DE19646552A1 - High activity catalyst for wet oxidation of organic or inorganic contaminants - Google Patents
High activity catalyst for wet oxidation of organic or inorganic contaminantsInfo
- Publication number
- DE19646552A1 DE19646552A1 DE19646552A DE19646552A DE19646552A1 DE 19646552 A1 DE19646552 A1 DE 19646552A1 DE 19646552 A DE19646552 A DE 19646552A DE 19646552 A DE19646552 A DE 19646552A DE 19646552 A1 DE19646552 A1 DE 19646552A1
- Authority
- DE
- Germany
- Prior art keywords
- catalyst according
- organic
- chelate complexes
- catalyst
- compounds
- 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.)
- Ceased
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 238000009279 wet oxidation reaction Methods 0.000 title claims description 6
- 230000000694 effects Effects 0.000 title description 7
- 239000000356 contaminant Substances 0.000 title description 2
- 230000003647 oxidation Effects 0.000 claims abstract description 17
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 17
- -1 chelate complex compounds Chemical class 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 239000003446 ligand Substances 0.000 claims abstract description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical class O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001991 dicarboxylic acids Chemical class 0.000 claims abstract description 9
- 150000002484 inorganic compounds Chemical class 0.000 claims abstract description 9
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 9
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 9
- 150000007513 acids Chemical class 0.000 claims abstract description 7
- 150000002148 esters Chemical class 0.000 claims abstract description 7
- 239000008346 aqueous phase Substances 0.000 claims abstract description 4
- 125000005594 diketone group Chemical group 0.000 claims abstract description 3
- 150000002085 enols Chemical class 0.000 claims abstract description 3
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000003344 environmental pollutant Substances 0.000 claims description 23
- 231100000719 pollutant Toxicity 0.000 claims description 23
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 13
- 239000002351 wastewater Substances 0.000 claims description 12
- 239000013522 chelant Substances 0.000 claims description 11
- 239000003673 groundwater Substances 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 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
- 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
- 238000010525 oxidative degradation reaction Methods 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 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
- 239000011159 matrix material Substances 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 238000001556 precipitation Methods 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
- 230000035622 drinking Effects 0.000 claims description 2
- 239000003651 drinking water Substances 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 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
- 238000002360 preparation method Methods 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
- 239000011669 selenium Substances 0.000 claims description 2
- 229920003002 synthetic resin Polymers 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims 1
- 150000001721 carbon Chemical group 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
- 238000005470 impregnation Methods 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 description 11
- 238000006731 degradation reaction Methods 0.000 description 9
- 239000007983 Tris buffer Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 5
- 125000005575 polycyclic aromatic hydrocarbon group Polymers 0.000 description 5
- 239000010802 sludge Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 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
- 150000008282 halocarbons Chemical class 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
- 239000000126 substance Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000010865 sewage Substances 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
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-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
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-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
- 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
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 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
- 238000004519 manufacturing process Methods 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
- 238000010979 pH adjustment Methods 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical class OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 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
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000012153 distilled water Substances 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
- 238000001914 filtration Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 150000004680 hydrogen peroxides Chemical class 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
- 238000009413 insulation Methods 0.000 description 1
- 239000000543 intermediate Substances 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
- 150000003893 lactate salts Chemical class 0.000 description 1
- 230000007774 longterm Effects 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
- 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
- 229910052763 palladium Inorganic materials 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
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000009419 refurbishment Methods 0.000 description 1
- 238000009418 renovation 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
- 238000002791 soaking Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 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
- 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
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- 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
-
- 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
- B01J31/2234—Beta-dicarbonyl ligands, e.g. acetylacetonates
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- 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
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- 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
- B01J21/12—Silica and alumina
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- 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
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- 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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- 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
- B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
- B01J2531/56—Vanadium
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- 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
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/64—Molybdenum
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- 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
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/66—Tungsten
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- 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
- B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
- B01J2531/72—Manganese
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- 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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
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- 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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
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Abstract
Description
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 Abwässer 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 in carried out aqueous phase, as a result of which wastewater is generated Output, intermediate, by-products, and end products are contaminated. More with wastewater contaminated with organic substances arises during insulation and Refurbishment of the products. All of this sewage and sludge must be done before they are released into the environment, cleaned. The usual Cleaning method is provided the waste water in the sewer be initiated (indirect discharge), the biological cleaning in Sewage treatment plants. In many cases, however, the wastewater contains substances in the Wastewater treatment plants are not or only very slowly degradable, e.g. B. 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.In addition, groundwater and leachate can be dissolved, biologically difficult or contain non-degradable, organic ingredients that are too constant lead to growing disposal problems.
