WO2011097956A1 - Catalyst for treatment of industrial wastewater at normal temperature and pressure, and method for preparing same - Google Patents
Catalyst for treatment of industrial wastewater at normal temperature and pressure, and method for preparing same Download PDFInfo
- Publication number
- WO2011097956A1 WO2011097956A1 PCT/CN2011/000210 CN2011000210W WO2011097956A1 WO 2011097956 A1 WO2011097956 A1 WO 2011097956A1 CN 2011000210 W CN2011000210 W CN 2011000210W WO 2011097956 A1 WO2011097956 A1 WO 2011097956A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- activated carbon
- salt
- soluble
- precursor
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 151
- 238000000034 method Methods 0.000 title claims abstract description 61
- 239000010842 industrial wastewater Substances 0.000 title description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 195
- 239000002351 wastewater Substances 0.000 claims abstract description 61
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 26
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 23
- 229910052802 copper Inorganic materials 0.000 claims abstract description 21
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 19
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims description 63
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 61
- 229910052751 metal Inorganic materials 0.000 claims description 46
- 239000002184 metal Substances 0.000 claims description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 239000011701 zinc Substances 0.000 claims description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000001556 precipitation Methods 0.000 claims description 26
- 239000010949 copper Substances 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 23
- 238000001354 calcination Methods 0.000 claims description 22
- 239000011572 manganese Substances 0.000 claims description 22
- 150000003839 salts Chemical class 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 229910052742 iron Inorganic materials 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- 230000032683 aging Effects 0.000 claims description 15
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 230000001590 oxidative effect Effects 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- -1 iron ions Chemical class 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 230000001376 precipitating effect Effects 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000007654 immersion Methods 0.000 claims description 9
- 150000001879 copper Chemical class 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 8
- 150000003751 zinc Chemical class 0.000 claims description 8
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 150000002505 iron Chemical class 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 239000012692 Fe precursor Substances 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 6
- 239000011707 mineral Substances 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 150000001868 cobalt Chemical class 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 150000002696 manganese Chemical class 0.000 claims description 5
- 150000002815 nickel Chemical class 0.000 claims description 5
- 239000012691 Cu precursor Substances 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 4
- 230000005070 ripening Effects 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 229910052570 clay Inorganic materials 0.000 claims description 3
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 3
- 229910001431 copper ion Inorganic materials 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001437 manganese ion Inorganic materials 0.000 claims description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 3
- 150000004692 metal hydroxides Chemical class 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 229910001453 nickel ion Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 159000000009 barium salts Chemical class 0.000 claims description 2
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims 1
- 229910052703 rhodium Inorganic materials 0.000 claims 1
- 239000010948 rhodium Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 44
- 230000003647 oxidation Effects 0.000 abstract description 26
- 238000007254 oxidation reaction Methods 0.000 abstract description 26
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 150000004706 metal oxides Chemical class 0.000 description 45
- 229910044991 metal oxide Inorganic materials 0.000 description 44
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 22
- 239000003245 coal Substances 0.000 description 21
- 238000002309 gasification Methods 0.000 description 19
- 239000011206 ternary composite Substances 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 16
- 239000000126 substance Substances 0.000 description 16
- 239000007800 oxidant agent Substances 0.000 description 13
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 11
- 238000004065 wastewater treatment Methods 0.000 description 11
- 238000004939 coking Methods 0.000 description 10
- 239000002131 composite material Substances 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000005273 aeration Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 229910017566 Cu-Mn Inorganic materials 0.000 description 5
- 229910017871 Cu—Mn Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 235000010755 mineral Nutrition 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 229910017518 Cu Zn Inorganic materials 0.000 description 4
- 229910017752 Cu-Zn Inorganic materials 0.000 description 4
- 229910017943 Cu—Zn Inorganic materials 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 3
- 229910003286 Ni-Mn Inorganic materials 0.000 description 3
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000011219 quaternary composite Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 150000000703 Cerium Chemical class 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- 229910002482 Cu–Ni Inorganic materials 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-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
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000007824 aliphatic compounds Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 229910001422 barium ion Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000002431 foraging effect Effects 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000008239 natural water Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 229910002551 Fe-Mn Inorganic materials 0.000 description 1
- 229910002549 Fe–Cu Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- JVMRPSJZNHXORP-UHFFFAOYSA-N ON=O.ON=O.ON=O.N Chemical compound ON=O.ON=O.ON=O.N JVMRPSJZNHXORP-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229920005372 Plexiglas® Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 1
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 229940062993 ferrous oxalate Drugs 0.000 description 1
- 239000003864 humus Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 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
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 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
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B01J35/617—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Definitions
- the present invention relates to a catalyst for catalytic oxidation of industrial wastewater at normal temperature and pressure.
- Coal gasification is a clean and efficient method of coal utilization, but the coal gasification process produces a large amount of highly polluted wastewater, which contains various pollutants such as phenol, cyanide, ammonia nitrogen and several aliphatic and aromatic compounds. It can be disposed of effectively before it can be discharged.
- other industrial wastewaters such as coking wastewater, printing and dyeing plant wastewater, chemical plant wastewater, etc. also contain a variety of pollutants, such as phenol, cyanide, ammonia nitrogen and several aliphatic and aromatic compounds, which also need to be effectively treated. Emissions can be made.
- COD chemical demand
- ammonia nitrogen ammonia nitrogen
- nitrate nitrogen nitrite nitrogen
- color is often used to indicate the type and/or amount of pollutants in wastewater.
- COD also known as chemical oxygen demand, refers to the amount of oxidant consumed when a water sample is treated with a certain strong oxidizing agent under certain conditions. It is an indicator of how much reducing substances are present in the water.
- the reducing substances in water are various organic substances, nitrites, sulfides, ferrous salts, etc., but mainly organic substances. Therefore, COD is often used as an indicator to measure the amount of organic matter in water. The larger the COD, the more serious the water is contaminated by organic matter.
- Ammonia nitrogen A nitrogen element in the form of ammonia or ammonium ions in water.
- B0D5 Refers to the five-day biological oxygen consumption, that is, the total amount of oxygen consumed during the biodegradation of organic matter in water for 5 days.
- Chroma The color of water is the color quantification of natural water or treated water The index at the time of measurement. Natural water often shows different colors such as light yellow, light brown or yellowish green. The reason for the color is due to humus, organic or inorganic substances dissolved in water. In addition, when the water body is contaminated by industrial wastewater, it will also have different colors. These colors are divided into true and color. True color is caused by dissolved substances in water, that is, the color after removing suspended solids in water. The color is the color produced when the suspended matter in the water is not removed. The degree of quantification of these colors is chromaticity.
- the colorimetric measurement of industrial wastewater is carried out by the dilution factor method, as described in GB11903-89, and the wastewater sample is diluted with optically pure water to a visual comparison of the dilution factor when the color is invisible compared to the optically pure water.
- the mode is in multiples. The higher the general multiple, the deeper the color of the wastewater.
- Wet catalytic oxidation is a treatment technology developed in the 1980s to treat high-concentration biodegradable organic wastewater (US 4699720, 1987).
- the process directly oxidizes the organic matter in the sewage into C0 2 , H 2 0, etc. under the action of a catalyst under the action of a catalyst under high temperature and high pressure with an oxidizing agent such as H 2 O 2 , 0 3 , C 10 2 or an oxygen oxidizing agent. Harmless ingredients to achieve the purpose of purifying water. Due to the complicated design, high operation and high maintenance cost of high temperature and high pressure catalytic oxidation reactor, it is difficult to be industrially applied. Therefore, normal temperature and atmospheric pressure catalytic oxidation and solid catalysts have become the focus of research. At present, most of the solid catalysts studied include noble metal catalysts, oxides of transition metals such as Fe, Cu, N i, Co, Mn, and the like, and oxides of rare earth metals such as La, Ce, and the like.
- Chinese patent CN1876232A discloses an activated carbon supported copper oxide catalyst for coking wastewater treatment.
- the catalyst was co-oxidized at room temperature and pressure with H 2 O 2 to treat the coking wastewater of Anshan Iron and Steel Plant.
- the COD value decreased from 1190 mg/L to 48. lmg/L, and the removal rate was 96%.
- Chinese patent CN1872730A discloses a ⁇ - ⁇ 1 2 3 supported copper oxide catalyst for advanced treatment of coking wastewater. The catalyst and co-acting ⁇ 2 0 2 coking wastewater catalytic oxidation at normal temperature and pressure, COD removal efficiency of 98%.
- Chinese patent CN1919452A discloses an activated carbon supported iron oxide catalyst for the treatment of phenol-containing wastewater and coking wastewater. The catalyst was subjected to catalytic oxidation treatment of coking wastewater under normal temperature and normal pressure and without H 2 O 2 , and the COD removal rate was 95.7%.
- All of the above catalysts are catalysts formed by a metal oxide such as activated carbon or Y-alumina supported by Fe, Cu, Zn, Ni, Co or Mn.
- the main active component is only one metal oxide, and the catalytic activity of the catalyst. And the catalytic selectivity is limited. Under normal temperature and pressure, even if it co-oxidizes coking wastewater with H 2 0 2 , the COD removal rate can only reach 98%.
- the catalyst of a single major active component is due to the absence of complex compounds (see Ca ta lys is Communica t ions 7).
- metal ion elution is prone to occur during use, which leads to easy failure of catalytic activity of the catalyst and poor stability of the catalyst, which greatly limits industrial applications.
- Application No. 200910177026. 2 also discloses a coconut shell granular activated carbon supported Fe-Cu-Zn ternary composite catalyst for coal gasification wastewater treatment.
- the catalyst was subjected to catalytic oxidation treatment of coal gasification wastewater under normal temperature and atmospheric pressure and air as an oxidant, and the COD removal rate was 99.0%.
- the ternary composite metal oxide catalyst greatly improves the catalytic activity of the catalyst and slows the loss of the active component of the catalyst in the wastewater treatment process, but still has the problem of insufficient catalytic activity and stability.
- C10 2 or 0 3 is used as an oxidant for wet catalytic oxidation to treat phenol-containing wastewater and coking wastewater, and the COD removal rate is over 90%.
- the present invention relates to a catalyst for catalytic oxidation of wastewater at normal temperature and pressure, comprising: Activated carbon as a carrier;
- the present invention relates to a method for preparing a catalyst for catalytic oxidation of wastewater under normal temperature and pressure, comprising the steps of:
- the iron source and any two, three or four sources selected from the group consisting of a copper source, a zinc source, a manganese source, a cobalt source, a nickel source or a helium source by an immersion precipitation method are iron precursors and selected from copper Any two, three or four precursors of a body, a zinc precursor, a manganese precursor, a cobalt precursor, a nickel precursor or a ruthenium precursor are supported on the activated carbon obtained in the step a, and The order of impregnation of each source and the order of precipitation of each precursor are not limited, and wherein the activated carbon is not loaded with iron precursor, copper precursor and zinc precursor at the same time;
- the present invention relates to a method for preparing a catalyst for catalytic oxidation of wastewater under normal temperature and pressure, comprising the steps of:
- aqueous solution comprising a soluble iron salt or a ferrous salt and comprising any two, three or four of a soluble copper salt, a soluble zinc salt, a soluble manganese salt, a soluble cobalt salt, a soluble nickel salt or a soluble barium salt; And wherein the aqueous solution does not contain a soluble iron or ferrous salt with a soluble copper salt and a soluble zinc salt;
- step c heating the aqueous solution, and adding the activated carbon pretreated by the step a, stirring the mixture and cooling to room temperature;
- An aqueous solution of a water-soluble salt of a metal is collectively referred to as a "source", such as an aqueous solution of ferric sulfate, ferrous sulfate, iron acetate, or the like. , can be usually referred to as "iron source”; and so on.
- the catalyst of the invention consists of a support and an active component supported on a support.
- the carrier is activated carbon, preferably activated carbon having a specific surface area of 800-900 m 2 /g, the surface area is measured by a BET adsorption method; and the active component further comprises a main active component and a secondary active component, wherein the main active component is Fe.
- the oxide, the secondary active component is an oxide of any two, three or four elements selected from the group consisting of Cu, Zn, Mn, Co, N i or Ce, but wherein the secondary active component is Oxides of Cu and oxides of Zn are not present at the same time.
- the mass of activated carbon is 94-96% of the total mass of the catalyst; the amount of Fe of Fe 2 O 3 is 2-5% of the total mass of the catalyst; Cu0, Zn0, Mn0 2 , Co 2 respectively 03, the oxide Ce0 2 or NiO meter selected from Cu, Zn, Mn, Co, Ni or Ce in any two of three or four elements, and the mass of the total mass of the catalyst 0. 5- 2°/. .
- the mass of activated carbon is 95% of the total mass of the catalyst; the mass of Fe of Fe 2 O 3 is 3-4% of the total mass of the catalyst; Cu0, Zn0, Mn0 2 , Co 2 , respectively 0 3 , Ni O or Ce0 2
- the sum of the masses of oxides of any two, three or four elements selected from Cu, Zn, Mn, Co, N i or Ce is 1 - the total mass of the catalyst 2 %.
- the second and third aspects of the invention relate generally to a process for the preparation of a catalyst.
- the catalyst of the present invention is mainly prepared by an immersion precipitation method, which mainly comprises: firstly impregnating a carrier with an aqueous solution of a water-soluble salt of a metal, and then adding a precipitant to make each metal hardly soluble in water The salt form is precipitated on the support and then subjected to some subsequent treatment.
- an immersion precipitation method one metal may be first impregnated and precipitated, and the remaining metal may be impregnated or precipitated; or a certain metal may be impregnated simultaneously or sequentially, and another metal may be precipitated simultaneously or sequentially. Impregnation precipitation method.
- the activated carbon is pretreated with a step comprising washing, drying and heat treatment.
- a step comprising washing, drying and heat treatment.
- the activated carbon is washed with deionized water, the washed activated carbon is dried at 110 -, and then the dried activated carbon is heat treated at 150 - 2 Q0 X for 2-5 hours.
- the source of iron is selected by a immersion precipitation method and is selected from the group consisting of a copper source, a zinc source, a manganese source, a cobalt source, a nickel source or a ruthenium Any two, three or four sources in the source are iron precursors and any two or three selected from the group consisting of copper precursors, precursors, manganese precursors, cobalt precursors, nickel precursors or ruthenium precursors.
- the form of the seed or the four precursors is supported on the activated carbon obtained in the step a, and the order of impregnation of the respective sources and the order of precipitation of the respective precursors are not limited, and wherein the activated carbon is not loaded with iron beforehand.
- the immersion precipitation method means that the carrier is sufficiently impregnated with an aqueous solution of a metal-soluble salt (ie, a metal source), and then a precipitant is added to precipitate the metal as a poorly soluble salt (ie, a precursor) in the carrier. On the process.
- the precipitating agent is selected from the group consisting of soluble metal hydroxides, soluble metal carbonates, hydrogencarbonates or aqueous ammonia or mixtures thereof, such as NaOH, Na 2 CO 3 or NaHC 0 3 and the like.
- the amount of precipitant should be sufficient to allow complete precipitation of each metal ion onto the activated carbon to control the mass percentage of the primary active component and the secondary active component in the final catalyst.
- Each of the precursors includes carbonates or hydroxides of various valence states of the respective metals or any other salt which is poorly soluble in water.
- suitable precipitant species, precipitating doses, and precipitation sequences based on the nature and expected amount of each metal and precursor to optimize the process, making these choices within the capabilities of the skilled person. .
- the active component precursor supported on activated carbon is aged.
- the aging can be carried out in two ways: The first is to not perform solid-liquid separation of the product of step b, and the active component precursor supported on the activated carbon is allowed to stand in the solution at room temperature for 24 hours in situ. The aging is carried out; the second solid-liquid separation separates the active component precursor supported on the activated carbon, and then the precursor is allowed to stand at room temperature for 24 hours for aging.
- the solid-liquid separation may be a conventional solid-liquid separation means in the art, such as filtration, centrifugation and the like. The effect of the ripening is to sufficiently uniformly and stably disperse the active component precursor on the surface of the activated carbon.
- step d of the process of the invention the active component precursor supported on activated carbon is washed, dried and calcined to obtain said catalysis Agent.
- said washing refers to a process of washing away soluble ions remaining on the solid matter with any solvent, preferably water; said drying is carried out at 120-150 ° C for a drying time of 2-5 hours;
- the calcination is carried out in a muffle furnace at 270-300 X and in the presence of oxygen, and the calcination time is 8-10 hours.
- the atmosphere in which oxygen is present is preferably an air atmosphere.
- the active component precursor such as a metal carbonate or hydroxide, decomposes to form a metal oxide.
- the metal oxides formed during the prolonged calcination process in the presence of oxygen as described herein, preferably under an air atmosphere are generally stable oxides of higher valence of these metals, ie Fe 2 0 3 , Cu0, Zn0, Mn0 2 , Co 2 0 3 , N iO or Ce0 2 , so when the content of these active components is mentioned in the present invention, it is converted into Fe 2 O 3 , Cu0, The mass of each metal oxide of Zn0, Mn0 2 , Co 2 0 3 , N iO or Ce0 2 .
