
在另一方面,公开了从水性溶液中除去氯胺的方法,所述方法包括:加热金属盐以形成热解产物,其中所述盐选自含氮氧阴离子、含硫阴离子、氯化物、磷酸盐以及它们的组合;使所述热解产物冷却;以及使经冷却的热解产物与包含氯胺的水性溶液接触。
在另一方面,描述了制备复合碳制品的方法,所述方法包括:提供包含以下的混合物:(a)含金属颗粒,其中所述含金属颗粒包含铁盐的热解产物,其中所述盐选自含氮氧阴离子、含硫阴离子、氯化物、磷酸盐以及它们的组合;和(b)可熔融加工的聚合物;使所述混合物与高频率磁场接触,其中所述高频率磁场在约103Hz至约1015Hz的范围内振荡。
上述发明内容并非意图描述每个实施例。本发明的一个和多个实施例的细节还在下面的描述中示出。根据以下“具体实施方式”和“权利要求书”,本发明的其它特征、目标和优点将显而易见。
具体实施方式
如本文所用,术语:
“一个”、“一种”和“所述”可互换使用并且意指一个或多个;和
“和/或”用于表示所说明的情况之一或两者均可能发生,例如,A和/或B包括(A和B)和(A或B)。
另外,本文中由端点描述的范围包括该范围内所包含的所有数值(如,1到10包括1.4、1.9、2.33、5.75、9.98等)。
另外,本文中“至少一个”的表述包括一个和更大的所有数目(如,至少2个、至少4个、至少6个、至少8个、至少10个、至少25个、至少50个、至少100个等)。
本公开涉及包含金属盐的热解产物的组合物,其中所述盐选自含氮氧阴离子、含硫阴离子、氯化物、磷酸盐以及它们的组合。
已经发现这种组合物可用于从水性溶液中除去氯胺。
金属盐的热解产物
本公开的金属盐包括其中所述盐选自含氮氧阴离子、含硫阴离子、氯化物、磷酸盐以及它们的组合的那些。优选的金属盐包括为水溶性的且具有低于1000℃的热分解温度的那些,然而可采用更高的温度。
所述含氮氧阴离子盐可包括硝酸根和/或亚硝酸根离子。
含硫阴离子包含氧阴离子。含硫盐可包括硫酸盐、氨基磺酸盐、亚硫酸盐、硫酸氢盐、亚硫酸氢盐和/或硫代硫酸盐。
氯化物盐是包含氯离子的盐,并且磷酸盐是包含磷酸根离子的盐。
所述金属盐的金属部分可包括任何金属,然而,优选可接受在饮用水中存在的金属。示例性的金属包括:铜、铁、银和锰。
本公开的示例性的金属盐包括:硝酸铁、硫酸锰、硝酸锰、硫酸铜以及它们的组合。
本公开涉及金属盐的热解产物。热解涉及处于或高于所述金属盐开始失去金属束缚水(如果存在的话)并且所述化合物的阴离子部分开始分解的温度下加热所述金属盐。如本文所使用的“热解产物”指通过热由化合物的解离或分解产生的产物。据信,这种热解过程将所述金属盐的性质改变为具有不同化学计量、组成和/或不同的化学特性的材料,其中所述盐的至少一部分被热分解并且通过挥发作为气体而除去。
在一个实施例中,热解时,所述金属的氧化状态改变。例如,在本公开的一个实施例中,所述热解产物中的金属包括氧化状态例如为Cu0、Cu+1或Fe+2的金属的至少一部分。
虽然不想受到理论的限制,但在另一个实施例中,认为所述金属盐的热解产生具有活性表面位点的材料,所述活性表面位点表现出催化氯胺分解的活性增强。由所述金属盐的热解产生的这些表面位点导致产生这样的材料(诸如通过所述热解产物的X射线衍射分析所观察的),其氯胺除去性能优于利用由非热解方法产生的类似金属化合物所产生的那些,例如,来自更传统的方法或细分金属的金属氧化物。在本公开中,所述含金属颗粒包含金属盐的热解产物,其中所述盐选自含氮氧阴离子、含硫阴离子、氯化物、磷酸盐以及它们的组合。
在一个实施例中,所述金属盐经热处理以形成所述热解产物。