Typische in Ab- bzw. Grund- und Sickerwässern oder Schlämmen enthaltene Schadstoffe sind polycyclische aromatische Kohlenwasserstoffe, halogenierte Kohlenwasserstoffe, Mineralölkohlenwasserstoffe, Cyanide, Phenole, Schwermetalle, Pestizide, polychlorierte Biphenyle u. a..Typical contained in sewage, groundwater and leachate or sludge Pollutants are polycyclic aromatic hydrocarbons, halogenated Hydrocarbons, mineral oil hydrocarbons, cyanides, phenols, Heavy metals, pesticides, polychlorinated biphenyls and the like a ..
Polycyclische aromatische Kohlenwasserstoffe (PAK), adsorbierbare organische Halogene (AOX), polychlorierte Biphenyle (PCB), Ethylendiamintetraessigsäure (EDTA) und organische Amine stellen besonders schwer abbaubare Schadstoffe dar.Polycyclic aromatic hydrocarbons (PAH), adsorbable organic halogens (AOX), polychlorinated biphenyls (PCB), Provide ethylenediaminetetraacetic acid (EDTA) and organic amines pollutants that are particularly difficult to decompose.
Aus dem Stand der Technik sind eine Reihe von Abwasserbehandlungsverfahren bekannt, wie: Adsoptionsverfahren, insbesondere an Aktivkohlen und aktivierten Adsorbentien, biologische Reinigung, Fällung/Flockung, Umkehrosmose, Eindampfung/Trocknung.A number of are from the prior art Wastewater treatment processes known, such as: adsorption processes, especially on activated carbon and activated adsorbents, biological Cleaning, 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 the pollutants has been caused by Chemical wet oxidation is becoming 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 41 18 626). 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.Methods are known in which the oxidative effect of Hydrogen peroxides and ozone are increased by catalysts can. Metal oxides and metal salts are preferred as catalysts of transition elements (e.g. Fentons reagent, oxides, sulfates and chlorides of copper, zinc, nickel, iron, tungsten) (DE-OS 43 14 521, DE-OS 29 27 911, DE-OS 27 35 892, DE-OS 41 18 626). The disadvantage here is the formation of large amounts of Contaminated metal sludge, e.g. B. iron hydroxide sludge must be specially deposited or disposed of. Furthermore, for those with Iron (II) ion catalyzed oxidation (Fenton's reagent) is an acidic one pH range required, which adversely affects the 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 erhöhten Temperaturen und Drücken durchgeführt, was zu hohen Investitions- und Betriebskosten führt.Often there is a risk that the catalysts are often in the Waste water contained suspended matter can be deactivated. The well-known Methods for wet oxidation are usually elevated Temperatures and pressures are carried out, leading to high investment and Operating costs.
Bei Verfahren, die in unteren Temperatur- (150-175°C) 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. Trotzdem wird bei diesen Verfahren keine vollständige Oxidation der Schadstoffe zu Wasser und Kohlendioxid erreicht.For processes in the lower temperature (150-175 ° C) and pressure ranges (10-20 bar) must work in addition to the presence of a catalyst pH to be adjusted to 0.5-1.5 to allow oxidation. Nevertheless, these processes do not completely oxidize the Pollutants to water and carbon dioxide reached.
Es sind auch Verfahren bekannt, bei denen die Oxidation in Gegenwart von Vollmetallkatalysatoren durchgeführt wird (DE-OS 41 31 596, DE-PS 195 03 865).Methods are also known in which the oxidation is carried out in the presence of Full metal catalysts is carried out (DE-OS 41 31 596, 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.The oxidation on activated carbons is also described, the Catalytic effectiveness of the coals by using anodic oxidized and then with molybdenum VI and / or tungsten VI and / or vanadium-V compounds increased doped carbon carriers becomes. The salt compounds are used for doping the carriers mentioned elements used (DE-OS 34 30 484). Also come Metals or metal oxides of the elements platinum, nickel, titanium, cobalt, Manganese, molybdenum, copper and tungsten for the doping of activated carbon to use.