- the stoichiometric ratio of the precipitation reaction and the decomposition reaction is calculated according to the amount of the soluble salt of each metal in the starting solution. Decomposes the amount of metal oxide formed. Moreover, without being bound by any particular theory, it is believed that these metal oxides do not exist independently in mutually incoherent manner, but rather form a composite of metal oxides that cause their metal oxidation to exist independently of each other. Compared with materials, metal loss is less likely to occur under wastewater treatment conditions. This will be manifested in the following examples with an increase in the single life of the catalyst.
- the active component of the catalyst represented by various metal oxide forms in the present invention is merely a chemical representation and does not represent the true chemistry of the active component of the catalyst.
- the structure is these metal oxides.
- the determination of the true chemical structure of the active component is quite complicated.
- two catalysts that look identical in chemical expression are entirely likely to have distinct real chemical structures and be used in very different environments. Indeed When determining the true composition and true chemical structure of the catalyst, the environmental factors of the catalyst should be taken into account.
- the activated carbon is pretreated by a step comprising washing, drying and heat treatment.
- the activated carbon is washed with deionized water, the washed activated carbon is dried at 110-120, and the dried activated charcoal is then heat treated at 150-200 for 2-5 hours.
- the preparation comprises a soluble iron or ferrous salt and comprises a soluble copper salt, a soluble zinc salt, a soluble manganese salt, a soluble cobalt salt, a soluble nickel salt or a soluble Any two, three or four aqueous solutions of the cerium salt, and wherein the aqueous solution does not simultaneously contain a soluble iron or ferrous salt with a soluble copper salt and a soluble zinc salt.
- the soluble salts of the respective metals include inorganic or organic acid salts of various valence states of the respective metals.
- the soluble iron salt includes an iron salt of a mineral acid such as iron chloride, iron nitrate or iron sulfate, or an iron salt of an organic acid such as iron acetate, iron oxalate or the like, and an iron salt of a mineral acid is preferably used.
- the soluble ferrous salt includes a ferrous salt of a mineral acid such as ferrous chloride, ferrous nitrate or ferrous sulfate, or a ferrous salt of an organic acid, such as ferrous acetate, ferrous oxalate or the like, preferably using a mineral acid.
- a ferrous salt a soluble copper salt, a soluble zinc salt, a soluble manganese salt, a soluble cobalt salt, a soluble nickel salt or a soluble cerium salt including inorganic or organic acid salts of these metals, wherein a mineral acid salt such as chloride That is, hydrochloride, nitrate or sulfate, organic acid salts such as acetate, oxalate, and the like.
- the iron salt or the ferrous salt and the salt of each of the secondary active components may be separately mixed into a solution and then mixed together, or may be directly formulated into a mixed solution.
- the amount of each metal precursor precipitated onto the support is sufficient to cause the oxide of Fe in the final catalyst to be 2-5% by mass of the total mass of the catalyst in terms of Fe 2 O 3 , and to make Cu0, Any two or three selected from the group consisting of Cu, Zn, Mn, Co, N i or Ce in terms of Zn0, Mn0 2 , Co 2 O 3 , N iO or Ce0 2 5-2% ⁇ The mass of the total mass of the catalyst is 0. 5-2%.
- the amount of each metal precursor precipitated onto the support is sufficient to cause the oxide of Fe in the final catalyst to be 3-4% by mass of the total mass of the catalyst in terms of Fe 2 O 3 , and The mass of an oxide of any two, three or four elements selected from Cu, Zn, Mn, Co, N i or Ce in terms of Cu0, Zn0, Mn0 2 , Co 2 O 3 , NiO or CeO 2 And account for 1-2% of the total mass of the catalyst.
- the amount of the precipitant added can be controlled such that the precipitation occurring in the step d below is completely precipitated, and the decomposition occurring in the calcination process of the step f below is also completely decomposed, both the precipitation reaction and the decomposition reaction occur in a stoichiometric ratio, so that the field
- the skilled person can easily calculate the soluble iron or ferrous salt and the soluble copper salt and soluble zinc salt added in this step according to the percentage of the main active component and the secondary active component in the final catalyst as a percentage of the total shield of the catalyst. a specific amount of any two, three or four of a soluble manganese salt, a soluble cobalt salt, a soluble nickel salt or a soluble phosphonium salt.
- the aqueous solution is heated, and the pretreated activated carbon is added thereto, stirred and cooled to room temperature.
- the aqueous solution is heated to 60-70. C, and the stirring is continued for 3-5 hours.
- the cooling can be natural cooling.
- the addition of iron ions to the aqueous solution and any of copper ions, zinc ions, manganese ions, cobalt ions, nickel ions or barium ions can be added to the aqueous solution.
- Two, three or four ion-precipitating precipitants provide the active component precursor supported on activated carbon.
- the precipitating agent is selected from a soluble metal hydroxide, a soluble metal carbonate, bicarbonate, or ammonia, or mixtures thereof, e.g. NaOH, ⁇ 0 3 NaHC0 3 or the like.
- the amount of precipitant should be sufficient to allow complete precipitation of each metal ion onto the activated carbon to control the mass percentage of the primary active component and the secondary active component in the final catalyst.
- all metal ions are precipitated by hydroxide, carbonate precipitated or bicarbonate precipitated or The form of their mixture (these precipitates may also be referred to as active component precursors) is precipitated in the pores of the activated carbon to support the active component precursor on the activated carbon.
- the amount of precipitant added and the pH of the solution are selected such that these metal ions are substantially completely precipitated onto the activated carbon as a precipitate.
- the active component precursor supported on activated carbon is aged.
- the aging can be carried out in two ways: The first is to not perform solid-liquid separation on the product of step d, and the active component precursor supported on the activated carbon is allowed to stand in the solution at room temperature for 24 hours in situ. The aging is carried out; the second solid-liquid separation separates the active component precursor supported on the activated carbon, and then the precursor is allowed to stand at room temperature for 24 hours for aging.
- the solid-liquid separation may be a conventional solid-liquid separation means in the art, such as filtration, centrifugation and the like. The effect of the ripening is to sufficiently uniformly and stably disperse the active component precursor on the surface of the activated carbon.
- the active component precursor supported on activated carbon is washed, dried and calcined to obtain the catalyst.
- the washing refers to a process of washing away soluble ions remaining on the solid matter with any solvent, preferably water; the drying is carried out at 120-150 X, and the drying time is 2-5 hours.
- the calcination is carried out in a muffle furnace in an atmosphere of 270-300 and in the presence of oxygen for a calcination time of 8-10 hours.
- the atmosphere in which oxygen is present is preferably an air atmosphere.
- the active component precursor such as a metal carbonate or hydroxide, decomposes to form a metal oxide.
- the metal oxides formed during the prolonged calcination in the presence of oxygen in the presence of oxygen are generally the stable oxides of the highest valence of these metals, ie Fe 2 0 3 , Cu0, Zn0, Mn0 2 , Co 2 0 3 , N iO or Ce0 2 , so when the content of these active components is mentioned in the present invention, it is converted into Fe 2 O 3 , Cu0, The mass of each metal oxide of Zn0, Mn0 2 , Co 2 0 3 , N i O or Ce0 2 , since the precipitation in step d is completely precipitated and the calcination decomposition reaction in step f is also completed In the present invention, the amount of the metal oxide formed by the decomposition is estimated from the stoichiometric ratio of the precipitation reaction and the decomposition reaction according to the amount of the soluble salt of each metal in the starting solution.
- these metal oxides do not exist independently in mutually incoherent manner, but instead form a composite of metal oxides that interacts with the metal oxides in their respective independent presences in wastewater treatment. It is less likely to cause metal loss under conditions. This will be manifested in the following examples with an increase in the single life of the catalyst.
- the catalysis of the catalyst of the present invention was examined by the following wastewater treatment experiments.
- Waste water There are two kinds of waste water: One is the coal gasification wastewater raw liquid, the composition of the wastewater is complex and the toxicity is large, and the COD is 20000 mg/L or more.
- the other is the effluent of the coal gasification wastewater raw liquid by pretreatment -0A02 (pretreatment, one-stage immobilized biofilm, aerobic aeration, immobilized biofilm, anaerobic one-stage immobilized biofilm, aerobic aeration).
- the wastewater is extremely biodegradable, difficult to biodegrade, high in chroma, and has a COD of 180-300 mg/L.
- the reactor is a fixed bed reactor.
- the material of the reactor is plexiglass, the size is ⁇ 65*5, the height is 300 legs, and the bottom of the reactor is provided with a sewage outlet and a gas outlet respectively, and the side at a distance of l-2cm from the bottom and 5-6cm from the top.
- Catalyst loading First, a 18 mesh polyethylene mesh was laid on the gas plate at the bottom of the reactor, and then 60 g of the catalyst prepared by the present invention was charged into the reactor. A layer of gas plate is laid on the upper plane of the catalyst particles, and 1-4 mesh quartz sand particles are added to make the catalyst layer relatively fixed.
- Example 1 Catalyst for supporting 5% Fe-Cu-Ni ternary composite metal oxide on activated carbon
- composition and content of the catalyst are: 95% by mass of the activated carbon carrier, and 5% by mass of the active component Fe-Cu-Ni ternary composite metal oxide, wherein Fe 2 0 3 , Cu0, The 5% by mass of the metal oxides of the NiO is 4%, 0.5% and 0.5%, respectively.
- the preparation method of the catalyst comprises the following steps:
- the activated carbon is washed with deionized water, dried under 120 times and heat treated at 150X for 2 hours to complete the pretreatment, taking 190 g;
- the activated carbon particles pretreated by the step a are added, uniformly immersed for 4 hours, and then cooled to room temperature;
- the composition and content of the catalyst are: the mass percentage content of the activated carbon carrier is 95%, and the mass percentage of the active component Fe-Ni-Mn ternary composite metal oxide is 5%, wherein Fe 2 0 3 , Ni0, The 5% by mass of the Mn0 2 is 0.4%, 0.5% and 0.5%, respectively.
- the preparation method of the catalyst comprises the following steps:
- the catalytic activity and stability of the catalyst were tested using a fixed bed reactor.
- the reactor and catalyst loading method and experimental conditions used in the experiment are the same as the examples. 1.
- the test results show that under the conditions of normal temperature and pressure and air as oxidant, COD is reduced to 200mg/L after catalytic oxidation treatment of coal gasification wastewater with COD of 21500mg/L for 1h; catalytic oxidation by pretreatment -0A02 treatment process COD 200- 220mg/L coal gasification wastewater effluent, the catalyst is used continuously for 4.5 months (single life of the catalyst), the effluent pH is 7-8, COD is 60-80mg/L, the color of the wastewater is treated from The previous 300-400 times is reduced to 30 times after treatment, 80 is 20mg/L, ammonia nitrogen is 4-6mg/L, suspended matter is 20mg/L and other indicators can meet GB8978-1996 Integrated Wastewater Discharge Standard The first level standard in .
- Example 3 Catalyst for supporting 5% Fe-Cu-Mn ternary composite metal oxide
- the composition and content of the catalyst are: the mass percentage content of the activated carbon carrier is 95%, and the mass percentage of the main active component Fe-Cu-Mn ternary composite metal oxide is 5%, wherein Fe 2 0 3 , CuO , Mn0 2 meter mass percentage content of 4%, respectively, 0.5% and 0.5%.
- the preparation method of the catalyst comprises the following steps:
- Step f the preparation of the activated carbon-supported 5% Fe-Cu-Mn ternary composite metal oxide catalyst is completed by dipping, precipitating, aging, washing, drying and calcining, and the actual conditions are the same as those in the step c in the first embodiment. Step f.
- the catalytic activity and stability of the catalyst were tested using a fixed bed reactor.
- Example 2 The reactor, catalyst loading and experimental conditions were the same as in Example 1.
- the test results show that under the conditions of normal temperature and pressure and air as oxidant, the COD is reduced to 200mg/L after catalytic oxidation treatment of 24000mg/L coal gasification wastewater.
- COD 200-220mg / L of coal gasification wastewater effluent the catalyst after 5 months of continuous use (single life of the catalyst) effluent pH 7-8, COD 60-80mg / L
- the color of wastewater is reduced from 300-400 times before treatment to 30 times after treatment, B0D 5 is 20 mg/L, ammonia nitrogen is 4-6 mg/L, suspended matter is 20 mg/L, and other indicators can meet GB8978.
- Example 4 Catalyst for supporting 5% Fe-Cu-Mn ternary composite metal oxide on activated carbon
- the composition and content of the catalyst are: the mass percentage content of the activated carbon carrier is 95%, and the mass percentage of the active component Fe-Cu-Mn ternary composite metal oxide is 5%, wherein Fe 2 O 3 , CuO, 5% ⁇ 0. 5°/ ⁇ ⁇
- the mass percentage content of Mn0 2 is 4%, 0.5% and 0. 5°/ ⁇ ⁇
- the preparation method of the catalyst adopts the sequential immersion precipitation method, which is different from the simultaneous impregnation precipitation method used in the other examples.
- the sequential immersion precipitation method includes the following steps: a. Pretreatment of activated carbon is the same as in Example 1, taking 190 g ;
- the catalytic activity and stability of the catalyst were tested using a fixed bed reactor.
- the reactor, catalyst loading and experimental conditions were the same as in Example 1.
- the test results show that under the conditions of normal temperature and pressure and air as oxidant, COD is reduced to 200mg/L after catalytic oxidation treatment of coal-fired wastewater with COD of 24000mg/L for 1h; catalytic oxidation of COD after pretreatment -0A02 treatment 200-220mg/L coal gasification wastewater effluent, the catalyst is used continuously for 5 months (single life of the catalyst).
- the effluent pH is 7-8, the COD is 60-80mg/L, and the color of the wastewater is 300 before treatment.
- B0D 5 is 20mg/L
- ammonia nitrogen is 4-6mg/L
- suspended matter is 20mg/L and other indicators can meet GB8978-1996 "Integrated Wastewater Discharge Standard" First-class standard.
- Example 5 Catalyst for 5% Fe-Cu-Mn-Ce quaternary composite metal oxide supported on activated carbon
- the composition and content of the catalyst are: the content of the activated carbon carrier is 95% by mass, and the active component is Fe-Cu-Mn-Ce quaternary composite metal oxide having a mass percentage of 5%, wherein Fe 2 0 3 The 5%, 0. 4%, 0. 4%, and 0. 2°/, respectively, the content of the mass percentages of the CuO, the Mn0 2 , and the CeO 2 . .
- the preparation method of the catalyst comprises the following steps:
- the 5% Fe-Cu-Mn-Ce quaternary composite metal oxide catalyst is prepared by the impregnation, the precipitation, the aging, the washing, the drying and the calcination, and the solution is added with 13.9 g of NaOH precipitant, and the like.
- the experimental conditions are the same as the step c in the embodiment 1. Go to step f.
- the catalytic activity and stability of the catalyst were tested using a fixed bed reactor.
- Example 1 The reactor, catalyst loading and experimental conditions were the same as in Example 1.
- the test results show that under the conditions of normal temperature and pressure and air as oxidant, COD is reduced to 200mg/L after catalytic oxidation treatment of 25000mg/L coal gasification wastewater, and COD is reduced by catalytic oxidation-pretreatment-0A02 treatment process.
- coal gasification wastewater effluent 200-220mg/L coal gasification wastewater effluent, one continuous use for 6 months (single life of catalyst), the final effluent pH is 7-8, COD is 60-80mg/L, the color of wastewater is from 300 before treatment -400 times reduced to 30 times after treatment, B0D 5 is 20mg/L, ammonia nitrogen is 4-6mg/L, suspended matter is 20mg/L and other indicators can meet GB8978-1996 "Integrated Wastewater Discharge Standard" First-class standard.
- Example 6 Catalyst for 5% Fe-Cu-Mn-Ni-Ce five-component composite metal oxide supported on activated carbon
- the composition and content of the catalyst are: the mass percentage content of the activated carbon carrier is 95%, and the main active component is 5% Fe-Cu-Mn-Ni-Ce five-component composite metal oxide, the mass percentage content is 5%, wherein to Fe 2 0 3, CuO, Mn0 2, NiO , and Ce0 2 meter mass percent of respectively 3%, 0.5%, 0.5%, 0.5% and 0.5%.
- the preparation method of the catalyst comprises the following steps:
- the NaOH precipitant is added to the solution.
- the 5% Fe-Cu-Mn-Ni-Ce pentad composite metal oxide catalyst is prepared by the impregnation, the precipitation, the aging, the washing, the drying and the calcination.
- the other experimental conditions are the same as the steps c to f in the first embodiment.
- the catalytic activity and stability of the catalyst were tested using a fixed bed reactor.
- Example 1 The reactor and catalyst were loaded as in Example 1, and the other experimental conditions were the same as in Example 1.
- the test results show that under the conditions of normal temperature and pressure and air as oxidant, COD is reduced to 200mg/L after catalytic oxidation treatment of 24000mg/L coal gasification wastewater.
- the catalytic oxidation is treated with pretreatment-0A02.
