EP1027109B1 - Method for reductive dehalogenation of halogen-organic substances - Google Patents
Method for reductive dehalogenation of halogen-organic substances Download PDFInfo
- Publication number
- EP1027109B1 EP1027109B1 EP98954202A EP98954202A EP1027109B1 EP 1027109 B1 EP1027109 B1 EP 1027109B1 EP 98954202 A EP98954202 A EP 98954202A EP 98954202 A EP98954202 A EP 98954202A EP 1027109 B1 EP1027109 B1 EP 1027109B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- process according
- substances
- grinding
- reducing agent
- mixture
- 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.)
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- 238000000034 method Methods 0.000 title claims abstract description 52
- 239000000126 substance Substances 0.000 title claims abstract description 38
- 230000002829 reductive effect Effects 0.000 title claims abstract description 6
- 238000005695 dehalogenation reaction Methods 0.000 title abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 34
- 239000007787 solid Substances 0.000 claims abstract description 31
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 16
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 16
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims description 31
- 238000000227 grinding Methods 0.000 claims description 27
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000000292 calcium oxide Substances 0.000 claims description 16
- 239000006185 dispersion Substances 0.000 claims description 16
- 229910052708 sodium Inorganic materials 0.000 claims description 16
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 8
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- 238000002360 preparation method Methods 0.000 claims description 7
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- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 238000011282 treatment Methods 0.000 claims description 6
- 150000001298 alcohols Chemical group 0.000 claims description 5
- 239000010953 base metal Substances 0.000 claims description 5
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- 239000000654 additive Substances 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 150000002896 organic halogen compounds Chemical class 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 239000013543 active substance Substances 0.000 claims description 2
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- 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 14
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- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 11
- -1 aliphatic alcohols Chemical class 0.000 description 10
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 9
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 description 9
- 238000007792 addition Methods 0.000 description 8
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- 229910052786 argon Inorganic materials 0.000 description 7
- 231100000331 toxic Toxicity 0.000 description 7
- 230000002588 toxic effect Effects 0.000 description 7
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
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- 238000004458 analytical method Methods 0.000 description 5
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- 125000001931 aliphatic group Chemical group 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
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- APTNPYLLOMXCMR-UHFFFAOYSA-N calcium sodium oxygen(2-) Chemical compound [O-2].[Na+].[Ca+2] APTNPYLLOMXCMR-UHFFFAOYSA-N 0.000 description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 4
- ONXPZLFXDMAPRO-UHFFFAOYSA-N decachlorobiphenyl Chemical group ClC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl ONXPZLFXDMAPRO-UHFFFAOYSA-N 0.000 description 4
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 4
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- 238000000498 ball milling Methods 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
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- 239000000969 carrier Substances 0.000 description 3
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- IGARGHRYKHJQSM-UHFFFAOYSA-N cyclohexylbenzene Chemical compound C1CCCCC1C1=CC=CC=C1 IGARGHRYKHJQSM-UHFFFAOYSA-N 0.000 description 3
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- JLYXXMFPNIAWKQ-UHFFFAOYSA-N γ Benzene hexachloride Chemical class ClC1C(Cl)C(Cl)C(Cl)C(Cl)C1Cl JLYXXMFPNIAWKQ-UHFFFAOYSA-N 0.000 description 3
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- ASUDFOJKTJLAIK-UHFFFAOYSA-N 2-methoxyethanamine Chemical compound COCCN ASUDFOJKTJLAIK-UHFFFAOYSA-N 0.000 description 2
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- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- 235000012216 bentonite Nutrition 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- KTHXBEHDVMTNOH-UHFFFAOYSA-N cyclobutanol Chemical compound OC1CCC1 KTHXBEHDVMTNOH-UHFFFAOYSA-N 0.000 description 1
- QCRFMSUKWRQZEM-UHFFFAOYSA-N cycloheptanol Chemical compound OC1CCCCCC1 QCRFMSUKWRQZEM-UHFFFAOYSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- NISGSNTVMOOSJQ-UHFFFAOYSA-N cyclopentanamine Chemical compound NC1CCCC1 NISGSNTVMOOSJQ-UHFFFAOYSA-N 0.000 description 1
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 1
- YOXHCYXIAVIFCZ-UHFFFAOYSA-N cyclopropanol Chemical compound OC1CC1 YOXHCYXIAVIFCZ-UHFFFAOYSA-N 0.000 description 1
- GUDMZGLFZNLYEY-UHFFFAOYSA-N cyclopropylmethanol Chemical compound OCC1CC1 GUDMZGLFZNLYEY-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 208000001848 dysentery Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000012458 free base Substances 0.000 description 1
- JLYXXMFPNIAWKQ-GNIYUCBRSA-N gamma-hexachlorocyclohexane Chemical compound Cl[C@H]1[C@H](Cl)[C@@H](Cl)[C@@H](Cl)[C@H](Cl)[C@H]1Cl JLYXXMFPNIAWKQ-GNIYUCBRSA-N 0.000 description 1
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910001502 inorganic halide Inorganic materials 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 229960002809 lindane Drugs 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- CLJWSVLSCYWCMP-UHFFFAOYSA-N n,n-diethyl-2-methylpropanamide Chemical compound CCN(CC)C(=O)C(C)C CLJWSVLSCYWCMP-UHFFFAOYSA-N 0.000 description 1
- RWIVICVCHVMHMU-UHFFFAOYSA-N n-aminoethylmorpholine Chemical compound NCCN1CCOCC1 RWIVICVCHVMHMU-UHFFFAOYSA-N 0.000 description 1
- 229930189110 naamine Natural products 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- PFWWZGINJSDVGU-UHFFFAOYSA-N piperidine Chemical compound C1CCNCC1.C1CCNCC1 PFWWZGINJSDVGU-UHFFFAOYSA-N 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000006042 reductive dechlorination reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/37—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by reduction, e.g. hydrogenation
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/34—Dehalogenation using reactive chemical agents able to degrade
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/22—Organic substances containing halogen
Definitions
- the invention relates to a method for reductive dehalogenation of halogenated organic substances in solid and liquid Mixtures of substances in which the substance or mixture of substances under Addition of elemental alkali metal, alkaline earth metal, aluminum or iron as a reducing agent and at least one Reagent with at least slightly activated hydrogen as a hydrogen source is treated. It is particularly useful for detoxification of organically contaminated soils and others complex materials, but also for decontamination and optionally recycling liquid or predominantly liquid halogen organically contaminated substances.
- Toxic polyhalogenated organic pollutants can be So far under economically and ecologically equally advantageous and forward-looking terms with none of the nowadays known detoxification technologies. Frequently are these substances as impurities, also in large quantities, in soils, river or marine sediments, sewage sludge, filter dust, Building materials, seepage oils, waste oils etc. before, i.e. associated with an indefinable number of foreign and Accompanying substances with different properties.
- the detoxification and remediation of such complex, heterogeneous, solid, solid-liquid or liquid materials and contaminated sites poses particularly extensive problems.
- Halogenated organics contained in solids can be due to the high Transport inhibitions common in solid-solid reactions difficult to be reached by reagents.
- polyhalogenated organic matter in the environment can be polyhalogenated organic matter in the environment as impurities z. B. in soils, river or marine sediments, Sewage sludge, filter dust, building materials or Seepage oils, therefore solid or liquid, without exception very much heterogeneous materials can be found in large quantities, due to the complex state forms of these matrices and the resulting diverse transport inhibitions in particular difficult to attack and therefore only incomplete or not at all Bring reaction.
- the problem underlying the invention is therefore a process for the reductive dehalogenation of organic halogen Design fabrics so that it is possible to create different ones heterogeneous solid and liquid mixtures, in particular also complex mixtures and contaminated soils with partially unknown other ingredients in one to dehalogenate universal processes as far as possible, whereby no new harmful by-products should arise.
- the method should be as easy to use as possible Own process flow and work relatively quickly.
- the invention is applicable to organohalogen compounds which in solid or liquid foreign substances or foreign substance mixtures are included, but also as solid or liquid pure substances or can be present in mixtures of these. These substances or mixtures of substances, as far as the basic process is concerned, in dealt with in a single process step, i.e. it will all components including mild reaction conditions at least one reducing agent and one hydrogen source, intimate mixed.
- the process includes grinding the reactants under Entry of a more or less large amount of mechanical Energy.
- a fine distribution in very small particles and therefore an intensive mixing of all Components of the mixture causes so that between the used reagents and the organohalogen in time Intensive contact is established and this means be brought to the desired reaction.
- the reactivity of the solid components through the fine distribution increased due to surface physical effects.
- the method according to the invention has the Advantage that under mild reaction conditions, i.e. in general at room temperature and under normal pressure, feasible and is technically far less complex. It is therefore also can be designed for small mobile systems. Another advantage is there in the fact that there may be recycling or reuse of the materials to be decontaminated is possible with a Combustion would be destroyed in principle.
- the process basically works at low temperatures, preferably at room temperature under normal pressure. there it is possible, however, that due to the intensive mechanical input Energy and / or that released during dehalogenation Heat of reaction in the course of the process a warming entry.
- the metallic reducing agent is advantageously at least in little excess used.
- the required amount of reducing agent can be carried out in preliminary tests on samples of the specific decontamination object be determined.
- Common metals are reducing agents, namely in particular alkali metals, alkaline earth metals, aluminum and Iron provided.
- alkali metals are sodium and potassium preferred, among the alkaline earths magnesium and calcium.
- other base metals can also be used, taking into account is that the formation of toxic products should be avoided.
- a hydrogen source with at least slightly activated hydrogen are preferably alcohols, ethers, polyethers, amines or hydroxides, such as.
- As calcium hydroxide, or metal or Non-metal hydrides such as Calcium hydride, sodium hydride, sodium boranate, Lithium alanate, trialkylsilanes, polyalkylhydrogensiloxanes, used individually or in combination.
- low molecular weight aliphatic alcohols can be used.
- Low molecular weight alcohols are, for example, aliphatic
- alcohols with 1 to 7 carbon atoms such as methanol, Ethanol, propanol, isopropanol, butanol, sec- and tert-butanol, Pentanol, hexanol, heptanol, cyclopropanol, cyclobutanol, Cyclopentanol, cyclohexanol, cycloheptanol, 2-methylcyclopropanol, Cyclopropylmethanol, polyalkylene glycols, simply etherified polyalkylene glycols, amino alcohols, polyols, such as. Ethylene glycol, glycerin, pentaerythritol, etc.
- Simple symmetrical groups can be selected from the ether group or asymmetric aliphatic ethers, cyclic ethers or polyether can be used. Examples include diethyl ether, Propyl ether, isopropyl ether, n-butyl ether and dimers or trimeric polyethers, coronands, cryptands, spherands, Ether amines, e.g. 2-methoxyethylamine etc.
- aliphatic amines from the group of amines are aliphatic amines and below lower primary or secondary aliphatic amines are preferred.
- suitable amines are: primary, secondary or tertiary aliphatic and alicyclic mono- or polyamines, Methylamine, ethylamine, 1- and 2-propylamine, 1- and 2-butylamine, Ethylenediamine, tri-, tetra-, penta-, hexamethylenediamine, dimethylamine, Diethylamine, di-n-propylamine, cyclopentylamine and cyclohexylamine, Nitrogen heterocycles and perhydro nitrogen heterocycles, e.g.
- Piperidine 1- (2-aminoethyl) piperazine, 1- (2-aminoethyl) pyrrolidine and 1- (2-aminoethyl) piperidine, 4- (2-aminoethyl) morpholine. It is also suitable for the same purpose liquid ammonia.
- 1,3 dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidone can be used (Dimethylpropylene, DMPU), 1,3-dimethyl-2-imidazolidinone (N, N-dimethylethylene urea, DMEU), 1-methyl-2-pyrrolidone (NMP), 1-ethyl-2-pyrrolidone, N, N-diethylacetamide, N, N-diethylpropionamide, N, N-diethylisobutyramide.
