EP2209875A1 - Verbesserte detektion von markierstoffen - Google Patents
Verbesserte detektion von markierstoffenInfo
- Publication number
- EP2209875A1 EP2209875A1 EP08848991A EP08848991A EP2209875A1 EP 2209875 A1 EP2209875 A1 EP 2209875A1 EP 08848991 A EP08848991 A EP 08848991A EP 08848991 A EP08848991 A EP 08848991A EP 2209875 A1 EP2209875 A1 EP 2209875A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- markers
- polar
- liquids
- polar liquid
- alkyl
- 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.)
- Withdrawn
Links
- 238000001514 detection method Methods 0.000 title claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 98
- 238000000034 method Methods 0.000 claims abstract description 60
- 239000003550 marker Substances 0.000 claims abstract description 21
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 35
- 239000002480 mineral oil Substances 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 9
- 235000010446 mineral oil Nutrition 0.000 claims description 9
- 239000002283 diesel fuel Substances 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 7
- 238000002372 labelling Methods 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 4
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 3
- -1 Dimethylpropyl Chemical group 0.000 description 120
- 125000003118 aryl group Chemical group 0.000 description 19
- 125000001033 ether group Chemical group 0.000 description 17
- 125000004430 oxygen atom Chemical group O* 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 16
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 description 10
- 239000012071 phase Substances 0.000 description 10
- 125000000623 heterocyclic group Chemical group 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 125000004104 aryloxy group Chemical group 0.000 description 7
- 239000000975 dye Substances 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 150000004056 anthraquinones Chemical class 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 125000005842 heteroatom Chemical group 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- 125000005916 2-methylpentyl group Chemical group 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 3
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 2
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical compound CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000000980 acid dye Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 239000000987 azo dye Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 238000001917 fluorescence detection Methods 0.000 description 2
- 238000001506 fluorescence spectroscopy Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 2
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 description 1
- 125000005919 1,2,2-trimethylpropyl group Chemical group 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 1
- XTFIVUDBNACUBN-UHFFFAOYSA-N 1,3,5-trinitro-1,3,5-triazinane Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)C1 XTFIVUDBNACUBN-UHFFFAOYSA-N 0.000 description 1
- 125000004214 1-pyrrolidinyl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- QLVKECUOHNDWOI-UHFFFAOYSA-N 2-oxo-1,3,2$l^{5}-diazaphosphonan-2-amine Chemical compound NP1(=O)NCCCCCCN1 QLVKECUOHNDWOI-UHFFFAOYSA-N 0.000 description 1
- GSOFREOFMHUMMZ-UHFFFAOYSA-N 3,4-dicarbamoylnaphthalene-1,2-dicarboxylic acid Chemical class C1=CC=CC2=C(C(O)=N)C(C(=N)O)=C(C(O)=O)C(C(O)=O)=C21 GSOFREOFMHUMMZ-UHFFFAOYSA-N 0.000 description 1
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- HJUFTIJOISQSKQ-UHFFFAOYSA-N fenoxycarb Chemical compound C1=CC(OCCNC(=O)OCC)=CC=C1OC1=CC=CC=C1 HJUFTIJOISQSKQ-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- BSIHWSXXPBAGTC-UHFFFAOYSA-N isoviolanthrone Chemical compound C12=CC=CC=C2C(=O)C2=CC=C3C(C4=C56)=CC=C5C5=CC=CC=C5C(=O)C6=CC=C4C4=C3C2=C1C=C4 BSIHWSXXPBAGTC-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 125000004194 piperazin-1-yl group Chemical group [H]N1C([H])([H])C([H])([H])N(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- GGVMPKQSTZIOIU-UHFFFAOYSA-N quaterrylene Chemical group C12=C3C4=CC=C2C(C2=C56)=CC=C5C(C=57)=CC=CC7=CC=CC=5C6=CC=C2C1=CC=C3C1=CC=CC2=CC=CC4=C21 GGVMPKQSTZIOIU-UHFFFAOYSA-N 0.000 description 1
- 239000000700 radioactive tracer Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Chemical group 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- BIGSSBUECAXJBO-UHFFFAOYSA-N terrylene Chemical group C12=C3C4=CC=C2C(C=25)=CC=CC5=CC=CC=2C1=CC=C3C1=CC=CC2=CC=CC4=C21 BIGSSBUECAXJBO-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/224—Amides; Imides carboxylic acid amides, imides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/003—Marking, e.g. coloration by addition of pigments
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/223—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond having at least one amino group bound to an aromatic carbon atom
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/26—Oils; Viscous liquids; Paints; Inks
- G01N33/28—Oils, i.e. hydrocarbon liquids
- G01N33/2835—Specific substances contained in the oils or fuels
- G01N33/2882—Markers
Definitions
- the present invention relates to a method for the detection of markers in contaminated non-polar liquids using polar liquids.