- the catalyst is used continuously for 5 months (single life of catalyst), the effluent pH is 7-8, COD is 60-80mg/L, the color of wastewater is from pre-treatment 300-400 times reduced to 30 times after treatment, 800 5 is 20mg/L, ammonia nitrogen is 4-6mg/L, suspended matter is 20mg/L and other indicators can meet GB8978-1996 "Integrated Wastewater Discharge Standard" The first level standard.
- Example 7 - 21 Catalyst for Supporting Other Mixed Metal Oxides on Activated Carbon A catalyst formed by separately loading other composite metal oxides on activated carbon was prepared by a co-impregnation method similar to that of Example 1, and carried out in the same manner as in Example 1. The same ripening, drying and calcining steps were carried out, and the catalytic activity and stability of these catalysts for wastewater treatment were examined in the same manner as in Example 1.
- Catalyst for Fe-Cu-Zn ternary composite metal oxide The composition and content of the catalyst are: 95% by mass of the activated carbon support, and the mass percentage of the main active component Fe-Cu-Zn ternary composite metal oxide content of 5%, with 0 3, CuO ZnO meter mass Fe 2, the percentage of metal oxide is 4%, 0.5% and 0.5%, respectively.
- the preparation method of the catalyst comprises the following steps:
- the catalytic activity and stability of the catalyst were tested using a fixed bed reactor: reactor, catalyst loading and experimental conditions were the same as in Example 1.
- the test results showed that under normal temperature and pressure and air as oxidant conditions, the catalytic oxidation treatment of COD was 20200mg / L of coal gasification wastewater lh, COD decreased to 205mg / L; catalytic oxidation by pretreatment -0A02 treatment process COD
- the water is used continuously for 4 months (single life of the catalyst), the final effluent pH is 7-8, the COD is 70-80mg/L, and the color of the wastewater is from before treatment.
- B0D5 is 20mg/L
- ammonia nitrogen is 4-6mg/L
- suspended matter is 20mg/L and other indicators can meet GB8978-1996 "Integrated Wastewater Discharge Standard" First-class standard.
- Fe, Cu, Zn, Mn, Co, Ni, Ce in the above table represent vapors Fe 2 0 3 , Cu0, Zn0, Mn0 2 , Co, 0, Ni0, Ce0 2
- the catalyst of the present invention has the advantages of simple preparation process and low preparation cost.
- the catalyst of the present invention is also suitable for effective treatment of other industrial waste water such as coking wastewater, printing and dyeing plant wastewater, chemical plant wastewater, etc. under normal temperature and normal pressure.
- the patent of the present invention produces a better synergistic effect through the various multi-composite of transition metal oxidation, and the catalytic activity and stability of each active component, thereby exhibiting better catalytic activity and stability.
Abstract
A catalyst for catalytic oxidation of wastewater at normal temperature and pressure comprises active carbon as a support, an oxide of Fe as a primary active component, and oxides of any two, three or four elements selected from a group consisting of Cu, Zn, Mn, Co, Ni and Ce as secondary active components. A method for preparing the catalyst is also provided.
Description
用于在常温常压下处理 For treatment at normal temperature and pressure
工业废水的催化剂及其制备方法 技术领域 Catalyst for industrial wastewater and preparation method thereof
本发明涉及一种用于在常温常压下对工业废水进行催化氧化 的催化剂。 The present invention relates to a catalyst for catalytic oxidation of industrial wastewater at normal temperature and pressure.
背景技术 Background technique
以煤炭作为能源和化工原料的应用越来越受到重视。 煤气化 是清洁、 高效的煤炭利用方式， 但煤气化工艺过程产生大量的高 污染废水， 这种废水含有多种污染质， 例如酚、 氰、 氨氮和数种 脂肪族以及芳香族化合物， 需要对其进行有效的处理， 方可进行 排放。 此外， 其它工业废水例如焦化废水、 印染厂废水、 化工厂 废水等也含有多种污染质， 例如酚、 氰、 氨氮和数种脂肪族以及 芳香族化合物， 也需要对其进行有效的处理， 方可进行排放。 The use of coal as an energy source and chemical raw materials has received increasing attention. Coal gasification is a clean and efficient method of coal utilization, but the coal gasification process produces a large amount of highly polluted wastewater, which contains various pollutants such as phenol, cyanide, ammonia nitrogen and several aliphatic and aromatic compounds. It can be disposed of effectively before it can be discharged. In addition, other industrial wastewaters such as coking wastewater, printing and dyeing plant wastewater, chemical plant wastewater, etc. also contain a variety of pollutants, such as phenol, cyanide, ammonia nitrogen and several aliphatic and aromatic compounds, which also need to be effectively treated. Emissions can be made.
废水处理领域常常用化学需氡量（COD )、 氨氮、 硝态氮、 亚 硝态氮和色度等指标来表示废水中的污染物的类型和 /或量。其中 COD, 也称作化学需氧量， 是指在一定的条件下， 釆用一定的强氧 化剂处理水样时， 所消耗的氧化剂量。 它是表示水中还原性物质 多少的指标。 水中的还原性物质有各种有机物、 亚硝酸盐、 硫化 物、 亚铁盐等，但主要的是有机物。 因此， COD又往往作为衡量水 中有机物质含量多少的指标。 COD 越大， 说明水体受有机物的污 染越严重。 In the field of wastewater treatment, indicators such as chemical demand (COD), ammonia nitrogen, nitrate nitrogen, nitrite nitrogen and color are often used to indicate the type and/or amount of pollutants in wastewater. COD, also known as chemical oxygen demand, refers to the amount of oxidant consumed when a water sample is treated with a certain strong oxidizing agent under certain conditions. It is an indicator of how much reducing substances are present in the water. The reducing substances in water are various organic substances, nitrites, sulfides, ferrous salts, etc., but mainly organic substances. Therefore, COD is often used as an indicator to measure the amount of organic matter in water. The larger the COD, the more serious the water is contaminated by organic matter.
氨氮： 指水中以氨或铵离子形式存在的氮元素。 Ammonia nitrogen: A nitrogen element in the form of ammonia or ammonium ions in water.
B0D5: 是指五日生物耗氧量， 即生物降解水中有机物 5天过程 中所消耗的氧气的总量。 B0D5: Refers to the five-day biological oxygen consumption, that is, the total amount of oxygen consumed during the biodegradation of organic matter in water for 5 days.
色度： 水的色度是对天然水或处理后的各种水进行颜色定量
测定时的指标。 天然水经常显示出浅黄、 浅褐或黄绿等不同的颜 色。 产生颜色的原因是由于溶于水的腐殖质、 有机物或无机物质 所造成的。 另外， 当水体受到工业废水的污染时也会呈现不同的 颜色。 这些颜色分为真色与表色。 真色是由于水中溶解性物质引 起的， 也就是除去水中悬浮物后的颜色。 而表色是没有除去水中 悬浮物时产生的颜色。 这些颜色的定量程度就是色度。 工业废水 色度测定采用稀释倍数法，如国标 GB11903- 89所述，将废水样品 用光学纯水稀释至用目视比较与光学纯水相比刚好看不见颜色时 的稀释倍数作为表达色度的方式，单位为倍，一般倍数越高说明废 水颜色越深。 Chroma: The color of water is the color quantification of natural water or treated water The index at the time of measurement. Natural water often shows different colors such as light yellow, light brown or yellowish green. The reason for the color is due to humus, organic or inorganic substances dissolved in water. In addition, when the water body is contaminated by industrial wastewater, it will also have different colors. These colors are divided into true and color. True color is caused by dissolved substances in water, that is, the color after removing suspended solids in water. The color is the color produced when the suspended matter in the water is not removed. The degree of quantification of these colors is chromaticity. The colorimetric measurement of industrial wastewater is carried out by the dilution factor method, as described in GB11903-89, and the wastewater sample is diluted with optically pure water to a visual comparison of the dilution factor when the color is invisible compared to the optically pure water. The mode is in multiples. The higher the general multiple, the deeper the color of the wastewater.
湿式催化氧化法是八十年代国际上发展起来的一种处理高浓 度难生物降解有机废水的处理技术（US 4699720 , 1987 ) 。 该工 艺是在反应釜中在催化剂的作用下， 于高温高压条件下用 H202、 03、C 102或氧气氧化剂等氧化剂直接将污水中的有机物氧化成 C02、 H20等无害成分，从而达到净化处理水的目的。 由于高温高压催化 氧化反应器设计复杂、 操作困难、 维护成本高， 很难工业应用， 因此常温常压催化氧化及其固体催化剂成为研究的焦点。 目前， 研究较多的固体催化剂有贵金属催化剂、过渡金属如 Fe、 Cu、 N i、 Co、 Mn等的氧化物和稀土金属如 La、 Ce等的氧化物。 Wet catalytic oxidation is a treatment technology developed in the 1980s to treat high-concentration biodegradable organic wastewater (US 4699720, 1987). The process directly oxidizes the organic matter in the sewage into C0 2 , H 2 0, etc. under the action of a catalyst under the action of a catalyst under high temperature and high pressure with an oxidizing agent such as H 2 O 2 , 0 3 , C 10 2 or an oxygen oxidizing agent. Harmless ingredients to achieve the purpose of purifying water. Due to the complicated design, high operation and high maintenance cost of high temperature and high pressure catalytic oxidation reactor, it is difficult to be industrially applied. Therefore, normal temperature and atmospheric pressure catalytic oxidation and solid catalysts have become the focus of research. At present, most of the solid catalysts studied include noble metal catalysts, oxides of transition metals such as Fe, Cu, N i, Co, Mn, and the like, and oxides of rare earth metals such as La, Ce, and the like.
中国专利 CN1876232A 公开了一种用于焦化废水处理的活性 炭负载氧化铜催化剂。 该催化剂在常温常压下和 H202共同作用催 化氧化处理鞍山钢铁厂焦化废水， COD 值从 1190mg/L 降至 48. lmg/L , 去除率为 96%。 Chinese patent CN1876232A discloses an activated carbon supported copper oxide catalyst for coking wastewater treatment. The catalyst was co-oxidized at room temperature and pressure with H 2 O 2 to treat the coking wastewater of Anshan Iron and Steel Plant. The COD value decreased from 1190 mg/L to 48. lmg/L, and the removal rate was 96%.
中国专利 CN1872730A 公开了一种用于焦化废水深度处理的 γ -Α1203负载氧化铜催化剂。 该催化剂在常温常压下和 Η202共同 作用催化氧化处理焦化废水， COD去除率高达 98%。
中国专利 CN1919452A 公开了一种用于含酚废水和焦化废水 处理的活性炭负载氧化铁催化剂。 该催化剂在常温常压和不加 H202条件下催化氧化处理焦化废水， COD去除率为 95. 7%。 Chinese patent CN1872730A discloses a γ-Α1 2 3 supported copper oxide catalyst for advanced treatment of coking wastewater. The catalyst and co-acting Η 2 0 2 coking wastewater catalytic oxidation at normal temperature and pressure, COD removal efficiency of 98%. Chinese patent CN1919452A discloses an activated carbon supported iron oxide catalyst for the treatment of phenol-containing wastewater and coking wastewater. The catalyst was subjected to catalytic oxidation treatment of coking wastewater under normal temperature and normal pressure and without H 2 O 2 , and the COD removal rate was 95.7%.
以上这些催化剂均为活性炭或 Y -氧化铝等载体单一负载 Fe、 Cu、 Zn、 Ni、 Co或 Mn等金属氧化物形成的催化剂， 其主要 活性组分只有一种金属氧化物， 催化剂的催化活性和催化选择性 受到限制， 在常温常压下， 即使和 H202共同作用催化氧化焦化废 水， COD去除率最高也只能达到 98%。 另外， 单一主要活性组分的 催化剂由于不存在复合化合物（见 Ca ta lys i s Communica t ions 7All of the above catalysts are catalysts formed by a metal oxide such as activated carbon or Y-alumina supported by Fe, Cu, Zn, Ni, Co or Mn. The main active component is only one metal oxide, and the catalytic activity of the catalyst. And the catalytic selectivity is limited. Under normal temperature and pressure, even if it co-oxidizes coking wastewater with H 2 0 2 , the COD removal rate can only reach 98%. In addition, the catalyst of a single major active component is due to the absence of complex compounds (see Ca ta lys is Communica t ions 7).
(2006) 478 - 483, Appl ied Cata lys i s B: Env i ronmenta l 72(2006) 478 - 483, Appl ied Cata lys i s B: Env i ronmenta l 72
(2007) 205 211)， 在使用过程中容易出现金属离子溶出， 从而 导致催化剂的催化活性容易失效和催化剂的稳定性差， 大大限制 了工业应用。 (2007) 205 211), metal ion elution is prone to occur during use, which leads to easy failure of catalytic activity of the catalyst and poor stability of the catalyst, which greatly limits industrial applications.
申请号 200910177026. 2也公开了一种用于煤气化废水处理 的椰壳颗粒活性炭负载 Fe-Cu - Zn三元复合催化剂。 该催化剂在 常温常压和空气作为氧化剂的条件下催化氧化处理煤气化废水， COD去除率为 99. 0%。该种三元复合金属氧化物催化剂很大程度上 提高了催化剂的催化活性和减緩了催化剂活性组分在废水处理过 程中的流失， 但仍存在催化活性和稳定性不够高的问题。 Application No. 200910177026. 2 also discloses a coconut shell granular activated carbon supported Fe-Cu-Zn ternary composite catalyst for coal gasification wastewater treatment. The catalyst was subjected to catalytic oxidation treatment of coal gasification wastewater under normal temperature and atmospheric pressure and air as an oxidant, and the COD removal rate was 99.0%. The ternary composite metal oxide catalyst greatly improves the catalytic activity of the catalyst and slows the loss of the active component of the catalyst in the wastewater treatment process, but still has the problem of insufficient catalytic activity and stability.
废水处理工程实际中，也有采用 C102或 03作为湿式催化氧化 共同作用的氧化剂， 处理含酚废水和焦化废水， COD 去除率达到 90%以上。 发明概述 In the actual wastewater treatment project, C10 2 or 0 3 is used as an oxidant for wet catalytic oxidation to treat phenol-containing wastewater and coking wastewater, and the COD removal rate is over 90%. Summary of invention
第一方面， 本发明涉及一种用于在常温常压下对废水进行催 化氧化的催化剂， 其包含：
作为载体的活性炭； In a first aspect, the present invention relates to a catalyst for catalytic oxidation of wastewater at normal temperature and pressure, comprising: Activated carbon as a carrier;
作为主要活性组分的 Fe的氧化物； 和 An oxide of Fe as a main active component; and
作为次要活性组分的选自 Cu、 Zn、 Mn、 Co、 Ni或 Ce中的任 意两种、 三种或四种元素的氧化物， 但其中所述次要活性组分中 不同时存在 Cu的氧化物和 Zn的氧化物。 An oxide of any two, three or four elements selected from the group consisting of Cu, Zn, Mn, Co, Ni or Ce as a secondary active component, but wherein Cu is not present in the secondary active component at the same time Oxides and oxides of Zn.