- the mechanical preparation according to the invention can be carried out in one Ground in a mechanical mill, for example a ball mill, hammer mill or vibrating mill. Additional grinding aids can be used for this grinding become. Substances are generally used as grinding aids the surface energy and / or the plastic deformation of Can reduce solids when exposed to mechanical energy. These include, for example: Surface-active substances in various forms of condition or preparation, e.g.
- quaternary ammonium compounds that are not only in pure substance can be used, but also immobilized on inert, surface-active carriers, such as layered silicates, clays (so-called “organophilic bentonites”) also substituted alkylimidazolines and sulfosuccinamides, fatty acids, fatty acid esters and - amides, primary, secondary and tertiary alkyl and fatty amines with one or more amine groups, alicyclic amines, such as, for example Cyclohexylamine, polyhydrogen nitrogen heterocycles, such as.
- surface-active carriers such as layered silicates, clays (so-called “organophilic bentonites") also substituted alkylimidazolines and sulfosuccinamides, fatty acids, fatty acid esters and - amides, primary, secondary and tertiary alkyl and fatty amines with one or more amine groups, alicyclic amines,
- Piperidine mono-, di- or trialkanolamines, simple glycols, polyalkylene glycols, e.g. polyethylene and polypropylene glycols, and their mono- or diether, Organosilicon compounds, especially silicones, special for inorganic salts suitable for the purpose, e.g. Aluminum chloride.
- reaction accelerators be reinforced or accelerated.
- a reaction accelerator can be used fabrics that are able to base Metals, especially alkali and alkaline earth metals, partially or completely dissolve and / or dissociate them in metal cations and anions and / or the formation of solvated To transport electrons and / or organometallic compounds, such as. alkali or alkaline earth metal organic compounds, to solvate and / or stabilize, e.g.
- liquid Ammonia primary, secondary or tertiary aliphatic and alicyclic mono- or polyamines, polyhydrogen nitrogen heterocycles, aliphatic and cyclic monoethers, podands, coronands, Cryptands, spherands, ether amines, e.g.
- 2-methoxyethylamine Amides such as -pyrimidone, 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) (Dimethyl propylene urea, DMPU), 1,3-dimethyl-2-imidazolidinone (N, N-dimethylethylene urea, DMEU), 1-methyl-2-pyrrolidone (NMP), 1-ethyl-2-pyrrolidone, N, N-diethylacetamide, N, N-diethylpropionamide, N / N-diethylisobutyramide.
- the grinding aid (s) and / or reaction accelerator can Substance or mixture of substances in a subsequent step, i.e. separately after adding the reactants, added and mechanically be incorporated.
- the metallic reducing agent can on the one hand be mixed can be added directly in pure form. This is particularly useful alkaline earth metals, less in the air are more reactive than the alkali metals, e.g. with magnesium chips.
- the metallic reducing agent can be in a preparation are dispersed or suspended, for example dispersed in a non-oxidizing liquid or the liquid hydrogen source.
- Dispersions are advantageous to use from the selected metal in white oil, paraffin or in Ethers, including polyethers such as diglyme, triglyme, tetraglyme, polyethylene glycol and polyethylene glycol derivatives, etherified diund Polyglymen.
- the metallic reducing agent can be mixed with a solid Carrier mixed or applied to this.
- advantageous preparation has e.g. a mixture of alkali metal, especially sodium, with calcium silicate or Calcium oxide proven.
- the method can thus also be designed in two stages , e.g. by ball milling in a first step pre-produced finely divided metal only in a second Step with the addition of reaction accelerators and if necessary other additives are ground. It is also possible also alkali metal dispersions obtained by conventional means, i.e. both dispersions in inert fluids as well on inert solid supports, with reaction accelerators and If necessary, other additives in an organohalogenous Solid grinding or mixing and thereby dehalogenation to effect.
- the method can also be used to complement other methods, e.g. of washing processes, used or combined with these become.
- the process can be carried out batchwise, batchwise or continuously be performed.
- first of all Reaction partner i.e. at least the substance to be treated or the mixture / mixture, the metallic reducing agent and the Hydrogen donor, placed in a device that is mechanical Machining enables, like a mill or a (dynamic) Mixer.
- a device that is mechanical Machining enables, like a mill or a (dynamic) Mixer.
- a mill e.g. a ball mill, a hammer mill or a vibratory mill can be used while at a mixer can be sufficient for liquid systems.
- a mixer For example, friction, screw or roller mixers are suitable.
- the model floor was artificial by adding a mixture of 5 g of Chlophen A30 and 150 g of calcium oxide / calcium hydroxide, the five Minutes, were contaminated.
- ESM 234 In an eccentric vibratory mill "ESM 234" (data see example 1) 3.8 kg quartz sand (bulk density 1.27 g / ml) with 200g calcium oxide mixed by grinding for drying for ten minutes. A mixture is mixed, likewise by grinding from 5 g of Chlophen A30 and 150 g of calcium oxide / calcium hydroxide, 18.2 g n-butylamine and 51.1 g tetraethylene glycol dimethyl ether (Tetraglyme) for two minutes. Finally, 102 g of magnesium shavings ground in for two hours.
- the GC-ECD analysis confirms a 99.7% reduction in PCB.
- the presence or education other halogenated substances can be excluded.
- Pretreated PCB contaminated soil / Na / n-propylamine Treated is a PCB-contaminated, cohesive soil that previously was subjected to a washing process with water and surfactants. From the suspended fraction of this process, which is carried out with the help of Flocculants based on polyamide was precipitated do not remove residual contamination of approx. 250 ppm PCB.
- ESM 234" eccentric vibratory mill "ESM 234" (for data see Example 1). 3 kg of this PCB-contaminated soil fraction, residual moisture after thermal predrying approx. 2%, with 200 g calcium oxide mixed by grinding for drying for 30 minutes. you mixes, likewise by grinding, 150 g of n-propylamine Minute and waits 5 minutes. Finally, 200 g Sodium in the form of cylindrical pieces (each 1 to 2 cm long and thick) ground in for 45 minutes.
- the GC-ECD analysis confirms a 98.5% reduction in PCB.
- the presence or education other halogenated substances can be excluded.
- the GC-ECD analysis confirms 92% degradation of the PCB after 90 minutes after standing over 99.9% overnight. The presence or The formation of other halogenated substances can be excluded.
- argon 5.0, Linde
- the GC-MS analysis shows that the PCB has been completely degraded (Main degradation product phenylcyclohexane). The presence or education other halogenated substances can be excluded.
- Preparation of a 52% Sodium Calcium Oxide Dispersion One way to dryly distribute sodium onto calcium oxide is to grind small pieces of sodium with calcium oxide in a centrifugal ball mill for 5 to 15 minutes, as described for surface-active materials (see above). In this way, 5% of the alkali metal can be homogeneously distributed on the support.
- Useful sodium-calcium oxide dispersions are obtained if the alkali metal is first allowed to act on calcium oxide in the presence of toluene under reflux conditions and then the mixture is mixed at high speed with a high-speed stirrer or dispersant, for example Ultra-Turrax from "Janke &Kunkel" mixed.
- the method can be used very flexibly: for example, it can also be used to prepare a 25% potassium calcium oxide dispersion that looks like the sodium dispersion. A dark gray, completely homogeneous powder is obtained. However, it is pyrophoric in air and therefore cannot be used for the dechlorination of polychloroaromatics in solid or solid-liquid matrices. Such a potassium-calcium oxide dispersion would, however, have interesting applications for organic-chemical implementations on the laboratory scale with suitable protective gas and security technology.
- a centrifugal ball mill S 1 (see example 5), 15 g of sea sand (p.A.), 1 g calcium oxide-calcium hydroxide mixture, 0.25 ml n-propylamine, 0.1 g Chlophen A30, and 0.76 g magnesium shavings grind for 1 hour at maximum speed.
- polychloroaromatics such as 1,3,5-TCB can be dechlorinated much better with sodium in the presence of even small amounts of n-butylamine than in other systems investigated.
- the mechanical processing can be done by stirring in a reactor or done in a suitable mixer.
- the process according to the invention offers itself as an alternative to existing processes (Degussa sodium, NaPEG, KPEG, KPEG-PLUS), since it has a simpler and safer design and can be implemented with simple means under mild conditions. This offers the possibility of recycling contaminated oils to a large extent instead of having to burn them. Especially have transformer oils a high material and thus reuse value, which would, however, be completely written off if incinerated.
- the organic pollutants can be classified under ecological and economically favorable conditions at room temperature and in a short time Time, especially when it is in different Mixtures occur, completely eliminate them.
- the pollutants are directly in the matrix in which they are distributed are degraded by simply structured reagents.
- these can be materials that elsewhere in large quantities as residues, and thereby lead to a meaningful utilization to let.
- Detoxified materials such as Building materials or waste oils can be fed into useful recycling measures or recycled become.
- the new process consequently eliminates the disadvantages of today practiced on a larger scale during the remediation of contaminated sites Processes such as high temperature combustion avoided.
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Abstract
Description
Die Erfindung betrifft ein Verfahren zur reduktiven Dehalogenierung von halogenorganischen Stoffen in festen und flüssigen Stoffgemischen, bei welchem der Stoff oder das Stoffgemisch unter Zusatz von elementarem Alkalimetall, Erdalkalimetall, Aluminium oder Eisen als Reduktionsmittel und wenigstens einem Reagenz mit zumindest leicht aktiviertem Wasserstoff als Wasserstoffquelle behandelt wird. Es ist insbesondere zur Detoxifizierung von halogenorganisch kontaminierten Böden und anderen komplex zusammengesetzten Materialien, aber auch zur Dekontaminierung und gegebenenfalls Recyclierung flüssiger oder überwiegend flüssiger halogenorganisch belasteter Stoffe geeignet.The invention relates to a method for reductive dehalogenation of halogenated organic substances in solid and liquid Mixtures of substances in which the substance or mixture of substances under Addition of elemental alkali metal, alkaline earth metal, aluminum or iron as a reducing agent and at least one Reagent with at least slightly activated hydrogen as a hydrogen source is treated. It is particularly useful for detoxification of organically contaminated soils and others complex materials, but also for decontamination and optionally recycling liquid or predominantly liquid halogen organically contaminated substances.
Toxische polyhalogenierte organische Schadstoffe lassen sich bislang unter ökonomisch wie ökologisch gleichermaßen vorteilhaften und zukunftsweisenden Bedingungen mit keiner der heutzutage bekannten Sanierungstechnologien detoxifizieren. Häufig liegen diese Stoffe als Verunreinigungen, zudem in großen Mengen, in Böden, Fluß- oder Meeressedimenten, Klärschlämmen, Filterstäuben, Baumaterialien, Sickerölen, Altölen etc. vor, d.h. vergesellschaftet mit einer undefinierbaren Zahl von Fremd- und Begleitstoffen unterschiedlichster Eigenschaften. Die Entgiftung und Sanierung solcher komplex zusammengesetzten, heterogenen, festen, fest-flüssigen oder flüssigen Materialien und Altlasten wirft besonders umfangreiche Probleme auf.Toxic polyhalogenated organic pollutants can be So far under economically and ecologically equally advantageous and forward-looking terms with none of the nowadays known detoxification technologies. Frequently are these substances as impurities, also in large quantities, in soils, river or marine sediments, sewage sludge, filter dust, Building materials, seepage oils, waste oils etc. before, i.e. associated with an indefinable number of foreign and Accompanying substances with different properties. The detoxification and remediation of such complex, heterogeneous, solid, solid-liquid or liquid materials and contaminated sites poses particularly extensive problems.