Die bekannten Katalysatoren zur katalytischen Naßoxidation haben den Nachteil, daß sie insbesondere 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 wet catalytic oxidation have the Disadvantage that they are particularly heavy or heavy pollution degradable pollutants do not completely break down the pollutants enable the efficiency and the 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 Verbindungen eine hohe Abbaurate und unter Normalbedingungen eine hohe Wirksamkeit aufweist.The invention has for its object a simple to produce Catalyst for the oxidation of organic and inorganic To provide compounds in water, the even with high pollutant loads with poorly degradable compounds a high degradation rate and high effectiveness under normal conditions having.
Diese Aufgabe wird erfindungsgemäß durch einen Katalysator gelöst, der eine oder mehrere Chelatkomplexverbindungen der Elemente der 1., 2., 4. bis 8. Nebengruppe des Periodensystems der Elemente enthält.According to the invention, this object is achieved by a catalyst which has a or more chelate complex compounds of the elements of the 1st, 2nd, 4th to 8. Subgroup of the Periodic Table of the Elements contains.
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 subgroup of the Periodic Table of the Elements a high Efficacy for the oxidative degradation of organic and inorganic Show connections in water. Are particularly suitable Chelate complex compounds with dichalkogens as ligand atom.
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 exhibit high activity Normal conditions and ensure almost complete degradation also of poorly degradable pollutants, such as polychlorinated biphenyls (PCB), volatile halogenated hydrocarbons (LHKW), Ethylenediaminetetraacetic acid (EDTA), organic amines, pesticides, adsorbable organic halogenated hydrocarbons (AOX) and other oxidizable compounds (COD). It was not foreseeable that these compounds are highly catalytic even at neutral pH Have activity so that when using the catalysts of the invention there is no additional salting of the water and the formation of too disposal sludge is eliminated.
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 Katalysatorgifte bekannten Schwermetallionen und Schwefelverbindungen inhibieren die erfindungsgemäßen Katalysatoren überraschenderweise nicht.The catalysts according to the invention face those in waste water contained metal compounds, inorganic salts and suspended matter a high stability. The activity of the catalysts is affected by this Substances not negatively affected. As a result, the catalysts have a high catalytic activity and a long service life. Also as catalyst poisons known heavy metal ions and sulfur compounds inhibit the Surprisingly, the catalysts of the invention are not.
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.Chelate complex compounds with are particularly suitable catalysts same or different ligands selected from the group below can be selected: oxyketones, oxyaldehydes, oxyquinones, diketones, enols, Oxyacids, dicarboxylic acids, ketocarboxylic acids and their acid esters as well the analogous compounds containing sulfur or selenium. The ligands can be an aliphatic, cycloaliphatic, aromatic or araliphatic Have structure. Chelate complexes with are preferred Oxygen ligand atoms used.
Dabei sind Oxyketone, Oxysäuren, Ketocarbonsäuren, Dicarbonsäuren und β-Diketone sowie die entsprechenden Säureester als chelatbildende Liganden besonders geeignet.These include oxyketones, oxyacids, ketocarboxylic acids, dicarboxylic acids and β-diketones and the corresponding acid esters as chelating ligands particularly suitable.
Vertreter dieser Liganden sind beispielsweise: Glykolate, Lactate, Citrate, Salicylate, Oxalate, Oxychinone, o-Oxyacetophenon, Benzoylacetonat, Acetessigsäurealkylester.Representatives of these ligands are, for example: 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 der 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.The ligands of the complexes can be attached to one or more Carbon atoms can be substituted by one or more of the following groups: halogen, nitro, hydroxy, carbonyl, carboxy, Alkoxy, aralkoxy, phenoxy, alkyl, aryl, and aralkyl, where the Carbonyl, carboxy, alkyl and aryl radicals optionally also by one or more of the groups mentioned can be substituted.
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.Show a particularly high catalytic activity under normal conditions the chelate complex compounds of iron, vanadium, manganese, copper, Cobalt, molybdenum, tungsten, ruthenium, rhodium, palladium, platinum and their mixtures.
Bevorzugt werden ein oder mehrere Chelatkomplexe der Elemente der 7. und 8. Nebengruppe eingesetzt. One or more chelate complexes of the elements of 7th and 7th are preferred 8. Subgroup used.