第二方面， 本发明涉及一种用于在常温常压下对废水进行催 化氧化的催化剂的制备方法， 包括以下步骤： In a second aspect, the present invention relates to a method for preparing a catalyst for catalytic oxidation of wastewater under normal temperature and pressure, comprising the steps of:
a. 用包括洗涤、干燥和热处理在内的步骤对活性炭进行预处 理； a. pre-treating the activated carbon with steps including washing, drying and heat treatment;
b. 通过浸渍沉淀法将铁源以及选自铜源、锌源、锰源、钴源、 镍源或铈源中的任意两种、 三种或四种源以铁前体以及选自铜前 体、 锌前体、 锰前体、 钴前体、 镍前体或铈前体中的任意两种、 三种或四种前体的形式负载在由步骤 a得到的活性炭上， 且对所 述各源的浸渍顺序以及各前体的沉淀顺序不加以限制， 且其中所 述活性炭上不同时负载有铁前 ^、 铜前体和锌前体； b. The iron source and any two, three or four sources selected from the group consisting of a copper source, a zinc source, a manganese source, a cobalt source, a nickel source or a helium source by an immersion precipitation method are iron precursors and selected from copper Any two, three or four precursors of a body, a zinc precursor, a manganese precursor, a cobalt precursor, a nickel precursor or a ruthenium precursor are supported on the activated carbon obtained in the step a, and The order of impregnation of each source and the order of precipitation of each precursor are not limited, and wherein the activated carbon is not loaded with iron precursor, copper precursor and zinc precursor at the same time;
c 熟化所述负载在活性炭上的活性组分前体； 然后 c aging the active component precursor supported on activated carbon;
d. 洗涤、 干燥并煅烧所述负载在活性炭上的活性组分前体， 得到所述催化剂。 第三方面， 本发明涉及一种用于在常温常压下对废水进行催 化氧化的催化剂的制备方法， 包括以下步骤： d. washing, drying and calcining the active component precursor supported on activated carbon to obtain the catalyst. In a third aspect, the present invention relates to a method for preparing a catalyst for catalytic oxidation of wastewater under normal temperature and pressure, comprising the steps of:
a. 用包括洗涤、干燥和热处理在内的步骤对活性炭进行预处 理； a. pre-treating the activated carbon with steps including washing, drying and heat treatment;
b. 配制包含可溶性铁盐或亚铁盐并包含可溶性铜盐、可溶性 锌盐、 可溶性锰盐、 可溶性钴盐、 可溶性镍盐或可溶性铈盐中的 任意两种、 三种或四种的水溶液； 且其中所述水溶液不同时含有
可溶性铁盐或亚铁盐与可溶性铜盐和可溶性锌盐； b. formulating an aqueous solution comprising a soluble iron salt or a ferrous salt and comprising any two, three or four of a soluble copper salt, a soluble zinc salt, a soluble manganese salt, a soluble cobalt salt, a soluble nickel salt or a soluble barium salt; And wherein the aqueous solution does not contain a soluble iron or ferrous salt with a soluble copper salt and a soluble zinc salt;
c 加热所述水溶液，并向其中加入经步骤 a预处理后的活性 炭， 搅袢均勾后冷却至室温； c heating the aqueous solution, and adding the activated carbon pretreated by the step a, stirring the mixture and cooling to room temperature;
d. 向水溶液中加入能使铁离子或亚铁离子沉淀并能使铜离 子、 锌离子、 锰离子、 钴离子、 镍离子或铈离子中的任意两种、 三种或四种离子沉淀的沉淀剂， 得到负载在活性炭上的活性组分 前体 d. adding to the aqueous solution a precipitate capable of precipitating iron or ferrous ions and precipitating any two, three or four ions of copper ions, zinc ions, manganese ions, cobalt ions, nickel ions or barium ions Agent to obtain an active component precursor supported on activated carbon
e. 熟化所述负载在活性炭上的活性组分前体； 然后 e. aging the active component precursor supported on the activated carbon;
f. 洗涤、 干燥并煅烧所述负载在活性炭上的活性组分前体， 得到所述催化剂。 发明详述 f. washing, drying and calcining the active component precursor supported on activated carbon to obtain the catalyst. Detailed description of the invention
出于清楚起见， 做如下约定： 将某金属的可溶于水的盐的水 溶液， 不论该金属的价态如何， 统称为 "某源" ， 例如硫酸铁、 硫酸亚铁、 乙酸铁等的水溶液， 均可被通常为 "铁源" ； 以此类 推。 For the sake of clarity, the following conventions are made: An aqueous solution of a water-soluble salt of a metal, regardless of the valence state of the metal, is collectively referred to as a "source", such as an aqueous solution of ferric sulfate, ferrous sulfate, iron acetate, or the like. , can be usually referred to as "iron source"; and so on.
将某金属的难溶于水的盐， 不论该金属的价态如何， 统称为 "某金属的前体" ， 例如氢氧化铁、 氢氧化亚铁、 碳酸铁等， 均 可被统称为 "铁前体" ， 以此类推。 A salt that is insoluble in water of a metal, regardless of the valence state of the metal, collectively referred to as "a precursor of a metal", such as iron hydroxide, ferrous hydroxide, iron carbonate, etc., may be collectively referred to as "iron Precursor", and so on.
在本发明的第一方面， 本发明的催化剂由载体和负载在载体 上的活性组分组成。 其中载体为活性炭， 优选比表面积为 800-900m2/g的活性炭，该表面积由 BET吸附法测量； 而活性组分 又包括主要活性组分和次要活性组分， 其中主要活性组分为 Fe 的氧化物， 次要活性组分为选自 Cu、 Zn、 Mn、 Co、 N i或 Ce中的 任意两种、 三种或四种元素的氧化物， 但其中所述次要活性组分 中不同时存在 Cu的氧化物和 Zn的氧化物。
在一个实施方案中， 活性炭质量占催化剂总质量的 94- 96%; 以 Fe203计的 Fe 的氧化物 量占催化剂总质量的 2-5%; 分别以 Cu0、 Zn0、 Mn02、 Co203、 NiO或 Ce02计的选自 Cu、 Zn、 Mn、 Co、 Ni或 Ce 中的任意两种、 三种或四种元素的氧化物的质量之和占 催化剂总质量的 0. 5-2°/。。 In a first aspect of the invention, the catalyst of the invention consists of a support and an active component supported on a support. Wherein the carrier is activated carbon, preferably activated carbon having a specific surface area of 800-900 m 2 /g, the surface area is measured by a BET adsorption method; and the active component further comprises a main active component and a secondary active component, wherein the main active component is Fe. The oxide, the secondary active component is an oxide of any two, three or four elements selected from the group consisting of Cu, Zn, Mn, Co, N i or Ce, but wherein the secondary active component is Oxides of Cu and oxides of Zn are not present at the same time. In one embodiment, the mass of activated carbon is 94-96% of the total mass of the catalyst; the amount of Fe of Fe 2 O 3 is 2-5% of the total mass of the catalyst; Cu0, Zn0, Mn0 2 , Co 2 respectively 03, the oxide Ce0 2 or NiO meter selected from Cu, Zn, Mn, Co, Ni or Ce in any two of three or four elements, and the mass of the total mass of the catalyst 0. 5- 2°/. .
在优选的实施方案中， 活性炭质量占催化剂总质量的 95%; 以 Fe203计的 Fe 的氧化物质量占催化剂总质量的 3-4%; 分别以 Cu0、 Zn0、 Mn02、 Co203、 Ni O或 Ce02计的选自 Cu、 Zn、 Mn、 Co、 N i或 Ce 中的任意两种、 三种或四种元素的氧化物的质量之和占 催化剂总质量的 1-2 %。 In a preferred embodiment, the mass of activated carbon is 95% of the total mass of the catalyst; the mass of Fe of Fe 2 O 3 is 3-4% of the total mass of the catalyst; Cu0, Zn0, Mn0 2 , Co 2 , respectively 0 3 , Ni O or Ce0 2 The sum of the masses of oxides of any two, three or four elements selected from Cu, Zn, Mn, Co, N i or Ce is 1 - the total mass of the catalyst 2 %.
本发明的第二方面和第三方面主要涉及催化剂的制备方法。 本发明的催化剂主要通过浸渍沉淀法来制备， 该浸渍沉淀方法主 要包括： 首先用某金属的可溶于水的盐的水 液充分浸渍载体， 然后加入沉淀剂以使得各金属以难溶于水的盐的形式沉淀在载体 上， 然后再进行一些后续处理。 在该浸渍沉淀法的实践中， 可以 先浸渍并沉淀某一种金属， 再浸渍或沉淀其余的金属； 或者同时 或先后浸渍某几种金属， 再同时或先后沉淀另几种金属， 这些都 属于浸渍沉淀法。 The second and third aspects of the invention relate generally to a process for the preparation of a catalyst. The catalyst of the present invention is mainly prepared by an immersion precipitation method, which mainly comprises: firstly impregnating a carrier with an aqueous solution of a water-soluble salt of a metal, and then adding a precipitant to make each metal hardly soluble in water The salt form is precipitated on the support and then subjected to some subsequent treatment. In the practice of the immersion precipitation method, one metal may be first impregnated and precipitated, and the remaining metal may be impregnated or precipitated; or a certain metal may be impregnated simultaneously or sequentially, and another metal may be precipitated simultaneously or sequentially. Impregnation precipitation method.
根据本发明的第二方面， 在本发明的方法的步骤 a中， 用包 括洗涤、 干燥和热处理在内的步骤对活性炭进行预处理。 本领域 技术人员可以根据需要选择其中洗涤、 干燥和热处理的条件。 例 如， 在一个实施方案中， 用去离子水对活性炭进行洗涤， 在 110- 下对洗涤后的活性炭进行干燥， 然后在 150- 2 Q0 X下对 干燥后的活性炭热处理 2-5小时。 According to a second aspect of the invention, in step a of the process of the invention, the activated carbon is pretreated with a step comprising washing, drying and heat treatment. Those skilled in the art can select conditions in which washing, drying and heat treatment are required as needed. For example, in one embodiment, the activated carbon is washed with deionized water, the washed activated carbon is dried at 110 -, and then the dried activated carbon is heat treated at 150 - 2 Q0 X for 2-5 hours.
根据本发明的第二方面， 在本发明的方法的步骤 b中， 通过 浸渍沉淀法将铁源以及选自铜源、 锌源、 锰源、 钴源、 镍源或铈
源中的任意两种、 三种或四种源以铁前体以及选自铜前体、 辞前 体、 锰前体、 钴前体、 镍前体或铈前体中的任意两种、 三种或四 种前体的形式负载在由步骤 a得到的活性炭上， 且对所述各源的 浸渍顺序以及各前体的沉淀顺序不加以限制， 且其中所述活性炭 上不同时负载有铁前体、 铜前体和锌前体。 其中所述浸渍沉淀法 是指用金属的可溶于水的盐的水溶液（即金属源）充分浸渍载体， 然后加入沉淀剂以使得该金属以难溶性盐 （即前体） 的形式沉淀 在载体上的过程。 其中沉淀剂选自可溶性的金属氢氧化物、 可溶 性的金属碳酸盐、 碳酸氢盐或氨水或它们的混合物， 例如 NaOH、 Na2C03或 NaHC03等。 沉淀剂的量应该足以使得各金属离子完全沉 淀到活性炭上， 以便控制最终催化剂中的主要活性组分和次要活 性组分的质量百分比。 其中各前体包括各金属的各种价态的碳酸 盐或氢氧化物或任何其它难溶于水的盐。 本领域技术人员能够根 据各金属和各前体的性质和预期的量来选择合适的沉淀剂种类、 沉淀剂量和沉淀顺序， 以对方法进行优化， 做出这些选择是技术 人员能力之内的事情。 According to a second aspect of the invention, in step b of the method of the invention, the source of iron is selected by a immersion precipitation method and is selected from the group consisting of a copper source, a zinc source, a manganese source, a cobalt source, a nickel source or a ruthenium Any two, three or four sources in the source are iron precursors and any two or three selected from the group consisting of copper precursors, precursors, manganese precursors, cobalt precursors, nickel precursors or ruthenium precursors. The form of the seed or the four precursors is supported on the activated carbon obtained in the step a, and the order of impregnation of the respective sources and the order of precipitation of the respective precursors are not limited, and wherein the activated carbon is not loaded with iron beforehand. Body, copper precursor and zinc precursor. Wherein the immersion precipitation method means that the carrier is sufficiently impregnated with an aqueous solution of a metal-soluble salt (ie, a metal source), and then a precipitant is added to precipitate the metal as a poorly soluble salt (ie, a precursor) in the carrier. On the process. Wherein the precipitating agent is selected from the group consisting of soluble metal hydroxides, soluble metal carbonates, hydrogencarbonates or aqueous ammonia or mixtures thereof, such as NaOH, Na 2 CO 3 or NaHC 0 3 and the like. The amount of precipitant should be sufficient to allow complete precipitation of each metal ion onto the activated carbon to control the mass percentage of the primary active component and the secondary active component in the final catalyst. Each of the precursors includes carbonates or hydroxides of various valence states of the respective metals or any other salt which is poorly soluble in water. Those skilled in the art will be able to select suitable precipitant species, precipitating doses, and precipitation sequences based on the nature and expected amount of each metal and precursor to optimize the process, making these choices within the capabilities of the skilled person. .
根据本发明的第二方面， 在本发明的方法的步骤 c中， 熟化 所述负载在活性炭上的活性组分前体。 所述熟化可以以两种方式 进行： 第一种是不对步骤 b的产物进行固液分离， 使所述负载在 活性炭上的活性组分前体在溶液中在室温下静置 24 小时来原位 进行熟化； 第二种先固液分离得到负载在活性炭上的活性组分前 体， 然后使该前体在室温下静置 24小时来进行熟化。其中固液分 离可以是本领域常规的固液分离手段， 如过滤、 离心分离等。 熟 化的作用是使活性组分前体充分均勾、稳定地分散于活性炭表面。 According to a second aspect of the invention, in step c of the process of the invention, the active component precursor supported on activated carbon is aged. The aging can be carried out in two ways: The first is to not perform solid-liquid separation of the product of step b, and the active component precursor supported on the activated carbon is allowed to stand in the solution at room temperature for 24 hours in situ. The aging is carried out; the second solid-liquid separation separates the active component precursor supported on the activated carbon, and then the precursor is allowed to stand at room temperature for 24 hours for aging. The solid-liquid separation may be a conventional solid-liquid separation means in the art, such as filtration, centrifugation and the like. The effect of the ripening is to sufficiently uniformly and stably disperse the active component precursor on the surface of the activated carbon.
根据本发明的第二方面， 在本发明的方法的步骤 d中， 洗涤、 干燥并煅烧所述负载在活性炭上的活性组分前体， 得到所述催化
剂。 其中所述洗涤是指用任何溶剂， 优选水， 来洗去残留在固体 物质上的可溶性离子的过程； 所述干燥在 120- 150 °C下进行， 干 燥时间为 2-5 小时； 而所述煅烧在马弗炉中在 270-300 X和有氧 气存在的气氛下进行，煅烧时间 8-10小时。 所述有氧气存在的气 氛优选为空气气氛。 经过煅烧后， 活性组分前体， 例如金属碳酸 盐或氢氧化物， 会分解生成金属氧化物。 一般认为， 在本文所述 的有氧气存在的气氛下 （优选在空气气氛下） 进行的长时间煅烧 过程中， 所生成的金属氧化物通常是这些金属的较高价态的稳定 的氧化物， 即 Fe203、 Cu0、 Zn0、 Mn02、 Co203、 N iO或 Ce02， 故当 在本发明中提到这些活性组分的含量时， 均采用折算成 Fe203、 Cu0、 Zn0、 Mn02、 Co203、 N iO或 Ce02的各金属氧化物的质量。 由 于步骤 b中的沉淀为完全沉淀且步骤 d中的煅烧分解反应也是完 全反应， 故本发明中根据起始溶液中的各金属的可溶性盐的量来 按沉淀反应和分解反应的化学计量比推算分解生成的金属氧化物 的量。 而且， 不受限于任何具体理论， 认为这些金属氧化物并非 以互不相干的方式独立存在， 而是形成了金属氧化物的复合物， 这种交互作用使得它们与各自独立存在时的金属氧化物相比， 在 废水处理条件下更不容易造成金属流失。 这将在以下实施例中以 催化剂的单次使用寿命的提高而得以体现。 且鉴于形成了金属氧 化物的复合物， 因此本发明中以各种金属氧化物形式表示的催化 剂的活性组分仅仅是一种化学上的表示形式， 并不代表催化剂的 活性组分的真实化学结构就是这些金属氧化物， 事实上， 鉴于各 活性金属的变价性和各金属氧化物彼此之间的相互作用， 活性组 分的真实化学结构的确定是相当复杂的事情。 此外， 本领域技术 人员会认可， 两种在化学表示上看起来相同的催化剂完全有可能 具有截然不同的真实化学结构并在截然不同的环境下使用。 故确
定催化剂的真实组成和真实化学结构时， 要将其使用环境的因素 考虑在内。 According to a second aspect of the invention, in step d of the process of the invention, the active component precursor supported on activated carbon is washed, dried and calcined to obtain said catalysis Agent. Wherein said washing refers to a process of washing away soluble ions remaining on the solid matter with any solvent, preferably water; said drying is carried out at 120-150 ° C for a drying time of 2-5 hours; The calcination is carried out in a muffle furnace at 270-300 X and in the presence of oxygen, and the calcination time is 8-10 hours. The atmosphere in which oxygen is present is preferably an air atmosphere. After calcination, the active component precursor, such as a metal carbonate or hydroxide, decomposes to form a metal oxide. It is believed that the metal oxides formed during the prolonged calcination process in the presence of oxygen as described herein, preferably under an air atmosphere, are generally stable oxides of higher valence of these metals, ie Fe 2 0 3 , Cu0, Zn0, Mn0 2 , Co 2 0 3 , N iO or Ce0 2 , so when the content of these active components is mentioned in the present invention, it is converted into Fe 2 O 3 , Cu0, The mass of each metal oxide of Zn0, Mn0 2 , Co 2 0 3 , N iO or Ce0 2 . Since the precipitation in the step b is completely precipitated and the calcination decomposition reaction in the step d is also a complete reaction, in the present invention, the stoichiometric ratio of the precipitation reaction and the decomposition reaction is calculated according to the amount of the soluble salt of each metal in the starting solution. Decomposes the amount of metal oxide formed. Moreover, without being bound by any particular theory, it is believed that these metal oxides do not exist independently in mutually incoherent manner, but rather form a composite of metal oxides that cause their metal oxidation to exist independently of each other. Compared with materials, metal loss is less likely to occur under wastewater treatment conditions. This will be manifested in the following examples with an increase in the single life of the catalyst. And in view of the formation of a metal oxide complex, the active component of the catalyst represented by various metal oxide forms in the present invention is merely a chemical representation and does not represent the true chemistry of the active component of the catalyst. The structure is these metal oxides. In fact, in view of the valence of each active metal and the interaction of the respective metal oxides with each other, the determination of the true chemical structure of the active component is quite complicated. Moreover, those skilled in the art will recognize that two catalysts that look identical in chemical expression are entirely likely to have distinct real chemical structures and be used in very different environments. Indeed When determining the true composition and true chemical structure of the catalyst, the environmental factors of the catalyst should be taken into account.
