EP0250748B1 - Process for the dehalogenation of hydrocarbon oils - Google Patents
Process for the dehalogenation of hydrocarbon oils Download PDFInfo
- Publication number
- EP0250748B1 EP0250748B1 EP87105740A EP87105740A EP0250748B1 EP 0250748 B1 EP0250748 B1 EP 0250748B1 EP 87105740 A EP87105740 A EP 87105740A EP 87105740 A EP87105740 A EP 87105740A EP 0250748 B1 EP0250748 B1 EP 0250748B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkoxide
- process according
- dehalogenation
- oils
- sodium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims description 26
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 12
- 229930195733 hydrocarbon Natural products 0.000 title claims description 12
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 12
- 238000005695 dehalogenation reaction Methods 0.000 title claims description 8
- 239000003921 oil Substances 0.000 title description 31
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 239000011734 sodium Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- -1 alkali metal alkoxide Chemical class 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 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 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 150000004703 alkoxides Chemical class 0.000 claims 5
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 claims 1
- WOFPPJOZXUTRAU-UHFFFAOYSA-N 2-Ethyl-1-hexanol Natural products CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 claims 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims 1
- 229910001508 alkali metal halide Inorganic materials 0.000 claims 1
- 150000008045 alkali metal halides Chemical class 0.000 claims 1
- 150000005309 metal halides Chemical class 0.000 claims 1
- 150000001298 alcohols Chemical class 0.000 description 9
- 239000002699 waste material Substances 0.000 description 9
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000006298 dechlorination reaction Methods 0.000 description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 239000010687 lubricating oil Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000000382 dechlorinating effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- ZRLAJSMFDYQOTR-UHFFFAOYSA-N cycloheptadecanol Chemical compound OC1CCCCCCCCCCCCCCCC1 ZRLAJSMFDYQOTR-UHFFFAOYSA-N 0.000 description 2
- OCIZMIIUCQFIBS-UHFFFAOYSA-N cyclooctadecanol Chemical compound OC1CCCCCCCCCCCCCCCCC1 OCIZMIIUCQFIBS-UHFFFAOYSA-N 0.000 description 2
- FFVHXGZXDRXFLQ-UHFFFAOYSA-N cyclopentadecanol Chemical compound OC1CCCCCCCCCCCCCC1 FFVHXGZXDRXFLQ-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000010720 hydraulic oil Substances 0.000 description 2
- 238000007037 hydroformylation reaction Methods 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 150000004045 organic chlorine compounds Chemical class 0.000 description 2
- 150000002896 organic halogen compounds Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- PKQYSCBUFZOAPE-UHFFFAOYSA-N 1,2-dibenzyl-3-methylbenzene Chemical compound C=1C=CC=CC=1CC=1C(C)=CC=CC=1CC1=CC=CC=C1 PKQYSCBUFZOAPE-UHFFFAOYSA-N 0.000 description 1
- GDPISEKNRFFKMM-UHFFFAOYSA-N 1,3-diphenylpropan-2-ylbenzene Chemical class C=1C=CC=CC=1CC(C=1C=CC=CC=1)CC1=CC=CC=C1 GDPISEKNRFFKMM-UHFFFAOYSA-N 0.000 description 1
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 1
- WAPNOHKVXSQRPX-UHFFFAOYSA-N 1-phenylethanol Chemical compound CC(O)C1=CC=CC=C1 WAPNOHKVXSQRPX-UHFFFAOYSA-N 0.000 description 1
- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical compound CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 description 1
- CETWDUZRCINIHU-UHFFFAOYSA-N 2-heptanol Chemical compound CCCCCC(C)O CETWDUZRCINIHU-UHFFFAOYSA-N 0.000 description 1
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 1
- LWHKUVOYICRGGR-UHFFFAOYSA-N 3-bicyclo[2.2.1]heptanylmethanol Chemical compound C1CC2C(CO)CC1C2 LWHKUVOYICRGGR-UHFFFAOYSA-N 0.000 description 1
- QDTDKYHPHANITQ-UHFFFAOYSA-N 7-methyloctan-1-ol Chemical compound CC(C)CCCCCCO QDTDKYHPHANITQ-UHFFFAOYSA-N 0.000 description 1
- PLLBRTOLHQQAQQ-UHFFFAOYSA-N 8-methylnonan-1-ol Chemical compound CC(C)CCCCCCCO PLLBRTOLHQQAQQ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000723347 Cinnamomum Species 0.000 description 1
- 238000007869 Guerbet synthesis reaction Methods 0.000 description 1
- RZKSECIXORKHQS-UHFFFAOYSA-N Heptan-3-ol Chemical compound CCCCC(O)CC RZKSECIXORKHQS-UHFFFAOYSA-N 0.000 description 1
- YVBCULSIZWMTFY-UHFFFAOYSA-N Heptan-4-ol Chemical compound CCCC(O)CCC YVBCULSIZWMTFY-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000008043 acidic salts Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 235000017803 cinnamon Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- WFRBMXFCEAHLGH-UHFFFAOYSA-N cyclodecanol Chemical compound OC1CCCCCCCCC1 WFRBMXFCEAHLGH-UHFFFAOYSA-N 0.000 description 1
- SFVWPXMPRCIVOK-UHFFFAOYSA-N cyclododecanol Chemical compound OC1CCCCCCCCCCC1 SFVWPXMPRCIVOK-UHFFFAOYSA-N 0.000 description 1
- QCRFMSUKWRQZEM-UHFFFAOYSA-N cycloheptanol Chemical compound OC1CCCCCC1 QCRFMSUKWRQZEM-UHFFFAOYSA-N 0.000 description 1
- RCIINNRHOWANBV-UHFFFAOYSA-N cyclohexadecanol Chemical compound OC1CCCCCCCCCCCCCCC1 RCIINNRHOWANBV-UHFFFAOYSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- UDEKCKABZJKCKG-UHFFFAOYSA-N cyclononanol Chemical compound OC1CCCCCCCC1 UDEKCKABZJKCKG-UHFFFAOYSA-N 0.000 description 1
- FHADSMKORVFYOS-UHFFFAOYSA-N cyclooctanol Chemical compound OC1CCCCCCC1 FHADSMKORVFYOS-UHFFFAOYSA-N 0.000 description 1
- ZJJOMKBDHWVFIU-UHFFFAOYSA-N cyclotetradecanol Chemical compound OC1CCCCCCCCCCCCC1 ZJJOMKBDHWVFIU-UHFFFAOYSA-N 0.000 description 1
- IWOZRHJPQVIPNH-UHFFFAOYSA-N cyclotridecanol Chemical compound OC1CCCCCCCCCCCC1 IWOZRHJPQVIPNH-UHFFFAOYSA-N 0.000 description 1
- WFXNFNGXUAKZAY-UHFFFAOYSA-N cycloundecanol Chemical compound OC1CCCCCCCCCC1 WFXNFNGXUAKZAY-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 150000004826 dibenzofurans Chemical class 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- QILSFLSDHQAZET-UHFFFAOYSA-N diphenylmethanol Chemical compound C=1C=CC=CC=1C(O)C1=CC=CC=C1 QILSFLSDHQAZET-UHFFFAOYSA-N 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229940043348 myristyl alcohol Drugs 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- URXNVXOMQQCBHS-UHFFFAOYSA-N naphthalene;sodium Chemical compound [Na].C1=CC=CC2=CC=CC=C21 URXNVXOMQQCBHS-UHFFFAOYSA-N 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000000135 prohibitive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229940023144 sodium glycolate Drugs 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- JEJAMASKDTUEBZ-UHFFFAOYSA-N tris(1,1,3-tribromo-2,2-dimethylpropyl) phosphate Chemical compound BrCC(C)(C)C(Br)(Br)OP(=O)(OC(Br)(Br)C(C)(C)CBr)OC(Br)(Br)C(C)(C)CBr JEJAMASKDTUEBZ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- A62D3/34—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
-
- 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
- A62D2101/28—Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S210/00—Liquid purification or separation
- Y10S210/902—Materials removed
- Y10S210/908—Organic
- Y10S210/909—Aromatic compound, e.g. pcb, phenol
Definitions
- the invention relates to a process for the dehalogenation of hydrocarbon oils.
