DE29619606U1 - Catalyst for the oxidation of organic and inorganic compounds in the aqueous phase - Google Patents
Catalyst for the oxidation of organic and inorganic compounds in the aqueous phaseInfo
- Publication number
- DE29619606U1 DE29619606U1 DE29619606U DE29619606U DE29619606U1 DE 29619606 U1 DE29619606 U1 DE 29619606U1 DE 29619606 U DE29619606 U DE 29619606U DE 29619606 U DE29619606 U DE 29619606U DE 29619606 U1 DE29619606 U1 DE 29619606U1
- Authority
- DE
- Germany
- Prior art keywords
- catalyst according
- catalyst
- chelate complexes
- compounds
- oxidation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003054 catalyst Substances 0.000 title claims description 58
- 230000003647 oxidation Effects 0.000 title claims description 18
- 238000007254 oxidation reaction Methods 0.000 title claims description 18
- 150000002484 inorganic compounds Chemical class 0.000 title claims description 10
- 229910010272 inorganic material Inorganic materials 0.000 title claims description 10
- 150000002894 organic compounds Chemical class 0.000 title claims description 10
- 239000008346 aqueous phase Substances 0.000 title claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- -1 chelate complex compounds Chemical class 0.000 claims description 16
- 239000003446 ligand Substances 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical class O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- 239000013522 chelant Substances 0.000 claims description 9
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 150000005840 aryl radicals Chemical class 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 125000005594 diketone group Chemical group 0.000 claims description 2
- 150000002085 enols Chemical class 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- 239000002952 polymeric resin Substances 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 239000011669 selenium Substances 0.000 claims description 2
- 229920003002 synthetic resin Polymers 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 150000001721 carbon Chemical group 0.000 claims 1
- 229910052681 coesite Inorganic materials 0.000 claims 1
- 229910052906 cristobalite Inorganic materials 0.000 claims 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 1
- 229910052682 stishovite Inorganic materials 0.000 claims 1
- 229910052905 tridymite Inorganic materials 0.000 claims 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 31
- 239000003344 environmental pollutant Substances 0.000 description 22
- 231100000719 pollutant Toxicity 0.000 description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 21
- 238000000034 method Methods 0.000 description 15
- 239000002351 wastewater Substances 0.000 description 13
- 230000015556 catabolic process Effects 0.000 description 12
- 238000006731 degradation reaction Methods 0.000 description 12
- 239000000126 substance Substances 0.000 description 10
- 239000003673 groundwater Substances 0.000 description 8
- 239000007983 Tris buffer Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 5
- 239000010802 sludge Substances 0.000 description 5
- 238000009279 wet oxidation reaction Methods 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Chemical class 0.000 description 4
- 239000002184 metal Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 150000008282 halocarbons Chemical class 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000010525 oxidative degradation reaction Methods 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 239000012028 Fenton's reagent Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 229940052308 general anesthetics halogenated hydrocarbons Drugs 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- MGZTXXNFBIUONY-UHFFFAOYSA-N hydrogen peroxide;iron(2+);sulfuric acid Chemical compound [Fe+2].OO.OS(O)(=O)=O MGZTXXNFBIUONY-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- XFNJYAKDBJUJAJ-UHFFFAOYSA-N 1,2-dibromopropane Chemical compound CC(Br)CBr XFNJYAKDBJUJAJ-UHFFFAOYSA-N 0.000 description 1
- QMSVNDSDEZTYAS-UHFFFAOYSA-N 1-bromo-1-chloroethane Chemical compound CC(Cl)Br QMSVNDSDEZTYAS-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical class OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 231100001240 inorganic pollutant Toxicity 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N iron (II) ion Substances [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000003893 lactate salts Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 150000003873 salicylate salts Chemical class 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011270 tar paper Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/165—Polymer immobilised coordination complexes, e.g. organometallic complexes
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- C02F1/722—Oxidation by peroxides
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
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Description
Katalysator für die Oxidation von organischen und anorganischen Verbindungen in wässriger PhaseCatalyst for the oxidation of organic and inorganic compounds in aqueous phase
Die Erfindung betrifft einen Katalysator für die Oxidation von organischen und/oder anorganischen Verbindungen, die in Wässern enthalten sind.The invention relates to a catalyst for the oxidation of organic and/or inorganic compounds contained in water.
Viele organische Synthesen und industrielle Produktionsabläufe werden in wäßriger Phase durchgeführt, in deren Ergebnis Abwässer entstehen, die mit Ausgangs-, Zwischen-, Neben-, und Endprodukten belastet sind. Weitere mit organischen Substanzen belastete Abwässer entstehen bei der Isolierung und Aufarbeitung der Produkte. All diese Abwässer und Schlämme müssen, bevor sie an die Umwelt abgegeben werden, gereinigt werden. Die übliche Reinigungsmethode ist, sofern die Abwasser in den Schmutzwasserkanal eingeleitet werden (Indirekteinleitung), die biologische Reinigung in Kläranlagen. In vielen Fällen enthalten die Abwässer jedoch Substanzen die in Kläranlagen nicht oder nur sehr langsam abbaubar sind, z. B. polycyclische aromatische Kohlenwasserstoffe (PAK) und adsorbierbare organische Halogenverbindungen (AOX).Many organic syntheses and industrial production processes are carried out in the aqueous phase, resulting in wastewater that is contaminated with starting materials, intermediates, by-products and end products. Other wastewater contaminated with organic substances is produced during the isolation and processing of the products. All of this wastewater and sludge must be cleaned before it is released into the environment. The usual cleaning method, if the wastewater is discharged into the sewer (indirect discharge), is biological cleaning in sewage treatment plants. In many cases, however, the wastewater contains substances that cannot be broken down in sewage treatment plants or only very slowly, e.g. polycyclic aromatic hydrocarbons (PAH) and adsorbable organic halogen compounds (AOX).