Besonders hohe Abbauraten bei organischen und anorganischen Verbindungen, insbesondere bei schwer abbaubaren Verbindungen werden durch den Einsatz von Chelatkomplexverbindungen der Oxyketone, Oxysäuren, Ketocarbonsäuren, Dicarbonsäuren, β-Diketone, insbesondere der Dicarbonsäuren und β-Diketone, und der entsprechenden Säureester mit Elementen der 7. und 8. Nebengruppe erzielt.Particularly high degradation rates for organic and inorganic Connections, especially in the case of compounds that are difficult to decompose through the use of chelate complex compounds of the oxyketones, Oxyacids, ketocarboxylic acids, dicarboxylic acids, β-diketones, especially the Dicarboxylic acids and β-diketones, and the corresponding acid ester with Achieved elements of the 7th and 8th subgroup.
Geeignete Katalysatoren sind zum Beispiel Komplexe des Tris(benzoylacetonato)cuprats(II), Tris(alkylsalicylato)ferrats(III), Bis(thlo bisphenolato)niccolats(II), Bis(dialkyl-dithiocarbamato)cobaltats(II), Tris(oxalato)manganats(III), Tris(2-hydroxyacetophenonato)ferrats(III), Bis(2-hydroxy-5-methylbenzo-phenonato)manganats(III).Suitable catalysts are, for example, complexes of Tris (benzoylacetonato) cuprates (II), tris (alkylsalicylato) ferrates (III), bis (thlo bisphenolato) niccolats (II), bis (dialkyl-dithiocarbamato) cobaltats (II), Tris (oxalato) manganate (III), tris (2-hydroxyacetophenonato) ferrate (III), Bis (2-hydroxy-5-methylbenzo-phenonato) manganate (III).
Die erfindungsgemäßen Katalysatoren können als homogene oder heterogene Katalysatoren im Fluidbett-, Festbett- oder Wirbelbettverfahren eingesetzt werden.The catalysts of the invention can be homogeneous or heterogeneous Catalysts used in fluid bed, fixed bed or fluidized bed processes will.
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 are preferred, in particular supported catalysts. This ensures optimal use of the activity of the catalysts and a high rate of degradation of the pollutants. Activated carbon, polymeric resins, Al 2 O 3 , SiO 2 and zeolites are used as carriers, the activated carbon being preferred because of the 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 manufacture. The Chelate complex compound can in a known manner by ion exchange, Soaking or precipitation from a solution can be fixed to the carrier matrix. The complex compounds are prepared in a known manner.
Ein Vorteil der erfindungsgemäßen Katalysatoren ist, daß sie vollständig recyclebar sind. An advantage of the catalysts of the invention is that they are complete are recyclable.
Die erfindungsgemäßen Katalysatoren werden insbesondere für 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 of the invention are used in particular for Catalytic wet oxidation of organic and inorganic compounds used in the aqueous phase. The wet oxidation is carried out in the presence of a or more of the oxidizing agents mentioned below: 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 of the invention can be used for the oxidative purification of waste water containing organic and / or inorganic compounds, Process, drinking and ground water as well as for the treatment of aqueous extractants contaminated with pollutants from floor washing be used.
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 organic and inorganic compounds to environmentally compatible reaction products reduced. In most cases, depending on the type of oxidized pollutants carbon dioxide, water, chlorides, sulfates and others Salts and some nitrogen-containing compounds, such as ammonia, nitrogen oxides and nitrogen. The risk of release of dangerous, toxic or non-biodegradable materials in the air, water or There is no floor.
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 langzeitstabile Bedingungen gewährleistet.A particular advantage of the catalysts is that their Use the treatment of the water that takes place under normal conditions due to high breakdown rates, short treatment times and relatively low Use of oxidizing agents can be carried out inexpensively. Through the relatively long service lives of the catalyst are also long-term stable Conditions guaranteed.
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 höheren oder niederen Drücken und Temperaturen sowie bei pH-Werten von 2,5 bis 9,5 durchgeführt werden.The oxidation of the complex compounds Pollutants already at normal temperature, normal pressure and a pH value optimally catalyzed from 6 to 7. The oxidation can also occur at higher ones or low pressures and temperatures as well as at pH values of 2.5 to 9.5 can be performed.
Optimale Abbauraten werden bei 20°C bis 25°C, Normaldruck und in einem pH-Bereich von 5 bis 7,5 erzielt.Optimal degradation rates are at 20 ° C to 25 ° C, normal pressure and in one pH range from 5 to 7.5 achieved.