- the invention further relates to methods for labeling contaminated nonpolar liquids.
- WO 95/10581 discloses a method for detecting azo dyes in labeled mineral oils. The detection is carried out by treating the labeled mineral oil with an extractant containing water, a solvent and base, wherein the azo dye is extracted from the mineral oil in the aqueous phase and detected in the aqueous phase.
- US 5,205,840 describes methods for marking mineral oils and methods for detecting the markers.
- the markers are extracted and reacted with the aid of a mixture containing water, a strong base and an additional solvent from the mineral oil.
- the detection of the marker takes place in the extracted mixture.
- markers for non-polar liquids are often used in very low concentrations in the ppb or ppm range. Sufficient extraction for later detection of these markers with common polar extractants is therefore often difficult.
- the nonpolar liquids, such as oils, especially mineral oils are often contaminated by substances that make reliable detection of the markers in the often used low concentrations difficult or even impossible.
- the object of the present invention was therefore to provide methods for the detection of markers in contaminated non-polar liquids which do not have the abovementioned problems.
- non-polar liquids are liquids or mixtures of liquids having a dielectric constant (18 ° C., 50 Hz) of less than 4.
- the non-polar liquids are generally available commercially.
- the nonpolar liquids preferably contain oils, more preferably mineral oils and in particular diesel fuels.
- the non-polar liquid is a mineral oil, in particular a diesel fuel.
- the non-polar liquid contains impurities.
- impurities of the non-polar liquid are to be understood as meaning substances which detect the markers in Disrupt or make impossible step (c) of the above-mentioned process.
- the impurities are substances that are more soluble in the polar liquid than in the non-polar liquid.
- the contaminated nonpolar liquid is preferably contaminated mineral oils, in particular contaminated diesel fuels.
- Terms of the form C 3 -Cb in the context of this invention designate chemical compounds or substituents with a certain number of carbon atoms.
- the number of carbon atoms can be selected from the entire range from a to b, including a and b, a is at least 1 and b is always greater than a.
- Further specification of the chemical compounds or substituents is made by expressions of the form Ca-Cb-V.
- V here stands for a chemical compound class or substituent class, for example for alkyl compounds or alkyl substituents.
- Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, particularly preferably fluorine or chlorine.
- C 1 -C 20 -alkyl straight-chain or branched hydrocarbon radicals having up to 20 carbon atoms, for example C 1 -C 10 -alkyl or C 2 -C 20 -alkyl, preferably C 1 -C 10 -alkyl, for example C 1 -C 3 -alkyl, such as methyl, ethyl, propyl, isopropyl or C 4 -C 6 -alkyl, n-butyl, sec-butyl, tert-butyl, 1, 1-dimethylethyl, pentyl, 2-methylbutyl, 1, 1
- Dimethylpropyl 1, 2-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 2-methylpentyl, 3-methyl-pentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2, 2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl- 2-methylpropyl, or C 7 -Cio-alkyl, such as heptyl, octyl, 2-ethyl-hexyl, 2,4,4-trimethylpentyl, 1, 1, 3,3-tetramethylbutyl, nonyl or decyl and their isomers.
- C 1 -C 20 -alkoxy denotes a straight-chain or branched alkyl group having 1 to 20 carbon atoms (as mentioned above) which are attached via an oxygen atom (-O-), for example C 1 -C 10 -alkoxy or C 2 -C 20 -alkoxy C 1 -C 10 -alkyloxy, particularly preferably C 1 -C 3 -alkoxy, for example methoxy, ethoxy, propoxy.
- C3-C15-cycloalkyl monocyclic, saturated hydrocarbon groups having 3 to 15 carbon ring members, preferably Cs-Cs-cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl and a saturated or unsaturated cyclic system such as.
- Aryl a mono- to trinuclear aromatic ring system containing 6 to 14 carbon ring members, e.g. As phenyl, naphthyl or anthracenyl, preferably a mono- to binuclear, more preferably a mononuclear aromatic ring system.