Es gibt zwar eine Anzahl thermischer und anderer hochenergetischer Verfahren zur Zerstörung gefährlicher Kohlenwasserstoffe der oben genannten Art, auch für solche, die speziell in komplex aufgebauten Materialien verteilt vorliegen. Dazu gehören u. a. die Hochtemperaturverbrennung und die Verbrennung in Glas- oder Salzbädern. Jedes dieser Verfahren weist allerdings einige spezifische Nachteile auf, so daß Entwicklungsbedarf für alternative Technologien vorhanden ist.There are a number of thermal and other high energy ones Process for the destruction of dangerous hydrocarbons of the type mentioned above, even for those that are special in complex built materials are distributed. This includes u. a. the high temperature combustion and the combustion in Glass or salt baths. However, each of these methods points some specific disadvantages, so that development needs for alternative technologies exist.
Beispielsweise ist die Hochtemperaturverbrennung nicht nur äußerst kostenintensiv, sondern sie wirft auch neue Probleme auf. Bei polychlorierten Verbindungen führt sie etwa zur Bildung von PCDD/PCDF, die in aufwendigen nachgeschalteten Verfahrensschritten aus dem Rauchgas und den Filterstäuben entfernt und schließlich entsorgt werden müssen. Die heute gängige Art der "Entsorgung" dieser hochtoxischen Stäube besteht dabei vielfach in einer Ablagerung auf sogenannten Sondermülldeponien.For example, high temperature combustion is not just extreme costly, but also poses new problems. With polychlorinated compounds it leads to the formation of PCDD / PCDF, which are in complex downstream process steps removed from the flue gas and filter dust and eventually need to be disposed of. The current type of There is often "disposal" of these highly toxic dusts in a deposit on so-called hazardous waste landfills.
Biologische Methoden zum Abbau toxischer organischer Verbindungen in komplexen Matrizes weisen ebenfalls methodenspezifische Nachteile auf, die ihre generelle Einsetzbarkeit beschränken.Biological methods to break down toxic organic compounds in complex matrices also have method-specific ones Disadvantages that limit their general applicability.
Eine gewisse Verbreitung haben alkalimetallgestützte Verfahren gefunden, bei denen feinverteilte Metallsuspensionen oder -dispersionen in indifferenten flüssigen Medien, wie z. B. Weißöl, eingesetzt werden; sie sind in ihrer Anwendbarkeit jedoch überwiegend beschränkt auf wenige Spezialprobleme, d.h. die Detoxifizierung von relativ reinen, flüssigen Schadstoffen oder Schadstoffgemischen oder praktisch homogenen, kontaminierten, waserfreien Flüssigkeiten, wie z. B. PCB-haltigen Transformatoren- oder Motorenaltölen.Processes based on alkali metals have a certain spread found in which finely divided metal suspensions or -Dispersions in indifferent liquid media, such as. B. White oil, are used; however, they are in their applicability mostly limited to a few special problems, i.e. the detoxification of relatively pure, liquid pollutants or mixtures of pollutants or practically homogeneous, contaminated, water-free liquids, such as B. PCB-containing transformers or used engine oils.
Weitere Verfahren, bei denen allein andere unedele Metalle mit
geringer Reduktionskraft zum Einsatz kommen, wie z. B. Aluminium,
Zink, oder Eisen, sind nicht zur Detoxifizierung wichtiger
spezieller Stoffgruppen, z. B. polychlorierter Aromaten, geeignet,
weil letztere mit diesen Metallen nicht vollständig dechloriert
werden können. Nicht alle Chloratome eines polychlorierten
Moleküls werden so entfernt, und eine Detoxifizierung
wird nicht erreicht oder nur in Gegenwart toxischer Katalysatoren
oder Promotoren, beispielsweise Triphenylphosphin, Nickel
oder Nickelverbindungen, was ebenfalls aus toxikologischen
Gründen große Probleme verursacht. Die Verwendung von toxischen
Substanzen zur Dehalogenierung von Organohalogenen in Böden,
Sedimenten etc.
bedeutet lediglich den Austausch einer bestehenden Kontaminierung
durch eine andere und bietet damit keine Lösung des Problems.Other processes in which other base metals with low reducing power are used alone, such as. B. aluminum, zinc, or iron are not for detoxification of important special groups of substances, for. B. polychlorinated aromatics, suitable because the latter can not be fully dechlorinated with these metals. Not all chlorine atoms of a polychlorinated molecule are removed in this way, and detoxification is not achieved or only in the presence of toxic catalysts or promoters, for example triphenylphosphine, nickel or nickel compounds, which also causes major problems for toxicological reasons. The use of toxic substances for dehalogenation of organohalogen in soils, sediments etc.
means only the replacement of existing contamination by another and does not offer a solution to the problem.
Die für Flüssigkeiten oder Flüssig-Gemische bekannten Verfahren lassen sich nicht ohne weiteres auf Feststoffe übertragen. In Feststoffen enthaltene Halogenorganika können aufgrund der hohen Transporthemmungen bei Feststoff-Feststoff-Reaktionen häufig nur schwer von Reagentien erreicht werden. Insbesondere lassen sich polyhalogenierte organische Stoffe, die in der Umwelt als Verunreinigungen z. B. in Böden, Fluß- oder Meeressedimenten, Klärschlämmen, Filterstäuben, Baumaterialien oder Sickerölen, mithin festen oder fest-flüssigen, ausnahmslos sehr heterogenen Materialien, in großen Mengen angetroffen werden, aufgrund der komplexen Zustandsformen dieser Matrizes und den daraus resultierenden vielfältigen Transporthemmungen besonders schwer angreifen und damit nur unvollständig oder gar nicht zur Reaktion bringen.The processes known for liquids or liquid mixtures cannot be easily transferred to solids. In Halogenated organics contained in solids can be due to the high Transport inhibitions common in solid-solid reactions difficult to be reached by reagents. In particular can be polyhalogenated organic matter in the environment as impurities z. B. in soils, river or marine sediments, Sewage sludge, filter dust, building materials or Seepage oils, therefore solid or liquid, without exception very much heterogeneous materials can be found in large quantities, due to the complex state forms of these matrices and the resulting diverse transport inhibitions in particular difficult to attack and therefore only incomplete or not at all Bring reaction.
Das der Erfindung zugrundeliegende Problem besteht daher darin, ein Verfahren zur reduktiven Dehalogenierung von halogenorganischen Stoffen so auszugestalten, daß es möglich ist, verschiedene heterogene feste und flüssige Stoffgemische, insbesondere auch komplex zusammengesetzte Mischungen und kontaminierte Böden mit teilweise unbekannten anderen Inhaltsstoffen in einem universellen Verfahren weitestgehend zu dehalogenieren, wobei keine neuen schädlichen Nebenprodukte entstehen sollen.The problem underlying the invention is therefore a process for the reductive dehalogenation of organic halogen Design fabrics so that it is possible to create different ones heterogeneous solid and liquid mixtures, in particular also complex mixtures and contaminated soils with partially unknown other ingredients in one to dehalogenate universal processes as far as possible, whereby no new harmful by-products should arise.
Das Verfahren soll dabei einen möglichst einfach zu handhabenden Verfahrensablauf besitzen und relativ schnell arbeiten.The method should be as easy to use as possible Own process flow and work relatively quickly.
Zur Lösung dieses Problems ist gemäß der Erfindung bei einem Verfahren der eingangs genannten Art vorgesehen, daß der halogenorganische Stoff oder das Stoffgemisch in einer sämtliche Stoffe umfassenden Mahlung unter mechanischer Aktivierung in einem Schritt reduktiv praktisch vollständig dehalogeniert wird.To solve this problem is according to the invention in one Process of the type mentioned provided that the halogen organic Substance or the mixture of substances in one all Grinding material with mechanical activation in reductively practically completely dehalogenated in one step becomes.
Die Erfindung ist anwendbar auf Organohalogenverbindungen, die in festen oder flüssigen Fremdstoffen oder Fremdstoffgemischen enthalten sind, aber auch als feste oder flüssige Reinstoffe oder in Gemischen aus diesen vorliegen können. Diese Stoffe oder Stoffgemische werden, was das Grundverfahren angeht, in nur einem einzigen Verfahrensschritt behandelt, d.h. es werden unter milden Reaktionsbedingungen alle Komponenten, darunter wenigstens ein Reduktionsmittel und eine Wasserstoffquelle, innig vermischt.The invention is applicable to organohalogen compounds which in solid or liquid foreign substances or foreign substance mixtures are included, but also as solid or liquid pure substances or can be present in mixtures of these. These substances or mixtures of substances, as far as the basic process is concerned, in dealt with in a single process step, i.e. it will all components including mild reaction conditions at least one reducing agent and one hydrogen source, intimate mixed.
Das Verfahren umfaßt die Vermahlung der Reaktionspartner unter Eintrag eines mehr oder weniger großen Betrages an mechanischer Energie. Hierdurch wird zumindest eine Feinverteilung in sehr kleine Partikel und dadurch eine intensive Vermischung sämtlicher Bestandteile des Gemisches bewirkt, so daß zwischen den eingesetzten Reagentien und den Organohalogenen im zeitlichen Mittel ein intensiver Kontakt hergestellt wird und diese dadurch zur gewünschten Reaktion gebracht werden. Zusätzlich wird die Reaktivität der festen Bestandteile durch die Feinverteilung aufgrund von oberflächenphysikalischen Effekten gesteigert.The process includes grinding the reactants under Entry of a more or less large amount of mechanical Energy. As a result, at least a fine distribution in very small particles and therefore an intensive mixing of all Components of the mixture causes so that between the used reagents and the organohalogen in time Intensive contact is established and this means be brought to the desired reaction. In addition, the reactivity of the solid components through the fine distribution increased due to surface physical effects.
Darüber hinaus wird bei genügendem Energieeintrag die Reaktivität stark erhöht. Die mechanisch aktivierte Behandlung in fester oder fest-flüssiger Phase scheint besonders geeignet für' den vollständigen oder nahezu vollständigen Abbau polyhalogenierter Verbindungen mit Hilfe von Wasserstoffdonoren.In addition, the reactivity becomes with sufficient energy input greatly increased. The mechanically activated treatment in solid or solid-liquid phase seems particularly suitable for ' the complete or almost complete degradation of polyhalogenated Compounds using hydrogen donors.
Durch die Steigerung der Reaktivität von Feststoffen infolge spezieller mechanischer Aktivierung, können auch Stoffe, die in komplexen festen oder fest-flüssigen Materialien verteilt sind, chemisch angegriffen und effizient umgesetzt werden. Folglich lassen sich auch organische Schadstoffe, die in festen Matrizes wie Böden, Sedimenten usw. vorliegen, durch mittels mechanischer Aktivierung unterstützte Abbaureaktionen gezielt zerstören.By increasing the reactivity of solids as a result special mechanical activation, can also substances in complex solid or solid-liquid materials are distributed, are attacked chemically and implemented efficiently. consequently organic pollutants can also be found in solid matrices such as soils, sediments, etc., by means of mechanical Activation of targeted degradation reactions.
Im Vergleich zur Hochtemperaturverbrennung und anderen hochenergetischen Verfahren hat das erfindungsgemäße Verfahren den Vorteil, daß es unter milden Reaktionsbedingungen, d.h. im allgemeinen bei Raumtemperatur und unter Normaldurck, durchführbar und technisch weitaus weniger aufwendig ist. Es ist daher auch für kleine mobile Anlagen auslegbar. Ein weiterer Vorteil besteht darin, daß ggf. ein Recycling oder eine Weiterverwertung der zu dekontaminierenden Materialien möglich ist, die bei einer Verbrennung grundsätzlich vernichtet würden.Compared to high temperature combustion and other high energy The method according to the invention has the Advantage that under mild reaction conditions, i.e. in general at room temperature and under normal pressure, feasible and is technically far less complex. It is therefore also can be designed for small mobile systems. Another advantage is there in the fact that there may be recycling or reuse of the materials to be decontaminated is possible with a Combustion would be destroyed in principle.