根据本发明的第三方面， 在本发明的方法的步骤 a中， 用包 括洗涤、 干燥和热处理在内的步骤对活性炭进行预处理。 在一个 实施方案中， 用去离子水对活性炭进行洗涤， 在 110-120 下对 洗涤后的活性炭进行干燥， 然后在 150-200 下对干燥后的活性 炭热处理 2-5小时。 According to a third aspect of the invention, in step a of the process of the invention, the activated carbon is pretreated by a step comprising washing, drying and heat treatment. In one embodiment, the activated carbon is washed with deionized water, the washed activated carbon is dried at 110-120, and the dried activated charcoal is then heat treated at 150-200 for 2-5 hours.
根据本发明的第三方面， 在本发明的方法的步骤 b中， 配制 包含可溶性铁盐或亚铁盐并包含可溶性铜盐、 可溶性锌盐、 可溶 性锰盐、 可溶性钴盐、 可溶性镍盐或可溶性铈盐中的任意两种、 三种或四种的水溶液， 且其中所述水溶液不同时含有可溶性铁盐 或亚铁盐与可溶性铜盐和可溶性锌盐。 各金属的可溶性盐包括各 金属的各种价态的无机酸盐或有机酸盐。 例如， 其中所述可溶性 铁盐包括无机酸的铁盐如氯化铁、 硝酸铁或硫酸铁等， 或有机酸 的铁盐， 如乙酸铁、 草酸铁等， 优选使用无机酸的铁盐。 所述可 溶性亚铁盐包括无机酸的亚铁盐如氯化亚铁、 硝酸亚铁或硫酸亚 铁等， 或有机酸的亚铁盐， 如乙酸亚铁、 草酸亚铁等， 优选使用 无机酸的亚铁盐； 所述可溶性铜盐、 可溶性锌盐、 可溶性锰盐、 可溶性钴盐、 可溶性镍盐或可溶性铈盐包括这些金属的无机酸盐 或有机酸盐， 其中无机酸盐例如氯化物 （即盐酸盐） 、 硝酸盐或 硫酸盐等， 有机酸盐例如乙酸盐、 草酸盐等。 铁盐或亚铁盐以及 各次要活性组分的盐可以先单独配成溶液后再混合在一起， 也可 以直接配成混合溶液。 在实施方案中， 沉淀到载体上的各金属前 体的量足以使最终的催化剂中以 Fe203计的 Fe的氧化物质量占催 化剂总质量的 2-5% , 并使得分别以 Cu0、 Zn0、 Mn02、 Co203、 N iO 或 Ce02计的选自 Cu、 Zn、 Mn、 Co、 N i或 Ce中的任意两种、 三种
或四种元素的氧化物的质量之和占催化剂总质量的 0. 5-2%。在优 选的实施方案中， 沉淀到载体上的各金属前体的量足以使最终的 催化剂中以 Fe203计的 Fe的氧化物质量占催化剂总质量的 3-4%， 并使得分别以 Cu0、 Zn0、 Mn02、 Co203、 NiO或 Ce02计的选自 Cu、 Zn、 Mn、 Co、 N i或 Ce中的任意两种、 三种或四种元素的氧化物 的质量之和占催化剂总质量的 1-2%。 According to a third aspect of the invention, in step b of the method of the invention, the preparation comprises a soluble iron or ferrous salt and comprises a soluble copper salt, a soluble zinc salt, a soluble manganese salt, a soluble cobalt salt, a soluble nickel salt or a soluble Any two, three or four aqueous solutions of the cerium salt, and wherein the aqueous solution does not simultaneously contain a soluble iron or ferrous salt with a soluble copper salt and a soluble zinc salt. The soluble salts of the respective metals include inorganic or organic acid salts of various valence states of the respective metals. For example, the soluble iron salt includes an iron salt of a mineral acid such as iron chloride, iron nitrate or iron sulfate, or an iron salt of an organic acid such as iron acetate, iron oxalate or the like, and an iron salt of a mineral acid is preferably used. The soluble ferrous salt includes a ferrous salt of a mineral acid such as ferrous chloride, ferrous nitrate or ferrous sulfate, or a ferrous salt of an organic acid, such as ferrous acetate, ferrous oxalate or the like, preferably using a mineral acid. a ferrous salt; a soluble copper salt, a soluble zinc salt, a soluble manganese salt, a soluble cobalt salt, a soluble nickel salt or a soluble cerium salt including inorganic or organic acid salts of these metals, wherein a mineral acid salt such as chloride That is, hydrochloride, nitrate or sulfate, organic acid salts such as acetate, oxalate, and the like. The iron salt or the ferrous salt and the salt of each of the secondary active components may be separately mixed into a solution and then mixed together, or may be directly formulated into a mixed solution. In an embodiment, the amount of each metal precursor precipitated onto the support is sufficient to cause the oxide of Fe in the final catalyst to be 2-5% by mass of the total mass of the catalyst in terms of Fe 2 O 3 , and to make Cu0, Any two or three selected from the group consisting of Cu, Zn, Mn, Co, N i or Ce in terms of Zn0, Mn0 2 , Co 2 O 3 , N iO or Ce0 2 5-2%。 The mass of the total mass of the catalyst is 0. 5-2%. In a preferred embodiment, the amount of each metal precursor precipitated onto the support is sufficient to cause the oxide of Fe in the final catalyst to be 3-4% by mass of the total mass of the catalyst in terms of Fe 2 O 3 , and The mass of an oxide of any two, three or four elements selected from Cu, Zn, Mn, Co, N i or Ce in terms of Cu0, Zn0, Mn0 2 , Co 2 O 3 , NiO or CeO 2 And account for 1-2% of the total mass of the catalyst.
由于可控制沉淀剂的加入量以使得下文步骤 d中发生的沉淀 是完全沉淀，且下文步骤 f 的煅烧过程发生的分解也是完全分解， 沉淀反应和分解反应均按化学计量比发生， 故本领域技术人员很 容易根据上述最终催化剂中的主要活性组分和次要活性组分占催 化剂总盾量的百分比来计算在本步骤中加入的可溶性铁盐或亚铁 盐以及可溶性铜盐、 可溶性锌盐、 可溶性锰盐、 可溶性钴盐、 可 溶性镍盐或可溶性铈盐中的任意两种、 三种或四种的具体量。 Since the amount of the precipitant added can be controlled such that the precipitation occurring in the step d below is completely precipitated, and the decomposition occurring in the calcination process of the step f below is also completely decomposed, both the precipitation reaction and the decomposition reaction occur in a stoichiometric ratio, so that the field The skilled person can easily calculate the soluble iron or ferrous salt and the soluble copper salt and soluble zinc salt added in this step according to the percentage of the main active component and the secondary active component in the final catalyst as a percentage of the total shield of the catalyst. a specific amount of any two, three or four of a soluble manganese salt, a soluble cobalt salt, a soluble nickel salt or a soluble phosphonium salt.
根据本发明的第三方面， 在本发明的方法的步骤 c中， 加热 所述水溶液， 并向其中加入预处理后的活性炭， 搅拌均勾后冷却 至室温。 在一个实施方案中， 将所述水溶液加热至 60-70。C， 和 所述搅拌持续 3-5小时。 所述冷却可以是自然冷却。 According to a third aspect of the present invention, in the step c of the method of the present invention, the aqueous solution is heated, and the pretreated activated carbon is added thereto, stirred and cooled to room temperature. In one embodiment, the aqueous solution is heated to 60-70. C, and the stirring is continued for 3-5 hours. The cooling can be natural cooling.
根据本发明的第三方面， 在本发明的方法的步骤 d中， 向水 溶液中加入能使铁离子沉淀并能使铜离子、 锌离子、 锰离子、 钴 离子、 镍离子或铈离子中的任意两种、 三种或四种离子沉淀的沉 淀剂， 得到负载在活性炭上的活性组分前体。 其中沉淀剂选自可 溶性的金属氢氧化物、 可溶性的金属碳酸盐、 碳酸氢盐或氨水或 它们的混合物， 例如 NaOH、 ^ 03或 NaHC03等。 沉淀剂的量应该 足以使得各金属离子完全沉淀到活性炭上， 以便控制最终催化剂 中的主要活性组分和次要活性组分的质量百分比。加入沉淀剂后， 所有金属离子均以氢氧化物沉淀、 碳酸盐沉淀或碳酸氢盐沉淀或
它们的混合物的形式 （这些沉淀物亦可称为活性组分前体）沉淀 在活性炭的微孔内， 从而将活性组分前体负载在活性炭上。 选择 加入的沉淀剂的量和溶液的 pH 值以使得这些金属离子基本上完 全以沉淀物的形式沉淀到活性炭上。 According to a third aspect of the present invention, in the step d of the method of the present invention, the addition of iron ions to the aqueous solution and any of copper ions, zinc ions, manganese ions, cobalt ions, nickel ions or barium ions can be added to the aqueous solution. Two, three or four ion-precipitating precipitants provide the active component precursor supported on activated carbon. Wherein the precipitating agent is selected from a soluble metal hydroxide, a soluble metal carbonate, bicarbonate, or ammonia, or mixtures thereof, e.g. NaOH, ^ 0 3 NaHC0 3 or the like. The amount of precipitant should be sufficient to allow complete precipitation of each metal ion onto the activated carbon to control the mass percentage of the primary active component and the secondary active component in the final catalyst. After the addition of the precipitant, all metal ions are precipitated by hydroxide, carbonate precipitated or bicarbonate precipitated or The form of their mixture (these precipitates may also be referred to as active component precursors) is precipitated in the pores of the activated carbon to support the active component precursor on the activated carbon. The amount of precipitant added and the pH of the solution are selected such that these metal ions are substantially completely precipitated onto the activated carbon as a precipitate.
根据本发明的第三方面， 在本发明的方法的步骤 e中， 熟化 所述负载在活性炭上的活性组分前体。 所述熟化可以以两种方式 进行： 第一种是不对步骤 d的产物进行固液分离， 使所述负载在 活性炭上的活性组分前体在溶液中在室温下静置 24 小时来原位 进行熟化； 第二种先固液分离得到负载在活性炭上的活性组分前 体， 然后使该前体在室温下静置 24小时来进行熟化。其中固液分 离可以是本领域常规的固液分离手段， 如过滤、 离心分离等。 熟 化的作用是使活性组分前体充分均勾、稳定地分散于活性炭表面。 According to a third aspect of the invention, in step e of the process of the invention, the active component precursor supported on activated carbon is aged. The aging can be carried out in two ways: The first is to not perform solid-liquid separation on the product of step d, and the active component precursor supported on the activated carbon is allowed to stand in the solution at room temperature for 24 hours in situ. The aging is carried out; the second solid-liquid separation separates the active component precursor supported on the activated carbon, and then the precursor is allowed to stand at room temperature for 24 hours for aging. The solid-liquid separation may be a conventional solid-liquid separation means in the art, such as filtration, centrifugation and the like. The effect of the ripening is to sufficiently uniformly and stably disperse the active component precursor on the surface of the activated carbon.
根据本发明的第三方面，在本发明的方法的步驟 f 中， 洗涤、 干燥并煅烧所述负载在活性炭上的活性组分前体， 得到所述催化 剂。 其中所述洗涤是指用任何溶剂， 优选水， 来洗去残留在固体 物质上的可溶性离子的过程； 所述千燥在 120-150 X下进行， 干 燥时间为 2-5 小时。 而所述煅烧在马弗炉中在 270- 300 和有氧 气存在的气氛下进行，煅烧时间 8-10小时。所述有氧气存在的气 氛优选为空气气氛。 经过煅烧后， 活性组分前体， 例如金属碳酸 盐或氢氧化物， 会分解生成金属氧化物。 一般认为， 在本文所述 的有氧气存在的气氛下 （优选在空气气氛下） 进行的长时间煅烧 过程中， 所生成的金属氧化物通常是这些金属的最高价态的稳定 的氧化物， 即 Fe203、 Cu0、 Zn0、 Mn02、 Co203、 N iO或 Ce02， 故当 在本发明中提到这些活性组分的含量时， 均采用折算成 Fe203、 Cu0、 Zn0、 Mn02、 Co203、 N i O或 Ce02的各金属氧化物的质量， 由 于步骤 d中的沉淀为完全沉淀且步骤 f 中的煅烧分解反应也是完
全反应， 故本发明中根据起始溶液中的各金属的可溶性盐的量来 按沉淀反应和分解反应的化学计量比推算分解生成的金属氧化物 的量。 而且， 据信这些金属氧化物并非以互不相干的方式独立存 在， 而是形成了金属氧化物的复合物， 这种交互作用使得它们与 各自独立存在时的金属氧化物相比， 在废水处理条件下更不容易 造成金属流失。 这将在以下实施例中以催化剂的单次使用寿命的 提高而得以体现。 According to a third aspect of the invention, in step f of the process of the invention, the active component precursor supported on activated carbon is washed, dried and calcined to obtain the catalyst. The washing refers to a process of washing away soluble ions remaining on the solid matter with any solvent, preferably water; the drying is carried out at 120-150 X, and the drying time is 2-5 hours. The calcination is carried out in a muffle furnace in an atmosphere of 270-300 and in the presence of oxygen for a calcination time of 8-10 hours. The atmosphere in which oxygen is present is preferably an air atmosphere. After calcination, the active component precursor, such as a metal carbonate or hydroxide, decomposes to form a metal oxide. It is generally believed that the metal oxides formed during the prolonged calcination in the presence of oxygen in the presence of oxygen (preferably under an air atmosphere) are generally the stable oxides of the highest valence of these metals, ie Fe 2 0 3 , Cu0, Zn0, Mn0 2 , Co 2 0 3 , N iO or Ce0 2 , so when the content of these active components is mentioned in the present invention, it is converted into Fe 2 O 3 , Cu0, The mass of each metal oxide of Zn0, Mn0 2 , Co 2 0 3 , N i O or Ce0 2 , since the precipitation in step d is completely precipitated and the calcination decomposition reaction in step f is also completed In the present invention, the amount of the metal oxide formed by the decomposition is estimated from the stoichiometric ratio of the precipitation reaction and the decomposition reaction according to the amount of the soluble salt of each metal in the starting solution. Moreover, it is believed that these metal oxides do not exist independently in mutually incoherent manner, but instead form a composite of metal oxides that interacts with the metal oxides in their respective independent presences in wastewater treatment. It is less likely to cause metal loss under conditions. This will be manifested in the following examples with an increase in the single life of the catalyst.
本发明的催化剂的催化作用通过以下废水处理实验来检验。 废水有两种： 一种是煤气化废水原液， 废水的成分复杂、 毒 性大， COD为 20000mg/L以上。 另一种是煤气化废水原液经预处 理 -0A02(预处理一一级固定化生物膜好氧曝气一固定化生物膜厌 氧一二级固定化生物膜好氧曝气） 工艺的出水， 该废水的可生化 性极差， 很难生物降解， 色度高， COD为 180-300mg/L。 The catalysis of the catalyst of the present invention was examined by the following wastewater treatment experiments. There are two kinds of waste water: One is the coal gasification wastewater raw liquid, the composition of the wastewater is complex and the toxicity is large, and the COD is 20000 mg/L or more. The other is the effluent of the coal gasification wastewater raw liquid by pretreatment -0A02 (pretreatment, one-stage immobilized biofilm, aerobic aeration, immobilized biofilm, anaerobic one-stage immobilized biofilm, aerobic aeration). The wastewater is extremely biodegradable, difficult to biodegrade, high in chroma, and has a COD of 180-300 mg/L.
采用固定床反应器测试了催化剂的催化活性和稳定性: The catalytic activity and stability of the catalyst were tested using a fixed bed reactor:
1.反应器： 反应器为固定床反应器。 反应器的材料为有机玻 璃， 其尺寸为 Φ 65*5讓， 高度为 300腿， 反应器的底部分别设有 排污口和瞰气口， 距底部 l-2cm处和距顶部 5-6cm处的侧面分别 设有进水口和排水口， 距底部 3- 4cm处固定有布气板， 单层反应 器。 1. Reactor: The reactor is a fixed bed reactor. The material of the reactor is plexiglass, the size is Φ 65*5, the height is 300 legs, and the bottom of the reactor is provided with a sewage outlet and a gas outlet respectively, and the side at a distance of l-2cm from the bottom and 5-6cm from the top. There are water inlets and drains respectively, and a gas plate and a single-layer reactor are fixed at a distance of 3-4 cm from the bottom.
2.催化剂的装填：首先在反应器底部的布气板上铺设 18 目聚 乙烯网片， 然后将 60g本发明制备的催化剂装填于反应器中。 催 化剂颗粒的上平面铺设一层布气板， 加入 1-4 目的石英砂颗粒使 催化剂层相对固定。 2. Catalyst loading: First, a 18 mesh polyethylene mesh was laid on the gas plate at the bottom of the reactor, and then 60 g of the catalyst prepared by the present invention was charged into the reactor. A layer of gas plate is laid on the upper plane of the catalyst particles, and 1-4 mesh quartz sand particles are added to make the catalyst layer relatively fixed.