- hydrocarbon oils can be used lubricating oils, for example, which can be used again in a resource-saving and environmentally friendly manner for the production of secondary raffinates, or also aromatic heat transfer oils, which in this way remove the corrosiveness emanating from organochlorine compounds.
- Lubricating oils accumulate during their use with metal abrasion, degradation and oxidation products of their components as well as fuel components. Nonetheless, used lubricating oils are not considered waste products, since they can be processed through various operations, such as filtration, distillation, refining with concentrated sulfuric acid or oleum and treatment with bleaching earth, to the extent that full lubricants are formed after additional additives. Although the measures mentioned return a perfect base oil in terms of lubrication technology, they are unable to remove some impurities which are considered to be very harmful from an environmental toxicological point of view. These contaminants include some polychlorinated aromatics, some of which have been mixed with the used lubricating oils through negligence, but sometimes also deliberately or through technical breakdowns.
- PCB polychlorinated biphenyls
- naphthalene sodium as a dechlorinating agent in homogeneous solution, but this can only be achieved by using an additional solvent.
- Tetrahydrofuran is primarily used as an additional solvent. A rapid reaction takes place even at low temperatures, but the high solvent expenditure makes the process unsuitable for economical execution on an industrial scale. A high excess of dechlorinating agents is also required here.
- the auxiliary naphthalene as an aromatic hydrocarbon is itself an environmental risk.
- EP-PS 0 021 294 the dechlorination of toxic organic aromatic chlorine compounds is described, mainly production residues from the production of 2.4.5-trichlorophenol being treated.
- the products are used together with alkali metal alcoholates of monohydric alcohols with 1 to 5 carbon atoms or of polyoxyalkylene glycols with 4 to 20 carbon atoms or of polyols with 2 to 5 carbon atoms and 2 to 3 hydroxyl groups or of monoalkyl ethers from these latter polyols and Alcohols with 1 to 4 carbon atoms in the presence of 0.5 to 1 equivalent of the free alcohol, based on organically bound halogen, heated.
- mixtures of these alcohols with alkali metal hydroxides or carbonates can be used.
- dechlorination is carried out with sodium glycolate / ethylene glycol. If sodium methylate / methanol is used instead, high pressures have to be bought be taken.
- the process is used for the total destruction of such production residues and, due to the disclosed reaction conditions, is not suitable for refining large quantities of only slightly contaminated oils and for further use of certain oils. It also exhibits heterogeneous reactions and is therefore difficult to integrate into continuous production processes.
- the object is achieved in that the hydrocarbon oils contaminated with organic halogen compounds are treated at 120 to 400 ° C. with alkali or alkaline earth metal alcoholates with 6 to 25 carbon atoms in a homogeneous phase without the use of additional solvents.
- Excess reagent can be converted into insoluble inorganic salts by the slight addition of acids or acidic salts or can be filtered off bound to bleaching earth. They are not a new threat to the environment.
- Hydrocarbon oils such as heat transfer oils, insulating oils, hydraulic oils, heavy oils, lubricating oils, neutral oils, waste oil fractions, paraffin oils or organic hydrocarbon intermediates can be used for the process according to the invention.
- the alcoholate used is soluble in the hydrocarbon oils under the reaction conditions.
- the conditions of solubility are fulfilled by all alcoholates with straight-chain, branched and cyclic alkyl radicals with at least 6 carbon atoms.
- An upper limit of 25 carbon atoms is determined less by the effectiveness than by the availability of the associated alcohols.
- the proportion of the active alcoholate group is small in the case of large alkyl residues.
- Alcoholates with alkyl radicals with 8 to 20 C atoms are technically interesting, with a particularly favorable compromise for alkyl groups with 8 to 14 C atoms, where good solubility and availability are combined with a still favorable proportion of active groups.
- the alcohols suitable for the preparation of the dehalogenating agents according to the invention include, for example, hexanol-1, -2 and -3, heptanol-1, -2, -3 and -4, octanol-1, -3 and -4, nonanol-1, 2, 3, -4 and -5, decanol-1, -2, -3, -4 and -5, undecanol-1, -2, -3, -4, -5 and -6, dodecanol-1, -2, -3, -4, -5 and -6, tridecanol-1, -2, -3, -4, -5, -6 and -7, tetradecanol-1, -2, -3, -4, -5, -6 and -7 (myristyl alcohol), pentadecanol-1, -2, -3, -4, -5, -6, -7 and -8, heptadecanol-1, -2, -3, -4, -5
- branched alcohols with 8 to 14 carbon atoms that are usually used in the production of plasticizers for PVC, such as 2-ethylhexanol-1, "isononanol”, “isodecanol”, “isotridecanol” (hydroformylation products of dimerbutene, trimer propene, trimerbutene or Tetramer propene) because their alcoholates have particularly good solubility in hydrocarbon oils.
- the alcoholates formed by the above alcohols with alkali and / or alkaline earth metals can be used, among the alkali alcoholates preferably those of sodium and potassium, among the alkaline earth alcoholates that of magnesium and calcium. Alkali alcoholates are particularly preferably used.
- the alcoholates can be prepared in all known ways, i. H. by reacting metal or metal hydride with alcohol with the formation of hydrogen, by reacting lower alcoholate with higher alcohol while distilling off the lower alcohol, and from metal hydroxide and alcohol with azeotropic removal of the water in equilibrium.
- the representation can also take place in situ in the presence of the substrate to be dehalogenated. It is not necessary to use the alcoholate in the presence of excess alcohol, but a small excess does not interfere.
- the stoichiometrically required amount is calculated from the chlorine content, taking into account the moisture content and the acid and ester groups that also react with alcoholate.