Das Verfahren arbeitet grundsätzlich bei niedrigen Temperaturen, vorzugsweise bei Raumtemperatur unter Normaldruck. Dabei ist es jedoch möglich, daß durch den intensiven Eintrag mechanischer Energie und/oder die bei der Dehalogenierung frei werdende Reaktionswärme im Verlaufe des Verfahrens eine Erwärmung eintritt.The process basically works at low temperatures, preferably at room temperature under normal pressure. there it is possible, however, that due to the intensive mechanical input Energy and / or that released during dehalogenation Heat of reaction in the course of the process a warming entry.
Das metallische Reduktionsmittel wird vorteilhaft wenigstens in geringem Überschuß eingesetzt. Die erforderliche Menge an Reduktionsmittel kann in Vorversuchen an Proben des konkreten Dekontaminierungsobjekts bestimmt werden.The metallic reducing agent is advantageously at least in little excess used. The required amount of reducing agent can be carried out in preliminary tests on samples of the specific decontamination object be determined.
Als Reduktionsmittel sind allgemein unedele Metalle, und zwar im besonderen Alkalimetalle, Erdalkalimetalle, Aluminium und Eisen vorgesehen. Unter den Alkalimetallen sind Natrium und Kalium bevorzugt, unter den Erdalkalien Magnesium und Calcium. Unter Anwendung der Prinzipien dieser Erfindung können jedoch auch andere unedle Metalle eingesetzt weren, wobei zu beachten ist, daß die Bildung toxischer Produkte vermieden werden sollte.Common metals are reducing agents, namely in particular alkali metals, alkaline earth metals, aluminum and Iron provided. Among the alkali metals are sodium and potassium preferred, among the alkaline earths magnesium and calcium. However, using the principles of this invention other base metals can also be used, taking into account is that the formation of toxic products should be avoided.
Die reduktive Entfernung von Halogenen aus halogenorganischen Stoffen mit Hilfe von unedlen Metallen, insbesondere Alkalimetallen, ist im Prinzip seit langem bekannt und mechanistisch gut untersucht. Bis heute ist jedoch nur unzureichend erkannt worden, daß sich einige dieser Reaktionen auch zur Eliminierung von toxischen organischen Stoffen in unserer Umwelt nutzen lassen. Nach der Erfindung wird die Reduktion mit dem Metall'außerdem durch die Zuführung mechanischer Energie und Zugabe wenigstens eines Wasserstoffdonors unterstützt.Reductive removal of halogens from organic halogen Fabrics using base metals, in particular In principle, alkali metals have long been known and mechanistic well examined. To date, however, has been insufficient It has been recognized that some of these reactions can also be used for elimination of toxic organic matter in our environment let use. According to the invention, the reduction with Metal 'by the addition of mechanical energy and Supported addition of at least one hydrogen donor.
Überraschend ist, daß polychlorierte Aromaten in flüssigen, festen oder fest-flüssigen Stoffen auch mit Magnesium in einer Eintopfreaktion bei Raumtemperatur reduktiv vollständig dechlorierbar sind. U.a. wurden Magnesium-Späne eingesetzt, die im Laboratorium wie auch in der Industrie seit Jahrzehnten in großem Umfang zur Erzeugung von Grignard-Reagentien verwendet werden. Im Gegensatz zur landläufigen Auffassung, daß Grignard-Reaktionen praktisch nur in speziellen, hochgereinigten, toxikologisch bedenklichen und leicht entzündlichen Lösungsmitteln, wie z. B. Diethylether oder Tetrahydrofuran, dazu unter striktem Feuchtigkeitsausschluß, mit Schutzgas und unter Einsatz spezieller Katalysatoren durchführbar sind, zeigte sich beispielsweise, daß in einer rein flüssigen Phase allein durch Auflösung des Metalls in Methanol, in einer festen Matrix durch Anwendung einer Kugelmahlung unter geringem Zusatz von Methanol, Ethanol oder niedermolekularen primären Aminen die Durchführung von miteinander gekoppelten Grignard- und Zerewitinoff-Reaktionen in einer festen Sandmatrix gelang.It is surprising that polychlorinated aromatics in liquid, solid or solid-liquid substances also with magnesium in one One-pot reaction can be completely dechlorinated at room temperature are. Et al Magnesium chips were used, which in the Laboratory as well as in industry for decades on a large scale Scope used to generate Grignard reagents. Contrary to popular belief that Grignard reactions practically only in special, highly cleaned, toxicologically questionable and highly flammable solvents, such as As diethyl ether or tetrahydrofuran, to this under strict Exclusion of moisture, with protective gas and under use special catalysts are feasible, for example, that in a purely liquid phase by itself Dissolution of the metal in methanol, in a solid matrix Application of ball milling with the slight addition of methanol, Performing ethanol or low molecular weight primary amines of coupled Grignard and Zerewitinoff reactions succeeded in a solid sand matrix.
Als Wasserstoffquelle mit zumindest leicht aktiviertem Wasserstoff werden vorzugsweise Alkohole, Ether, Polyether, Amine oder Hydroxide, wie z. B. Calciumhydroxid, oder Metall- oder Nichtmetallhydride wie z.B. Calciumhydrid, Natriumhydrid, Natriumboranat, Lithiumalanat, Trialkylsilane, Polyalkylhydrogensiloxane, einzeln oder in Kombination, eingesetzt.As a hydrogen source with at least slightly activated hydrogen are preferably alcohols, ethers, polyethers, amines or hydroxides, such as. As calcium hydroxide, or metal or Non-metal hydrides such as Calcium hydride, sodium hydride, sodium boranate, Lithium alanate, trialkylsilanes, polyalkylhydrogensiloxanes, used individually or in combination.
Aus der Gruppe der Alkohole können beispielsweise niedermolekulare aliphatische Alkohole verwendet werden. Unter niedermolekularen Alkoholen sind beispielsweise aliphatische Alkohole mit 1 bis 7 Kohlenstoffatomen zu verstehen wie Methanol, Ethanol, Propanol, Isopropanol, Butanol, sek.- und tert.-Butanol, Pentanol, Hexanol, Heptanol, Cyclopropanol, Cyclobutanol, Cyclopentanol, Cyclohexanol, Cycloheptanol, 2-Methylcyclopropanol, Cyclopropylmethanol, Polyalkylenglykole, einfach veretherte Polyalkylenglykole, Aminoalkohole, Polyole, wie z.B. Ethylenglykol, Glycerin, Pentaerythrit u.a.m.From the group of alcohols, for example, low molecular weight aliphatic alcohols can be used. Under Low molecular weight alcohols are, for example, aliphatic To understand alcohols with 1 to 7 carbon atoms such as methanol, Ethanol, propanol, isopropanol, butanol, sec- and tert-butanol, Pentanol, hexanol, heptanol, cyclopropanol, cyclobutanol, Cyclopentanol, cyclohexanol, cycloheptanol, 2-methylcyclopropanol, Cyclopropylmethanol, polyalkylene glycols, simply etherified polyalkylene glycols, amino alcohols, polyols, such as. Ethylene glycol, glycerin, pentaerythritol, etc.
Aus der Gruppe der Ether können beispielsweise einfache symmetrische oder asymmetrische aliphatische Ether, cyclische Ether oder Polyether verwendet werden. Beispiele umfassen Diethylether, Propylether, Isopropylether, n-Butylether sowie dimere oder trimere Polyether, Coronanden, Cryptanden, Spheranden, Etheramine, wie z.B. 2-Methoxyethylamin usw.Simple symmetrical groups, for example, can be selected from the ether group or asymmetric aliphatic ethers, cyclic ethers or polyether can be used. Examples include diethyl ether, Propyl ether, isopropyl ether, n-butyl ether and dimers or trimeric polyethers, coronands, cryptands, spherands, Ether amines, e.g. 2-methoxyethylamine etc.
Aus der Gruppe der Amine sind aliphatische Amine und darunter niedere primäre oder sekundäre aliphatische Amine bevorzugt. Beispiele für geeignete Amine sind: Primäre, sekundäre oder tertiäre aliphatische und alicyclische Mono- oder Polyamine, Methylamin, Ethylamin, 1- und 2-Propylamin, 1- und 2-Butylamin, Ethylendiamin, Tri-, Tetra-, Penta-, Hexamethylendiamin, Dimethylamin, Diethylamin, Di-n-propylamin, Cyclopentyl- und Cyclohexylamin, Stickstoffheterocyclen und Perhydrostickstoffheterocyclen, z.B. Piperidin, 1-(2-Aminoethyl)-piperazin, 1-(2-Aminoethyl)-pyrrolidin und 1-(2-Aminoethyl)-piperidin, 4-(2-Aminoethyl)-morpholin. Ferner eignet sich für denselben Zweck flüssiger Ammoniak.From the group of amines are aliphatic amines and below lower primary or secondary aliphatic amines are preferred. Examples of suitable amines are: primary, secondary or tertiary aliphatic and alicyclic mono- or polyamines, Methylamine, ethylamine, 1- and 2-propylamine, 1- and 2-butylamine, Ethylenediamine, tri-, tetra-, penta-, hexamethylenediamine, dimethylamine, Diethylamine, di-n-propylamine, cyclopentylamine and cyclohexylamine, Nitrogen heterocycles and perhydro nitrogen heterocycles, e.g. Piperidine, 1- (2-aminoethyl) piperazine, 1- (2-aminoethyl) pyrrolidine and 1- (2-aminoethyl) piperidine, 4- (2-aminoethyl) morpholine. It is also suitable for the same purpose liquid ammonia.
Alternativ zu den Aminen kommen auch bestimmte Amide in betracht. Verwendet werden können beispielsweise: 1,3 Dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidon (Dimethylpropylenharnstoff, DMPU), 1,3-Dimethyl-2-imidazolidinon (N,N-Dimethylethylenharnstoff, DMEU), 1-Methyl-2-pyrrolidon (NMP), 1-Ethyl-2-pyrrolidon, N,N-Diethylacetamid, N,N-Diethylpropionamid, N,N-Diethylisobutyramid. As an alternative to the amines, certain amides can also be considered. For example: 1,3 dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidone can be used (Dimethylpropylene, DMPU), 1,3-dimethyl-2-imidazolidinone (N, N-dimethylethylene urea, DMEU), 1-methyl-2-pyrrolidone (NMP), 1-ethyl-2-pyrrolidone, N, N-diethylacetamide, N, N-diethylpropionamide, N, N-diethylisobutyramide.
Auf die gesonderte Zugabe einer Wasserstoffquelle kann verzichtet werden, wenn bekannt ist, daß sich in dem zu behandelnden Gemisch bereits eine als Wasserstoffquelle geeignete Substanz in ausreichender Menge befindet.There is no need to add a hydrogen source separately if it is known that the subject to be treated Mixture already a substance suitable as a hydrogen source is in sufficient quantity.