Außerdem können auch Grund-und Sickerwässer gelöste, biologisch schwer
oder nicht abbaubare, organische Inhaltsstoffe enthalten, die zu ständig wachsenden Entsorgungsproblemen führen.
Typische in Ab- bzw. Grund- und Sickerwässern oder Schlämmen enthaltene Schadstoffe sind polycyclische aromatische Kohlenwasserstoffe, halogenierteIn addition, groundwater and seepage water can also contain dissolved organic ingredients that are difficult or impossible to biodegrade, leading to ever-increasing disposal problems.
Typical pollutants contained in waste water, groundwater, seepage water or sludge are polycyclic aromatic hydrocarbons, halogenated
Kohlenwasserstoffe, Mineralölkohlenwasserstoffe, Cyanide, Phenole, Schwermetalle, Pestizide, polychlorierte Biphenyle u.a..Hydrocarbons, mineral oil hydrocarbons, cyanides, phenols, heavy metals, pesticides, polychlorinated biphenyls, etc.
Polycyclisch« aromatische Kohlenwasserstoffe (PAK), adsorbierbare organische Halogene (AOX), polychlorierte Biphenyle (PCB), Ethylendiamintetraessigsäure (EDTA) und organische Amine stellen besonders schwer abbaubare Schadstoffe dar.Polycyclic aromatic hydrocarbons (PAHs), adsorbable organic halogens (AOX), polychlorinated biphenyls (PCBs), ethylenediaminetetraacetic acid (EDTA) and organic amines are particularly difficult to break down pollutants.
Aus dem Stand der Technik sind eine Reihe von Abwasserbehandlungsverfahren bekannt, wie: Adsoptionsverfahren, insbesondere an Aktivkohlen und aktivierten Adsorbentien, biologische Reinigung, Fällung/Flockung, Umkehrosmose, Eindampfiing/Trocknung.A number of wastewater treatment processes are known from the state of the art, such as: adsorption processes, especially with activated carbon and activated adsorbents, biological purification, precipitation/flocculation, reverse osmosis, evaporation/drying.
In den letzten Jahren hat der oxidative Abbau der Schadstoffe durch chemische Naßoxidation zunehmend an Bedeutung gewonnen.In recent years, the oxidative degradation of pollutants by chemical wet oxidation has become increasingly important.
Es sind Verfahren bekannt, bei denen die oxidative Wirkung des Wasserstoffperoxides und des Ozons durch Katalysatoren erhöht werden kann. Als Katalysatoren werden Metalloxide und Metallsalze, vorzugsweise von Übergangselementen (z.B. Fentons-Reagens, Oxide, Sulfate und Chloride des Kupfers, Zinks, Nickels, Eisens, Wolframs) enthält (DE-OS 43 14 521, DE-OS 29 27 911, DE-OS 27 35 892, DE-OS 4118 626). Nachteilig ist dabei die Bildung von großen Mengen von Schadstoff belastetem Metallschlamm, z. B. Eisenhydroxidschlamm, die speziell deponiert oder entsorgt werden müssen. Ferner ist für die mit Eisen(II)-Ionen katalysierte Oxidation (Fentons Reagens) ein saurer pH-Bereich erforderlich, was sich nachteilig auf die Materialbeständigkeit (Korrosion) und Fischtoxizität auswirkt.Processes are known in which the oxidative effect of hydrogen peroxide and ozone can be increased by catalysts. Metal oxides and metal salts, preferably of transition elements (e.g. Fenton's reagent, oxides, sulfates and chlorides of copper, zinc, nickel, iron, tungsten) are used as catalysts (DE-OS 43 14 521, DE-OS 29 27 911, DE-OS 27 35 892, DE-OS 4118 626). The disadvantage here is the formation of large quantities of contaminated metal sludge, e.g. iron hydroxide sludge, which must be specially disposed of or disposed of. Furthermore, the oxidation catalyzed by iron(II) ions (Fenton's reagent) requires an acidic pH range, which has a detrimental effect on material resistance (corrosion) and fish toxicity.
Häufig besteht die Gefahr, daß die Katalysatoren durch den häufig im Abwasser enthaltenen Schwebstoffanteil desaktiviert werden. Die bekannten Verfahren zur Naßoxidation werden in der Regel unter erhöhtenThere is often a risk that the catalysts will be deactivated by the suspended matter often contained in the waste water. The known wet oxidation processes are usually carried out under increased
Temperaturen und Drücken durchgeführt, was zu hohen Investitions- und Betriebskosten führt.temperatures and pressures, which leads to high investment and operating costs.