- Aryloxy is a mono- to trinuclear aromatic ring system (as mentioned above), which is attached via an oxygen atom (-O-), preferably a mononuclear to dinuclear, more preferably a mononuclear aromatic ring system.
- Heterocycles five- to twelve-membered, preferably five- to nine-membered, particularly preferably five- to six-membered, oxygen, nitrogen and / or sulfur atoms, ring rings optionally containing several rings such as furyl, thiophenyl, pyrryl, pyridyl, indolyl, benzoxazolyl, Dioxolyl, dioxyl, benzimidazolyl, benzthiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyrryl, methoxyfuryl, dimethoxypyridyl, difluoropyridyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl.
- the heterocycles may be attached in any manner chemically to the compounds of the general formula (I), for example via a bond to a carbon atom of the heterocycle or a bond to one of the heteroatoms.
- five- or six-membered saturated nitrogen-containing ring systems which are attached via a ring nitrogen atom and which may contain one or two further nitrogen atoms or another oxygen or sulfur atom.
- C 1 -C 20 -alkylamino means an amine group which is substituted by one, straight-chain or branched alkyl groups having 1 to 20 carbon atoms (as mentioned above), for example C 1 -C 2 -dialkylamino or C 3 -C 4 -dialkylamino, preferably C 1 -C 2 -cycloalkyl Dialkylamino attached via the nitrogen.
- C 1 -C 20 -dialkylamino means a substituted amine group with two, identical or different, straight-chain or branched alkyl groups having 1 to 20 carbon atoms (as mentioned above), for example C 1 -C 2 -dialkylamino or C 3 -C 4 -dialkylamino, preferably C 1 -C 2 -cycloalkyl Dialkylamino attached via the nitrogen.
- markers which can be detected in nonpolar liquids by means of physical and / or chemical processes are suitable as markers. Preferred are markers which can be detected in low concentrations in the ppb or ppm range.
- concentration units ppm and ppb in the context of this invention refer to the ratio of weight units unless stated otherwise.
- marking does not mean the coloring of the non-polar liquids with the aid of dyes.
- the marking substances are chemical compounds from the classes of phthalocyanine, naphthalocyanines, nickel-dithiolene complexes, aminium compounds of aromatic amines, methine dyes, azulenesquaric acid dyes, anthraquinones, quaterrylene, terrylene, perylene dyes, naphthalene tetracarboxylic diimides, dibene - zanthrone and isodibenzanthrone.
- these compounds have their absorption maximum in the range of 600 to 1200 nm.
- PCT / EP2007 / 052122 European application 07105776.4, PCT application PCT / EP2007 / 051745 and WO 2006/097434 A2.
- phthalocyanines page (p. 1), line (Z.) 37 - p. 3, Z.9), naphthalocyanines (p. 3, Z.11 - p. 4, Z.20), nickel-dithiolene complexes (S.4, Z. 22 - P. 4, Z. 46), aminium compounds of aromatic amines (S. 5, Z. 1 - Z. 31), methine dyes ( P. 5, Z. 33 - p. 6, line 29), azulenesquaric acid dyes (p. 6, p. 31 - p. 7, line 16).
- the markers can be prepared by methods known to those skilled in the art or known per se. Most preferably, the markers are given by anthraquinones of the general formulas (I) to
- the variables R, R 1 and R 2 independently of one another are C 1 -C 20 -alkyl which is optionally interrupted by 1 to 4 oxygen atoms in ether function, or aryl which may optionally have one or a plurality of C 1 -C 20 -alkyl optionally interrupted by 1 to 4 oxygen atoms in ether function.
- X in the formulas (I) to (III) assumes either the meaning of two hydrogen atoms, two cyano groups in the 2,3- or 6,7-position or two identical groups CH (R 9 ) (R 10 ) in 2,3- or 6,7-position of Anthrachinongerüstes.
- the latter two groups CH (R 9 ) (R 10 ) are either two groups CH (COOR ') 2, CH (CN) COOR' or CH (CN) 2, where the radicals R 'are preferably Ci-C 2 o-alkyl, which is optionally interrupted by 1 to 4 oxygen atoms in ether function, or aryl, which is optionally substituted by one or more Ci-C2o-alkyl which is optionally interrupted by 1 to 4 oxygen atoms in ether function, mean.