在另一个实施例中,在载体(例如碳基质或无机氧化物基质)的存在下,将所述金属盐进行热处理。可将所述金属盐在热解之前浸渍入所述载体中。例如,可将金属盐溶于溶剂中并且使所得溶液与所述载体接触。然后可将所述浸渍的载体加热以形成设置在载体表面(或孔的表面)上的热解产物。
在另一个实施例中,可通过将所述金属盐和所述载体加入到所述溶剂,使并非充分可溶的以溶于所述溶剂(即,不完全溶于所述实验中使用的溶剂体积)的金属盐浸渍入所述载体中。适时地,溶于所述溶剂的所述金属盐可扩散进所述载体并设置在其上,以使得所述金属盐随时间推移结合到所述载体之中或之上。
如本文所使用“含金属颗粒”包括所述金属盐的热解产物和设置(连续地或间断地)在碳基质或无机氧化物基质上的金属盐的热解产物,此类基质可包括颗粒状材料、粉状材料、纤维、管和泡沫。
在一个实施例中,含金属颗粒产物优选为多孔的。该多孔性质将能够例如有更大的表面积以用于氯胺的除去。优选地具有大表面积(例如,基于BET(Brunauer Emmet Teller方法)氮吸附,至少100、500、600或甚至700m2/g;并且至多1000、1200、1400、1500或甚至1800m2/g)。可通过使用高度多孔碳基质或无机氧化物基质和/或通过应用用于降低所得产物的粒度的物理技术(诸如压碎或磨碎)来实现这种大表面积。
碳基质和无机氧化物基质
在一个实施例中,将所述热解产物设置在所述载体诸如碳或无机氧化物基质的表面上。这可能是有利的,因为所述碳或无机氧化物基质可为所述热解产物提供载体,所述热解产物可渗透进所述基质中或驻留在所述基质的表面。另外所述碳或无机氧化物基质也可提供补充氯胺除去的另外除去能力,例如提供有机物、游离氯或金属的除去。
碳基质的形态无特别限制并且可以包括非颗粒状、颗粒状或聚集体。另外的示例性形态包括:碳块、碳整块材料(monolith)、泡沫、薄膜、纤维和纳米颗粒,诸如纳米管和纳米微球。非颗粒状为并非由可分辨的、不同粒子构成的基质。颗粒状基质为具有可分辨粒子的基质,其中该粒子可以为球形或不规则形状并且具有至少0.1、1、5、10、20、或甚至40微米(μm)至最多75μm、100μm、500μm、1毫米(mm)、2mm、4mm、6.5mm或甚至7mm的平均直径。通过较小粒子彼此或与较大载体粒子或表面的接合或凝聚,形成聚集体(或复合材料)。聚集体可以为自立式(抗重力自支撑)。
通常,碳基质的形态将根据应用来选择。例如,当本发明的组合物用于需要低压降的应用(例如在其中通过气体或液体的床中)时,具有大粒度的颗粒状是理想的。在另一个实例中,当用于碳块整块材料时,20至200微米的粒度可能是优选的。
可商购的碳基质包括:在水处理时,以商品名“RGC”得自维吉尼亚州里士满的米德西瓦可(Mead Westvaco Corp,Richmond,VA)的颗粒状活性炭可能是优选的。也可以使用以商品名“KURARAY PGW”得自日本冈山的Kuraray化学品有限公司(Kuraray Chemical Co.,LTD,Okayama,Japan)的活性椰子碳。
碳基质的孔的尺寸可根据应用选择。碳基质可以是微孔碳、大孔碳、介孔碳,或它们的混合物。
所述碳基质可含有较大的晶体区域、石墨畴或它们可以是基本上无序的。特别有用的是基本上无序且具有高表面积的碳基质。如本文所用,基本上无序意指所述碳基质具有约1-10nm的面内畴尺寸。
在一个实施例中,碳基质由活性炭构成,换句话讲,经处理以使其高度多孔(即每单元体积具有大量的孔)而赋予高表面积的碳。
无机氧化物基质的形态不是特别限制的并且可包括非颗粒状的、颗粒状的或聚集体。示例性的形态包括:纤维和纳米颗粒,诸如纳米管和纳米微球。