3.实验条件： 常温常压， 废水的 pH值大约为 5. 0-7. 5， 水力 停留时间是 0. 5-5. 0小时， 釆用连续曝气和连续进样的方式， 曝 气流量为 0· 2-0. 3mL/min。
以上对本发明的实施进行了详细描述， 这些描述是说明性的 而非限制性的。 阅读过以上描述后， 本领域技术人员显然还可以 想到本发明的其它变形实^方案， 例如釆用其它多孔载体如氧化 硅、 氧化铝、 粘土、 沸石、 分子筛等代替本发明中的活性炭， 认 为这样的变形方式也落在本发明的范围之内。 3. The experimental conditions: normal temperature and pressure, the pH of the wastewater is about 5. 0-7. 5, hydraulic retention time is 0. 5-5. 0 hours, using continuous aeration and continuous injection, aeration The flow rate was 0·2-0. 3 mL/min. The embodiments of the present invention have been described in detail, and the description is illustrative and not restrictive. After reading the above description, it will be apparent to those skilled in the art that other variants of the invention are also contemplated, such as using other porous supports such as silica, alumina, clay, zeolite, molecular sieves, etc. instead of the activated carbon of the present invention, Such variations are also within the scope of the invention.
实施例 Example
举出以下实施例以说明本发明， 但不对本发明进行限制。 实施例 1 在活性炭上负载 5%Fe-Cu-Ni三元复合金属氧化物的催化 剂 The following examples are given to illustrate the invention but are not intended to limit the invention. Example 1 Catalyst for supporting 5% Fe-Cu-Ni ternary composite metal oxide on activated carbon
该催化剂的组分和含量为： 活性炭栽体的质量百分比为 95%， 活性组分 Fe-Cu-Ni三元复合金属氧化物的质量百分比含量为 5%， 其中以 Fe203、 Cu0、 NiO计的金属氧化物的质量百分比含量分别为 4%, 0. 5%和 0. 5%。 The composition and content of the catalyst are: 95% by mass of the activated carbon carrier, and 5% by mass of the active component Fe-Cu-Ni ternary composite metal oxide, wherein Fe 2 0 3 , Cu0, The 5% by mass of the metal oxides of the NiO is 4%, 0.5% and 0.5%, respectively.
该催化剂的制备方法， 包括以下步骤： The preparation method of the catalyst comprises the following steps:
a.把活性炭用去离子水洗涤干净， 经 120 下干燥和 150X下 热处理 2小时完成预处理， 取 190g; a. The activated carbon is washed with deionized water, dried under 120 times and heat treated at 150X for 2 hours to complete the pretreatment, taking 190 g;
b.称取 27. lg FeCl3 ·6Η20、 2. lg CuCl2 ·2Η20和 3. 2g NiCl2 · 6Η20 三种金属盐， 分别用去离子水配制成溶液， 然后混合均匀， 混合溶 液的体积为 230mL; b. Weigh 27.lg lg FeCl 3 ·6Η 2 0, 2. lg CuCl 2 ·2Η 2 0 and 3. 2g NiCl 2 · 6Η 2 0 three kinds of metal salts, respectively prepared with deionized water into a solution, and then mixed evenly , the volume of the mixed solution is 230 mL;
c.混合溶液加热至 70 后加入经步骤 a预处理后的活性炭颗 粒， 均匀搅拌浸渍 4个小时后冷却至室温； c. After heating the mixed solution to 70, the activated carbon particles pretreated by the step a are added, uniformly immersed for 4 hours, and then cooled to room temperature;
d.向溶液中加入 13. 3g NaOH沉淀剂， 得到沉淀物； d. Add 13.3 g of NaOH precipitant to the solution to obtain a precipitate;
e.不进行固液分离， 原位进行熟化 24小时； e. without solid-liquid separation, in-situ aging for 24 hours;
f.过滤出固体， 用去离子水洗涤固体至无金属离子析出， 在 下干燥 2h,然后在马弗炉中在空气气氛下在 270 下煅烧 8h， 制得在活性炭上负载 5%Fe- Cu- Ni三元复合金属氧化物的催化剂。
釆用前述固定床反应器测试了该催化剂的催化活性和稳定性， 试验结果发现， 在常温常压下和空气作为氧化剂条件下， 催化氧化 处理 COD为 21500mg/L的煤气化废水原液 lh后， COD降至 200mg/L; 催化氧化处理经预处理 -0A02 (预处理一一级固定化生物膜好氧曝 气一固定化生物膜厌氧一二级固定化生物膜好氧曝气）工艺 COD为 200-220mg/L的煤气化废水出水，催化剂一次连续使用 4. 5个月（即 催化剂的单次使用寿命）后， 出水 pH为 7-8， COD为 60-80mg/L， 废水色度从处理前的 300-400倍降低到处理后的 30倍， B0D5 为 20mg/L,氨氮为 4-6mg/L， 悬浮物为 20mg/L和其它各项指标均能满 足 GB8978— 1996 《污水综合排放标准》 中的一级标准。 实施例 2 在活性炭上负载 5%Fe- Ni- Mn三元复合金属氧化物的 催化剂 f. The solid was filtered off, the solid was washed with deionized water until no metal ions were precipitated, dried underneath for 2 h, and then calcined in a muffle furnace under an air atmosphere at 270 for 8 h to obtain 5% Fe-Cu supported on activated carbon. A catalyst for Ni ternary composite metal oxide. The catalytic activity and stability of the catalyst were tested by the above fixed bed reactor. The test results showed that after normal temperature and pressure and air as an oxidant, the catalytic oxidation treatment of COD was 21500 mg/L of coal gasification wastewater for 1 h. COD reduced to 200mg / L; catalytic oxidation treatment by pretreatment -0A02 (pretreatment one-stage immobilized biofilm aerobic aeration - immobilized biofilm anaerobic one or two immobilized biofilm aerobic aeration) process COD For the 200-220mg/L coal gasification wastewater effluent, the catalyst is used continuously for 4.5 months (ie, the single service life of the catalyst), the effluent pH is 7-8, COD is 60-80mg/L, the color of the wastewater From 300-400 times before treatment to 30 times after treatment, B0D5 is 20mg/L, ammonia nitrogen is 4-6mg/L, suspended matter is 20mg/L and other indicators can meet GB8978-1996 Level 1 standard in the Emission Standards. Example 2 Catalyst for supporting 5% Fe-Ni-Mn ternary composite metal oxide on activated carbon
该催化剂的组分和含量为： 活性炭载体的质量百分比含量为 95%,活性组分 Fe- Ni-Mn三元复合金属氧化物的质量百分比含量为 5%, 其中以 Fe203、 Ni0、 Mn02计的氧化物质量百分比含量分别为 4%， 0. 5%和 0. 5%。 The composition and content of the catalyst are: the mass percentage content of the activated carbon carrier is 95%, and the mass percentage of the active component Fe-Ni-Mn ternary composite metal oxide is 5%, wherein Fe 2 0 3 , Ni0, The 5% by mass of the Mn0 2 is 0.4%, 0.5% and 0.5%, respectively.
该催化剂的制备方法， 包括以下步骤： The preparation method of the catalyst comprises the following steps:
a.活性炭的预处理同实施例 1， 取 190g; a. The pretreatment of activated carbon is the same as in Example 1, taking 190g;
b.称取 27. lg FeCl3 ·6Η20、 3. 2g NiCl2 ·6Η20和 2. 8g MnCl2 ·4Η20 三种金属盐， 用去离子水配制成 230mL的混合溶液； b. Weighing 27. lg FeCl 3 ·6Η 2 0, 3. 2g NiCl 2 ·6Η 2 0 and 2. 8g MnCl 2 ·4Η 2 0 three metal salts, formulated into 230mL mixed solution with deionized water;
c - f.然后通过浸渍、 沉淀、 熟化、 洗涤、 干燥和焙烧完成活 性炭负载 5%Fe- Ni-Mn三元复合金属氧化物催化剂的制备， 实验条 件均同实施例 1中的步骤 c至步骤 f。 c - f. Then, the preparation of the activated carbon-supported 5% Fe-Ni-Mn ternary composite metal oxide catalyst is completed by dipping, precipitating, aging, washing, drying and calcination, and the experimental conditions are the same as those in the step c to the step in the embodiment 1. f.
釆用固定床反应器测试了该催化剂的催化活性和稳定性。 The catalytic activity and stability of the catalyst were tested using a fixed bed reactor.
试验采用的反应器和催化剂的装填方式和实验条件同实施例
1。 试验结果发现， 在常温常压下和空气作为氧化剂条件下， 催化 氧化处理 COD 为 21500mg/L 的煤气化废水原液 lh后， COD 降至 200mg/L; 催化氧化经预处理 -0A02 处理工艺 COD为 200- 220mg/L 的煤气化废水出水， 催化剂一次连续使用 4. 5个月 （催化剂的单次 使用寿命）后， 出水 pH为 7-8， COD为 60-80mg/L， 废水色度从处 理前的 300- 400倍降低到处理后的 30倍， 80 为 20mg/L， 氨氮为 4-6mg/L,悬浮物为 20mg/L和其它各项指标均能满足 GB8978— 1996 《污水综合排放标准》 中的一级标准。 实施例 3 在活性炭上负载 5%Fe-Cu-Mn三元复合金属氧化物的 催化剂 The reactor and catalyst loading method and experimental conditions used in the experiment are the same as the examples. 1. The test results show that under the conditions of normal temperature and pressure and air as oxidant, COD is reduced to 200mg/L after catalytic oxidation treatment of coal gasification wastewater with COD of 21500mg/L for 1h; catalytic oxidation by pretreatment -0A02 treatment process COD 200- 220mg/L coal gasification wastewater effluent, the catalyst is used continuously for 4.5 months (single life of the catalyst), the effluent pH is 7-8, COD is 60-80mg/L, the color of the wastewater is treated from The previous 300-400 times is reduced to 30 times after treatment, 80 is 20mg/L, ammonia nitrogen is 4-6mg/L, suspended matter is 20mg/L and other indicators can meet GB8978-1996 Integrated Wastewater Discharge Standard The first level standard in . Example 3 Catalyst for supporting 5% Fe-Cu-Mn ternary composite metal oxide on activated carbon
该催化剂的组分和含量为： 活性炭载体的质量百分比含量为 95%,主要活性组分 Fe-Cu-Mn三元复合金属氧化物的质量百分比含 量为 5%, 其中以 Fe203、 CuO、 Mn02计的质量百分比含量分别为 4%, 0. 5%和 0. 5%。 The composition and content of the catalyst are: the mass percentage content of the activated carbon carrier is 95%, and the mass percentage of the main active component Fe-Cu-Mn ternary composite metal oxide is 5%, wherein Fe 2 0 3 , CuO , Mn0 2 meter mass percentage content of 4%, respectively, 0.5% and 0.5%.
该催化剂的制备方法， 包括以下步骤： The preparation method of the catalyst comprises the following steps:
a.活性炭的预处理同实施例 1 , 取 190g; a. The pretreatment of activated carbon is the same as in Example 1, taking 190g;
b.称取 27. lg FeCl3 ' 6Η20、 2. lg CuCl2 · 2Η20和 2. 8g MnCl2 ·4Η20 三种金属盐， 用去离子水配制成 230mL的混合溶液； b. Weighing 27. lg FeCl 3 ' 6Η 2 0, 2. lg CuCl 2 · 2Η 2 0 and 2. 8g MnCl 2 · 4Η 2 0 three metal salts, formulated into a 230mL mixed solution with deionized water;
c - f.然后通过浸渍、 沉淀、 熟化、 洗涤、 干燥和焙烧完成活 性炭负载 5%Fe-Cu-Mn三元复合金属氧化物催化剂的制备， 实猃条 件均同实施例 1中的步驟 c至步骤 f。 c - f. Then, the preparation of the activated carbon-supported 5% Fe-Cu-Mn ternary composite metal oxide catalyst is completed by dipping, precipitating, aging, washing, drying and calcining, and the actual conditions are the same as those in the step c in the first embodiment. Step f.
采用固定床反应器测试了该催化剂的催化活性和稳定性。 The catalytic activity and stability of the catalyst were tested using a fixed bed reactor.
反应器、 催化剂装填和实验条件同实施例 1。 试验结果发现， 在常温常压下和空气作为氧化剂条件下， 催化氧化处理 COD 为 24000mg/L的煤气化废水原液 lh后， COD降至 200mg/L; 催化氧化
经预处理 -0A02处理工艺 COD为 200- 220mg/L的煤气化废水出水， 催化剂一次连续使用 5 个月后 （催化剂的单次使用寿命） 出水 pH 为 7-8， COD为 60-80mg/L，废水色度从处理前的 300-400倍降低到 处理后的 30倍， B0D5为 20mg/L,氨氮为 4-6mg/L,悬浮物为 20mg/L 和其它各项指标均能满足 GB8978— 1996《污水综合排放标准》中的 一级标准。 实施例 4 在活性炭上负载 5%Fe- Cu- Mn三元复合金属氧化物的 催化剂 The reactor, catalyst loading and experimental conditions were the same as in Example 1. The test results show that under the conditions of normal temperature and pressure and air as oxidant, the COD is reduced to 200mg/L after catalytic oxidation treatment of 24000mg/L coal gasification wastewater. After the pretreatment -0A02 treatment process COD 200-220mg / L of coal gasification wastewater effluent, the catalyst after 5 months of continuous use (single life of the catalyst) effluent pH 7-8, COD 60-80mg / L The color of wastewater is reduced from 300-400 times before treatment to 30 times after treatment, B0D 5 is 20 mg/L, ammonia nitrogen is 4-6 mg/L, suspended matter is 20 mg/L, and other indicators can meet GB8978. — The first level standard in the 1996 Integrated Wastewater Discharge Standard. Example 4 Catalyst for supporting 5% Fe-Cu-Mn ternary composite metal oxide on activated carbon
该催化剂的组分和含量为： 活性炭载体的质量百分比含量为 95%,活性组分 Fe-Cu- Mn三元复合金属氧化物的质量百分比含量为 5%, 其中以 Fe203、 CuO、 Mn02计的质量百分比含量分别为 4%, 0. 5% 和 0. 5°/ο β The composition and content of the catalyst are: the mass percentage content of the activated carbon carrier is 95%, and the mass percentage of the active component Fe-Cu-Mn ternary composite metal oxide is 5%, wherein Fe 2 O 3 , CuO, 5%和0. 5°/ο β The mass percentage content of Mn0 2 is 4%, 0.5% and 0. 5°/ο β
该催化剂的制备方法采用顺序浸渍沉淀法，这与其余实施例中 釆用的同时浸溃沉淀法有所不同， 该顺序浸渍沉淀法包括以下步 a.活性炭的预处理同实施例 1 , 取 190g; The preparation method of the catalyst adopts the sequential immersion precipitation method, which is different from the simultaneous impregnation precipitation method used in the other examples. The sequential immersion precipitation method includes the following steps: a. Pretreatment of activated carbon is the same as in Example 1, taking 190 g ;
bl.称取 2. lg CuC l2 · 2H20， 用 230mL去离子水配制成溶液， 加 热至 70 后加入经步骤 a预处理后的活性炭颗粒， 均匀搅拌浸渍 4 个小时后冷却至室温， 向溶液中加入 0. 98g NaOH沉淀剂， 得到沉 淀物； Bl. Weigh 2. lg CuC l 2 · 2H 2 0, prepare a solution with 230 mL of deionized water, heat to 70, then add activated carbon granules pretreated in step a, uniformly immersed for 4 hours, and then cooled to room temperature. Adding 0.98 g of NaOH precipitant to the solution to obtain a precipitate;
b2.再称取 27. lg FeC l3 - 6H20, 按前述 b步骤完成浸渍， 然后 向溶液中加入 12. 02g NaOH沉淀剂； . b2 weighed and then 27. lg FeC l 3 - 6H 2 0, by the completion of impregnating step b, then 12. 02g NaOH was added to the solution precipitating agent;
b3. 再称取 2. 8g MnC l2 · 4H20, 按前述 b步骤完成浸渍， 然后 向溶液中加入 1. 13g NaOH沉淀剂； . b3 then weighed 2. 8g MnC l 2 · 4H 2 0, by the completion of impregnating step b was added 1. 13g NaOH precipitating agent to the solution;
c - f.然后通过熟化、 洗涤、 干燥和焙烧完成活性炭负载
5%Cu-Fe-Mn三元复合金属氧化物催化剂的制备，实验条件均同实施 例 1中的步骤 c至步骤 f。 c - f. then complete the activated carbon load by aging, washing, drying and roasting The preparation of the 5% Cu-Fe-Mn ternary composite metal oxide catalyst was carried out under the same conditions as the steps c to f in Example 1.
采用固定床反应器测试了该催化剂的催化活性和稳定性。 The catalytic activity and stability of the catalyst were tested using a fixed bed reactor.