Bei Verfahren, die in unteren Temperatur- (150-175 0C) und Druckbereichen (10-20 bar) arbeiten, muß zusätzlich zur Anwesenheit eines Katalysators der pH-Wert auf 0,5 -1,5 eingestellt werden, um die Oxidation zu ermöglichen.In processes operating in lower temperature (150-175 0 C) and pressure ranges (10-20 bar), in addition to the presence of a catalyst, the pH value must be adjusted to 0.5 -1.5 to enable oxidation.
Trotzdem wird bei diesen Verfahren keine vollständige Oxidation der Schadstoffe zu Wasser und Kohlendioxid erreicht.Nevertheless, these processes do not achieve complete oxidation of the pollutants into water and carbon dioxide.
Es sind auch Verfahren bekannt, bei denen die Oxidation in Gegenwart von Vollmetallkatalysatoren durchgeführt wird (DE-OS 4131 596,Processes are also known in which the oxidation is carried out in the presence of full metal catalysts (DE-OS 4131 596,
DE-PS 195 03 865).DE-PS 195 03 865).
Auch die Oxidation an aktivierten Kohlen wird beschrieben, wobei die katalytische Wirksamkeit der Kohlen durch Verwendung von anodisch oxydierten und anschließend mit Molybdän-VI- und/oder Wolfram VI- und/oder Vanadium-V-verbindungen dotierten Kohlenstoffträgern erhöht wird. Für die Dotierung der Träger werden die Salzverbindungen der genannten Elemente eingesetzt (DE-OS 34 30 484). Ferner kommen auch Metalle oder Metalloxide der Elemente Platin, Nickel, Titan, Kobalt, Mangan, Molybdän, Kupfer und Wolfram für die Dotierung von Aktivkohle zur Anwendung.Oxidation on activated carbons is also described, whereby the catalytic effectiveness of the carbons is increased by using carbon supports that are anodically oxidized and then doped with molybdenum VI and/or tungsten VI and/or vanadium V compounds. The salt compounds of the elements mentioned are used to dope the supports (DE-OS 34 30 484). Metals or metal oxides of the elements platinum, nickel, titanium, cobalt, manganese, molybdenum, copper and tungsten are also used to dope activated carbon.
Die bekannten Katalysatoren zur katalytischen Naßoxidation haben den Nachteil, daß sie msbesondere bei hohen Schadstoffbelastungen oder schwer abbaubaren Schadstoffen keinen vollständigen Abbau der Schadstoffe ermöglichen, der Wirkungsgrad und die Standzeiten der Katalysatoren begrenzt sind.The known catalysts for catalytic wet oxidation have the disadvantage that they do not allow complete degradation of the pollutants, particularly in the case of high pollutant loads or pollutants that are difficult to degrade, and the efficiency and service life of the catalysts are limited.
Der Erfindung liegt die Aufgabe zugrunde, einen einfach herstellbaren Katalysator für die Oxidation von organischen und anorganischen Verbindungen in Wässern zur Verfügung zu stellen, der auch bei hohen Schadstoffbelastungen mit schwer abbaubaren VerbindungenThe invention is based on the object of providing an easily produced catalyst for the oxidation of organic and inorganic compounds in water, which is also effective in the presence of high levels of pollutants containing compounds that are difficult to degrade.
&Mgr;« «t t· · ♦* *♦ *! &Mgr;« «tt· · ♦* *♦ *!
eine hohe Abbaurate und unter Normalbedingungen eine hohe Wirksamkeit aufweist.has a high degradation rate and high effectiveness under normal conditions.
Diese Aufgabe wird erfindungsgemäß durch einen Katalysator gelöst, der eine oder mehrere Chelatkomplexverbindungen der Elemente der 1., 2., 4. bisThis object is achieved according to the invention by a catalyst which contains one or more chelate complex compounds of the elements of the 1st, 2nd, 4th to
8. Nebengruppe des Periodensystems der Elemente enthält.8th subgroup of the periodic table of elements.
Es wurde gefunden, daß Chelatkomplexverbindungen der Elemente der 1., 2. und 4. bis 8. Nebengruppe des Periodensystems der Elemente eine hohe Wirksamkeit für den oxidativen Abbau von organischen und anorganischen Verbindungen in Wässern aufweisen. Besonders geeignet sind Chelatkomplexverbindungen mit Dichalkogenen als Ligandatom.It has been found that chelate complex compounds of the elements of the 1st, 2nd and 4th to 8th subgroups of the Periodic Table of the Elements are highly effective for the oxidative degradation of organic and inorganic compounds in water. Chelate complex compounds with dichalcogens as ligand atoms are particularly suitable.