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 waters of the oxidation without previous pH adjustment can be fed directly. Show after oxidation these waters have a pH of 7 to 7.5, so the legal specified introduction conditions 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.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 decomposed within a short time with the addition of hydrogen peroxide. Even very heavily contaminated wastewater 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 recycled as process water.
Die Behandlung des organisch kontaminierten Wassers kann im Durchlauf- oder Chargenbetrieb erfolgen.The treatment of organically contaminated water can be in the 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 excellent properties of the catalysts are also evident in the Reaction speeds when processing phenolic water can be achieved. For example, catalytic oxidation takes place in the presence of Hydrogen peroxide is practically completely broken down after just 30 minutes of the phenol, so that the phenol concentration significantly below that of Legislative limit for indirect discharge is.
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 bei besonders schwer abbaubaren Schadstoffen die Abbaurate noch weiter erhöht werden.The catalysts of the invention also accelerate the oxidative Degradation of pollutants in the presence of UV light. Through this additional Activation of the hydrogen peroxide and the pollutant species can pollutants that are particularly difficult to degrade further increase the degradation rate will.
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.Degradation rates of 95% to 99% can be achieved. These catalysts also allow the breakdown of Hardly biodegradable organic and inorganic pollutants, which are also found in high concentrations in water and aqueous suspensions can. The degradation of 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.It can also cause organically bound heavy metals Catalysts are prepared so that the heavy metal ions present converted into defined oxidation levels and thus separable and complex-bound ligands are also oxidatively destroyed.
Bemerkenswert ist außerdem, daß die erfindungsgemäßen Katalysatoren die hohen Abbauraten auch bei stark schwankenden Schadstofffrachten, wie es in der Regel bei Sanierungsvorhaben der Fall ist, gewährleistet.It is also noteworthy that the catalysts of the invention high degradation rates even with heavily fluctuating pollutant loads, as in the case with renovation projects is guaranteed.
Die Erfindung soll nachfolgend anhand von Beispielen näher erläutert werden, ohne die erfindungsgemäßen Katalysatoren auf diese Ausführungsvarianten zu beschränken.The invention will be explained in more detail below with the aid of examples, without the catalysts of the invention to these variants restrict.
Herstellung des Katalysators:
In 100 ml Wasser werden 10 g Trikalium-tris(alkylsalicylato)-ferrat(III)
gelöst. In diese Lösung werden 50 g eines SiO2/Al2O3-Trägermaterials
eingerührt und nach einer Verweilzeit von 10 Minuten abfiltriert und dreimal
mit dest. Wasser gewaschen. Anschließend wird der Katalysator getrocknet.Preparation of the catalyst:
10 g of tripotassium tris (alkyl salicylato) ferrate (III) are dissolved in 100 ml of water. 50 g of a SiO 2 / Al 2 O 3 support material are stirred into this solution and, after a dwell time of 10 minutes, filtered off and three times with distilled water. Washed water. The catalyst is then dried.
Einsatz des erfindungsgemäßen Katalysators:
20 g des hergestellten Katalysators wird in 1 l eines braun gefärbten, trüben
phenolisch riechenden Abwassers (pH = 8) gegeben.Use of the catalyst according to the invention:
20 g of the catalyst prepared is placed in 1 l of a brown-colored, cloudy phenolic-smelling waste water (pH = 8).
Bei Temperaturen von 20°C wurde 1,8 ml Wasserstoffperoxid (30%) zugesetzt. Nach 30 Minuten waren < 95% der organischen Verunreinigungen oxidiert. Das behandelte Wasser war klar, farb- und geruchlos.At temperatures of 20 ° C, 1.8 ml of hydrogen peroxide (30%) added. After 30 minutes, <95% of the organic contaminants were 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. Der nachfolgenden Tabelle können die Schadstoffwerte des unbehandelten und des behandelten Wassers entnommen werden. After the treatment, the cleaned wastewater was separated off and the The catalyst was treated again with the same waste water. It was after the same Treatment time achieved the same results as the first Treatment, which indicates a high catalyst activity and service life. The table below shows the pollutant values of the untreated and the treated water.