- the amount of reagent used is 0.5 to 5 times the stoichiometrically required amount. Although higher surpluses do not hurt either, they are avoided for procedural and cost reasons. Amounts of reagent which correspond to 1.5 to 5 times the stoichiometric amount are preferably used. Small excesses are usually sufficient if you work in the upper part of the temperature range.
- Temperatures of 120 to 400 ° C are suitable for dehalogenation.
- the response time can be up to 10 hours at the lower limit and a few seconds at the upper limit.
- Temperatures of 180 to 380 ° C are preferred, a temperature range of 220 to 350 ° C is particularly advantageous.
- the process can therefore be used both for small discontinuous batches and can be integrated into fully continuous processes.
- the dehalogenation can be carried out in a homogeneous phase without solvents. This enables minimal chemical consumption and short reaction times. In addition, the residues arising during disposal do not pose any safety and environmental problems.
- Hydrocarbon oil A recycled waste oil is used that is not readditivated.
- the waste oil is cooled to room temperature. Excess Na ethyl hexoxide is concentrated by. Sulfuric acid destroyed. After filtration of the inorganic salts, the waste oil is distilled under vacuum.
- 500 g of a dibenzyltoluene isomer mixture to be used as heat transfer oil contain 1,200 ppm chlorine.
- the chlorine content is reduced to 4 ppm by distillation twice at normal pressure and 360 ° C. above 5 times the stoichiometric amount of Na ethyl hexoxide. 93% by weight of the crude product used is obtained as the distillate.
Landscapes
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Die Erfindung betrifft ein Verfahren zur Enthalogenierung von Kohlenwasserstoffölen. Dabei kann es sich beispielsweise um gebrauchte Schmieröle handeln, die durch diese Behandlung wieder ressourcenschonend und umweltfreundlich zur Herstellung von Zweitraffinaten verwendet werden können, oder auch um aromatische Wärmeträgeröle, denen auf diese Weise die von Organochlorverbindungen ausgehende Korrosivität genommen wird.The invention relates to a process for the dehalogenation of hydrocarbon oils. These can be used lubricating oils, for example, which can be used again in a resource-saving and environmentally friendly manner for the production of secondary raffinates, or also aromatic heat transfer oils, which in this way remove the corrosiveness emanating from organochlorine compounds.
Schmieröle reichern sich während ihres Einsatzes mit Metallabrieb, Abbau- und Oxidationsprodukten ihrer Bestandteile sowie Kraftstoffkomponenten an. Dennoch gelten gebrauchte Schmieröle nicht als Abfallprodukte, da sie durch verschiedene Operationen, zu denen Filtration, Destillation, Raffination mit konzentrierter Schwefelsäure bzw. Oleum und Behandlung mit Bleicherde gehören, so weit aufbereitet werden können, daß nach erneuter Additivierung vollwertige Schmierstoffe entstehen. Die erwähnten Maßnahmen liefern zwar ein schmiertechnisch einwandfreies Grundöl zurück, sind aber nicht imstande, einige Verunreinigungen zu entfernen, die vom umwelttoxikologischen Aspekt her als sehr bedenklich gelten. Zu diesen Verunreinigungen gehören einige polychlorierte Aromaten, die teilweise durch Fahrlässigkeiten, teilweise aber auch vorsätzlich oder durch technische Pannen mit den gebrauchten Schmierölen vermengt wurden. Besonders hervorzuheben sind die wegen ihrer Unbrennbarkeit als Hydrauliköle im Bergbau, aber auch als Isolieröle bzw. Dielektrika für Transformatoren bzw. Kondensatoren weit verbreiteten polychlorierten Biphenyle (PCB). Sie stellten nicht nur wegen ihrer Anreicherung in Nahrungsketten analog dem DDT, sondern auch wegen der Möglichkeit, daß bei Verbrennungstemperaturen unterhalb von 1 000 °C daraus weit gefährlichere Stoffe - nämlich polychlorierte Dibenzodioxine bzw. Dibenzofurane - entstehen können, ein seit Jahren mit Besorgnis betrachtetes Problem dar. Die Befürchtung, daß derartige Bedingungen gelegentlich auch in Verbrennungsmotoren herrschen könn ten, führt zu der Folgerung, daß PCB-kontaminierte Altöle nur noch einer Hochtemperaturverbrennung statt einer Sekundärnutzung zugeführt werden können, falls es nicht gelingt, sie mit vertretbarem Aufwand zu entchlorieren. Es ist daher aus Gründen des Umweltschutzes und der Rohstoffersparnis eine dringende Aufgabe, Verfahren zu entwickeln, durch die auf wirtschaftliche Weise Altöle für eine Wiederverwendung einsetzbar gemacht werden.Lubricating oils accumulate during their use with metal abrasion, degradation and oxidation products of their components as well as fuel components. Nonetheless, used lubricating oils are not considered waste products, since they can be processed through various operations, such as filtration, distillation, refining with concentrated sulfuric acid or oleum and treatment with bleaching earth, to the extent that full lubricants are formed after additional additives. Although the measures mentioned return a perfect base oil in terms of lubrication technology, they are unable to remove some impurities which are considered to be very harmful from an environmental toxicological point of view. These contaminants include some polychlorinated aromatics, some of which have been mixed with the used lubricating oils through negligence, but sometimes also deliberately or through technical breakdowns. Particularly noteworthy are the polychlorinated biphenyls (PCB), which are widely used because of their non-flammability as hydraulic oils in mining, but also as insulating oils and dielectrics for transformers and capacitors. Not only because of their accumulation in food chains analogous to the DDT, but also because of the possibility that far more dangerous substances - namely polychlorinated dibenzodioxins or dibenzofurans - can be generated at combustion temperatures below 1000 ° C, a problem that has been considered with concern for years The fear that such conditions could occasionally also exist in internal combustion engines leads to the conclusion that PCB-contaminated waste oils can only be used for high-temperature combustion instead of secondary use if it is not possible to dechlorinate them with reasonable effort. It is therefore an urgent task, for reasons of environmental protection and the saving of raw materials, to develop processes which make waste oils economically usable for reuse.
Ein naheliegender Weg, halogenhaltige Verbindungen zu entfernen, besteht im Erhitzen des Öls mit dispergierten Alkalimetallen. Dieser Weg wird beispielsweise in GB-PSS 2 063 908 und 2 081 298 und US-PS 4 465 590 beschritten. Er bringt zwar zufriedenstellende Ergebnisse, erfordert aber wegen der nur an der Grenzfläche Metall/Öl stattfindenden Reaktion große Metallüberschüsse, deren spätere Beseitigung auch Sicherheitsprobleme bringt.An obvious way to remove halogen-containing compounds is to heat the oil with dispersed alkali metals. This route is followed, for example, in GB-PSS 2 063 908 and 2 081 298 and US Pat. No. 4,465,590. Although it gives satisfactory results, it requires large excesses of metal because of the reaction that only takes place at the metal / oil interface, the later elimination of which also poses safety problems.