Die erfindungsgemäße mechanische Aufbereitung kann in einem Vermahlen in einer mechanischen Mühle bestehen, beispielsweise einer Kugelmühle, einer Hammermühle oder einer Schwingmühle. Bei diesem Vermahlen können zusätzlich Mahlhilfen eingesetzt werden. Als Mahlhilfen kommen allgemein Stoffe zum Einsatz, die die Oberflächenenergie und/oder die plastische Deformation von Feststoffen bei Einwirkung mechanischer Energie reduzieren können. Hierzu zählen beispielweise: Oberflächenaktive Stoffe in verschiedenen Zustands- oder Aufbereitungsformen, wie z.B. quartäre Ammoniumverbindungen, die nicht nur in Reinsubstanz eingesetzt werden können, sondern auch immobilisiert an inerten, oberflächenaktiven Trägern, wie Schichtsilikaten, Tonen (sog. "organophilen Bentoniten") ferner substituierte Alkylimidazoline und Sulfosuccinamide, Fettsäuren, Fettsäureester und - amide, primäre, sekundäre und tertiäre Alkyl- und Fettamine mit einer oder mehreren Amingruppen, alicyclische Amine, wie beispielsweise Cyclohexylamin, Polyhydrostickstoffheterocyclen, wie z.B. Piperidin (Hexahydropyridin) Mono-, Di- oder Trialkanolamine, einfache Glykole, Polyalkylenglykole, wie z.B. Polyethylen- und Polypropylenglykole, und deren Mono- oder Diether, Organosliziumverbindungen, insbesondere Silikone, spezielle für den Zweck geeignete anorganische Salze, z.B. Aluminiumchlorid.The mechanical preparation according to the invention can be carried out in one Ground in a mechanical mill, for example a ball mill, hammer mill or vibrating mill. Additional grinding aids can be used for this grinding become. Substances are generally used as grinding aids the surface energy and / or the plastic deformation of Can reduce solids when exposed to mechanical energy. These include, for example: Surface-active substances in various forms of condition or preparation, e.g. quaternary ammonium compounds that are not only in pure substance can be used, but also immobilized on inert, surface-active carriers, such as layered silicates, clays (so-called "organophilic bentonites") also substituted alkylimidazolines and sulfosuccinamides, fatty acids, fatty acid esters and - amides, primary, secondary and tertiary alkyl and fatty amines with one or more amine groups, alicyclic amines, such as, for example Cyclohexylamine, polyhydrogen nitrogen heterocycles, such as. Piperidine (hexahydropyridine) mono-, di- or trialkanolamines, simple glycols, polyalkylene glycols, e.g. polyethylene and polypropylene glycols, and their mono- or diether, Organosilicon compounds, especially silicones, special for inorganic salts suitable for the purpose, e.g. Aluminum chloride.
Der mechanisch bereits aktivierte Reaktionsablauf kann durch den zusätzlichen Einsatz von Reaktionsbeschleunigern weiter verstärkt bzw. beschleunigt werden. Als Reaktionsbeschleuniger können Stoffe verwendet werden, die in der Lage sind, unedle Metalle, insbesondere Alkali- und Erdalkalimetalle, teilweise oder vollständig zu lösen und/oder deren Dissoziation in Metallkationen und -anionen und/oder die Bildung solvatisierter Elektronen zu befördern und/oder metallorganische Verbindungen, wie z.B. alkali- oder erdalkalimetallorganische Verbindungen, zu solvatisieren und/oder zu stabilisieren, wie z.B. flüssiger Ammoniak, primäre, sekundäre oder tertiäre aliphatische und alicyclische Mono- oder Polyamine, Polyhydrostickstoffheterocyclen, aliphatische und cyclische Monoether, Podanden, Coronanden, Cryptanden, Spheranden, Etheramine, wie z.B. 2-Methoxyethylamin, Amide, wie z.B. 1,3-Dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidon (Dimethylpropylen-harnstoff, DMPU), 1,3-Dimethyl-2-imidazolidinon (N,N-Dimethylethylenharnstoff, DMEU), 1-Methyl-2-pyrrolidon (NMP), 1-Ethyl-2-pyrrolidon, N,N-Diethylacetamid, N,N-Diethylpropionamid, N/N-Diethylisobutyramid.The mechanically activated reaction process can be carried out by the additional use of reaction accelerators be reinforced or accelerated. As a reaction accelerator can be used fabrics that are able to base Metals, especially alkali and alkaline earth metals, partially or completely dissolve and / or dissociate them in metal cations and anions and / or the formation of solvated To transport electrons and / or organometallic compounds, such as. alkali or alkaline earth metal organic compounds, to solvate and / or stabilize, e.g. liquid Ammonia, primary, secondary or tertiary aliphatic and alicyclic mono- or polyamines, polyhydrogen nitrogen heterocycles, aliphatic and cyclic monoethers, podands, coronands, Cryptands, spherands, ether amines, e.g. 2-methoxyethylamine, Amides such as -pyrimidone, 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) (Dimethyl propylene urea, DMPU), 1,3-dimethyl-2-imidazolidinone (N, N-dimethylethylene urea, DMEU), 1-methyl-2-pyrrolidone (NMP), 1-ethyl-2-pyrrolidone, N, N-diethylacetamide, N, N-diethylpropionamide, N / N-diethylisobutyramide.
Die Mahlhilfe(n) und/oder Reaktionsbeschleuniger können dem Stoff oder Stoffgemisch in einem nachgeschalteten Schritt, d.h. gesondert nach Zugabe der Reaktanden, zugegeben und mechanisch eingearbeitet werden.The grinding aid (s) and / or reaction accelerator can Substance or mixture of substances in a subsequent step, i.e. separately after adding the reactants, added and mechanically be incorporated.
Das metallische Reduktionsmittel kann einerseits dem Gemenge direkt in reiner Form zugegeben werden. Dies bietet sich insbesondere bei den Erdalkalimetallen an, die an der Luft weniger reaktiv sind als die Alkalimetalle, z.B. bei Magnesiumspänen.The metallic reducing agent can on the one hand be mixed can be added directly in pure form. This is particularly useful alkaline earth metals, less in the air are more reactive than the alkali metals, e.g. with magnesium chips.
Alternativ kann das metallische Reduktionsmittel in einer Zubereitung dispergiert oder suspendiert vorliegen, beispielsweise dispergiert in einer nicht oxidierenden Flüssigkeit oder der flüssigen Wasserstoffquelle. Vorteilhaft zu verwenden sind Dispersionen aus dem gewählten Metall in Weißöl, Paraffin oder in Ethern, auch Polyethern wir Diglyme, Triglyme, Tetraglyme, Polyethylenglykol und Polyethylenglykolderivaten, verätherten Diund Polyglymen.Alternatively, the metallic reducing agent can be in a preparation are dispersed or suspended, for example dispersed in a non-oxidizing liquid or the liquid hydrogen source. Dispersions are advantageous to use from the selected metal in white oil, paraffin or in Ethers, including polyethers such as diglyme, triglyme, tetraglyme, polyethylene glycol and polyethylene glycol derivatives, etherified diund Polyglymen.
Weiterhin kann das metallische Reduktionsmittel mit einem festen Träger vermengt bzw. auf diesen aufgebracht werden. Als vorteilhafte Zubereitung hat sich z.B. eine Mischung aus Alkalimetall, insbesondere Natrium, mit Calciumsilicat oder Calciumoxid erwiesen. Furthermore, the metallic reducing agent can be mixed with a solid Carrier mixed or applied to this. As advantageous preparation has e.g. a mixture of alkali metal, especially sodium, with calcium silicate or Calcium oxide proven.
Es wurde gefunden, daß sich die Kugelmahlung auch zur Reaktivitätssteigerung der Metalle allein in einem isolierten Arbeitsschritt durch mechanische Feinverteilung eignet, insbesondere zur Feinverteilung von Alkalimetallen auf oberflächenaktiven festen Inertträgerstoffen. Gegenüber herkömmlichen Verfahrensweisen, bei denen in einer Spezialapparatur unter Rühren bei hohen Temperaturen geschmolzenes Alkalimetall auf feste Inertträgerstoffe aufgebracht wird, bietet die neue Methode den Vorteil, daß bei Raumtemperatur gearbeitet wird und die Vorgehensweise einfacher und schneller ist, indem man das Alkalimetall und das Trägermaterial einfach zusammen in ein Mahlgefäß oder die Mühle füllt und innerhalb weniger Minuten zu einer homogenen, feinpulverigen Dispersion vermahlt.It has been found that ball milling is also used to increase reactivity of the metals alone in an isolated step suitable by mechanical fine distribution, in particular for the fine distribution of alkali metals on surface-active solid inert carriers. Compared to conventional procedures, in which in a special apparatus with stirring high temperature molten alkali metal on solid inert carriers applied, the new method offers the advantage that you work at room temperature and the procedure is easier and faster by using the alkali metal and the carrier material simply together in a grinding vessel or the mill fills and within a few minutes to a homogeneous, finely powdered dispersion.
Wahlweise kann das Verfahren somit auch zweistufig gestaltet werden, wobei z.B. durch Kugelmahlung in einem ersten Schritt vorproduziertes feinverteiltes Metall erst in einem zweiten Schritt unter Zusatz von Reaktionsbeschleunigern sowie ggf. weiteren Zuschlagsstoffen vermahlen wird. Weiterhin ist es möglich, auch auf konventionellem Weg gewonnene Alkalimetalldispersionen, d.h. sowohl Dispersionen in inerten Fluiden als auch auf inerten festen Trägern, mit Reaktionsbeschleunigern und ggf. weiteren Zuschlagsstoffen in einen organohalogenhaltigen Feststoff einzumahlen oder einzumischen und dadurch die Enthalogenierung zu bewirken.The method can thus also be designed in two stages , e.g. by ball milling in a first step pre-produced finely divided metal only in a second Step with the addition of reaction accelerators and if necessary other additives are ground. It is also possible also alkali metal dispersions obtained by conventional means, i.e. both dispersions in inert fluids as well on inert solid supports, with reaction accelerators and If necessary, other additives in an organohalogenous Solid grinding or mixing and thereby dehalogenation to effect.
Das Verfahren kann auch zur Ergänzung anderer Verfahren, z.B. von Waschprozessen, herangezogen oder mit diesen kombiniert werden. Eine vorherige Aufbereitung kontaminierter Böden mit Calciumoxid (Ätzkalk oder Branntkalk), die auch bei anderen Aufbereitungsverfahren bekannt ist und u.a. zur Trocknung des Gemisches dient, kann fallweise sinnvoll sein.The method can also be used to complement other methods, e.g. of washing processes, used or combined with these become. A previous treatment of contaminated soils with Calcium oxide (quicklime or quicklime), which is also found in others Preparation process is known and among other things to dry the Mixture can be useful in some cases.
Das Verfahren kann diskontinuierlich, batchweise, oder kontinuierlich durchgeführt werden. The process can be carried out batchwise, batchwise or continuously be performed.
Bei der diskontinuierlichen Arbeitsweise werden zunächst alle Reaktionspartner, d.h. wenigstens der zu behandelnde Stoff oder das Gemisch/Gemenge, das metallische Reduktionsmittel und der Wasserstoffdonor, in ein Gerät gegeben, das eine mechanische Bearbeitung ermöglicht, wie eine Mühle oder einen (dynamischen) Mischer. Bei der Dekontaminierung in festen oder fest-flüssigen Medien wird eher eine Mühle, z.B. eine Kugelmühle, eine Hammermühle oder eine Schwingmühle verwendet werden, während bei flüssigen Systemen ein Mischer genügen kann. Als Mischer sind beispielsweise Reib-, Schnecken- oder Walzenmischer geeignet.In the discontinuous mode of operation, first of all Reaction partner, i.e. at least the substance to be treated or the mixture / mixture, the metallic reducing agent and the Hydrogen donor, placed in a device that is mechanical Machining enables, like a mill or a (dynamic) Mixer. When decontaminating in solid or solid-liquid Media becomes more of a mill, e.g. a ball mill, a hammer mill or a vibratory mill can be used while at a mixer can be sufficient for liquid systems. As a mixer For example, friction, screw or roller mixers are suitable.
Es ist ein Vorteil der Erfindung, daß die Bearbeitung in nur einem Schritt erfolgen kann, wobei die Reaktionspartner nacheinander oder allmählich zugegeben werden können. Eine kontinuierliche Verfahrensführung könnte beispielsweise in einer Schneckenmühle oder einem Schneckenmischer erfolgen.It is an advantage of the invention that the machining in only one step can take place, the reactants being sequential or can be added gradually. A continuous one Procedures could, for example, in a Screw mill or a screw mixer.
Im folgenden wird das Verfahren anhand einiger Beispiele näher erläutert.In the following, the process is illustrated using a few examples explained.