反应器、 催化剂装填和实验条件同实施例 1。 试验结果发现， 在常温常压下和空气作为氧化剂条件下， 催化氧化处理 COD 为 24000mg/L的煤气化废水原液 lh后， COD降至 200mg/L; 催化氧化 经预处理 -0A02处理工艺 COD为 200-220mg/L的煤气化废水出水， 催化剂一次连续使用 5 个月后 （催化剂的单次使用寿命） 出水 pH 为 7-8 , COD为 60-80mg/L，废水色度从处理前的 300-400倍降低到 处理后的 30倍， B0D5为 20mg/L,氨氮为 4-6mg/L,悬浮物为 20mg/L 和其它各项指标均能满足 GB8978— 1996《污水综合排放标准》中的 一级标准。 The reactor, catalyst loading and experimental conditions were the same as in Example 1. The test results show that under the conditions of normal temperature and pressure and air as oxidant, COD is reduced to 200mg/L after catalytic oxidation treatment of coal-fired wastewater with COD of 24000mg/L for 1h; catalytic oxidation of COD after pretreatment -0A02 treatment 200-220mg/L coal gasification wastewater effluent, the catalyst is used continuously for 5 months (single life of the catalyst). The effluent pH is 7-8, the COD is 60-80mg/L, and the color of the wastewater is 300 before treatment. -400 times reduced to 30 times after treatment, B0D 5 is 20mg/L, ammonia nitrogen is 4-6mg/L, suspended matter is 20mg/L and other indicators can meet GB8978-1996 "Integrated Wastewater Discharge Standard" First-class standard.
实施例 5 在活性炭上负载 5%Fe-Cu-Mn-Ce 四元复合金属氧化 物的催化剂 Example 5 Catalyst for 5% Fe-Cu-Mn-Ce quaternary composite metal oxide supported on activated carbon
该催化剂的组分和含量为： 活性炭载体的质量百分比含量为 95%, 活性组分为 Fe- Cu-Mn-Ce四元复合金属氧化物的质量百分比 含量为 5%, 其中以 Fe203、 CuO、 Mn02、 Ce02计的质量百分比含量分 别为 4%， 0. 4%， 0. 4%和 0. 2°/。。 The composition and content of the catalyst are: the content of the activated carbon carrier is 95% by mass, and the active component is Fe-Cu-Mn-Ce quaternary composite metal oxide having a mass percentage of 5%, wherein Fe 2 0 3 The 5%, 0. 4%, 0. 4%, and 0. 2°/, respectively, the content of the mass percentages of the CuO, the Mn0 2 , and the CeO 2 . .
该催化剂的制备方法， 包括以下步骤： The preparation method of the catalyst comprises the following steps:
a.活性炭的预处理同实施例 1， 取 190g; a. The pretreatment of activated carbon is the same as in Example 1, taking 190g;
b.称取 27. 9g FeS04 · 7H20、 2. 5g CuS04 · 5H20、 1. 5g MnS04 · H20 和 0. 8gCeC l3 · 7H20四种金属盐， 用去离子水配制成 230mL的混合 溶液； b. Weighing 27. 9g FeS0 4 · 7H 2 0, 2. 5g CuS0 4 · 5H 2 0, 1. 5g MnS0 4 · H 2 0 and 0. 8gCeC l 3 · 7H 2 0 four metal salts, used Ionic water is formulated into a mixed solution of 230 mL;
c - f.然后通过浸渍、 沉淀、 熟化、 洗涤、 干燥和焙烧完成活 性炭负载 5%Fe-Cu-Mn-Ce四元复合金属氧化物催化剂的制备，溶液 中加入 13. 9g NaOH沉淀剂，其它实验条件均同实施例 1中的步骤 c
至步骤 f。 The 5% Fe-Cu-Mn-Ce quaternary composite metal oxide catalyst is prepared by the impregnation, the precipitation, the aging, the washing, the drying and the calcination, and the solution is added with 13.9 g of NaOH precipitant, and the like. The experimental conditions are the same as the step c in the embodiment 1. Go to step f.
采用固定床反应器测试了该催化剂的催化活性和稳定性。 The catalytic activity and stability of the catalyst were tested using a fixed bed reactor.
反应器、 催化剂装填和实验条件同实施例 1。 试验结果发现， 在常温常压下和空气作为氧化剂条件下， 催化氧化处理 COD 为 25000mg/L的煤气化废水原液 lh后， COD降至 200mg/L; 催化氧化 经预处理 -0A02处理工艺 COD为 200-220mg/L的煤气化废水出水， 一次连续使用 6个月 （催化剂的单次使用寿命） ， 最后出水 pH为 7-8， COD为 60- 80mg/L， 废水色度从处理前的 300-400倍降低到处 理后的 30倍， B0D5为 20mg/L， 氨氮为 4-6mg/L， 悬浮物为 20mg/L 和其它各项指标均能满足 GB8978— 1996《污水综合排放标准》中的 一级标准。 The reactor, catalyst loading and experimental conditions were the same as in Example 1. The test results show that under the conditions of normal temperature and pressure and air as oxidant, COD is reduced to 200mg/L after catalytic oxidation treatment of 25000mg/L coal gasification wastewater, and COD is reduced by catalytic oxidation-pretreatment-0A02 treatment process. 200-220mg/L coal gasification wastewater effluent, one continuous use for 6 months (single life of catalyst), the final effluent pH is 7-8, COD is 60-80mg/L, the color of wastewater is from 300 before treatment -400 times reduced to 30 times after treatment, B0D 5 is 20mg/L, ammonia nitrogen is 4-6mg/L, suspended matter is 20mg/L and other indicators can meet GB8978-1996 "Integrated Wastewater Discharge Standard" First-class standard.
实施例 6在活性炭上负载 5%Fe- Cu-Mn- Ni- Ce五元复合金属氧 化物的催化剂 Example 6 Catalyst for 5% Fe-Cu-Mn-Ni-Ce five-component composite metal oxide supported on activated carbon
该催化剂的组分和含量为： 活性炭载体的质量百分比含量为 95%,主要活性组分为 5%Fe-Cu- Mn-Ni-Ce五元复合金属氧化物的质 量百分比含量为 5% , 其中以 Fe203、 CuO、 Mn02、 NiO和 Ce02计的质 量百分比含量分别为 3%， 0. 5%, 0. 5%， 0. 5%和 0. 5%。 The composition and content of the catalyst are: the mass percentage content of the activated carbon carrier is 95%, and the main active component is 5% Fe-Cu-Mn-Ni-Ce five-component composite metal oxide, the mass percentage content is 5%, wherein to Fe 2 0 3, CuO, Mn0 2, NiO , and Ce0 2 meter mass percent of respectively 3%, 0.5%, 0.5%, 0.5% and 0.5%.
该催化剂的制备方法， 包括以下步驟： The preparation method of the catalyst comprises the following steps:
a.活性炭的预处理同实施例 1， 取 190g; a. The pretreatment of activated carbon is the same as in Example 1, taking 190g;
b.称取 20. 3g FeCl3 · 6Η20、 2. lg CuCl2 · 2Η20、 2. 8g MnC l2 · 4Η20、 3. 2g NiCl2 · 6H20和 2. 2gCeC l3 · 7H20五种金属盐， 用去离子水配 制成 230mL的混合溶液； b. Weigh 20. 3g FeCl 3 · 6Η20, 2. lg CuCl 2 · 2Η 2 0, 2. 8g MnC l 2 · 4Η 2 0, 3. 2g NiCl 2 · 6H 2 0 and 2. 2gCeC l 3 · 7H 20 kinds of five metal salts, prepared into 230mL mixed solution with deionized water;
c - f.然后通过浸渍、 沉淀、 熟化、 洗涤、 干燥和焙烧完成活 性炭负载 5%Fe-Cu-Mn-Ni-Ce五元复合金属氧化物催化剂的制备， 溶液中加入 13. 3g NaOH沉淀剂， 其它实验条件均同实施例 1 中的 步骤 c至步骤 f。
采用固定床反应器测试了该催化剂的催化活性和稳定性。 The NaOH precipitant is added to the solution. The 5% Fe-Cu-Mn-Ni-Ce pentad composite metal oxide catalyst is prepared by the impregnation, the precipitation, the aging, the washing, the drying and the calcination. The other experimental conditions are the same as the steps c to f in the first embodiment. The catalytic activity and stability of the catalyst were tested using a fixed bed reactor.
反应器和催化剂装填如同实施例 1 ,其它实验条件同实施例 1。 试验结果发现， 在常温常压下和空气作为氧化剂条件下， 催化氧化 处理 COD为 24000mg/L的煤气化废水原液 lh后， COD降至 200mg/L; 催化氧化经预处理 -0A02处理工艺 COD为 200- 220mg/L的煤气化废 水出水，催化剂一次连续使用 5个月（催化剂的单次使用寿命）后， 出水 pH为 7-8， COD为 60-80mg/L， 废水色度从处理前的 300-400 倍降低到处理后的 30倍， 8005为 20mg/L， 氨氮为 4-6mg/L， 悬浮 物为 20mg/L和其它各项指标均能满足 GB8978— 1996《污水综合排 放标准》 中的一级标准。 The reactor and catalyst were loaded as in Example 1, and the other experimental conditions were the same as in Example 1. The test results show that under the conditions of normal temperature and pressure and air as oxidant, COD is reduced to 200mg/L after catalytic oxidation treatment of 24000mg/L coal gasification wastewater. The catalytic oxidation is treated with pretreatment-0A02. 200- 220mg/L coal gasification wastewater effluent, the catalyst is used continuously for 5 months (single life of catalyst), the effluent pH is 7-8, COD is 60-80mg/L, the color of wastewater is from pre-treatment 300-400 times reduced to 30 times after treatment, 800 5 is 20mg/L, ammonia nitrogen is 4-6mg/L, suspended matter is 20mg/L and other indicators can meet GB8978-1996 "Integrated Wastewater Discharge Standard" The first level standard.
实施例 7 - 21 在活性炭上负载其它复合金属氧化物的催化剂 采用与实施例 1类似的共浸渍沉淀法， 制备在活性炭上分别负 载其它复合金属氧化物后形成的催化剂， 并进行与实施例 1相同的 熟化、 干燥和煅烧步骤， 并采用与实施例 1相同的方式考察了这些 催化剂用于废水处理时的催化活性和稳定性。 Example 7 - 21 Catalyst for Supporting Other Mixed Metal Oxides on Activated Carbon A catalyst formed by separately loading other composite metal oxides on activated carbon was prepared by a co-impregnation method similar to that of Example 1, and carried out in the same manner as in Example 1. The same ripening, drying and calcining steps were carried out, and the catalytic activity and stability of these catalysts for wastewater treatment were examined in the same manner as in Example 1.
对比例 Comparative example
在活性炭上负载 5°/。Fe- Cu- Zn三元复合金属氧化物的催化剂 该催化剂的组分和含量为： 活性炭载体的质量百分比含量为 95%,主要活性组分 Fe-Cu-Zn三元复合金属氧化物的质量百分比含 量为 5%， 其中以 Fe203、 CuO、 ZnO计的金属氧化物的质量百分比分 别为 4%， 0. 5%和 0. 5%。 Load 5 ° / on activated carbon. Catalyst for Fe-Cu-Zn ternary composite metal oxide The composition and content of the catalyst are: 95% by mass of the activated carbon support, and the mass percentage of the main active component Fe-Cu-Zn ternary composite metal oxide content of 5%, with 0 3, CuO ZnO meter mass Fe 2, the percentage of metal oxide is 4%, 0.5% and 0.5%, respectively.
该催化剂的制备方法， 包括以下步骤： The preparation method of the catalyst comprises the following steps:
a.活性炭的预处理同实施例 1， 取 190g; a. The pretreatment of activated carbon is the same as in Example 1, taking 190g;
b.称取 27. lg FeCl3 · 6H20、 2. lg CuC l2 · 2H20 和 1. 7g ZnC l2 三种金属盐， 用去离子水配制成 230mL的混合溶液； b. Weighing 27. lg FeCl 3 · 6H 2 0, 2. lg CuC l 2 · 2H 2 0 and 1. 7g ZnC l 2 three metal salts, formulated into 230mL mixed solution with deionized water;
c - f.然后通过浸渍、 沉淀、 熟化、 洗涤、 干燥和焙烧完成活
性炭负载 5%Fe- Cu-Zn三元复合金属氧化物催化剂的制备， 其它实 验条件均同实施例 1中的步骤 c至步骤 f。 c - f. then complete the work by dipping, precipitating, aging, washing, drying and roasting The preparation of a carbon-supported 5% Fe-Cu-Zn ternary composite metal oxide catalyst was carried out in the same manner as in the step c to the step f in Example 1.
采用固定床反应器测试了该催化剂的催化活性和稳定性： 反应器、 催化剂装填和实验条件同实施例 1。 试猃结果发现， 在常温常压下和空气作为氧化剂条件下， 催化氧化处理 COD 为 20200mg/L的煤气化废水原液 lh后， COD降至 205mg/L; 催化氧化 经预处理 -0A02处理工艺 COD为 180-220mg/L的煤气化废水出水， 一次连续使用 4个月 （催化剂的单次使用寿命） ， 最后出水 pH为 7-8 , COD为 70-80mg/L， 废水色度从处理前的 300-400倍降低到处 理后的 30倍， B0D5为 20mg/L, 氨氮为 4-6mg/L, 悬浮物为 20mg/L 和其它各项指标均能满足 GB8978— 1996《污水综合排放标准》中的 一级标准。 The catalytic activity and stability of the catalyst were tested using a fixed bed reactor: reactor, catalyst loading and experimental conditions were the same as in Example 1. The test results showed that under normal temperature and pressure and air as oxidant conditions, the catalytic oxidation treatment of COD was 20200mg / L of coal gasification wastewater lh, COD decreased to 205mg / L; catalytic oxidation by pretreatment -0A02 treatment process COD For the 180-220mg/L coal gasification wastewater, the water is used continuously for 4 months (single life of the catalyst), the final effluent pH is 7-8, the COD is 70-80mg/L, and the color of the wastewater is from before treatment. 300-400 times reduced to 30 times after treatment, B0D5 is 20mg/L, ammonia nitrogen is 4-6mg/L, suspended matter is 20mg/L and other indicators can meet GB8978-1996 "Integrated Wastewater Discharge Standard" First-class standard.
各实施例和对比例中催化剂组成和用于废水处理的实验结果 列于表 1中 The catalyst compositions in each of the examples and comparative examples and the experimental results for wastewater treatment are listed in Table 1.