Eine andere Methode, beschrieben in US-PSS 4 284 516, 4 326 090 und 4 447 667, verwendet Naphthalin-Natrium als Dechlorierungsmittel in homogener Lösung, die aber nur durch Verwendung eines zusätzlichen Lösemittels erzielt werden kann. Als zusätzliches Lösemittel wird dabei vor allem Tetrahydrofuran verwendet. Zwar findet eine rasche Reaktion auch bei niedrigen Temperaturen statt, aber der hohe Lösemittelaufwand macht das Verfahren ungeeignet für eine wirtschaftliche Ausführung im großtechnischen Maßstab. Auch hier wird ein hoher Überschuß an Dechlorierungsmitteln benötigt. Außerdem ist der Hilfsstoff Naphthalin als aromatischer Kohlenwasserstoff selbst ein Umweltrisiko.Another method, described in US Pat. Nos. 4,284,516, 4,326,090 and 4,447,667, uses naphthalene sodium as a dechlorinating agent in homogeneous solution, but this can only be achieved by using an additional solvent. Tetrahydrofuran is primarily used as an additional solvent. A rapid reaction takes place even at low temperatures, but the high solvent expenditure makes the process unsuitable for economical execution on an industrial scale. A high excess of dechlorinating agents is also required here. In addition, the auxiliary naphthalene as an aromatic hydrocarbon is itself an environmental risk.
Verfahren zur hydrierenden Dechlorierung sind ebenfalls bekannt. Sie erfordern hohe Investitionen wegen der dafür notwendigen Druckapparaturen. Deshalb lohnen sie sich erst bei größeren Kapazitäten.Processes for hydrogenating dechlorination are also known. They require high investments because of the necessary pressure equipment. Therefore, they only pay off with larger capacities.
Es wurden auch bereits Verfahren zur Dechlorierung von Organochlorverbindungen mit chemischen Reduktionsmitteln beschrieben. So kann man nach W. H. Dennis, Jr. et al., Bull. Environ, Contam. Toxicol. 22 (6), 750-753 (1979) mit Nickelchlorid und Natriumboranat in Isopropanol, nach US-PS 4 400 566 mit Nickelchlorid, einem Triarylphosphin und Zinkstaub in Dimethylformamid oder nach JP-PS 74-61143 mit Hydrazinhydrat in Gegenwart eines Palladiumkatalysators auf Aktivkohle dechlorieren. Allein die Natur der benutzten Hilfsreagenzien ist prohibitiv für eine Anwendung dieser Verfahren im großen Maßstab, da neue Entsorgungsprobleme für die anfallenden Rückstände aufgeworfen werden. Abgesehen davon sind die Hilfsreagenzien keineswegs wohlfeil.Processes for dechlorinating organochlorine compounds with chemical reducing agents have also been described. For example, according to W.H. Dennis, Jr. et al., Bull. Environ, Contam. Toxicol. 22 (6), 750-753 (1979) with nickel chloride and sodium boranate in isopropanol, according to US Pat. No. 4,400,566 with nickel chloride, a triarylphosphine and zinc dust in dimethylformamide or according to JP PS 74-61143 with hydrazine hydrate in the presence of a palladium catalyst on activated carbon dechlorinate. The very nature of the auxiliary reagents used is prohibitive for the large-scale use of these methods, since new disposal problems for the residues are raised. Apart from that, the auxiliary reagents are by no means cheap.
Auch bei den Verfahren, bei denen ein Gemisch von Alkalihydroxid und Polyethylenglykol in Abwesenheit (US-PS 4 351 718) oder in Gegenwart von Oxidationsmitteln (DE-OS 30 33 170, US-PSS 4 400 552 und 4 337 368 und EP-PS 0118 858) mit dem kontaminierten Öl umgesetzt werden, werden große Mengen an Reagenzien verbraucht.Also in the processes in which a mixture of alkali hydroxide and polyethylene glycol in the absence (US Pat. No. 4,351,718) or in the presence of oxidizing agents (DE-OS 30 33 170, US Pat. No. 4,400,552 and 4,337,368 and EP-PS 0118 858) are reacted with the contaminated oil, large amounts of reagents are consumed.
In EP-PS 0 021 294 wird die Dechlorierung von toxischen organischen aromatischen Chlorverbindungen beschrieben, wobei vorwiegend Produktionsrückstände aus der Herstellung von 2.4.5-Trichlorphenol behandelt werden.In EP-PS 0 021 294 the dechlorination of toxic organic aromatic chlorine compounds is described, mainly production residues from the production of 2.4.5-trichlorophenol being treated.
Dabei werden die Produkte zusammen mit Alkalialkoholaten von einwertigen Alkoholen mit 1 bis 5 C-Atomen oder von Polyoxyalkylenglykolen mit 4 bis 20 C-Atomen oder von Polyolen mit 2 bis 5 C-Atomen und 2 bis 3 Hydroxylgruppen oder von Monoalkylethern aus diesen letztgenannten Polyolen und Alkoholen mit 1 bis 4 C-Atomen in Gegenwart von 0,5 bis 1 Äquivalent des freien Alkohols, bezogen auf organisch gebundenes Halogen, erhitzt. Ersatzweise können auch Gemische dieser Alkohole mit Alkalihydroxiden bzw. -carbonaten eingesetzt werden. Im allgemeinen wird hier mit Natriumglykolat/Ethylenglykol dechloriert. Verwendet man statt dessen Natriummethylat/Methanol, so müssen hohe Drucke in Kauf genommen werden.The products are used together with alkali metal alcoholates of monohydric alcohols with 1 to 5 carbon atoms or of polyoxyalkylene glycols with 4 to 20 carbon atoms or of polyols with 2 to 5 carbon atoms and 2 to 3 hydroxyl groups or of monoalkyl ethers from these latter polyols and Alcohols with 1 to 4 carbon atoms in the presence of 0.5 to 1 equivalent of the free alcohol, based on organically bound halogen, heated. Alternatively, mixtures of these alcohols with alkali metal hydroxides or carbonates can be used. In general, dechlorination is carried out with sodium glycolate / ethylene glycol. If sodium methylate / methanol is used instead, high pressures have to be bought be taken.
Das Verfahren dient der totalen Zerstörung derartiger Produktionsrückstände und ist von den offenbarten Reaktionsbedingungen her nicht zur Raffination von großen Mengen nur geringfügig kontaminierter, zur weiteren Nutzung bestimmter Öle geeignet. Es weist außerdem heterogene Reaktionen auf und läßt sich daher schlecht in kontinuierliche Produktionsprozesse integrieren.The process is used for the total destruction of such production residues and, due to the disclosed reaction conditions, is not suitable for refining large quantities of only slightly contaminated oils and for further use of certain oils. It also exhibits heterogeneous reactions and is therefore difficult to integrate into continuous production processes.