- the selection of the variables R, R1 and R2 is preferably selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, hept-3-yl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, Undecyl, dodecyl, tridecyl, 3,5,5,7-tetramethylnonyl, isotridecyl, tetradecyl, penta-decyl
- the selection of the variables R, R 1 and R 2 is preferably carried out from the group consisting of unsubstituted phenyl simply in the 2-, 3- and 4-positions, the double in the 2,3-, 2,4- and 3,4-position and the triple in 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- and 3,4,5-substituted phenyl, which are substituted with the previously exemplarily enumerated, optionally interrupted with oxygen in ether function Ci-C2O alkyl radicals.
- Anthraquinone derivatives of the compounds of the formulas IV to VII shown below are also to be mentioned as markers to be used according to the invention:
- W is hydrogen or NHR ", p is 1, 2, 3 or 4, wherein for p greater than 1 the radicals are identical, and
- Heterocycle optionally substituted with one or more C 1 -C 20 -alkyl groups optionally interrupted by 1 to 4 oxygen atoms in ether function;
- Aryl which is optionally substituted by one or more C 1 -C 20 -alkyl which is optionally interrupted by 1 to 4 oxygen atoms in ether function, C 1 -C 20 -alkoxy, C 1 -C 20 -alkylamino or C 1 -C 20 -di- alkylamino;
- Phenyl-C 1 -C 4 -alkyl which is optionally interrupted in the phenyl radical by one or more C 1 -C 20 -alkyl which is optionally interrupted by 1 to 4 oxygen atoms in ether function, C 1 -C 20 -alkoxy, C 1 -C 20 -alkylamino or C 1 -C 20 -cycloalkyl
- Dialkylamino is substituted.
- R "in the formulas IV to VII is particularly preferably C 1 -C 20 -alkyl which is optionally interrupted by 1 to 4 oxygen atoms in ether function, or aryl which is optionally substituted by one or more C 1 -C 20 -alkyl which is optionally substituted by 1 to 4 Oxygen atoms in ether function is interrupted.
- R "in the formulas IV to VII is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, hept-3-yl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, 3,5,5,7-tetramethyl-nonyl, isotridecyl, Tetradecyl, pentadecyl, methoxymethyl, 2-ethyl-hexoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propyl
- the markers are most preferably given by Anthrachinondicarbonklareimide of the general formulas (VIII):
- R 11 , R 12 , R 13 , R 14 are independently, identical or different H, Ci-C 2 o-alkyl, aryl, heterocycles
- R 16 , R 17 , R 18 , R 19 independently of one another, identical or different, are H, C 1 -C 20 -alkyl, C 1 -C 20 -alkoxy, aryl, aryloxy, NR 1 R 2 , halogen, CN, NO 2 ,
- substituents R 11 to R 19 may each be interrupted at any position by one or more heteroatoms, the number of these heteroatoms being not more than 10, preferably not more than 8, very particularly preferably not more than 5 and in particular not more than 3 is, and / or in any position, but not more than five times, preferably not more than four times and more preferably not more than three times, by NR 1 R 2 , CONR 1 R 2 , COOR 1 , SO 3 R 1 , CN, NO 2 , C 1 -C 20 -alkyl, C 1 -C 20 -alkoxy, aryl, aryloxy, heterocycles or halogen may be substituted, which may also be substituted at most twice, preferably at most once with said groups.
- radicals R 21 , R 22 , R 23 and R 24 and R 26 , R 27 , R 28 and R 29 each represent a heterocyclic radical or an aryloxy.
- the aryloxy substituents may themselves be substituted with up to four, preferably with two, Ci-C4-alkyl groups.
- M is twice hydrogen, twice lithium, magnesium, zinc, copper, nickel, VO, TiO, AICI, AIOH, AlOCOCH 3 , AIOCOCF3, or SiR 29 R 30 .
- R 29 and R 30 are independently, the same or different, H, OH, Cl, C 1 -C 20 -alkyl, aryl, C 1 -C 20 -alkoxy or aryloxy.
- phthalocyanines are known per se and can be prepared by methods known per se, such as those used in the preparation of phthalocyanines or naphtha-locyanines and as described, for example, in F. H. Moser, A.L. Thomas “The Phthalocyanines", CRC Press, Boca Rota, Florida, 1983, or J. Am.
- synthesis of the phthalocyanines is carried out, for example, according to the methods described in WO 2005/070935.