Überraschenderweise weisen diese Verbindungen eine hohe Aktivität unter Normalbedingungen auf und gewährleisten den nahezu vollständigen Abbau auch von schwer abbaubaren Schadstoffen, wie polychlorierten Biphenylen (PCB), leichtflüchtigen halogenierten Kohlenwasserstoffe (LHKW), Ethylendiamintetraessigsäure (EDTA), organischen Aminen, Pestiziden, adsorbierbaren organischen Halogenkohlenwasserstoffen (AOX) sowie sonstigen oxidierbaren Verbindungen (CSB). Es war nicht vorhersehbar, daß diese Verbindungen auch bei neutralem pH-Wert eine hohe katalytische Aktivität besitzen, so daß bei Einsatz der erfindungsgemäßen Katalysatoren keine zusätzliche Aufsalzung des Wassers erfolgt und die Bildung von zu entsorgenden Schlämmen entfällt.Surprisingly, these compounds have a high level of activity under normal conditions and ensure the almost complete degradation of even difficult-to-degrade pollutants such as polychlorinated biphenyls (PCB), volatile halogenated hydrocarbons (VHC), ethylenediaminetetraacetic acid (EDTA), organic amines, pesticides, adsorbable organic halogenated hydrocarbons (AOX) and other oxidizable compounds (COD). It was not foreseeable that these compounds have a high catalytic activity even at a neutral pH value, so that when using the catalysts according to the invention there is no additional salting of the water and the formation of sludge that has to be disposed of is avoided.
Die erfindungsgemäßen Katalysatoren weisen gegenüber den in Abwässern enthaltenen Metallverbindungen, anorganischen Salzen und Schwebstoffen eine hohe Stabilität auf. Die Aktivität der Katalysatoren wird durch diese Stoffe nicht negativ beeinflußt. Dadurch besitzen die Katalysatoren eine hohe katalytische Aktivität und eine lange Standzeit. Auch die als KatalysatorgifteThe catalysts according to the invention are highly stable against the metal compounds, inorganic salts and suspended matter contained in waste water. The activity of the catalysts is not negatively affected by these substances. As a result, the catalysts have a high catalytic activity and a long service life. The catalyst poisons
Ml «« tt · ti ,&Lgr;*Ml «« tt · ti ,&Lgr;*
bekannten Schwermetallionen und Schwefelverbindungen inhibieren die erfindungsgemäßen Katalysatoren überraschenderweise nicht.Known heavy metal ions and sulfur compounds surprisingly do not inhibit the catalysts according to the invention.
Besonders geeignete Katalysatoren sind Chelatkomplexverbindungen mit gleichen oder verschiedenen Liganden, die aus der nachfolgenden Gruppe ausgewählt werden: Oxyketone, Oxyaldehyde, Oxychinone, Diketone, Enole, Oxysäuren, Dicarbonsäuren, Ketocarbonsäuren und deren Säureester sowie die analogen schwefel- oder selenhaltigen Verbindungen. Die Liganden können eine aliphatische, cycloaliphatische, aromatische oder araliphatische Struktur aufweisen. Bevorzugt werden Chelatkomplexe mit Sauerstoffligandatomen eingesetzt.Particularly suitable catalysts are chelate complex compounds with the same or different ligands, which are selected from the following group: oxyketones, oxyaldehydes, oxyquinones, diketones, enols, oxyacids, dicarboxylic acids, ketocarboxylic acids and their acid esters as well as the analogous sulfur or selenium-containing compounds. The ligands can have an aliphatic, cycloaliphatic, aromatic or araliphatic structure. Chelate complexes with oxygen ligand atoms are preferably used.
Dabei sind Oxyketone, Oxysäuren, Ketocarbonsäuren, Dicarbonsäuren und ß-Diketone sowie die entsprechenden Säureester als chelatbildende Liganden besonders geeignet.Oxyketones, oxyacids, ketocarboxylic acids, dicarboxylic acids and ß-diketones as well as the corresponding acid esters are particularly suitable as chelating ligands.
Vertreter dieser Liganden sind beispielsweise: Glykolate, Lactate, Citrate, Salicylate, Oxalate, Oxychinone, o-Oxyacetophenon, Benzoylacetonat, Acetessigsäurealkylester.Examples of these ligands are: glycolates, lactates, citrates, salicylates, oxalates, oxyquinones, o-oxyacetophenone, benzoylacetonate, alkyl acetoacetate.
Die Liganden der Komplexe können an einem oder mehreren Kohlenstoffatomen substituiert sein durch eine oder mehrere derThe ligands of the complexes can be substituted at one or more carbon atoms by one or more of the
nachfolgenden Gruppen: Halogen-, Nitro-, Hydroxy, Carbonyl-, Carboxy,
Alkoxy-, Aralkoxy-, Phenoxy-, Alkyl-, Aryl-, und Aralkyl-, wobei die Carbonyl-, Carboxy-, Alkyl- und Arylreste gegebenenfalls ebenfalls durch eine
oder mehrere der genannten Gruppen substituiert sein können.
25 the following groups: halogen, nitro, hydroxy, carbonyl, carboxy, alkoxy, aralkoxy, phenoxy, alkyl, aryl and aralkyl, where the carbonyl, carboxy, alkyl and aryl radicals may optionally also be substituted by one or more of the groups mentioned.
25
Eine besonders hohe katalytische Aktivität unter Normalbedingungen weisen die Chelatkomplexverbindungen des Eisens, Vanadiums, Mangans, Kupfers, Kobalts, Molybdäns, Wolframs, Rutheniums, Rhodiums, Palladiums, Platins und deren Gemische auf.The chelate complex compounds of iron, vanadium, manganese, copper, cobalt, molybdenum, tungsten, ruthenium, rhodium, palladium, platinum and their mixtures have a particularly high catalytic activity under normal conditions.