Aufgabe der vorliegenden Erfindung ist es, ein Verfahren zur Enthalogenierung von mit organischen Halogenverbindungen verunreinigten Kohlenwasserstoffölen bereitzustellen, das
- - schnell und vollständig verläuft,
- - geringe Mengen an preisgünstigen Hilfsreagenzien erfordert und
- - keine Sicherheits- und Umweltprobleme bei der Entsorgung der Rückstände mit sich bringt.
- - runs quickly and completely,
- - Requires small amounts of inexpensive auxiliary reagents and
- - does not pose any safety and environmental problems when disposing of the residues.
Die Aufgabe wird dadurch gelöst, daß man die mit organischen Halogenverbindungen kontaminierten Kohlenwasserstofföle bei 120 bis 400 °C mit Alkali- oder Erdalkalialkoholaten mit 6 bis 25 C-Atomen in homogener Phase ohne Verwendung zusätzlicher Lösemittel behandelt. Dabei entstehen Alkali- oder Erdalkalihalogenide, die ausfallen und durch Filtration, Auswaschen oder als Bestandteil eines Destillationsrückstandes entfernt werden können. Reagenzüberschüsse können durch geringe Zusätze von Säuren oder sauren Salzen in unlösliche anorganische Salze überführt oder auch an Bleicherde gebunden abfiltriert werden. Sie stellen keine neue Gefahr für die Umwelt dar.The object is achieved in that the hydrocarbon oils contaminated with organic halogen compounds are treated at 120 to 400 ° C. with alkali or alkaline earth metal alcoholates with 6 to 25 carbon atoms in a homogeneous phase without the use of additional solvents. This creates alkali or alkaline earth halides, which precipitate out and can be removed by filtration, washing out or as part of a distillation residue. Excess reagent can be converted into insoluble inorganic salts by the slight addition of acids or acidic salts or can be filtered off bound to bleaching earth. They are not a new threat to the environment.
Für das erfindungsgemäße Verfahren können Kohlenwasserstofföle wie Wärmeträgeröle, Isolieröle, Hydrauliköle, Schweröle, Schmieröle, Neutralöle, Altölfraktionen, Paraffinöle oder organische Kohlenwasserstoffzwischenprodukte eingesetzt werden.Hydrocarbon oils such as heat transfer oils, insulating oils, hydraulic oils, heavy oils, lubricating oils, neutral oils, waste oil fractions, paraffin oils or organic hydrocarbon intermediates can be used for the process according to the invention.
Wichtig bei diesem Verfahren ist, daß das verwendete Alkoholat unter den Reaktionsbedingungen in den Kohlenwasserstoffölen löslich ist. Die Bedingungen der Löslichkeit wird von allen Alkoholaten mit gradkettigen, verzweigten und cyclischen Alkylresten mit mindestens 6 C-Atomen erfüllt. Eine obere Grenze von 25 C-Atomen wird weniger von der Wirksamkeit als von der Verfügbarkeit der zugehörigen Alkohole bestimmt. Allerdings ist bei großen Alkylresten der Anteil der wirksamen Alkoholatgruppe gering. Technisch interessant sind Alkoholate mit Alkylresten mit 8 bis 20 C-Atomen, wobei ein besonders günstiger Kompromiß bei Alkylgruppen mit 8 bis 14 C-Atomen liegt, wo gute Löslichkeit und Verfügbarkeit mit noch günstigem Wirkgruppenanteil kombiniert sind.It is important in this process that the alcoholate used is soluble in the hydrocarbon oils under the reaction conditions. The conditions of solubility are fulfilled by all alcoholates with straight-chain, branched and cyclic alkyl radicals with at least 6 carbon atoms. An upper limit of 25 carbon atoms is determined less by the effectiveness than by the availability of the associated alcohols. However, the proportion of the active alcoholate group is small in the case of large alkyl residues. Alcoholates with alkyl radicals with 8 to 20 C atoms are technically interesting, with a particularly favorable compromise for alkyl groups with 8 to 14 C atoms, where good solubility and availability are combined with a still favorable proportion of active groups.
Zu den für die Herstellung der erfindungsgemäßen Enthalogenierungsmittel geeigneten Alkoholen gehören beipielsweise Hexanol-1, -2 und -3, Heptanol-1, -2, -3 und -4, Octanol-1, -3 und -4, Nonanol-1, -2, - 3, -4 und -5, Decanol-1, -2, -3, -4 und -5, Undecanol-1, -2, -3, -4, -5 und -6, Dodecanol-1, -2, -3, -4, -5 und -6, Tridecanol-1, -2, -3, -4, -5, -6 und -7, Tetradecanol-1, -2, -3, -4, -5, -6 und -7 (Myristylalkohol), Pentadecanol-1, -2, -3, -4, -5, -6, -7 und -8, Heptadecanol-1, -2, -3, -4, -5, -6, -7, -8 und -9, Octadecanol-1 (Stearylalkohol), -2, -3, -4, -5, -6, -7, -8 und -9, Nonadecanol-1, -2, -3, -4, -5, -6, -7, -8, -9 und -10 und Eicosanol-1, -2, -3, -4, -5, -6, -7, -8, -9 und -10, ihre höheren Homologen sowie ihre verzweigten Isomeren, weiterhin Cyclohexanol, Cycloheptanol, Cyclooctanol, Cyclononanol, Cyclodecanol, Cycloundecanol, Cyclododecanol, Cyclotridecanol, Cyclotetradecanol, Cyclopentadecanol, Cyclohexadecanol, Cycloheptadecanol, Cyclooctadecanol, Cyclononadecanol und Cycloeicosanol und ihre alkylierten sowie arylierten Derivate, hydrierte Naphthole, Benzylalkohol, Alpha- und Beta-Phenylethanol, Undecen-(1 )-0l-11, Oleylalkohol, Zimtalkohol, Benzhydrol, 2-Hydroxymethyl-bicyclo[2.2.1 ]-heptan und andere.The alcohols suitable for the preparation of the dehalogenating agents according to the invention include, for example, hexanol-1, -2 and -3, heptanol-1, -2, -3 and -4, octanol-1, -3 and -4, nonanol-1, 2, 3, -4 and -5, decanol-1, -2, -3, -4 and -5, undecanol-1, -2, -3, -4, -5 and -6, dodecanol-1, -2, -3, -4, -5 and -6, tridecanol-1, -2, -3, -4, -5, -6 and -7, tetradecanol-1, -2, -3, -4, -5, -6 and -7 (myristyl alcohol), pentadecanol-1, -2, -3, -4, -5, -6, -7 and -8, heptadecanol-1, -2, -3, -4, -5, -6, -7, -8 and -9, octadecanol-1 (stearyl alcohol), -2, -3, -4, -5, -6, -7, -8 and -9, nonadecanol-1, -2, -3, -4, -5, -6, -7, -8, -9 and -10 and eicosanol-1, -2, -3, -4, -5, -6, -7, - 8, -9 and -10, their higher homologues and their branched isomers, cyclohexanol, cycloheptanol, cyclooctanol, cyclononanol, cyclodecanol, cycloundecanol, cyclododecanol, cyclotridecanol, cyclotetradecanol, cyclopentadecanol, cyclohexadecanol, cycloheptadecanol, cyclooctadecanol and cyclooctadecanol cloeicosanol and its alkylated and arylated derivatives, hydrogenated naphthols, benzyl alcohol, alpha and beta-phenylethanol, undecen- (1) -0l-11, oleyl alcohol, cinnamon alcohol, benzhydrol, 2-hydroxymethyl-bicyclo [2.2.1] -heptane and others .