- phthalocyanines of the formulas (IX) or (X) in which all R 21 to R 28 are heterocyclic radicals and in each case pyrrolidin-1-yl, piperidin-1-yl, piperazin-1-yl or morpholine 4-yl, where these radicals may be monosubstituted to trisubstituted, preferably monosubstituted, by C 1 -C 4 -alkyl, benzyl, phenylethyl or phenyl.
- the markers are preferably given by naphthalocyanines of the general formula (XI):
- Y 1 to Y 8 are each independently hydrogen, hydroxy, C 1 -C 20 -alkyl or C 1 -C 20 -alkoxy, where the alkyl groups may each be interrupted by 1 to 4 oxygen atoms in ether function and are optionally substituted by phenyl, and
- Y 9 to Y 12 independently of one another are each hydrogen, C 1 -C 20 -alkyl or C 1 -C 20 -alkoxy, where the alkyl groups may each be interrupted by 1 to 4 oxygen atoms in ether function, halogen, hydroxysulfonyl or C 1 -C 4 -dialkylsulfamoyl.
- R 29 and R 30 independently of one another, identical or different, are H, OH, Cl, C 1 -C 20 -alkyl, aryl, C 1 -C 20 -alkoxy or aryloxy.
- naphthalocyanines of the formula (XI) in which at least one of the radicals Y 1 to Y 8 is different from hydrogen.
- naphthalocyanines are known per se and can be obtained according to the methods of the above-mentioned prior art (Moser, J. Am. Chem. Soc.).
- RSI 1 R ⁇ R 3 S 1 R 34 independently of one another, identically or differently H, C 1 -C 20 -alkyl, aryl, heterocycles, NR 35 R 36 ,
- R 3 S 1 R 36 independently of one another, identical or different, are H, C 1 -C 20 -alkyl, aryl, heterocycles,
- substituents R 31 to R 36 can each be interrupted at any position by one or more heteroatoms, the number of these heteroatoms not exceeding 10, preferably not more than 8, very particularly preferably not more than 5 and in particular not more than 3 is, and / or in any position, but not more than five times, preferably not more than four times and more preferably not more than three times, by C 1 -C 20 alkyl, C 1 -C 20 alkoxy, aryl, aryloxy or heterocycles may be substituted These may likewise be substituted at most twice, preferably at most once, with the abovementioned groups.
- the provision of the contaminated non-polar liquids containing markers according to step (a) of the process according to the invention can be carried out in any desired manner.
- the labels are used in the form of solutions, but may also have been added as solids to the contaminated nonpolar liquids to be labeled.
- Preferred solvents are aromatic hydrocarbons, such as toluene or xylene.
- a concentration of markers of from 2 to 50% by weight, based on the solution, is generally selected.
- polar liquids are liquids or mixtures of liquids having a dielectric constant greater than 30.
- the polar liquids are generally available commercially.
- the polar liquids preferably contain polar organic solvents.
- the polar liquids are aprotic.
- the polar liquids are aprotic polar solvents.
- Preferred polar liquids are also water, alcohols, ethers, ketones, esters or sulfones.
- alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, or tert-butyl alcohol are used as polar liquids.
- polar liquids acetic acid, acetone, acetonitrile, carbon tetrachloride, chlorobenzene, chloroform, 1, 2-dichloroethane, dimethylformamide (DMF), dimethylsulfoxide (DMSO), ethyl acetate, glycerol, hexamethylenephosphoramide, hexamethylphosphortriamid, methylene chloride, N-methyl- 2-pyrrolidinone (NMP), nitromethane, petroleum ether, pyridine, tetrahydrofuran, triethylamine, sulfolane use.
- DMF dimethylformamide
- DMSO dimethylsulfoxide
- NMP N-methyl- 2-pyrrolidinone
- the polar liquids used are preferably NMP, sulfolane, DMF or DMSO. Most preferred is NMP.
- the non-polar liquids are brought into contact with the polar liquid.
- the contact can be made by any method.
- the two liquids can be mixed with one another, but as a rule, if appropriate after the end of the mixing process, two liquid phases which barely miscible with one another are formed. Frequently one of the phases contains essentially the non-polar liquid and the other phase the polar liquid. Whether in this case the non-polar to the polar liquid is added or vice versa is generally irrelevant.
- the polar liquid is added to the nonpolar liquid and mixing is accomplished by, for example, shaking or stirring.