无机氧化物基质可包括例如二氧化硅(硅石)、氧化锆、二氧化钛、二氧化铈、氧化铝、氧化铁、氧化锌、氧化锡、氧化铝/硅石、氧化锆-硅石、粘土、含滑石材料、尖晶石结构化的氧化物诸如铝酸镁或钴铁氧化物等,以及铝或硅与其他金属氧化物材料的其他二元或三元氧化物。虽然所述无机氧化物可能基本上是纯的,但其可含有少量稳定离子,诸如铵和碱金属离子,或其可为氧化物的组合诸如二氧化钛和氧化锆的组合。
所述无机氧化物基质的孔的尺寸可根据应用选择。所述无机氧化物基质可为微孔的、大孔的、介孔的或它们的混合。特别有用的是具有高表面积的无机氧化物基质。
载体材料的选择相当宽泛并且可无限制地包括氧化铝、硅石、沸石、离子交换树脂和多孔有机材料、活性炭、金属氧化物和金属氧化物骨架(MOF)材料和无机氧化物。所有这些材料可彼此组合使用或与碳基质组合使用。
热解产物的制备
如此前所提及,将所述金属盐单独或在载体的存在下热处理以形成所述热解产物。
所述热处理可在空气环境或在惰性环境诸如在氮气或氩气环境中进行。
所述热解温度,即热解反应进行的温度,可在至少200、250、300、400或甚至500℃;并且至多650、700、800、900、1000、1200或甚至1400℃的温度下进行。通常可通过首先分析待处理的材料(例如,所述金属盐或所述金属盐浸渍的载体)来确定热解进行的温度,方式是通过在控制条件(气氛和加热速率)下进行的差热分析/热重分析(DTA/TGA)以确定其热分解表现。然后在以分解的起始温度开始的各种温度下通过热解所述材料来进行实验以确定在哪个点以及在什么条件(温度、时间和气氛)下形成最具活性的材料。
在一个实施例中,因为反应温度改变,所以所述金属盐的热解产物改变,并且根据所述金属盐和所使用的载体可能存在选择的温度(如果有的话),这提供更有效的氯胺除去。例如,所述金属盐的过度加热可导致所述反应产物的“过度焙烧(over-firing)”,并且所述材料的活性可减弱。在一个实施例中,在热解处理过程中碳载体的存在可改变分解温度。
尽管所述热解产物应该仅包含存在于所述金属盐中的元素,但是由于存在于所述金属盐、所使用的载体(如果有的话)和/或在热处理过程中使用的气氛中的杂质,可能存在少量的其他元素。在一个实施例中,所述含金属颗粒基本上不含硫原子(即,基于所述含金属颗粒的重量计少于5%、2%、1%、0.1%、0.05%或甚至0.01%的硫原子)。
在一个实施例中,所述热解产物包含硫。在一些实施例中加入硫对于氯胺的除去可能是有利的。在一个实施例中,所述含金属颗粒包含硫原子,其来源于含硫阴离子。
在一个实施例中,基于所述含金属颗粒的总质量计,所述含金属颗粒包含大于1.2、1.3、1.5、1.8、2.0、4.0、6.0、8.0或甚至10.0质量%的硫。
在一个实施例中,基于所述含金属颗粒的总质量计,本公开的所述含金属颗粒包含小于0.90、0.80、0.70、0.50、0.30、0.10、0.05、0.01或甚至0.005质量%的氮。
在一个实施例中,基于所述碳基质的总质量计,本公开的所述含金属颗粒包含氮和小于0.50、0.30、0.10、0.05、0.01或甚至0.005质量%的硫。
在一个实施例中,基于所述含金属颗粒的总质量计,本公开的所述含金属颗粒基本上不含氢,包含小于0.40、0.30、0.20、0.10、0.05或甚至0.01质量%的氢。
使用
在本公开的一个实施例中,所述含金属颗粒用作过滤介质。由于本公开的组合物除去氯胺的能力,本公开的组合物可用作过滤介质。可使用本领域已知的过滤方法。