Zahlreiche Vertreter dieser geeigneten Alkohole sind auf petrochemischer oder nativer Basis durch Reaktionen wie Hydrierung von Estern, Hydroformylierung oder Hydratisierung von Olefinen, Guerbet-Reaktion niederer Alkohole, Oxydation und nachfolgende Hydrolyse von höheren Aluminiumalkylen und durch andere Reaktionen im großtechnischen Maßstab zugänglich. Besonders bevorzugt sind die üblicherweise bei der Herstellung von Weichmachern für PVC benutzten verzweigten Alkohole mit 8 bis 14 C-Atomen, wie 2-Ethylhexanol-1, "Isononanol", "Isodecanol", "Isotridecanol" (Hydroformylierungsprodukte von Dimerbuten, Trimerpropen, Trimerbuten bzw. Tetramerpropen), da ihre Alkoholate besondere gute Löslichkeit in Kohlenwasserstoffölen aufweisen.Numerous representatives of these suitable alcohols are accessible on a petrochemical or native basis by reactions such as hydrogenation of esters, hydroformylation or hydration of olefins, Guerbet reaction of lower alcohols, oxidation and subsequent hydrolysis of higher aluminum alkyls and by other reactions on an industrial scale. Particularly preferred are the branched alcohols with 8 to 14 carbon atoms that are usually used in the production of plasticizers for PVC, such as 2-ethylhexanol-1, "isononanol", "isodecanol", "isotridecanol" (hydroformylation products of dimerbutene, trimer propene, trimerbutene or Tetramer propene) because their alcoholates have particularly good solubility in hydrocarbon oils.
Als Enthalogenierungsmittel sind die von obigen Alkoholen mit Alkali- und/oder Erdalkalimetallen gebildeten Alkoholate anwendbar, unter den Alkalialkoholaten vorzugsweise die des Natriums und Kaliums, unter den Erdalkalialkoholaten die des Magnesiums und Calciums. Dabei werden besonders bevorzugt Alkalialkoholate eingesetzt.As the dehalogenating agent, the alcoholates formed by the above alcohols with alkali and / or alkaline earth metals can be used, among the alkali alcoholates preferably those of sodium and potassium, among the alkaline earth alcoholates that of magnesium and calcium. Alkali alcoholates are particularly preferably used.
Die Alkoholate können auf alle dafür bekannten Weisen hergestellt werden, d. h. durch Umsatz von Metall oder Metallhydrid mit Alkohol unter Wasserstoffbildung, durch Umsatz von niederem Alkoholat mit höherem Alkohol unter Abdestillieren des niederen Alkohols sowie aus Metallhydroxid und Alkohol unter azeotroper Entfernung des im Gleichgewicht befindlichen Wassers. Die Darstellung kann auch in situ in Gegenwart des zu enthalogenierenden Substrats erfolgen. Es ist nicht erforderlich, das Alkoholat in Gegenwart von überschüssigem Alkohol einzusetzen, jedoch stört ein kleiner Überschuß nicht.The alcoholates can be prepared in all known ways, i. H. by reacting metal or metal hydride with alcohol with the formation of hydrogen, by reacting lower alcoholate with higher alcohol while distilling off the lower alcohol, and from metal hydroxide and alcohol with azeotropic removal of the water in equilibrium. The representation can also take place in situ in the presence of the substrate to be dehalogenated. It is not necessary to use the alcoholate in the presence of excess alcohol, but a small excess does not interfere.
Die stöchiometrisch erforderliche Menge errechnet sich aus dem Chlorgehalt unter Berücksichtigung von Feuchtigkeitsgehalt und enthaltenen Säure- und Estergruppen, die ebenfalls mit Alkoholat reagieren. Die aufgewendete Reagenzmenge beträgt das 0,5- bis 5fache der stöchiometrisch erforderlichen Menge. Obwohl auch höhere Überschüsse nicht schaden, werden sie aus verfahrenstechnischen Gründen und aus Kostengründen vermieden. Vorzugsweise werden Reagenzmengen eingesetzt, die das 1,5- bis 5fache der stöchiometrischen Menge entsprechen. Geringe Überschüsse genügen gewöhnlich, wenn man im oberen Teil des Temperaturbereichs arbeitet.The stoichiometrically required amount is calculated from the chlorine content, taking into account the moisture content and the acid and ester groups that also react with alcoholate. The amount of reagent used is 0.5 to 5 times the stoichiometrically required amount. Although higher surpluses do not hurt either, they are avoided for procedural and cost reasons. Amounts of reagent which correspond to 1.5 to 5 times the stoichiometric amount are preferably used. Small excesses are usually sufficient if you work in the upper part of the temperature range.
Für die Enthalogenierung sind Temperaturen von 120 bis 400 °C geeignet. Dabei kann die Reaktionszeit an der unteren Grenze bis zu 10 Stunden und an der oberen Grenze wenige Sekunden betragen. Bevorzugt werden Temperaturen von 180 bis 380 °C, besonders vorteilhaft ist ein Temperaturbereich von 220 bis 350 °C.Temperatures of 120 to 400 ° C are suitable for dehalogenation. The response time can be up to 10 hours at the lower limit and a few seconds at the upper limit. Temperatures of 180 to 380 ° C are preferred, a temperature range of 220 to 350 ° C is particularly advantageous.
Temperaturen der genannten Bereiche kommen im Verlaufe einer üblichen Altölaufarbeitung ohnehin in Destillationsstufen vor, so daß sich zusätzliche Reaktoren bei geschickter Einfügung in den Prozeß erübrigen. Andererseits können auch einzelne kleinere Chargen in einem üblichen Reaktionskessel absatzweise enthalogeniert werden.Temperatures in the ranges mentioned occur in the course of conventional waste oil processing anyway in distillation stages, so that additional reactors are unnecessary if they are skillfully inserted into the process. On the other hand, individual smaller batches can also be batch-dehalogenated in a conventional reaction kettle.
Das Verfahren ist also sowohl für kleine diskontinuierliche Chargen anwendbar als auch in vollkontinuierliche Prozesse integrierbar.The process can therefore be used both for small discontinuous batches and can be integrated into fully continuous processes.