Bevorzugt werden ein oder mehrere Chelatkomplexe der Elemente der 7. undPreference is given to one or more chelate complexes of the elements of the 7th and
8. Nebengruppe eingesetzt.8. Subgroup used.
if ·«if ·«
Besonders hohe Abbauraten bei organischen und anorganischen Verbindungen, insbesondere bei schwer abbaubaren Verbindungen werden durch den Einsatz von Chelatkomplexverbindungen der Oxyketone, Oxysäuren, Ketocarbonsäuren, Dicarbonsäuren, ß-Diketone, insbesondere der Dicarbonsäuren und ß-Diketone, und der entsprechenden Säureester mit Elementen der 7. und 8. Nebengruppe erzielt.Particularly high degradation rates for organic and inorganic compounds, especially for compounds that are difficult to degrade, are achieved by using chelate complex compounds of oxyketones, oxyacids, ketocarboxylic acids, dicarboxylic acids, ß-diketones, especially dicarboxylic acids and ß-diketones, and the corresponding acid esters with elements of the 7th and 8th subgroups.
Geeignete Katalysatoren sind zum Beispiel Komplexe des Tris(benzoylacetonato)cuprats(II), Tris(alkylsalicylato)ferrats(III), Bis(thiobisphenolato)niccolats(II), Bis(dialkyl-dithiocarbamato)cobaltats(II),Suitable catalysts are, for example, complexes of tris(benzoylacetonato)cuprate(II), tris(alkylsalicylato)ferrate(III), bis(thiobisphenolato)niccolate(II), bis(dialkyl-dithiocarbamato)cobaltate(II),
Tris(oxalato)manganats(III), Tris(2-hydroxyacetophenonato)ferrats(III), Bis(2-hydroxy-5-methylbenzo-phenonato)manganats(in).Tris(oxalato)manganate(III), tris(2-hydroxyacetophenonato)ferrate(III), bis(2-hydroxy-5-methylbenzophenonato)manganate(in).
Die erfindungsgemäßen Katalysatoren können als homogene oder heterogene Katalysatoren im Fluidbett-, Festbett- oder Wirbelbettverfahren eingesetzt werden.The catalysts according to the invention can be used as homogeneous or heterogeneous catalysts in fluidized bed, fixed bed or fluidized bed processes.
Bevorzugt sind jedoch heterogene Katalysatoren, insbesondere trägergebundene Katalysatoren. Dadurch wird eine optimale Nutzung der Aktivität der Katalysatoren und eine hohe Abbaurate der Schadstoffe erreicht. Als Träger werden Aktivkohle, polymere Harze, Al2O3, SiO2 und Zeolithe verwendet, wobei die Aktivkohle wegen der großen BET-Oberfläche bevorzugt ist.However, heterogeneous catalysts, especially supported catalysts, are preferred. This allows for optimal use of the activity of the catalysts and a high degradation rate of the pollutants. Activated carbon, polymeric resins, Al 2 O 3 , SiO 2 and zeolites are used as supports, with activated carbon being preferred due to its large BET surface area.
Diese Katalysatoren sind relativ einfach herstellbar. Die Chelatkomplexverbindung kann in bekannter Weise durch Ionenaustausch, Tränken oder Fällung aus einer Lösung an die Trägermatrix fixiert werden. Die Herstellung der Komplexverbindungen erfolgt in bekannter Weise.These catalysts are relatively easy to produce. The chelate complex compound can be fixed to the carrier matrix in a known manner by ion exchange, impregnation or precipitation from a solution. The complex compounds are produced in a known manner.
Ein Vorteil der erfindungsgemäßen Katalysatoren ist, daß sie vollständig recyclebar sind.An advantage of the catalysts according to the invention is that they are completely recyclable.
tt ·♦ ♦ ♦· ·· ··tt ·♦♦♦· ·· ··
Die erfindungsgemäßen Katalysatoren werden insbesondere fur die katalytische Naßoxidation von organischen und anorganischen Verbindungen in der wässrigen Phase verwendet. Die Naßoxidation wird in Gegenwart eines oder mehrerer der nachfolgend genannten Oxidationsmittel durchgeführt: Wasserstoffperoxid, Luft, Ozon, organische und anorganische Peroxide, wobei Wasserstoffperoxid bevorzugt ist.The catalysts according to the invention are used in particular for the catalytic wet oxidation of organic and inorganic compounds in the aqueous phase. The wet oxidation is carried out in the presence of one or more of the following oxidizing agents: hydrogen peroxide, air, ozone, organic and inorganic peroxides, with hydrogen peroxide being preferred.
Die erfindungsgemäßen Katalysatoren können zur oxidativen Reinigung von organische und/oder anorganische Verbindungen enthaltendem Abwasser, Prozeß-, Trink- und Grundwasser sowie zur Aufbereitung von schadstoffbelasteten wässrigen Extraktionsmitteln aus der Bodenwäsche eingesetzt werden.The catalysts according to the invention can be used for the oxidative purification of wastewater, process water, drinking water and groundwater containing organic and/or inorganic compounds as well as for the treatment of contaminated aqueous extraction agents from soil washing.