虽然所述含金属的颗粒可以未包含(整体形式)的形式使用,但是优选的是所述含金属颗粒可包含在一些类型的载体基质和/或容器中以便于使用。
本公开的所述含金属颗粒可以粉末形式、颗粒形式,或成型为所需形式来使用。例如,所述含金属颗粒可为碳基质的压缩共混物、所述金属盐的热解产物和粘结剂材料,诸如聚乙烯,例如,超高分子量聚乙烯或高密度聚乙烯(HDPE)。在另一实施例中,本公开的所述含金属颗粒可加载到幅材中,诸如吹塑微纤维,该幅材可压实或可不压实,例如以引用方式并入本文的美国公开号2009/0039028(Eaton等人)中所述。
因为所述含金属颗粒可包含铁磁材料,所以在一个实施例中,所述含金属颗粒可为碳载体诸如碳粒子的部分,其可通过感应加热来加热以形成复合块。通常,在制备碳块整块材料时,在烘箱中加热碳粒子以使所述碳粒子熔合在一起。当使用铁磁材料时,可使用高频率磁场来加热所述含金属颗粒,从而导致所述碳载体变为熔融的并且形成碳块整块材料。在一个实施例中,所述磁场可在范围为约103Hz至约1015Hz的频率下振荡。
使用感应加热制备复合块可能允许更均匀的加热和对所述复合碳块的核心更好的热渗透深度和/或增加所述碳块复合物的生产量。相对于其他金属盐,可改变铁盐的含量以使材料的铁磁特性和氯胺除去特性最佳。
在一个实施例中,所述含金属颗粒可用于从流体流,具体是液体流体流,更具体为水性流体流中除去氯胺。氯胺由从氨和氯(次氯酸盐)之间的水性反应形成。因此,将氨(NH3)加入使氯转化为氯胺的氯化系统。具体而言,低浓度的一氯胺(下文中称为“氯胺”)来自饮用水源的消毒。在一个实施例中,如本文所公开,在使所述水性溶液与包含含金属颗粒的组合物接触后,如通过在以下实例部分描述的在180秒时通过氯胺除去测试所测得,所得水性溶液包含减少量的氯胺,例如氯胺减少了至少10、20、25、30、50、70、80、90、95或甚至100%。注意到随着粒度下降,通常由于表面积的增加,氯胺除去量将增加。例如,在180秒内,氯胺除去百分比为至少50、70、90或甚至99%减少,其中中值粒度为约50微米。
先前的出版物,诸如Vikesland等,环境科学与技术,2004年,第34卷,第83-90页(Vikesland,et al.in Environmental Science and Technologies,200,34,83-90)已显示铁离子的水溶形式是在它们的材料中除去氯胺的原因。和现有技术不同,在本公开的一个实施例中,导致含金属颗粒中氯胺除去活性的金属在水中具有有限的溶解度(换句话讲,产生金属离子浓度小于20ppm、10ppm、5ppm、2ppm、1ppm、0.5ppm或甚至0.1ppm的溶解度)。当用水洗涤所述含金属颗粒时,在所述洗涤水中存在少量金属至不存在金属,并且所述经过洗涤的含金属颗粒保持其氯胺除去活性。在一个实施例中,当洗涤羧酸金属盐的热解产物时,其不失去原始氯胺除去活性的大于5、10、15、20、30、40、50或甚至60%。具有不溶或有限的溶解度的热解产物可能是有利的,因为金属将是固定的,防止沥滤进所述处理的水中,使得所述含金属颗粒在使用前经调解和/或产生所述过滤介质的较长使用期。
以下公开本公开的示例性实施例和示例性实施例的组合的非限制性列表。
实施例1.一种液体过滤装置,包括将流体入口流体地连接至流体出口的流体导管;以及设置在所述流体导管中的液体过滤介质;所述液体过滤介质包含含金属颗粒,其中所述含金属颗粒包含金属盐的热解产物,其中所述盐选自含氮氧阴离子、含硫阴离子、氯化物、磷酸盐以及它们的组合。
实施例2.根据实施例1所述的液体过滤装置,其中所述含氮氧阴离子包括硝酸根、亚硝酸根以及它们的组合。