In einer Exzenter-Schwingmühle "ESM 234", Fa. Siebtechnik, Mülheim
a. d. Ruhr, die zu 80% mit Stahlkugeln (Durchmesser je 20
mm) gefüllt ist, werden 3,8 kg Quarzsand (Schüttgewicht 1,27
g/ml) mit 180 g Calciumoxid zwecks Trocknung für zehn Minuten
durch Vermahlen vermengt. Man mischt, gleichfalls durch Vermahlen,
10,2 g n-Butylamin eine Minute lang ein. Zuletzt werden
156,7 g einer 26%igen Natrium-Calciumsilikat-Dispersion zugefügt
und für 30 Minuten mit dem kontaminierten Modellboden vermahlen.In an eccentric vibratory mill "ESM 234", from Siebtechnik, Mülheim
a. d. Ruhr, 80% with steel balls (
Der Modellboden war künstlich durch Zugabe einer Mischung aus 5 g Chlophen A30 und 150 g Calciummoxid/Calciumhydroxid, die fünf Minuten lang eingemahlen wurden, kontaminiert worden. The model floor was artificial by adding a mixture of 5 g of Chlophen A30 and 150 g of calcium oxide / calcium hydroxide, the five Minutes, were contaminated.
Die GC-ECD-Analyse (interner Standard: Decachlorbiphenyl) einer Modellbodenprobe nach dieser Behandlung belegt einen Abbau der PCB um 99,7%. Ferner kann aufgrund der GC-Befunde die Anwesenheit bzw. Bildung anderer halogenierter Stoffe ausgeschlossen werden.GC-ECD analysis (internal standard: decachlorobiphenyl) of one Model soil sample after this treatment shows that the PCB by 99.7%. Furthermore, the presence may be due to the GC findings or formation of other halogenated substances excluded become.
Herstellung der 25%igen Natrium-Calciumsilikat-Dispersion: In
einer Fliehkraftkugelmühle S1, Fa. Retsch, Haan, 500 ml-Edelstahl-Mahlbecher
mit 3 Edelstahlkugeln (Durchmesser je 20
mm) und Edelstahl-Verschlußdeckel mit Gummidichtring, werden
150 g oberflächenaktives Calciumsilikat (z.B. Fa. "Cape-Boards
Siborit" GmbH, Lüneburg, oder Xonolit, Fa. "Eternit" SA, Kapelle
Op den Bor, Belgien), versetzt mit 50 g Natriumstücken und
mit Argon überschichtet für 5 bis 15 Minuten bei höchster Drehzahl
(≈ 500min-1) vermahlen. Man erhält ein dunkelgraues, homogenes,
hochreaktives Pulver. Als weiterhin besonders günstige
Trägermaterialien haben sich wasserfreie Tone, z.B. Tixogel
oder Tixosorb der Fa. Südchemie, Moosburg, erwiesen. Production of the 25% sodium calcium silicate dispersion : 150 g of surface-active calcium silicate (in a centrifugal ball mill S1, Retsch, Haan, 500 ml stainless steel grinding bowl with 3 stainless steel balls (
In einer Exzenter-Schwingmühle "ESM 234" (Daten s. Bsp.1) werden 3,8 kg Quarzsand (Schüttgewicht 1,27 g/ml) mit 200g Calciumoxid zwecks Trocknung für zehn Minuten durch Vermahlen vermengt. Man mischt, gleichfalls durch Vermahlen, eine Mischung aus 5 g Chlophen A30 und 150 g Calciumoxid/Calciumhydroxid, 18,2 g n-Butylamin und 51,1 g Tetraethylenglykoldimethylether (Tetraglyme) zwei Minuten lang ein. Zuletzt werden 102 g Magnesium-Späne zwei Stunden lang eingemahlen.In an eccentric vibratory mill "ESM 234" (data see example 1) 3.8 kg quartz sand (bulk density 1.27 g / ml) with 200g calcium oxide mixed by grinding for drying for ten minutes. A mixture is mixed, likewise by grinding from 5 g of Chlophen A30 and 150 g of calcium oxide / calcium hydroxide, 18.2 g n-butylamine and 51.1 g tetraethylene glycol dimethyl ether (Tetraglyme) for two minutes. Finally, 102 g of magnesium shavings ground in for two hours.
Die GC-ECD-Analyse (interner Standard: Decachlorbiphenyl) belegt einen Abbau der PCB um 99,7%. Die Anwesenheit bzw. Bildung anderer halogenierter Stoffe kann ausgeschlossen werden. The GC-ECD analysis (internal standard: decachlorobiphenyl) confirms a 99.7% reduction in PCB. The presence or education other halogenated substances can be excluded.
Vorbehandelter PCB-kontaminierter Boden/Na/n-Propylamin Behandelt wird ein PCB-kontaminierter, bindiger Boden, der zuvor einem Waschprozeß mit wasser und Tensiden unterworfen wurde. Aus der Schwebfraktion dieses Prozesses, die mit Hilfe von Flockungsmitteln auf Polyamidbasis ausgefällt wurde, ließ sich eine Restkontamination von ca. 250 ppm PCB nicht mehr entfernen. In einer Exzenter-Schwingmühle "ESM 234" (Daten s. Bsp.1). werden 3 kg dieser PCB-kontaminierten Bodenfraktion, Restfeuchte nach thermischer Vortrocknung ca. 2 %, mit 200 g Calciumoxid zwecks Trocknung für 30 Minuten durch vermahlen vermengt. Man mischt, gleichfalls durch Vermahlen, 150 g n-Propylamin eine Minute lang ein und wartet noch 5 Minuten. Zuletzt werden 200 g Natrium in Form zylindrischer Stücke (jeweils 1 bis 2 cm lang und dick) 45 Minuten lang eingemahlen.Pretreated PCB contaminated soil / Na / n-propylamine Treated is a PCB-contaminated, cohesive soil that previously was subjected to a washing process with water and surfactants. From the suspended fraction of this process, which is carried out with the help of Flocculants based on polyamide was precipitated do not remove residual contamination of approx. 250 ppm PCB. In an eccentric vibratory mill "ESM 234" (for data see Example 1). 3 kg of this PCB-contaminated soil fraction, residual moisture after thermal predrying approx. 2%, with 200 g calcium oxide mixed by grinding for drying for 30 minutes. you mixes, likewise by grinding, 150 g of n-propylamine Minute and waits 5 minutes. Finally, 200 g Sodium in the form of cylindrical pieces (each 1 to 2 cm long and thick) ground in for 45 minutes.
Die GC-ECD-Analyse (interner Standard: Decachlorbiphenyl) belegt einen Abbau der PCB um 98,5%. Die Anwesenheit bzw. Bildung anderer halogenierter Stoffe kann ausgeschlossen werden.The GC-ECD analysis (internal standard: decachlorobiphenyl) confirms a 98.5% reduction in PCB. The presence or education other halogenated substances can be excluded.
Aufgrund der hohen Polyamid-Beimengungen mußte eine deutlich höhere Natrium-Portion eingesetzt_werden, als dies für die vollständige Dechlorierung der PCB allein erforderlich gewesen wäre.Due to the high polyamide admixtures, one had to be clear higher sodium portion than are used for the complete dechlorination of the PCB alone was required would.
Vorbehandelter PCB-kontaminierter Boden/Na/Tetraglyme In einer Exzenter-Schwingmühle "ESM 234" (Daten s. Bsp.1) werden 3 kg der in Beispiel 4 eingesetzten, PCB-kontaminierten Bodenfraktion aus einem Waschprozeß, Restfeuchte nach thermischer Vortrocknung ca. 2 %, mit 200 g Calciumoxid zwecks Trocknung für 30 Minuten durch Vermahlen vermengt. Man mischt, gleichfalls durch Vermahlen, 100 g Tetraglyme eine Minute lang ein. Zuletzt werden 200 g Natrium (zylindrische Stücke, 1 bis 2 cm lang und dick) 90 Minuten lang eingemahlen, und man läßt dann den Inhalt der Mühle über Nacht ohne weitere Maßnahmen stehen.Pretreated PCB contaminated soil / Na / tetraglyme In an eccentric vibratory mill "ESM 234" (data see example 1) 3 kg of the PCB-contaminated soil fraction used in Example 4 from a washing process, residual moisture after thermal Predrying approx. 2%, with 200 g calcium oxide for drying mixed by grinding for 30 minutes. You mix likewise by grinding, 100 g of tetraglyme for one minute on. Finally, 200 g of sodium (cylindrical pieces, 1 to 2 cm long and thick) ground in for 90 minutes and allowed to then the contents of the mill overnight without further action stand.
Die GC-ECD-Analyse (interner Standard: Decachlorbiphenyl) belegt einen Abbau der PCB nachg 90 Minuten um 92 %, nach Stehenlassen über Nacht von mehr als 99,9 %. Die Anwesenheit bzw. Bildung anderer halogenierter Stoffe kann ausgeschlossen werden.The GC-ECD analysis (internal standard: decachlorobiphenyl) confirms 92% degradation of the PCB after 90 minutes after standing over 99.9% overnight. The presence or The formation of other halogenated substances can be excluded.
0,05 g Chophen A30 werden mit 10 g Seesand p.A., 0,25 g Triglyme
und 0,52 g Ethanol (=19,1 Äquivalente pro Gesamtchlor) in
einer Fliehkraftkugelmühle S1, Fa. Retsch, Haan, 50 ml-Edelstahl-Mahlbecher
mit 3 Edelstahlkugeln (Durchmesser je 10
mm) und Edelstahl-Verschlußdeckel mit Gummidichtring, für eine
Minute bei höchster Drehzahl (≈500 min-1) vermahlen. Nach 1 Minute
Mahldauer entnimmt man das Mahlgefäß aus der Mühle, öffnet
es und spült es unter einem umgestülptem Trichter mit Argon
(5,0, Fa. Linde). Dann wird rasch unter einer Argon-Dusche Natrium-Calciumoxid-Dispersion
(52 % Na) hinzugefügt, noch kurz
mit Argon weiter begast und schließlich der Mahlbecherdeckel
wieder aufgesetzt. Die Mahldauer beträgt eine Stunde bei höchster
Drehzahl.0.05 g Chophen A30 are mixed with 10 g sea sand pA, 0.25 g triglyme and 0.52 g ethanol (= 19.1 equivalents per total chlorine) in a centrifugal ball mill S1, from Retsch, Haan, 50 ml stainless steel grinding bowl with 3 stainless steel balls (
Die GC-MS-Analyse belegt einen vollständigen Abbau der PCB (Hauptabbauprodukt Phenylcyclohexan). Die Anwesenheit bzw. Bildung anderer halogenierter Stoffe kann ausgeschlossen werden.The GC-MS analysis shows that the PCB has been completely degraded (Main degradation product phenylcyclohexane). The presence or education other halogenated substances can be excluded.