Durch die erfindungsgemäßen Katalysatoren werden die organischen und anorganischen Verbindungen zu umweltverträglichen Reaktionsprodukten abgebaut. In den meisten Fällen entstehen in Abhängigkeit von der Art der oxidierten Schadstoffe Kohlendioxid, Wasser, Chloride, Sulfate und andere Salze sowie einige stickstoffhaltige Verbindungen, wie Ammoniak, Stickoxide und Stickstoff. Die Gefahr des Freisetzens von gefährlichen, toxischen oder biologisch nicht abbaubaren Materialien in die Luft, das Wasser oder den Boden besteht nicht.The catalysts according to the invention break down the organic and inorganic compounds into environmentally friendly reaction products. In most cases, depending on the type of pollutants oxidized, carbon dioxide, water, chlorides, sulfates and other salts are formed, as well as some nitrogen-containing compounds such as ammonia, nitrogen oxides and nitrogen. There is no risk of dangerous, toxic or non-biodegradable materials being released into the air, water or soil.
Ein besonderer Vorteil der Katalysatoren besteht darin, daß durch ihren Einsatz die unter Normalbedingungen ablaufende Behandlung des Wassers durch hohe Abbauraten, kurze Behandlungszeiten und relativ geringem Oxidationsmitteleinsatz kostengünstig durchgeführt werden kann. Durch die relativ hohen Standzeiten des Katalysators werden außerdem langszeitstabile Bedingungen gewährleistet.A particular advantage of catalysts is that their use enables the treatment of water that occurs under normal conditions to be carried out cost-effectively through high degradation rates, short treatment times and relatively low use of oxidizing agents. The relatively long service life of the catalyst also ensures long-term stable conditions.
Durch die erfindungsgemäßen Komplexverbindungen wird die Oxidation der Schadstoffe bereits bei Normaltemperatur, Normaldruck und einem pH-Wert von 6 bis 7 optimal katalysiert. Die Oxidation kann aber auch bei höherenThe complex compounds according to the invention optimally catalyze the oxidation of the pollutants even at normal temperature, normal pressure and a pH value of 6 to 7. However, the oxidation can also take place at higher
oder niederen Drücken und Temperaturen sowie bei pH-Werten von 2,5 bis 9,5 durchgeführt werden.or low pressures and temperatures and at pH values from 2.5 to 9.5.
Optimale Abbauraten werden bei 20 0C bis 25 0C, Normaldruck und in einem pH-Bereich von 5 bis 7,5 erzielt.Optimum degradation rates are achieved at 20 0 C to 25 0 C, normal pressure and in a pH range of 5 to 7.5.
Vorteilhaft ist, daß auch saure Ausgangswässer der Oxidation ohne vorherige pH-Einstellung direkt zugeführt werden können. Nach der Oxidation weisen diese Wässer einen pH-Wert von 7 bis 7,5 auf, so daß die gesetzlich vorgegebenen Einleitbedingungen bereits ohne zusätzliche pH-Wert-Einstellung erfüllt werden.It is advantageous that acidic starting water can also be fed directly to the oxidation process without prior pH adjustment. After oxidation, this water has a pH value of 7 to 7.5, so that the legally specified discharge conditions are met without additional pH adjustment.
Aufgrund der hohen Aktivität der erfindungsgemäßen Katalysator werden
unter Zusatz von Wasserstoffperoxid oxidierbare Kohlenwasserstoffe wie Aromaten, Phenole, chlorierte Kohlenwasserstoffe, organische Farbstoffe und
Cyanide innerhalb kurzer Zeit abgebaut. Selbst sehr stark verunreinigte Abwässer mit Schadstoffmengen von 8-12 kg/m3 CSB werden innerhalb von
30-60 !Minuten effektiv gereinigt, so daß sie entweder in den Vorfluter
eingeleitet oder als Prozeßwasser wieder verwertet werden können.
Die Behandlung des organisch kontaminierten Wassers kann im Durchlaufoder Chargenbetrieb erfolgen.Due to the high activity of the catalyst according to the invention, oxidizable hydrocarbons such as aromatics, phenols, chlorinated hydrocarbons, organic dyes and cyanides are broken down within a short time with the addition of hydrogen peroxide. Even very heavily contaminated waste water with pollutant quantities of 8-12 kg/m 3 COD is effectively cleaned within 30-60 minutes, so that it can either be discharged into the receiving water or reused as process water.
The treatment of organically contaminated water can be carried out in continuous or batch operation.
Die hervorragenden Eigenschaften der Katalysatoren zeigen sich auch in den Reaktionsgeschwindigkeiten, die bei der Aufarbeitung phenolhaltiger Wässer erreicht werden. So erfolgt bei der katalytischen Oxidation in Gegenwart von Wasserstoffperoxid bereits nach 30 Minuten ein praktisch vollständiger Abbau des Phenols, so daß die Phenolkonzentration deutlich unter dem vom Gesetzgeber geforderten Grenzwert für die Indirekteinleitung liegt.The outstanding properties of the catalysts are also reflected in the reaction rates achieved when processing water containing phenol. In the catalytic oxidation in the presence of hydrogen peroxide, the phenol is almost completely broken down after just 30 minutes, so that the phenol concentration is well below the limit required by law for indirect discharge.