实施例3.根据实施例1所述的液体过滤装置,其中所述含硫阴离子包括硫酸根、氨基磺酸根、亚硫酸根、硫酸氢根、亚硫酸氢根、硫代硫酸根以及它们的组合。
实施例4.根据前述实施例中任一项所述的液体过滤装置,其中所述含金属颗粒基本上不含硫原子。
实施例5.根据实施例1或3所述的液体过滤装置,其中所述含金属颗粒包含硫原子并且所述硫原子来源于所述含硫阴离子。
实施例6.根据前述实施例中任一项所述的液体过滤装置,其中所述金属盐的所述金属是铜、铁、锰、银以及它们的组合。
实施例7.根据前述实施例中任一项所述的液体过滤装置,其中水过滤介质包含载体。
实施例8.根据实施例7所述的液体过滤装置,其中所述热解产物设置在所述载体的表面上。
实施例9.根据实施例7至8中任一项所述的液体过滤装置,其中所述载体选自含碳固体、无机氧化物粒子或纤维粒子。
实施例10.根据实施例8或9中任一项所述的液体过滤装置,其中所述载体是活性炭。
实施例11.根据前述实施例中任一项所述的液体过滤装置,其中金属盐的所述热解产物被固定在所述流体导管中。
实施例12.根据前述实施例中任一项所述的液体过滤装置,其中所述含金属颗粒是多孔的。
实施例13.根据前述实施例中任一项所述的液体过滤装置,其中基于所述含金属颗粒的总质量计,所述含金属颗粒包含小于0.90质量%的氮。
实施例14.根据前述实施例中任一项所述的液体过滤装置,其中基于所述含金属颗粒的总质量计,所述含金属颗粒包含大于2.0质量%的硫。
实施例15.一种用于从水性溶液中除去氯胺的方法,所述方法包括:提供包含氯胺的水性溶液并使所述水性溶液与包含含金属颗粒的组合物接触,其中所述含金属颗粒包含金属盐的热解产物,其中所述盐选自含氮氧阴离子、含硫阴离子、氯化物、磷酸盐以及它们的组合。
实施例16.根据实施例15所述的方法,其中所述含氮氧阴离子包括硝酸根、亚硝酸根以及它们的组合。
实施例17.根据实施例15所述的方法,其中所述含硫阴离子包括硫酸根、氨基磺酸根、亚硫酸根、硫酸氢根、亚硫酸氢根、硫代硫酸根以及它们的组合。
实施例18.根据实施例15或16中任一项所述的方法,其中所述含金属颗粒基本上不含硫原子。
实施例19.根据实施例15或17中任一项所述的方法,其中所述含金属颗粒包含硫原子并且所述硫原子来源于所述含硫阴离子。
实施例20.根据实施例15至19中任一项所述的方法,其中所述金属盐的所述金属是铜、铁、锰、银以及它们的组合。
实施例21.根据实施例15至20中任一项所述的方法,其中在使所述水性溶液与包含含金属颗粒的组合物接触后,所得水性溶液包含减少量的氯胺。
实施例22.根据实施例15至21中任一项所述的方法,其中基于所述含金属颗粒的总质量计,所述含金属颗粒包含小于0.90质量%的氮。
实施例23.根据实施例15至22中任一项所述的方法,其中基于所述含金属颗粒的总质量计,所述含金属颗粒包含大于2.0质量%的硫。
实施例24.一种用于从水性溶液中除去氯胺的方法,所述方法包括:
加热金属盐,其中所述盐选自含氮氧阴离子、含硫阴离子、氯化物、
磷酸盐以及它们的组合以形成热解产物;
使所述热解产物冷却;以及
使经冷却的热解产物与包含氯胺的水性溶液接触。
实施例25.根据实施例24所述的方法,其中所述加热在至少200℃的温度下进行。
实施例26.根据实施例24至25中任一项所述的方法,其中在所述加热步骤过程中将所述金属盐的至少一部分设置在载体上。
实施例27.根据实施例24至26中任一项所述的方法,其中所述加热在惰性气氛中进行。