Da kohlenwasserstofflösliche Alkoholate eingesetzt werden, kann die Enthalogenierung ohne Lösemittel in einer homogenen Phase durchgeführt werden. Dadurch werden ein minimaler Chemikalienverbrauch und kurze Reaktionszeiten ermöglicht. Darüber hinaus stellen die anfallenden Rückstände bei der Entsorgung keine Sicherheits- und Umweltprobleme dar.Since hydrocarbon-soluble alcoholates are used, the dehalogenation can be carried out in a homogeneous phase without solvents. This enables minimal chemical consumption and short reaction times. In addition, the residues arising during disposal do not pose any safety and environmental problems.
Die Erfindung wird durch folgende Beispiele erläutert:The invention is illustrated by the following examples:
Entchlorierungsreagens: 18 g Natrium und 130 g 2-Ethylhexanol-1 werden unter Stickstoff 6 Stunden bei 150 °C und eine Stunde bei 200 °C gerührt, wobei eine klare Flüssigkeit entsteht:
- 148 g 80 %iges Na-Ethylhexylat
- 148 g of 80% Na ethyl hexoxide
Kohlenwasserstofföl: Man verwendet ein wiederaufgearbeitetes Altöl, das nicht readditiviert ist.
Die theoretisch benötigte, stöchiometrische Menge beträgt danach:
- 3,1 g Na-Ethylhexylat / kg Öl
- 3.1 g Na ethyl hexoxide / kg oil
Entchlorierung: 500 g wiederaufgearbeitetes Altöl werden mit 7,9 g 80 %igem Na-Ethylhexylat versetzt und dann 30 Minuten bei 350 °C gerührt. Es wird eine Probe gezogen, in der nach Filtration von ausgefallenem NaCI organisch gebundenes Chlor durch Wickbold-Verbrennung bestimmt wird. Die Analysenergebnisse stehen in Tabelle 2.Dechlorination: 500 g of reprocessed waste oil are mixed with 7.9 g of 80% Na ethyl hexoxide and then stirred at 350 ° C for 30 minutes. A sample is taken in which, after filtration of precipitated NaCl, organically bound chlorine is determined by Wickbold combustion. The analysis results are shown in Table 2.
Das Altöl wird auf Raumtemperatur gekühlt. Überschüssiges Na-Ethylhexylat wird durch konz. Schwefelsäure zerstört. Nach Filtration der anorganischen Salze wird das Altöl unter Vakuum destilliert.The waste oil is cooled to room temperature. Excess Na ethyl hexoxide is concentrated by. Sulfuric acid destroyed. After filtration of the inorganic salts, the waste oil is distilled under vacuum.
Es wird wie in Beispiel 1 verfahren. Die verwendeten Kohlenwasserstofföle sind in Tabelle 1 zusammengestellt.
Die Ergebnisse der Entchlorierungsversuche gehen aus Tabelle 2 hervor.
500 g eines als Wärmeträgeröl einzusetzenden Dibenzyltoluol-Isomerengemisches enthalten 1 200 ppm Chlor.500 g of a dibenzyltoluene isomer mixture to be used as heat transfer oil contain 1,200 ppm chlorine.
Die theoretisch benötigte, stöchiometrische Menge Alkoholat beträgt:
- 5,1 g Na-Ethylhexylat / kg Öl
- 5.1 g Na ethyl hexoxide / kg oil
Durch zweimalige Destillation bei Normaldruck und 360 °C über der 5fachen stöchiometrischen Menge Na-Ethylhexylat wird der Chlorgehalt auf 4 ppm verringert. Als Destillat werden 93 Gew.-% des eingesetzten Rohproduktes erhalten.The chlorine content is reduced to 4 ppm by distillation twice at normal pressure and 360 ° C. above 5 times the stoichiometric amount of Na ethyl hexoxide. 93% by weight of the crude product used is obtained as the distillate.
Claims (9)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3621175 | 1986-06-25 | ||
DE19863621175 DE3621175A1 (en) | 1986-06-25 | 1986-06-25 | METHOD FOR ENTHALOGENATING HYDROCARBON OILS |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0250748A1 EP0250748A1 (en) | 1988-01-07 |
EP0250748B1 true EP0250748B1 (en) | 1989-07-19 |
Family
ID=6303601
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP87105740A Expired EP0250748B1 (en) | 1986-06-25 | 1987-04-16 | Process for the dehalogenation of hydrocarbon oils |
Country Status (4)
Country | Link |
---|---|
US (1) | US4776947A (en) |
EP (1) | EP0250748B1 (en) |
JP (1) | JPH0813973B2 (en) |
DE (2) | DE3621175A1 (en) |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5189105A (en) * | 1987-02-09 | 1993-02-23 | Mitsubishi Chemical Industries Limited | Alcohol mixture for plasticizer |
FR2620055B1 (en) * | 1987-09-03 | 1991-05-10 | Atochem | CHEMICAL PROCESS OF DESTRUCTION OF HALOGENATED ORGANIC PRODUCTS |
US5220109A (en) * | 1987-09-03 | 1993-06-15 | Atochem | Destruction of halogenated organic species |
DE3900159A1 (en) * | 1989-01-04 | 1990-07-05 | Geut Ag | METHOD FOR REFURBISHING ALTOEL |
DE3903105A1 (en) * | 1989-02-02 | 1990-08-09 | Huels Chemische Werke Ag | LIQUID ENTHALOGEN |
US5185488A (en) * | 1989-09-28 | 1993-02-09 | Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of Natural Resources | Process for the reductive dehalogenation of polyhaloaromatics with sodium or calcium in a lower alcohol |
FR2656603B1 (en) | 1989-12-28 | 1993-05-21 | Atochem | METHODS OF SYNTHESIS OF BENZYLTOLUENE AND LOW CHLORINE DIBENZYLTOLUENE. |
US5290432A (en) * | 1990-05-09 | 1994-03-01 | Chemical Waste Management, Inc. | Method of treating toxic aromatic halogen-containing compounds by electrophilic aromatic substitution |
US5141629A (en) * | 1990-05-15 | 1992-08-25 | State Of Israel, Atomic Energy Commission | Process for the dehalogenation of organic compounds |
US5490919A (en) * | 1990-08-14 | 1996-02-13 | State Of Isreal, Atomic Energy Commission | Process for the dehalogenation of organic compounds |
US5093011A (en) * | 1990-12-12 | 1992-03-03 | Chemical Waste Management, Inc. | Process for dehalogenation of contaminated waste materials |
WO1993005845A1 (en) * | 1991-09-20 | 1993-04-01 | Roger Charles Wilkinson | Method/process for the disposal of halogenated hydrocarbons and similar intractable materials |
JP2638483B2 (en) * | 1994-06-30 | 1997-08-06 | 株式会社関西テック | Method for treating polychlorinated aromatic compounds |
US6613723B2 (en) | 2001-12-06 | 2003-09-02 | Exxonmobil Chemical Patents Inc. | Overbased barium complexes of C8 to C10 carboxylic acids |
US20040087826A1 (en) * | 2002-11-04 | 2004-05-06 | Cash Alan B. | Method for treating dioxin contaminated incineration ash |
RU2287552C2 (en) * | 2004-12-22 | 2006-11-20 | Институт Проблем Химической Физики Российской Академии Наук (Ипхф Ран) | Method of production of the polyolefin bases of the synthetic oils |