Die erfindungsgemäßen Katalysatoren beschleunigen auch den oxidativen Abbau der Schadstoffe in Gegenwart von UV-Licht. Durch diese zusätzliche Aktivierung des Wasserstoffperoxides und der Schadstoffspezies kann beiThe catalysts according to the invention also accelerate the oxidative degradation of the pollutants in the presence of UV light. This additional activation of the hydrogen peroxide and the pollutant species can
besonders schwer abbaubaren Schadstoffen die Abbaurate noch weiter erhöht werden.For particularly difficult to break down pollutants, the degradation rate can be increased even further.
Mit den erfindungsgemäßen Katalysatoren können Abbauraten von 95 % bis 99 % erreicht werden. Diese Katalysatoren gestatten den Abbau auch von schwer abbaubaren organischen und anorganischen Schadstoffen, die auch in hohen Konzentrationen in Wässern und wässrigen Suspensionen enthalten sein können. Der Abbau der Schadstoffe erfolgt auch in trüben und gefärbten Wässern mit einer sehr komplexen Schadstoffmatrix.With the catalysts according to the invention, degradation rates of 95% to 99% can be achieved. These catalysts also allow the degradation of organic and inorganic pollutants that are difficult to degrade and that can be present in high concentrations in water and aqueous suspensions. The degradation of the pollutants also takes place in cloudy and colored water with a very complex pollutant matrix.
Außerdem können organisch gebundene Schwermetalle durch diese Katalysatoren so aufbereitet werden, daß die vorhandenen Schwermetallionen in definierte Oxidationsstufen überführt und damit separierbar werden und außerdem komplex gebundene Liganden oxidativ zerstört werden.In addition, organically bound heavy metals can be processed by these catalysts in such a way that the existing heavy metal ions are converted into defined oxidation states and thus become separable, and complexly bound ligands are destroyed oxidatively.
Bemerkenswert ist außerdem, daß die erfindungsgemäßen Katalysatoren die hohen Abbauraten auch bei stark schwankenden Schadstofifrachten, wie es in der Regel bei Sanierungsvorhaben der Fall ist, gewährleistet.It is also noteworthy that the catalysts according to the invention ensure high degradation rates even with strongly fluctuating pollutant loads, as is usually the case in remediation projects.
Die Erfindung soll nachfolgend anhand von Beispielen näher erläutert werden, ohne die erfindungsgemäßen Katalysatoren auf diese Ausfuhrungsvarianten zu beschränken.The invention will be explained in more detail below using examples, without restricting the catalysts according to the invention to these embodiments.
AusführungsbeispieleExamples of implementation
In 100 ml Wasser werden 10 g Trikalium-tris(alkylsalicylato)-ferrat(III) gelöst. In diese Lösung werden 50 g eines SiO/AJbCVTrägermaterials eingerührt und nach einer Verweilzeit von 10 Minuten abfiltriert und dreimal mit dest. Wasser gewaschen. Anschließend wird der Katalysator getrocknet.10 g of tripotassium tris(alkylsalicylato)ferrate(III) are dissolved in 100 ml of water. 50 g of a SiO/Al2CV support material are stirred into this solution and, after a residence time of 10 minutes, filtered off and washed three times with distilled water. The catalyst is then dried.
20 g des hergestellten Katalysators wird in 1 1 eines braun gefärbten, trüben phenolisch riechenden Abwassers (pH= 8) gegeben.20 g of the prepared catalyst is added to 1 liter of brown-colored, cloudy wastewater with a phenolic smell (pH= 8).
Bei Temperaturen von 20 0C wurde 1,8 ml Wasserstoffperoxid (30%) zugesetzt. Nach 30 Minuten waren > 95 % der organischen Verunreinigungen oxidiert. Das behandelte Wasser war klar, färb- und geruchlos.At temperatures of 20 0 C, 1.8 ml of hydrogen peroxide (30%) was added. After 30 minutes, > 95% of the organic contaminants had oxidized. The treated water was clear, colorless and odorless.
Nach der Behandlung wurde das gereinigte Abwasser abgetrennt und der Katalysator erneut mit gleichem Abwasser behandelt. Es wurden nach gleicher Behandlungszeit die gleichen Ergebnisse erreicht wie bei der ersten Behandlung, was auf eine hohe Katalysatoraktivität und Standzeit hinweist.After treatment, the purified wastewater was separated and the catalyst was treated again with the same wastewater. After the same treatment time, the same results were achieved as in the first treatment, which indicates high catalyst activity and service life.
Der nachfolgenden Tabelle können die Schadstofiwerte des unbehandelten und des behandelten Wassers entnommen werden.The pollutant values of the untreated and treated water can be found in the table below.
(aus der Originalsubstanz)Chemical parameters
(from the original substance)
40 kg einer mit Natrium- tris(benzoylacetonato)niccolat(II) dotierten
Aktivkohle wird für die Reinigung von Grundwasser aus einer Teerpappen-Produktionsanlage
eingesetzt. Das Grundwasser wird zunächst in einer Phasentrennstufe von der Ölphase getrennt. Danach wird es einer
Vorreinigung zugeführt, in der eine Enteisenung des Wassers in bekannter Weise erfolgt. Daran anschließend erfolgt eine Feinfiltration. Das
vorgereinigte Wasser wird kontinuierlich mit Wasserstoffperoxid versetzt und
anschließend in den Wirbelschichtreaktor eingeleitet. Der Reaktor war mit Natrium- trisibenzoylacetonato^ccolatill) dotierter Aktivkohle gefüllt. Die
Dosierung des Wasserstofiperoxides erfolgt volumengesteuert in einer Menge von 2,0 l/m3 Grundwasser.