实施例28.根据实施例24至27中任一项所述的方法,其中基于所述热解产物的总质量计,所述热解产物包含小于0.90质量%的氮。
实施例29.根据实施例24至28中任一项所述的方法,其中基于所述热解产物的总质量计,所述热解产物包含大于2.0质量%的硫。
实施例30.一种碳块,包含:(a)碳载体,(b)含金属颗粒,其中所述含金属颗粒包含金属盐的热解产物,其中所述盐选自含氮氧阴离子、含硫阴离子、氯化物、磷酸盐以及它们的组合,以及(c)粘结剂。
实施例31.根据实施例30所述的碳块,其中所述粘结剂选自聚乙烯。
实施例32.一种制备复合碳制品的方法,所述方法包括:
提供包含以下的混合物:(a)含金属颗粒,其中所述含金属颗粒包含金属盐的热解产物,其中所述盐选自含氮氧阴离子、含硫阴离子、氯化物、磷酸盐以及它们的组合;和(b)可熔融加工的聚合物;
使所述混合物与高频率磁场接触,其中所述高频率磁场在约103Hz至约1015Hz的范围内振荡。
实施例33.根据实施例32所述的方法,其中所述可熔融加工的聚合物是超高分子量聚乙烯。
实例
以下实例进一步说明了本发明的优点和实施例,但是这些实例中所引用的具体材料及其量以及其它条件和细节不应被解释为不当地限制本发明。除非特别指出,否则在这些实例中,所有的百分比、比例和比值都以重量计。
除非另外指明或显而易见,否则所有材料都可从例如威斯康星州密尔沃基的西格玛-奥德里奇化学公司(Sigma-AldrichChemical Company;Milwaukee,WI)购得,或为本领域的技术人员已知的。
以下实例中使用这些缩写:cc=立方厘米,g=克,hr=小时,in=英寸,kg=千克,min=分钟,mol=摩尔;M=摩尔,cm=厘米,mm=毫米,ml=毫升,L=升,N=正常,psi=每平方英寸的压力,MPa=兆帕,以及wt=重量。
测试方法
表观密度测定
通过在带刻度的圆筒中轻叩已称量的样品直至获得最密堆积,确定碳样品(根据公开的比较例或实例制备)的表观密度。当轻叩不能使得碳基质样品的体积进一步下降时,视为最密堆积。
氯胺测试
由样品中的总氯含量确定水样品的氯胺含量。通过DPD总氯法(Hach法8167,Hach Company声称等同于USEPA方法330.5)测量总氯(OCl-和氯胺)浓度。通过DPD游离氯胺分析(Hach法8021,Hach Company声称等同于EPA方法330.5)定期测量游离氯(OCl-)浓度。将游离氯保持在可忽略不计的浓度下(<0.2ppm),因此,所述总氯分析被认为是氯胺在水中的浓度的充分逼近。所有试剂和仪器为标准Hach法中所述的那些,并且可以得自哈希公司(Hach Company,Loveland,CO.)。
氯胺制备
通过向去离子水中加入适当量的商用漂白剂(5.25%的NaOCl),制备3ppm的氯胺。在搅拌同时,将1.5当量的氯化铵水溶液加入漂白剂溶液并且搅拌1小时。通过加入NaOH或HCl将pH调节至7.6,并且使用pH计(以商品名“ORION3-STAR”得自马萨诸塞州沃尔瑟姆的赛默飞世尔科技公司(Thermo Fisher Scientific,Inc.,Waltham,MA))测试。
氯胺除去测试
在约27℃在pH为约7.6下,制备氯胺测试水性溶液,其包含3ppm+/-0.3ppm的NH2Cl(如上所述制备)。如以上在氯胺测试中所述,在测试之前立即测量氯胺测试水性溶液的初始总氯含量。在连续搅拌下,将1.5cc等份试样的碳基质样品(即,根据本公开的比较例或实例制备的样品)加入到所述氯胺测试水性溶液中。已知表观密度通过质量来测量等份试样。混合后立即启动计时器。30秒之后,取出5mL的等分试样的混合物,并且在取出的5秒之内,使混合物通过1-微米注射过滤器以除去悬浮固体。在上述取得5mL的等分试样的30秒之内,测量过滤的等分试样的氯胺含量。在5分钟的过程中定期取得来自混合物的等分试样并且使用上述氯胺测试进行分析。氯胺除去的效率记录为由以下公式确定的氯胺减少%:
材料
比较例A-C
使用氯胺除去测试(Chlroamine Removal Test)来测试没有进行进一步处理的碳基质A、B和C。结果示出于表1中。
实例1
在有力的搅拌下将MnSO4·H2O(6.75g)加入到去离子水(35g)中。搅拌下将硫酸锰水性溶液加入到17.5g的碳基质B中。将浸渍的碳置入坩埚(有盖)并且然后在875℃下在氮气吹扫的马弗炉中加热15分钟。然后在氮气吹扫下将所述坩埚移开进行冷却。所述浸渍在碳上产生大约12.5重量%的锰(表示为Mn)。然后使用所述氯胺除去测试来测试所述样品。结果示出于表1中。
实例2
通过实例1的所述方法制备浸渍的碳样品,但是使用较低量的MnSO4·H2O,使得所述浸渍在碳上产生大约6.3重量%的锰(表示为Mn)。然后使用所述氯胺除去测试来测试所述样品。结果示出于表1中。
实例3
通过实例1的所述方法制备浸渍的碳样品,但是使用较大量的MnSO4·H2O,使得所述浸渍在碳上产生大约18.9重量%的锰(表示为Mn)。然后使用所述氯胺除去测试来测试所述样品。结果示出于表1中。
实例4
在实施例1中概述的相同程序后,将硫酸锰水性溶液加入到碳基质C中,使得所述浸渍在碳上产生大约19重量%的锰(表示为Mn)。然后使用所述氯胺除去测试来测试所述样品。结果示出于表1中。
实例5
将五水合硫酸铜(5g的CuSO4·5H2O)溶于15g的水中。在搅拌下将所述溶液加入到碳基质B(8.5克),使得所述浸渍在碳上产生大约12.5%的铜(表示为Cu)。将经浸渍的碳置于坩埚(有盖)中并且然后在800℃下在氮气吹扫的马弗炉中加热15分钟。然后在氮气吹扫下将所述坩埚移开进行冷却。然后使用所述氯胺除去测试来测试所述样品。结果示出于表1中。
表1
实例6
将硝酸铁(14.5g的Fe(NO3)3·9H2O)溶于20g的水中。将一半溶液加入到碳基质B(8克)。然后在100℃下干燥所述浸渍的碳基质。将所述剩余的铁盐溶液加入到所述浸渍的碳,从而在碳上产生大约20%的铁。然后在900℃下在N2中将所述浸渍的碳加热15分钟(在封闭的坩埚中在氮气吹扫的马弗炉中)。然后使用所述氯胺除去测试来测试所述样品。结果示出于上表1中。
测试实例6中的铁磁性。在上文实例6中保持小的条形磁铁。当所述磁铁距离所述样品约0.25英寸(0.6厘米)时,包含硝酸铁的热解产物的所述碳粒子被吸引到所述磁铁。
实例6
将0.374g的Cu(NO3)2·2.5H2O溶于8mL的去离子水中。将所述溶液加入到碳基质B(5.0g)。在90℃下使所述样品在烘箱中干燥并且随后在用N2吹扫的管式炉中加热至300℃。使所述样品在N2中冷却至室温,然后从炉中移开。
实例7
使用实例6中公开的相同方法,不同的是使用0.960g的Cu(NO3)2·2.5H2O。
实例8
使用实例6中公开的相同方法,不同的是使用2.03g的Cu(NO3)2·2.5H2O。
实例9
使用实例6中公开的相同方法,不同的是使用3.23g的Cu(NO3)2·2.5H2O。
实例10
使用实例6中公开的相同方法,不同的是使用碳基质D代替碳基质B。
实例11
使用实例7中公开的相同方法,不同的是使用碳基质D代替碳基质B。
实例12
使用实例8中公开的相同方法,不同的是使用碳基质D代替碳基质B。
实例13
使用实例9中公开的相同方法,不同的是使用碳基质D代替碳基质B。