表 1 实施例和对比例的催化剂组成用于废水处理的效果 Table 1 Effect of catalyst composition of the examples and comparative examples on wastewater treatment
6 24000 200 23800 5 6 24000 200 23800 5
-0. 5%Ni-0. 5%Ce -0. 5%Ni-0. 5%Ce
7 4 Fe-0. 5%Cu-0. 5 Ce 20300 198 20102 4. 5 7 4 Fe-0. 5%Cu-0. 5 Ce 20300 198 20102 4. 5
8 4%Fe-0. 5%Cu-0. 5%Co 20400 210 20190 4. 5 8 4%Fe-0. 5%Cu-0. 5%Co 20400 210 20190 4. 5
9 4%Fe-0. 5%Mn-0. 5%Zn 20350 199 20151 4. 5 9 4%Fe-0. 5%Mn-0. 5%Zn 20350 199 20151 4. 5
10 4%Fe-0. 5%Mn-0. 5%Ce 21000 198 20802 4. 5 10 4%Fe-0. 5%Mn-0. 5%Ce 21000 198 20802 4. 5
11 4%Fe-0. 5%Ni-0. 5%Zn 21050 199 20851 4. 5 11 4%Fe-0. 5%Ni-0. 5%Zn 21050 199 20851 4. 5
12 4%Fe-0. 5 Ni-0. 5%Co 21080 198 20882 4. 5 12 4%Fe-0. 5 Ni-0. 5%Co 21080 198 20882 4. 5
13 4%Fe-0. 5%Ni-0. 5%Ce 21100 198 20902 4. 5 13 4%Fe-0. 5%Ni-0. 5%Ce 21100 198 20902 4. 5
14 4%Fe-0. 5%Ce-0. 5%Zn 21200 199 21001 4. 5 14 4%Fe-0. 5%Ce-0. 5%Zn 21200 199 21001 4. 5
15 4%Fe-0. 5%Ce-0. 5%Cu 22900 190 22710 4. 5 15 4%Fe-0. 5%Ce-0. 5%Cu 22900 190 22710 4. 5
16 4%Fe-0. 5%Ce-0. 5%Ni 20900 190 20710 4. 5 16 4%Fe-0. 5%Ce-0. 5%Ni 20900 190 20710 4. 5
4%Fe-0. 4%Cu-0. 4%Co 4%Fe-0. 4%Cu-0. 4%Co
17 22200 212 21988 4. 5 17 22200 212 21988 4. 5
-0. 2%Ce -0. 2%Ce
4 Fe-0. 4%Cu-0. 4%Mn 4 Fe-0. 4%Cu-0. 4%Mn
18 20800 189 20611 4. 5 18 20800 189 20611 4. 5
-0. 2%Ni -0. 2%Ni
4%Fe-0.職- 0. 4%Co 4%Fe-0. Position - 0. 4%Co
19 20500 190 20310 4. 5 19 20500 190 20310 4. 5
-0. 2%Zn -0. 2%Zn
4%Fe-0.職 -0. 4%Zn 4%Fe-0. Position -0. 4%Zn
20 22300 193 22107 4. 5 20 22300 193 22107 4. 5
-0. 2%Ce -0. 2%Ce
4%Fe-0. 4%Cu-0. 4%Ni 4%Fe-0. 4%Cu-0. 4%Ni
21 21900 196 21704 4. 5 21 21900 196 21704 4. 5
-0. 2%Ce -0. 2%Ce
备注： 上表中的 Fe、 Cu、 Zn、 Mn、 Co, Ni、 Ce分别代表氣化物 Fe203、 Cu0、 Zn0、 Mn02、 Co,0,、 Ni0、 Ce02 Remarks: Fe, Cu, Zn, Mn, Co, Ni, Ce in the above table represent vapors Fe 2 0 3 , Cu0, Zn0, Mn0 2 , Co, 0, Ni0, Ce0 2
实施例 1 - 21和对比例的对比结果表明， 本发明的活性炭负载 的多元复合金属氧化物催化剂比对比例的 Fe - Cu - Zn/活性炭催化
剂表现出更好的催化活性和稳定性。众所周知，催化剂能去除的 COD 和催化剂的单次使用寿命分别是衡量催化剂催化活性和稳定性的 重要评价标准。催化剂能去除的 COD越高，催化剂的催化活性越高。 表 1中实施例比对比例能去除的 COD高出 100- 5000mg/L，说明实施 时实施例中的催化剂比对比例中的催化剂的一次连续使用时间即 单次使用寿命延长了 0. 5-2 个月， 催化剂的单次使用寿命延长了 12. 5-50. 0%, 说明催化剂的稳定性大大提高。 Comparison of Examples 1 - 21 and Comparative Examples shows that the activated carbon supported multicomponent composite metal oxide catalyst of the present invention catalyzes a comparative ratio of Fe - Cu - Zn / activated carbon The agent exhibits better catalytic activity and stability. It is well known that the COD of the catalyst and the single service life of the catalyst are important evaluation criteria for measuring the catalytic activity and stability of the catalyst, respectively. The higher the COD that the catalyst can remove, the higher the catalytic activity of the catalyst. The ratio of COD in the examples in Table 1 can be removed by 100-5000 mg / L, which indicates that the catalyst in the examples in the examples is more than one continuous use time of the catalyst in the comparative example. The stability of the catalyst is greatly improved by a period of 2. 5-50. 0%.
此外， 本发 的催化剂还有制备工艺简单， 制备成本低的优 点。 In addition, the catalyst of the present invention has the advantages of simple preparation process and low preparation cost.
此外， 本发明的催化剂也适用于在常温常压下对其它工业废 水例如焦化废水、 印染厂废水、 化工厂废水等进行有效处理。 Further, the catalyst of the present invention is also suitable for effective treatment of other industrial waste water such as coking wastewater, printing and dyeing plant wastewater, chemical plant wastewater, etc. under normal temperature and normal pressure.
本发明专利通过各种过渡金属氧化的多元复合， 各活性组分 的催化活性和稳定性产生了更好的协同作用， 从而表现出更好的 催化活性和稳定性。
The patent of the present invention produces a better synergistic effect through the various multi-composite of transition metal oxidation, and the catalytic activity and stability of each active component, thereby exhibiting better catalytic activity and stability.
Claims
1. 一种用于在常温常压下对废水进行催化氧化的催化剂， 其 包含: A catalyst for catalytically oxidizing wastewater at normal temperature and pressure, comprising:
作为载体的活性炭； Activated carbon as a carrier;
作为主要活性组分的 Fe的氧化物； 和 An oxide of Fe as a main active component; and
作为次要活性组分的选自 Cu、 Zn、 Mn、 Co、 Ni或 Ce中的任 意两种、 三种或四种元素的氧化物， 但 An oxide of any two, three or four elements selected from the group consisting of Cu, Zn, Mn, Co, Ni or Ce as a secondary active component, but
其中所述次要活性组分中不同时存在 Cu的氧化物和 Zn的氧 化物。 Wherein the oxide of Cu and the oxide of Zn are not present in the secondary active component at the same time.
2. 根据权利要求 1的催化剂， 其中活性炭质量占催化剂总质 量的 94-96%; 以 Fe203计的 Fe 的氧化物质量占催化剂总质量的 2-5%; 分别以 Cu0、 Zn0、 Mn02 > Co203、 N iO或 Ce02计的选自 Cu、 Zn、 Mn、 Co、 N i或 Ce中的任意两种、 三种或四种元素的氧化物 的质量之和占催化剂总质量的 0. 5-2%。 2. The catalyst according to claim 1, wherein the activated carbon accounted for 94-96% of the total mass of the catalyst mass; mass of Fe to Fe oxide in terms of accounting for 203% of the total mass of the catalyst 2-5; respectively Cu0, Zn0, The sum of the masses of oxides of any two, three or four elements selected from Cu, Zn, Mn, Co, N i or Ce in terms of Mn0 2 > Co 2 0 3 , N 2 O or Ce0 2 5-2%。 The total mass of 0. 5-2%.
3. 根据权利要求 1的催化剂， 其中活性炭质量占催化剂总质 量的 95%; 以 Fe203计的 Fe的氧化物质量占催化剂总质量的 3-4%; 分另 'J以 Cu0、 Zn0、 Mn02、 Co203、 N iO或 Ce02计的选自 Cu、 Zn、 Mn、 Co、 Ni或 Ce 中的任意两种、 三种或四种元素的氧化物的质量之 和占催化剂总盾量的 1-2 %。 3. A catalyst according to claim 1, wherein the activated carbon accounted for 95% by mass of the total mass of the catalyst; mass of Fe to Fe oxide in terms of accounting for 203% of the total mass of the catalyst 3-4; the other points' J to Cu0, Zn0 The sum of the masses of oxides of any two, three or four elements selected from the group consisting of Cu, Zn, Mn, Co, Ni or Ce in terms of Mn0 2 , Co 2 O 3 , N iO or CeO 2 1-2% of the total shield.
4. 根据权利要求 1-3的任一项的催化剂， 其中活性炭的比表 面积为 800-900m7g。 The catalyst according to any one of claims 1 to 3, wherein the activated carbon has a specific surface area of from 800 to 900 m7g.
5. 一种用于在常温常压下对废水进行催化氧化的催化剂的 制备方法， 包括以下步骤： 5. A method for preparing a catalyst for catalytically oxidizing wastewater at normal temperature and pressure, comprising the steps of:
a. 用包括洗涤、干燥和热处理在内的步骤对活性炭进行预处 理； b. 通过浸渍沉淀法将铁源以及选自铜源、锌源、锰源、钴源、 镍源或铈源中的任意两种、 三种或四种源以铁前体以及选自铜前 体、 辞前体、 锰前体、 钴前体、 镍前体或铈前体中的任意两种、 三种或四种前体的形式负载在由步骤 a得到的活性炭上， 且对所 述各源的浸渍顺序以及各前体的沉淀顺序不加以限制， 且其中所 述活性炭上不同时负载有铁前体、 铜前体和锌前体； a. pretreatment of activated carbon with steps including washing, drying and heat treatment; b. The iron source and any two, three or four sources selected from the group consisting of a copper source, a zinc source, a manganese source, a cobalt source, a nickel source or a helium source by an immersion precipitation method are iron precursors and selected from copper Any two, three or four precursors of a body, a precursor, a manganese precursor, a cobalt precursor, a nickel precursor or a ruthenium precursor are supported on the activated carbon obtained in the step a, and The order of impregnation of each source and the order of precipitation of each precursor are not limited, and wherein the activated carbon is not loaded with an iron precursor, a copper precursor and a zinc precursor at the same time;
c 熟化所述负载在活性炭上的活性组分前体； 然后 c aging the active component precursor supported on activated carbon;
d. 洗涤、 干燥并煅烧所述负载在活性炭上的活性组分前体， 得到所述催化剂。 d. washing, drying and calcining the active component precursor supported on activated carbon to obtain the catalyst.
6. 权利要求 5的方法， 其中步驟 b中的各前体包括各金属的 各种价态的碳酸盐或氢氧化物或任何其它难溶于水的盐。 6. The method of claim 5, wherein each precursor in step b comprises a carbonate or hydroxide of various valence states of each metal or any other salt that is poorly soluble in water.
7. 权利要求 5的方法， 其中所述浸渍沉淀法是用金属的可溶 于水的盐的水溶液充分浸溃载体， 然后加入沉淀剂以使得该金属 以难溶性盐的形式沉淀在载体上的过程。 7. The method of claim 5, wherein said immersion precipitation method is to fully impregnate the support with an aqueous solution of a metal water-soluble salt, and then adding a precipitant to precipitate the metal as a poorly soluble salt on the support. process.
8. 一种用于在常温常压下对废水进行催化氧化的催化剂的 制备方法， 包括以下步骤： 8. A method for preparing a catalyst for catalytically oxidizing wastewater at normal temperature and pressure, comprising the steps of:
a. 用包括洗涤、干燥和热处理在内的步骤对活性炭进行预处 理； a. pre-treating the activated carbon with steps including washing, drying and heat treatment;
b. 配制包含可溶性铁盐或亚铁盐并包含可溶性铜盐、可溶性 锌盐、 可溶性锰盐、 可溶性钴盐、 可溶性镍盐或可溶性铈盐中的 任意两种、 三种或四种的水溶液； 其中所述水溶液不同时含有可 溶性铁盐或亚铁盐与可溶性铜盐和可溶性锌盐; b. formulating an aqueous solution comprising a soluble iron salt or a ferrous salt and comprising any two, three or four of a soluble copper salt, a soluble zinc salt, a soluble manganese salt, a soluble cobalt salt, a soluble nickel salt or a soluble barium salt; Wherein the aqueous solution does not simultaneously contain a soluble iron or ferrous salt and a soluble copper salt and a soluble zinc salt;
c 加热所述水溶液，并向其中加入经步骤 a预处理后的活性 炭， 搅拌均勾后冷却至室温； c heating the aqueous solution, and adding the activated carbon after the step a pretreatment thereto, stirring and hooking, and then cooling to room temperature;
d. 向水溶液中加入能使铁离子或亚铁离子沉淀并能使铜离 子、 辞离子、 锰离子、 钴离子、 镍离子或铈离子中的任意两种、 三种或四种离子沉淀的沉淀剂， 得到负载在活性炭上的活性组分 前体； d. adding to the aqueous solution can precipitate iron ions or ferrous ions and can make any two of copper ions, rhodium ions, manganese ions, cobalt ions, nickel ions or cesium ions, a precipitant precipitated by three or four ions to obtain an active component precursor supported on activated carbon;
e. 熟化所述负载在活性炭上的活性组分前体； 然后 e. aging the active component precursor supported on the activated carbon;
f. 洗涤、 干燥并煅烧所述负载在活性炭上的活性组分前体， 得到所述催化剂。 f. washing, drying and calcining the active component precursor supported on activated carbon to obtain the catalyst.
9. 权利要求 5或 8的方法， 其中步骤 a中用去离子水对活性 炭进行洗涤， 在 110- 下对洗涤后的活性炭进行千燥， 然后 在 150-200 下 干燥后的活性炭热处理 2-5小时。 9. The method of claim 5 or 8, wherein in step a, the activated carbon is washed with deionized water, the washed activated carbon is dried at 110-, and then the dried activated carbon is dried at 150-200 for 2-5. hour.
10. 权利要求 8的方法， 其中步骤 b中各金属的可溶性盐包括 各金属的各种价态的无机酸盐或有机酸盐。 10. The method of claim 8 wherein the soluble salt of each metal in step b comprises a mineral or organic acid salt of various valence states of each metal.
11. 权利要求 8的方法， 其中在步骤 c中将所述水溶液加热至 60-70 X , 和所述搅拌持续 3-5小时。 11. The method of claim 8 wherein said aqueous solution is heated to 60-70 X in step c and said agitating for 3-5 hours.
12. 权利要求 8的方法， 其中步骤 d中所述沉淀剂选自可溶性 的金属氢氧化物、 可溶性的金属碳酸盐、 碳酸氢盐或氨水或它们 的混合物。 12. The method of claim 8 wherein the precipitating agent in step d is selected from the group consisting of soluble metal hydroxides, soluble metal carbonates, bicarbonates or aqueous ammonia or mixtures thereof.
1 3. 权利要求 5或 8的方法，其中所述沉淀剂选自 NaOH、 Na2C03 或 NaHC03。 The method of claim 1 or claim 8, wherein said precipitation agent is selected from NaOH, Na 2 C0 3 or NaHC0 3.
14. 权利要求 5或 8的方法， 其中在步骤 c或步骤 e中， 所述 熟化通过使所述负载在活性炭上的活性组分前体在溶液中在室温 下静置 24小时来原位进行，或者通过先固液分离得到负载在活性 炭上的活性组分前体， 然后使该前体在室温下静置 24 小时来进 行。 14. The method of claim 5 or 8, wherein in step c or step e, the ripening is carried out in situ by allowing the active component precursor supported on activated carbon to stand in solution at room temperature for 24 hours. Alternatively, the active component precursor supported on the activated carbon is obtained by first solid-liquid separation, and then the precursor is allowed to stand at room temperature for 24 hours.
15. 权利要求 5或 8的方法， 其中在步骤 d或步骤 f 中， 所述 洗涤用水来进行， 所述干燥在 120-150 下进行，干燥时间为 2-5 小时， 而所述煅烧在马弗炉中在 270- 300 和有氧气存在的气氛 下进行， 煅烧时间为 8-10小时。 15. The method of claim 5 or 8, wherein in step d or step f, the washing is carried out using water, the drying is carried out at 120-150, the drying time is 2-5 hours, and the calcination is in the horse The furnace is operated in an atmosphere of 270-300 and in the presence of oxygen, and the calcination time is 8-10 hours.
16. 权利要求 5或 8的方法， 其中加入的沉淀剂的量足以使所 有的金属离子完全沉淀到活性炭上。 16. The method of claim 5 or 8, wherein the amount of precipitant added is sufficient to completely precipitate all of the metal ions onto the activated carbon.
17. 权利要求 5或 8的方法， 其中沉淀到载体上的各金属前体 的量足以使最终的催化剂中以 Fe203计的 Fe的氧化物质量占催化 剂总质量的 2-5% , 分别以 Cu0、 Zn0、 Mn02、 Co203、 N iO或 Ce02 计的选自 Cu、 Zn、 Mn、 Co、 Ni或 Ce中的任意两种、 三种或四种 元素的氧化物的质量之和占催化剂总质量的 0. 5-2%。 17. A method as claimed in claim 5 or 8, wherein the amount of each metal to precipitate on the support precursor is sufficient to cause the final catalyst mass of Fe to Fe oxide in 203 meter accounting 2-5% of the total mass of the catalyst, The mass of oxides of any two, three or four elements selected from Cu, Zn, Mn, Co, Ni or Ce, respectively, based on Cu0, Zn0, Mn0 2 , Co 2 O 3 , N iO or Ce02 5-2%。 The total mass of the catalyst is 0. 5-2%.
18. 权利要求 5或 8的方法， 其中沉淀到载体上的各金属前体 的量足以使最终的催化剂中以 Fe203计的 Fe的氧化物质量占催化 剂总质量的 3-4%， 分别以 Cu0、 Zn0、 Mn02、 Co203、 N iO或 Ce02 计的选自 Cu、 Zn、 Mn、 Co、 Ni或 Ce中的任意两种、 三种或四种 元素的氧化物的质量之和占催化剂总质量的 1-2%。 18. A method as claimed in claim 5 or 8, wherein the amount of each metal to precipitate on the support precursor is sufficient to cause the final catalyst mass of Fe to Fe oxide in 203 meter accounting 3-4% of the total mass of the catalyst, The mass of oxides of any two, three or four elements selected from Cu, Zn, Mn, Co, Ni or Ce, respectively, based on Cu0, Zn0, Mn0 2 , Co 2 O 3 , N iO or Ce02 The sum accounts for 1-2% of the total mass of the catalyst.
19. 根据权利要求 1的催化剂， 其中用选自氧化硅、 氧化铝、 粘土、 沸石或分子筛的多孔载体代替活性炭载体。 19. A catalyst according to claim 1 wherein the activated carbon support is replaced by a porous support selected from the group consisting of silica, alumina, clay, zeolite or molecular sieves.
20. 根据权利要求 5或 8的方法，其中用选自氧化硅、氧化铝、 粘土、 沸石或分子筛的多孔载体代替活性炭载体。 20. A process according to claim 5 or claim 8 wherein the activated carbon support is replaced by a porous support selected from the group consisting of silica, alumina, clay, zeolite or molecular sieves.
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