US20080027252A1 (en) * | 2006-07-27 | 2008-01-31 | Burkholder Kermit L | Oil dehalogenation method |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3539653A (en) * | 1968-09-05 | 1970-11-10 | Dow Chemical Co | Method of removing alkyl halides from a hydrocarbon stream with an alkanol amine |
US4327027A (en) * | 1979-06-15 | 1982-04-27 | Vertac Chemical Corporation | Chemical detoxification of toxic chlorinated aromatic compounds |
US4337368A (en) * | 1980-04-21 | 1982-06-29 | The Franklin Institute | Reagent and method for decomposing halogenated organic compounds |
US4400552A (en) * | 1980-04-21 | 1983-08-23 | The Franklin Institute | Method for decomposition of halogenated organic compounds |
US4351718A (en) * | 1981-06-01 | 1982-09-28 | General Electric Company | Method for removing polyhalogenated hydrocarbons from nonpolar organic solvent solutions |
IT1161215B (en) * | 1983-03-10 | 1987-03-18 | Sea Marconi Decontamin Srl | PROCESS FOR THE DECOMPOSITION AND DECONTAMINATION OF ORGANIC COMPOUNDS AND HALOGENATED TOXIC AGENTS |
AU555461B2 (en) * | 1983-03-10 | 1986-09-25 | Sea Marconi Decontamination S.R.L. | Process for the decomposition and decontamination of organic substances and halogenated toxic materials |
IT1206508B (en) * | 1983-07-22 | 1989-04-27 | Sea Marconi Decontamin Srl | CONTINUOUS PROCESS FOR THE DECOMPOSITION AND DECONTAMINATION OF ORGANIC COMPOUNDS AND HALOGENATED TOXIC AGENTS. |
US4532028A (en) * | 1983-10-24 | 1985-07-30 | Niagara Mohawk Power Corporation | Method for reducing content of halogenated aromatics in hydrocarbon solutions |
US4574013A (en) * | 1985-04-18 | 1986-03-04 | Galson Research Corporation | Method for decontaminating soil |
US4663027A (en) * | 1986-03-03 | 1987-05-05 | General Electric Company | Method for removing polyhalogenated hydrocarbons from non-polar organic solvent solutions |
-
1986
- 1986-06-25 DE DE19863621175 patent/DE3621175A1/en not_active Withdrawn
-
1987
- 1987-04-16 EP EP87105740A patent/EP0250748B1/en not_active Expired
- 1987-04-16 DE DE8787105740T patent/DE3760321D1/en not_active Expired
- 1987-06-11 US US07/060,487 patent/US4776947A/en not_active Expired - Lifetime
- 1987-06-24 JP JP62155634A patent/JPH0813973B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
DE3760321D1 (en) | 1989-08-24 |
US4776947A (en) | 1988-10-11 |
JPS638482A (en) | 1988-01-14 |
DE3621175A1 (en) | 1988-01-07 |
EP0250748A1 (en) | 1988-01-07 |
JPH0813973B2 (en) | 1996-02-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0250748B1 (en) | Process for the dehalogenation of hydrocarbon oils | |
CA1174806A (en) | Method for removing polyhalogenated hydro-carbons from nonpolar organic solvent solutions | |
EP0160668B1 (en) | Method for reducing content of halogenated aromatics in hydrocarbon solutions | |
US4351718A (en) | Method for removing polyhalogenated hydrocarbons from nonpolar organic solvent solutions | |
US4377471A (en) | Method for removing polychlorinated biphenyls from transformer oil | |
DE3623430A1 (en) | METHOD FOR HYDROGENATING TREATMENT WITH CHLORBIPHENYLENE AND THE LIKE CONTAMINATED MINERAL OILS | |
EP0225849B1 (en) | Process for dehalogenating halogenated aliphatic and aromatic compounds | |
EP0324754B1 (en) | Process for dehalogenation of hydrocarbons | |
EP0299149A2 (en) | Process for working up used lubricants by hydrogenation | |
DE3713994A1 (en) | METHOD FOR DEGRADING HALOGENED ORGANIC COMPOUNDS | |
DE69004734T4 (en) | Process for the decomposition of halogenated organic compounds in a contaminated medium. | |
DE69612978T2 (en) | METHOD FOR REFINING CONSUMED LUBRICATING OILS BY ALKALI TREATMENT. | |
DD296847A5 (en) | PROCESS FOR REMOVING POLYCHLORATED BIPHENYLE | |
US5043054A (en) | Process for dehalogenation of contaminated waste materials | |
DE3232683A1 (en) | METHOD FOR RERAFFINATING ALTOEL | |
DE69026605T2 (en) | Process for the dehalogenation of organic compounds | |
DE3632366C2 (en) | Process for the removal of halogenated hydrocarbons from the gas phase | |
US5174893A (en) | Process for dehalogenation of contaminated waste materials | |
DE2939242A1 (en) | METHOD FOR PURIFYING FATTY ACIDS | |
DE670419C (en) | Process for the production of halogen-containing oxalkyl ethers | |
EP0572630B1 (en) | Method of regenerating used lubricants | |
US4504383A (en) | Rerefining used oil with borohydride reducing agents | |
DE3700520A1 (en) | METHOD FOR DEGRADING POLYHALOGENATED AROMATIC COMPOUNDS | |
DE867389C (en) | Process for working up the reaction mixture formed in the preparation of olefins by splitting off hydrogen chloride from alkyl chlorides | |
EP0442088A1 (en) | Process for the oxidation of water insoluble organic compounds |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): BE DE FR GB IT NL |
|
17P | Request for examination filed |
Effective date: 19871113 |
|
17Q | First examination report despatched |
Effective date: 19880713 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE DE FR GB IT NL |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) | ||
REF | Corresponds to: |
Ref document number: 3760321 Country of ref document: DE Date of ref document: 19890824 |
|
ET | Fr: translation filed | ||
ITF | It: translation for a ep patent filed | ||
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
ITTA | It: last paid annual fee | ||
REG | Reference to a national code |
Ref country code: GB Ref legal event code: 732E |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: TP |
|
NLS | Nl: assignments of ep-patents |
Owner name: HANS-DIETER MAIER |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20060411 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20060413 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20060419 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20060420 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20060430 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20060502 Year of fee payment: 20 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20070416 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: PE20 |
|
NLV7 | Nl: ceased due to reaching the maximum lifetime of a patent |
Effective date: 20070416 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20070415 |
|
BE20 | Be: patent expired |
Owner name: *MAIER HANS-DIETER Effective date: 20070416 |