然后使用所述氯胺除去测试来测试实例6-13和碳基质D(比较例D)。结果示出于2中。
表2
关于本发明的可预见的修改和改变对本领域技术人员来说将是显而易见的,并不背离本发明的范围和实质。为进行示意性的说明,本发明不应限于此专利申请中所列出的实施例。如果在本说明书和通过引用而并入本文的任何文件中的公开内容之间存在冲突或矛盾之处,则以本说明书为准。
Claims (10)
1.一种液体过滤装置,其包括将流体入口流体地连接至流体出口的流体导管;以及设置在所述流体导管中的液体过滤介质;所述液体过滤介质包含含金属颗粒,其中所述含金属颗粒包含金属盐的热解产物,其中所述盐选自含氮氧阴离子、含硫阴离子、氯化物、磷酸盐以及它们的组合。
2.根据权利要求1所述的液体过滤装置,其中所述含氮氧阴离子包括硝酸根、亚硝酸根以及它们的组合。
3.根据权利要求1所述的液体过滤装置,其中所述含硫阴离子包括硫酸根、氨基磺酸根、亚硫酸根、硫酸氢根、亚硫酸氢根、硫代硫酸根以及它们的组合。
4.根据前述权利要求中任一项所述的液体过滤装置,其中所述含金属颗粒基本上不含硫原子。
5.根据权利要求1或3所述的液体过滤装置,其中所述含金属颗粒包含硫原子并且所述硫原子来源于所述含硫阴离子。
6.根据前述权利要求中任一项所述的液体过滤装置,其中所述金属盐的金属为铜、铁、锰、银以及它们的组合。
7.一种从水性溶液中除去氯胺的方法,所述方法包括:提供包含氯胺的水性溶液并且使所述水性溶液与包含含金属颗粒的组合物接触,其中所述含金属颗粒包含金属盐的热解产物,其中所述盐选自含氮氧阴离子、含硫阴离子、氯化物、磷酸盐以及它们的组合。
8.一种从水性溶液中除去氯胺的方法,所述方法包括:
加热金属盐以形成热解产物,其中所述盐选自含氮氧阴离子、含硫阴离子、氯化物、磷酸盐以及它们的组合;
使所述热解产物冷却;以及
使经冷却的热解产物与包含氯胺的水性溶液接触。
9.一种碳块,其包含:(a)碳载体,(b)含金属颗粒,其中所述含金属颗粒包含金属盐的热解产物,其中所述盐选自含氮氧阴离子、含硫阴离子、氯化物、磷酸盐以及它们的组合,和(c)粘结剂。
10.一种制备复合碳制品的方法,所述方法包括:
提供包含以下的混合物:(a)含金属颗粒,其中所述含金属颗粒包含金属盐的热解产物,其中所述盐选自含氮氧阴离子、含硫阴离子、氯化物、磷酸盐以及它们的组合;和(b)可熔融加工的聚合物;
使所述混合物与高频率磁场接触,其中所述高频率磁场在约103Hz至约1015Hz的范围内振荡。
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CA2859895C (en) * | 2011-12-22 | 2021-02-09 | 3M Innovative Properties Company | Filtration medium comprising a thermolysis product of a carbon oxychalcogenide and a metal salt, method of removing chloramine with this filtration medium and method of making this filtration medium |
CN105102377A (zh) | 2013-03-12 | 2015-11-25 | 3M创新有限公司 | 从水性溶液中除去氯胺和汞 |
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