Herstellung einer 52%igen Natrium-Calciumoxid-Dispersion: Eine Möglichkeit, auf trockenem Wege Natrium auf Calciumoxid zu verteilen, besteht darin kleine Natriumstücke mit Calciumoxid in einer Fliehkraftkugelmühle für 5 bis 15 Minuten, wie bei oberflächenaktiven Materialien beschrieben (s.o.), zu vermahlen. Auf diese Weise lassen sich 5 % des Alkalimetalls auf dem Träger homogen verteilen. Man erhält brauchbare Natrium-Calciumoxid-Dispersionen, wenn man zunächst das Alkalimetall in Gegenwart von Toluol unter Rückflußbedingungen auf Calciumoxid einwirken läßt und anschließend den Ansatz mit einem Hochgeschwindigkeitsrührer oder Dispergator, z.B. Ultra-Turrax der Fa. "Janke & Kunkel", bei hoher Geschwindigkeit durchmischt. Nach Abdestillation des Toluols bleibt ein dunkelgrauer, fein gepulverter, bei visueller Prüfung völlig homogener Feststoff zurück. Nach dieser Vorgehensweise lassen sich praktisch stufenlos verschiedene Konzentrationen des Alkalimetalls in der Dispersion realisieren. Die Methode ist über das System Natrium-Calciumoxid hinaus sehr flexibel anwendbar: Beispielsweise gelingt mit ihr auch die Bereitung einer 25 %igen Kalium-Calciumoxid-Dispersion, die äußerlich der Natrium-Dispersion gleicht. Man gewinnt ein dunkelgraues, völlig homogenes Pulver. Es ist jedoch an der Luft pyrophor und kann daher nicht ohne weiteres für die Dechlorierung von Polychloraromaten in festen oder fest-flüssigen Matrizes herangezogen werden. Für organisch-chemische Umsetzungen im Laboratoriumsmaßstab mit geeigneter Schutzgas- und Sicherheitstechnik besäße eine derartige Kalium-Calciumoxid-Dispersion jedoch interessante Anwendungsmöglichkeiten. Preparation of a 52% Sodium Calcium Oxide Dispersion : One way to dryly distribute sodium onto calcium oxide is to grind small pieces of sodium with calcium oxide in a centrifugal ball mill for 5 to 15 minutes, as described for surface-active materials (see above). In this way, 5% of the alkali metal can be homogeneously distributed on the support. Useful sodium-calcium oxide dispersions are obtained if the alkali metal is first allowed to act on calcium oxide in the presence of toluene under reflux conditions and then the mixture is mixed at high speed with a high-speed stirrer or dispersant, for example Ultra-Turrax from "Janke &Kunkel" mixed. After the toluene has been distilled off, a dark gray, finely powdered solid which remains completely homogeneous on visual inspection remains. According to this procedure, different concentrations of the alkali metal in the dispersion can be realized practically continuously. In addition to the sodium calcium oxide system, the method can be used very flexibly: for example, it can also be used to prepare a 25% potassium calcium oxide dispersion that looks like the sodium dispersion. A dark gray, completely homogeneous powder is obtained. However, it is pyrophoric in air and therefore cannot be used for the dechlorination of polychloroaromatics in solid or solid-liquid matrices. Such a potassium-calcium oxide dispersion would, however, have interesting applications for organic-chemical implementations on the laboratory scale with suitable protective gas and security technology.
In einer Fliehkraftkugelmühle S 1 (s. Bsp. 5) werden 15 g Seesand (p.A.), 0,5 g Calciumoxid-Calciumhydroxid-Gemisch, hergestellt durch partielles Löschen von 56 g CaO mit 14 g H2O, 0,5 g Triglyme, 0,11 g Chlophen A30, 0,3544 g Methanol und 0,51 g Magnesium-Pulver, nachdem das Gemisch im offenen Mahlbecher mit Argon überschichtet wurde, für 5 Stunden bei höchster Drehzahl vermahlen.In a centrifugal ball mill S 1 (see Example 5), 15 g of sea sand (pA), 0.5 g of calcium oxide-calcium hydroxide mixture, produced by partially quenching 56 g of CaO with 14 g of H 2 O, 0.5 g of triglyme 0.11 g of Chlophen A30, 0.3544 g of methanol and 0.51 g of magnesium powder, after the mixture has been covered with argon in an open grinding bowl, milled for 5 hours at high speed.
Die GC-MS-Analyse belegt einen vollständigen Abbau der PCB (Hauptabbauprodukt: Biphenyl, daneben wenig Phenylcyclohexan). Die Anwesenheit bzw. Bildung anderer halogenierter Stoffe kann ausgeschlossen werden.The GC-MS analysis shows that the PCB has been completely degraded (Main breakdown product: biphenyl, little phenylcyclohexane in addition). The presence or formation of other halogenated substances can be excluded.
In einer Fliehkraftkugelmühle S 1 (s, Bsp.5) werden 15 g Seesand (p.A.), 1 g Calciumoxid-Calciumhydroxid-Gemisch, 0,25 ml n-Propylamin, 0,1 g Chlophen A30, und 0,76 g Magnesium-Späne für 1 Stunde bei höchster Drehzahl vermahlen.In a centrifugal ball mill S 1 (see example 5), 15 g of sea sand (p.A.), 1 g calcium oxide-calcium hydroxide mixture, 0.25 ml n-propylamine, 0.1 g Chlophen A30, and 0.76 g magnesium shavings grind for 1 hour at maximum speed.
Die GC-Analyse belegt einen vollständigen Abbau der PCB (Hauptabbauprodukt: Biphenyl, daneben 1-Phenylcyclohexen, wenig Phenylcyclohexan). Die Anwesenheit bzw. Bildung anderer halogenierter Stoffe kann ausgeschlossen werden.The GC analysis shows that the PCB has been completely degraded (Main breakdown product: biphenyl, alongside 1-phenylcyclohexene, little Phenylcyclohexan). The presence or formation of other halogenated Substances can be excluded.
Es wird überraschend gefunden, daß sich Polychloraromaten wie
1,3,5-TCB mit Natrium in Gegenwart selbst geringer Anteile an
n-Butylamin weitaus besser dechlorieren lassen als in anderen
untersuchten Systemen.
Die mechanische Bearbeitung kann durch Rühren in einem Reaktor oder in einem geeigneten Mischer geschehen.The mechanical processing can be done by stirring in a reactor or done in a suitable mixer.
In einer Fliehkraftkugelmühle S 1 (s. Bsp. 5) werden 7,5 g Seesand (p.A.) und 2,0 g Magnesium-Späne unter Argon für fünf Minuten vermahlen. Dann fügt man 0,1 g Chlophen A30,. 7,5 g Seesand (p.A.) und 0,5 g 1,3-Dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidon (Dimethylpropylenharnstoff, DMPU) hinzu, spült mit Argon und vermahlt bei höchster Drehzahl für 30 Minuten. Die GC-Analyse belegt einen vollständigen Abbau der PCB (Hauptabbauprodukt: Biphenyl). Der Versuch läßt sich mit weiteren speziellen Amiden anstatt von DMPU, wie z.B. 1,3-Dimethyl-2-imidazolidinon (N-N-Dimethylethylenharnstoff, DMEU) oder 1-Methyl-2-pyrrolidon (NMP), in sehr ähnlicher Ausgestaltung mit dem gleichen Resultat durchführen.In a centrifugal ball mill S 1 (see Example 5) 7.5 g of sea sand (p.A.) and 2.0 g of magnesium shavings under argon for five minutes ground. Then add 0.1 g of Chlophen A30. 7.5 g sea sand (p.A.) and 0.5 g of 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) pyrimidone (Dimethylpropylene urea, DMPU) added, rinses with Argon and ground at maximum speed for 30 minutes. The GC analysis shows a complete degradation of the PCB (Main breakdown product: biphenyl). The experiment can be done with others special amides instead of DMPU, e.g. 1,3-dimethyl-2-imidazolidinone (N-N-dimethylethylene urea, DMEU) or 1-methyl-2-pyrrolidone (NMP), in a very similar form with perform the same result.
In einer Fliehkraftkugelmühle S 1 (s. Bsp. 6) werden 7,0g Decan, in denen 0,8g Chlophen A 30 gelöst wurden und die noch 2g n-Propylamin enthalten, mit 9,4g Magnesium-Spänen bei höchster Drehzahl für 30 Minuten vermahlen.In a centrifugal ball mill S 1 (see Example 6), 7.0 g of decane, in which 0.8 g of Chlophen A 30 were dissolved and still Contain 2g n-propylamine, with 9.4g magnesium shavings at the highest Grind speed for 30 minutes.
Die GC-FID-Analyse belegt danach einen fast vollständigen Abbau der PCB (Abauprodukt: Biphenyl, daneben lediglich noch untergeordnet drei Mono- bzw. Dichlorbiphenyle).The GC-FID analysis then shows an almost complete breakdown the PCB (degradation product: biphenyl, next to it only subordinate three mono- or dichlorobiphenyls).
Unbehandelte und nach dem erfindungsgemäßen Verfahren behandelte
Proben wurden jeweils gaschromatographisch untersucht. Abbildungen
1 bis 6 zeigen die Ergebnisse einiger beispielhafter
gaschromatographischer Analysen jeweils vor und nach der Behandlung.
Die Analysen belegen, daß es möglich ist, auch komplexe
Gemische in kurzer Zeit effektiv zu behandeln (s. Abb. 3
bis 6)Untreated and treated according to the inventive method
Samples were examined by gas chromatography.
Mit Hilfe des erfindungsgemäßen Verfahrens gelingt es also polychlorierte organische Schadstoffe, die selbst mit einer Fülle von Fremd- und Begleitstoffen in komplexen festen oder fest-flüssigen Materialien verteilt vorliegen und an diese sogar stark adsorptiv gebunden sein können, selektiv durch vollständige reduktive Dechlorierung bei Raumtemperatur innerhalb von Minuten vollständig zu eliminieren. Selbstredend lassen sich Schadstoffe, die in relativ reiner Form angetroffen werden, wie z.B. hochkonzentrierte PCB-Öle oder insektizid unwirksame HCH-Isomere, die z.B. in der Größenordnung von mehreren 10.000 Tonnen in offenen Gruben im Bitterfelder Raum abgelagert wurden (Reinheitsgehalt bis zu 95%), besonders effektiv detoxifizieren.With the help of the method according to the invention, it is possible to use polychlorinated organic pollutants, even with an abundance of foreign substances and accompanying substances in complex solid or solid-liquid Materials are available and even distributed can be strongly adsorptively bound, selectively by complete reductive dechlorination at room temperature within Minutes completely. Of course, Pollutants that are found in relatively pure form, such as e.g. highly concentrated PCB oils or insecticidal HCH isomers, e.g. in the order of several 10,000 tons were deposited in open pits in the Bitterfeld area (Purity up to 95%), particularly effective detoxification.
Im Falle von Transformatorenölen bietet sich das erfindungsgemäße
Verfahren als Alternative zu bestehenden Verfahren
(Degussa-Natrium, NaPEG-, KPEG-, KPEG-PLUS) an, da es eine einfachere
und sichere Konzeption besitzt und mit einfachen Mitteln
unter milden Bedingungen realisierbar ist. Damit bietet
sich die Möglichkeit, belastete Öle in hohem Umfang einer Wiederverwertung
zuzuführen, anstatt sie verbrennen zu müssen.
Speziell Transformatorenöle besitzen
einen hohen Material- und damit Wiederverwendungswert, der bei
einer Verbrennung jedoch vollständig abzuschreiben wäre.In the case of transformer oils, the process according to the invention offers itself as an alternative to existing processes (Degussa sodium, NaPEG, KPEG, KPEG-PLUS), since it has a simpler and safer design and can be implemented with simple means under mild conditions. This offers the possibility of recycling contaminated oils to a large extent instead of having to burn them. Especially have transformer oils
a high material and thus reuse value, which would, however, be completely written off if incinerated.
Die organischen Schadstoffe lassen sich unter ökologisch und ökonomisch günstigen Bedingungen bei Raumtemperatur und in kurzer Zeit, insbesondere auch dann, wenn sie in unterschiedlichen Gemischen auftreten, vollständig eliminieren.The organic pollutants can be classified under ecological and economically favorable conditions at room temperature and in a short time Time, especially when it is in different Mixtures occur, completely eliminate them.
Die Schadstoffe werden direkt in der Matrix, in der sie verteilt sind, abgebaut durch einfach strukturierte Reagentien. Dabei kann es sich beispielsweise um Materialien handeln, die an anderer Stelle als Reststoffe in erheblichen Mengen anfallen, und sich hierdurch einer sinnvollen Verwertung zuführen lassen.The pollutants are directly in the matrix in which they are distributed are degraded by simply structured reagents. For example, these can be materials that elsewhere in large quantities as residues, and thereby lead to a meaningful utilization to let.