Die Oxidation erfolgt bei einer Normaltemperatur und unter Normaldruck.40 kg of activated carbon doped with sodium tris(benzoylacetonato)niccolate(II) is used to purify groundwater from a tar paper production plant. The groundwater is first separated from the oil phase in a phase separation stage. It is then fed to a pre-cleaning stage in which the water is de-ironed in a known manner. This is followed by fine filtration. The pre-cleaned water is continuously mixed with hydrogen peroxide and then fed into the fluidized bed reactor. The reactor was filled with activated carbon doped with sodium tris(benzoylacetonato)niccolate(II). The hydrogen peroxide is dosed volume-controlled in a quantity of 2.0 l/m 3 of groundwater.
The oxidation takes place at normal temperature and under normal pressure.
Die Schadstoffwerte wurden während der Behandlung aufgezeichnet. Der nachfolgenden Tabelle können die Werte für das unbehandelte und behandelte Wasser, die über eine Vielzahl von Meßergebnissen ermittelt wurden, entnommen werden.The pollutant levels were recorded during treatment. The following table shows the values for the untreated and treated water, which were determined from a variety of measurement results.
(aus der Originalsubstanz)Chemical parameters
(from the original substance)
Grundwasser vom Standort eines ehemaligen Pharmaziebetriebes mit einem pH-Wert von 3,5 wurde zunächst über einen Schwebstoffilter geführt. Danach wird dem Wasser kontinuierlich Wasserstoffperoxid zudosiert. Vorteilhaft hat sich die Dosierung von ca. 1,0 1 Wasserstoffperoxid/m3 Grundwasser erwiesen.Groundwater from the site of a former pharmaceutical company with a pH value of 3.5 was first passed through a suspended matter filter. Hydrogen peroxide is then continuously added to the water. A dosage of approx. 1.0 l hydrogen peroxide/m 3 groundwater has proven to be advantageous.
Das Wasser wird danach durch den Reaktor geführt, in welchem das Katalysatorträgermaterial, bestehend aus einem Aluminiumsilikatträger und Bis(2-hydroxy-5-methylbenzophenonato) manganat(III), in der Wirbelschicht gehalten wurde.The water is then passed through the reactor in which the catalyst support material, consisting of an aluminum silicate support and bis(2-hydroxy-5-methylbenzophenonato) manganate(III), was kept in the fluidized bed.
Zur Herstellung des Katalysators werden 5 kg Aluminiumsilikat mit 100 1 Wasser dispergiert und mit 1 1 einer wässrigen, Bis(2-hydroxy-5-methylbenzophenonato)manganat(in) enthaltenden Lösung versetzt. Die Lösung wurde mit Natronlauge neutralisiert. Danach wird mindestensTo prepare the catalyst, 5 kg of aluminum silicate are dispersed with 100 l of water and 1 l of an aqueous solution containing bis(2-hydroxy-5-methylbenzophenonato)manganate(in) is added. The solution is neutralized with sodium hydroxide solution. Then at least
6 Stunden gerührt, abfiltriert und der Niederschlag dreimal mit dest. Wasser gewaschen. Anschließend wird der Niederschlag getrocknet.Stirred for 6 hours, filtered and the precipitate washed three times with distilled water. The precipitate is then dried.
Die Oxidation wurde unter Normalbedingungen durchgeführt.The oxidation was carried out under standard conditions.
Die Schadstoffwerte des Wassers wurden während der Behandlung gemessen.The pollutant levels of the water were measured during treatment.
Der nachfolgenden Tabelle können die Werte des unbehandelten und des behandelten Wassers entnommen werden.The values for untreated and treated water can be found in the table below.
(aus der Originalsubstanz)Chemical parameters
(from the original substance)
Claims (1)
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DE29619606U DE29619606U1 (en) | 1996-10-29 | 1996-10-29 | Catalyst for the oxidation of organic and inorganic compounds in the aqueous phase |
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DE29619606U DE29619606U1 (en) | 1996-10-29 | 1996-10-29 | Catalyst for the oxidation of organic and inorganic compounds in the aqueous phase |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009013313A1 (en) * | 2007-07-23 | 2009-01-29 | Henkel Ag & Co. Kgaa | Toc degradation in wastewater using transition metal catalysts |
WO2010000798A1 (en) * | 2008-07-04 | 2010-01-07 | Unilever Plc | Waste water treatment |
CN115400725A (en) * | 2022-08-18 | 2022-11-29 | 中南大学 | Porous clay-based modified biochar composite material and preparation method and application thereof |
-
1996
- 1996-10-29 DE DE29619606U patent/DE29619606U1/en not_active Expired - Lifetime
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009013313A1 (en) * | 2007-07-23 | 2009-01-29 | Henkel Ag & Co. Kgaa | Toc degradation in wastewater using transition metal catalysts |
WO2010000798A1 (en) * | 2008-07-04 | 2010-01-07 | Unilever Plc | Waste water treatment |
CN115400725A (en) * | 2022-08-18 | 2022-11-29 | 中南大学 | Porous clay-based modified biochar composite material and preparation method and application thereof |
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