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-tris(benzoylacetonato)niccolat(II) dotierter Aktivkohle gefüllt. Die Dosierung des Wasserstoffperoxides erfolgt volumengesteuert in einer Menge von 2,0 l/m3 Grundwasser.40 kg of an activated carbon doped with sodium tris (benzoylacetonato) niccolate (II) is used to purify groundwater from a tar board production plant. The groundwater is first separated from the oil phase in a phase separation stage. Then it is 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 introduced into the fluidized bed reactor. The reactor was filled with sodium tris (benzoylacetonato) niccolate (II) doped activated carbon. The hydrogen peroxide is metered volume-controlled in an amount of 2.0 l / m 3 groundwater.
Die Oxidation erfolgt bei einer Normaltemperatur und unter Normaldruck. The oxidation takes place at a 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 values were recorded during the treatment. The table below shows the values for the untreated and treated water, which were determined using a large number of measurement results.
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 l Wasserstoffperoxid/m3 Grundwasser erwiesen.Groundwater from the site of a former pharmaceutical company with a pH value of 3.5 was first led through a suspended matter filter. Then hydrogen peroxide is continuously added to the water. The 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), in the fluidized bed was held.
Zur Herstellung des Katalysators werden 5 kg Aluminiumsilikat mit 100 l Wasser dispergiert und mit 1 l einer wäßrigen, Bis(2-hydroxy-5- methylbenzophenonato)manganat(III) enthaltenden Lösung versetzt. Die Lösung wurde mit Natronlauge neutralisiert. Danach wird mindestens 6 Stunden gerührt, abfiltriert und der Niederschlag dreimal mit dest. Wasser gewaschen. Anschließend wird der Niederschlag getrocknet.To produce the catalyst, 5 kg of aluminum silicate with 100 l Dispersed water and with 1 l of an aqueous, bis (2-hydroxy-5- solution containing methylbenzophenonato) manganate (III). The Solution was neutralized with sodium hydroxide solution. After that, at least Stirred for 6 hours, filtered off and the precipitate three times with dist. water washed. The precipitate is then dried.
Die Oxidation wurde unter Normalbedingungen durchgeführt.The oxidation was carried out under normal conditions.
Die Schadstoffwerte des Wassers wurden während der Behandlung gemessen.
Der nachfolgenden Tabelle können die Werte des unbehandelten und des
behandelten Wassers entnommen werden.
The pollutant values of the water were measured during the treatment. The table below shows the values for untreated and treated water.
..
Claims (16)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE29624604U DE29624604U1 (en) | 1996-10-29 | 1996-10-29 | High activity catalyst for wet oxidation of organic or inorganic contaminants - comprises chelate complex of sub-Group I, II and/or IV-VIII element and is used e.g. with hydrogen peroxide |
| DE19646552A DE19646552A1 (en) | 1996-10-29 | 1996-10-29 | High activity catalyst for wet oxidation of organic or inorganic contaminants |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19646552A DE19646552A1 (en) | 1996-10-29 | 1996-10-29 | High activity catalyst for wet oxidation of organic or inorganic contaminants |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE19646552A1 true DE19646552A1 (en) | 1998-04-30 |
Family
ID=7811319
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19646552A Ceased DE19646552A1 (en) | 1996-10-29 | 1996-10-29 | High activity catalyst for wet oxidation of organic or inorganic contaminants |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE19646552A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103360799A (en) * | 2013-07-23 | 2013-10-23 | 上海一品颜料有限公司 | Refined carbon black and preparation method thereof |
| CN105621764A (en) * | 2016-03-17 | 2016-06-01 | 浙江奇彩环境科技股份有限公司 | Treatment process of epoxy chloropropane production wastewater |
-
1996
- 1996-10-29 DE DE19646552A patent/DE19646552A1/en not_active Ceased
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103360799A (en) * | 2013-07-23 | 2013-10-23 | 上海一品颜料有限公司 | Refined carbon black and preparation method thereof |
| CN103360799B (en) * | 2013-07-23 | 2014-08-13 | 上海一品颜料有限公司 | Refined carbon black and preparation method thereof |
| CN105621764A (en) * | 2016-03-17 | 2016-06-01 | 浙江奇彩环境科技股份有限公司 | Treatment process of epoxy chloropropane production wastewater |
| CN105621764B (en) * | 2016-03-17 | 2018-05-15 | 浙江奇彩环境科技股份有限公司 | A kind for the treatment of process of epoxychloropropane production waste water |
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