Es werden nur wenige, nicht- oder mindertoxische und biologisch abbaubare Produkte gebildet. Die besondere Umweltverträglichkeit resultiert aus der vollständigen Umsetzung des Reduktionsmittels mit sämtlichem organisch gebundenem Halogen zu ungefährlichem, anorganischem Halogenid. Zugleich bilden sich die halogenfreien Grundkörper der polyhalogenierten Verbindungen.There are only a few, non- or less toxic and biological degradable products formed. The special environmental compatibility results from the complete implementation of the reducing agent with all organically bound halogen to a harmless, inorganic halide. At the same time, the halogen-free base body of the polyhalogenated compounds.
Detoxifizierte Materialien wie z.B. Baumaterialien oder Altöle können sinnvollen Verwertungsmaßnahmen zugeführt bzw. recycelt werden.Detoxified materials such as Building materials or waste oils can be fed into useful recycling measures or recycled become.
Auf umständliche und kostenintensive Nachbehandlungen, wie z.B. das Entfernen und Eliminieren überschüssiger Reagentien bzw. von toxischen Abbauprodukten kann meist verzichtet werden.For cumbersome and costly post-treatments, such as removing and eliminating excess reagents or toxic breakdown products can usually be dispensed with.
Bei dem neuen Verfahren werden folglich die Nachteile der heute bei der Altlastensanierung in größeren Maßstäben praktizierten Prozesse, wie z.B. die Hochtemperaturverbrennung, vermieden. The new process consequently eliminates the disadvantages of today practiced on a larger scale during the remediation of contaminated sites Processes such as high temperature combustion avoided.
Als Einsatzgebiete für das erfindungsgemäße Verfahren bieten
sich insbesondere an:
Claims (12)
- Process for the reductive dehydrogenation of organohalogen compounds in solid and liquid mixtures, in which the compound or the mixture is treated with addition of elemental alkali metal, alkaline earth metal, aluminium or iron as reducing agent and at least one reagent containing at least slightly activated hydrogen as hydrogen source, characterized in that the organohalogen compound or the mixture is reductively dehalogenated virtually completely with mechanical activation in one step in a grinding comprising all materials.
- Process according to Claim 1, characterized in that the reducing agent is preferably Na, K, Mg, Ca or Al.
- Process according to Claim 1 or 2, characterized in that the hydrogen source is alcohols, ethers, polyethers, amines, hydroxides or hydrides, individually or in combination.
- Process according to Claim 3, characterized in that the amine is at least one aliphatic amine, preferably primary or secondary aliphatic amine.
- Process according to one of Claims 1 to 4, characterized in that grinding aids and/or reaction accelerators are additionally used.
- Process according to Claim 5, characterized in that the grinding aids are substances which can reduce or prevent possible plastic deformation and/or agglomeration of solids under the action of mechanical energy, for example certain surface-active substances.
- Process according to Claim 5, characterized in that reaction accelerators are used which at least partially dissolve base metals and/or promote their dissociation into metal cations and metal anions and/or promote the formation of solvated electrons and/or solvate and/or stabilize organometallic compounds.
- Process according to one of Claims 5 to 7, characterized in that the grinding aid(s) and/or reaction accelerator(s) are added to the compound or mixture in an upstream or downstream step and are mechanically incorporated or ground.
- Process according to one of Claims 1 to 8, characterized in that the metallic reducing agent is present in a preparation, for example dispersed in a non-oxidizing liquid or the liquid-hydrogen source or an inert solid support.
- Process according to Claim 9, characterized in that the reducing agent is present in the form of a paraffin suspension, an ether dispersion or a polyether dispersion.
- Process according to one of Claims 1 to 10, characterized in that the mixture is treated and/or dried in an upstream process step with calcium oxide and/or other additives.
- Process according to one of Claims 1 to 11, characterized in that the mechanical treatment is performed in a mill, for example a ball mill, a hammer mill or a vibratory mill, or in a mixer which adequately transmits mechanical energy, preferably a dynamic mixer, for example a friction mixer, screw mixer or roller mixer.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19742297 | 1997-09-25 | ||
DE19742297A DE19742297C2 (en) | 1997-09-25 | 1997-09-25 | Process for reductive dehalogenation of halogenated organic substances |
PCT/DE1998/002787 WO1999015239A1 (en) | 1997-09-25 | 1998-09-19 | Method for reductive dehalogenation of halogen-organic substances |
Publications (2)
Publication Number | Publication Date |
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EP1027109A1 EP1027109A1 (en) | 2000-08-16 |
EP1027109B1 true EP1027109B1 (en) | 2002-10-23 |
Family
ID=7843573
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EP98954202A Revoked EP1027109B1 (en) | 1997-09-25 | 1998-09-19 | Method for reductive dehalogenation of halogen-organic substances |
Country Status (11)
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---|---|
US (1) | US6382537B1 (en) |
EP (1) | EP1027109B1 (en) |
JP (1) | JP2001517641A (en) |
AT (1) | ATE226466T1 (en) |
AU (1) | AU758391B2 (en) |
CA (1) | CA2304802A1 (en) |
DE (2) | DE19742297C2 (en) |
DK (1) | DK1027109T3 (en) |
ES (1) | ES2186237T3 (en) |
PT (1) | PT1027109E (en) |
WO (1) | WO1999015239A1 (en) |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
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DE19903986A1 (en) * | 1999-02-02 | 2000-08-10 | Friedrich Boelsing | Reductive dehalogenation of halohydrocarbons under mild conditions, e.g. for removing toxic chloroaromatic compounds from waste oil or soil, using reducing metal in presence of amine |
WO2001083038A1 (en) * | 2000-05-03 | 2001-11-08 | Environmental Decontamination Limited | Detoxification of halogenated compounds in contaminated media |
JP2002187858A (en) * | 2000-12-18 | 2002-07-05 | Nippon Soda Co Ltd | Method for decomposing recalcitrant halogen compound |
DE10112720A1 (en) * | 2001-03-14 | 2002-10-02 | Kaercher Gmbh & Co Alfred | Basic, non-aqueous decontamination liquid |
JP4697837B2 (en) * | 2001-08-03 | 2011-06-08 | ミヨシ油脂株式会社 | Solid waste treatment method |
US20050056598A1 (en) * | 2003-06-06 | 2005-03-17 | Chowdhury Ajit K. | Method for treating recalcitrant organic compounds |
JPWO2009087994A1 (en) * | 2008-01-07 | 2011-05-26 | 財団法人名古屋産業科学研究所 | Aromatic halide dehalogenation method |
KR101899291B1 (en) | 2010-08-18 | 2018-09-14 | 시오노 케미컬 가부시키가이샤 | Process for producing hydrogen or heavy hydrogens |
WO2013121997A1 (en) | 2012-02-17 | 2013-08-22 | シオノケミカル株式会社 | Method for producing hydrogen or deuterium, method for producing hydrogenated or deuterated organic compound, method for hydrogenating or deuterating organic compound, method for dehalogenating organic compound having halogen, and ball for use in mechanochemical reaction |
US10479711B2 (en) | 2016-05-05 | 2019-11-19 | Remediation Products, Inc. | Composition with a time release material for removing halogenated hydrocarbons from contaminated environments |
US11548802B2 (en) | 2016-05-05 | 2023-01-10 | Remediation Products, Inc. | Composition with a time release material for removing halogenated hydrocarbons from contaminated environments |
CN106881343A (en) * | 2016-11-29 | 2017-06-23 | 清华大学 | A kind of method that the mechanochemistry of halo persistence organic pollutant is decomposed in soil |
DE102018000418A1 (en) | 2018-01-20 | 2019-07-25 | Bürkle Consulting Gmbh | Mechanochemical process for the production of persistent organic pollutants and other organohalogen compounds free value products from wastes of plastics and plastic laminates |
DE102019006084A1 (en) | 2019-02-12 | 2020-08-13 | Elke Münch | Mechanochemical process |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4377471A (en) | 1980-12-03 | 1983-03-22 | General Electric Company | Method for removing polychlorinated biphenyls from transformer oil |
DE3410239A1 (en) * | 1984-03-21 | 1985-10-03 | Hivolin Gmbh | Process for the elimination of toxic polyhalogenated or perhalogenated organic compounds |
CH668709A5 (en) * | 1985-12-06 | 1989-01-31 | Ciba Geigy Ag | METHOD FOR ENTHALOGENATING POLYHALOGENATED ALIPHATIC AND AROMATIC COMPOUNDS. |
US4853040A (en) | 1987-03-30 | 1989-08-01 | A. L. Sandpiper Corporation | Processes for decontaminating polluted substrates |
CA1296744C (en) | 1988-03-18 | 1992-03-03 | Derek J. Mcphee | Dehalogenation of halogenated aromatic compounds |
US4950833A (en) | 1989-09-28 | 1990-08-21 | Her Majesty The Queen In Right Of Canada, As Represented By The National Research Council Of Canada | Process for the reductive dehalogenation of polyhaloaromatics |
US5043054A (en) * | 1990-05-09 | 1991-08-27 | Chemical Waste Management, Inc. | Process for dehalogenation of contaminated waste materials |
DE4022526C2 (en) | 1990-07-16 | 1994-03-24 | Degussa | Process for the dehalogenation of organic compounds by means of alkali metal on solid supports |
US5093011A (en) * | 1990-12-12 | 1992-03-03 | Chemical Waste Management, Inc. | Process for dehalogenation of contaminated waste materials |
US5648591A (en) * | 1992-12-18 | 1997-07-15 | University Of Western Australia | Toxic material disposal |
ITMI922961A1 (en) * | 1992-12-24 | 1994-06-24 | Sea Marconi Technologies Sas | PROCEDURE FOR THE CHEMICAL DEALOGENATION OF HALOGENIC ORGANIC COMPOUNDS. |
WO1995018652A1 (en) * | 1994-01-04 | 1995-07-13 | Neos Technology Inc. | Sodium dispersion and organohalide reaction processes |
-
1997
- 1997-09-25 DE DE19742297A patent/DE19742297C2/en not_active Revoked
-
1998
- 1998-09-19 DE DE59806075T patent/DE59806075D1/en not_active Expired - Fee Related
- 1998-09-19 US US09/508,515 patent/US6382537B1/en not_active Expired - Fee Related
- 1998-09-19 CA CA002304802A patent/CA2304802A1/en not_active Abandoned
- 1998-09-19 ES ES98954202T patent/ES2186237T3/en not_active Expired - Lifetime
- 1998-09-19 EP EP98954202A patent/EP1027109B1/en not_active Revoked
- 1998-09-19 PT PT98954202T patent/PT1027109E/en unknown
- 1998-09-19 AU AU11432/99A patent/AU758391B2/en not_active Ceased
- 1998-09-19 DK DK98954202T patent/DK1027109T3/en active
- 1998-09-19 JP JP2000512605A patent/JP2001517641A/en active Pending
- 1998-09-19 WO PCT/DE1998/002787 patent/WO1999015239A1/en not_active Application Discontinuation
- 1998-09-19 AT AT98954202T patent/ATE226466T1/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
PT1027109E (en) | 2003-03-31 |
WO1999015239A1 (en) | 1999-04-01 |
DE19742297C2 (en) | 2000-06-29 |
EP1027109A1 (en) | 2000-08-16 |
AU1143299A (en) | 1999-04-12 |
DE19742297A1 (en) | 1999-04-01 |
JP2001517641A (en) | 2001-10-09 |
AU758391B2 (en) | 2003-03-20 |
DK1027109T3 (en) | 2003-03-10 |
ATE226466T1 (en) | 2002-11-15 |
CA2304802A1 (en) | 1999-04-01 |
US6382537B1 (en) | 2002-05-07 |
ES2186237T3 (en) | 2003-05-01 |
DE59806075D1 (en) | 2002-11-28 |
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