- the methods known to those skilled in the art for extraction in step (b) can also be used analogously.
- the duration of the contact between polar and nonpolar liquid in step (b) of the method according to the invention may vary over a wide range depending on the nature of the liquids.
- the duration of the contact is in the range of 10 seconds to one week. More preferably, the duration of the contact is less than 48 hours. Most preferably, the duration of the contact is less than 10 minutes.
- slight mechanical agitation of the system improves the phase separation before detection in step (c).
- the amount of polar liquid used in the process according to the invention, based on the non-polar liquid, can vary within a wide range, depending on the chemical nature of the liquids used.
- the weight ratio of polar to nonpolar liquid is selected from the range of 20: 1 to 1:20.
- the selected range is preferably from 10: 1 to 1:10, in particular from 1: 1 to 1:10.
- non-polar and polar liquids which are used in the process according to the invention can vary over a wide range. Usually enough, for example, in a spectroscopic detection of a few milliliters of liquids. Preferably, less than 10 ml are used.
- the detection of the markers in step (c) is carried out with the aid of physical and / or chemical processes which are suitable for detecting the markers reliably, in particular also quantitatively.
- the detection preferably takes place with the aid of spectroscopic methods.
- Particularly preferred detection methods are the well-known methods of fluorescence spectroscopy, as described, for example, in WO 94/02570.
- An important parameter for the detection of the markers is the signal / noise ratio of the respective process.
- the signal-to-noise ratio should generally be better than 10.
- a signal-to-noise ratio better than 50 is preferred.
- the signal-to-noise ratio in fluorescence spectroscopic detection is defined by the ratio of tracer fluorescence and background fluorescence fraction.
- a separation of the phases formed in step (b) is often not necessary for the detection of the markers.
- the detection beam can be guided so that it interacts only with the phase which essentially contains the nonpolar liquid with marking substance.
- the two phases are separated from each other and the marker detected in the phase which contains substantially the nonpolar liquid.
- the detection of the total content of marker can be quantitative.
- a particularly advantageous embodiment of the method according to the invention is given when the marker is more soluble in the non-polar than in the polar liquid.
- One skilled in the art can determine this by routine experimentation to determine the distribution coefficient between polar and non-polar liquid.
- the solubility of impurities in the polar liquid is higher than in the non-polar liquid.
- the marker is more soluble in the non-polar than in the polar liquid, and the contaminant is more soluble in the polar rather than the nonpolar liquid.
- the contaminant is partially or completely removed from the non-polar liquid, thereby improving the signal / noise ratio for the detection of the marking substance.
- step (b) of the method according to the invention the interfering background fluorescence of the impurities for detection in step (c) is removed.
- Another object of the invention is a method for labeling contaminated nonpolar liquids, wherein the detection of the markers is carried out according to the inventive method.
- Another object of the invention is the use of polar liquids to improve the detectability of markers in contaminated non-polar liquids.
- markers in contaminated nonpolar liquids can be reliably detected even without separation and preparation.
- Optimized extractants for the markers need not be provided.
- the detection of the markers was carried out by means of fluorescence spectroscopy.
- the corresponding method and devices are described in WO 94/02570.
- the fluorescence intensity was determined as a function of the marker concentration.
- the excitation wavelength was 642 nm.
- two blocking filters with an optical density of 5 and edge wavelengths of 776 and 780 nm were used.
- a linear dependence of the fluorescence intensity on the labeling concentration was observed.
- the measuring solutions were shaken out with 20% by weight of NMP (based on the total amount of diesel and NMP) and the lower phase, which consisted essentially of NMP, was separated off after complete phase separation.
- the slope after extraction with NMP was about a factor of 2 lower (marker was extracted from the mineral oil phase into the NMP phase), but the signal-to-noise ratio had improved by more than a factor of 20.
- the excitation wavelength of the laser diode was 760 nm, in the detection channel of fluorescence there were 2 blocking filters with an edge wavelength of 776 nm and an optical density of 5 and 6, respectively.
- a straight-line equation with a strongly increased intercept and a correspondingly small figure of merit g 0.16 was obtained
- the signal / noise ratio had increased by the factor 60 by treatment with NMP.
- the excitation wavelength was 780 nm; in the detection channel only a simple blocking filter with an edge wavelength of 810 nm and an optical density of 3 was used. The following results were obtained:
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Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP08848991A EP2209875A1 (de) | 2007-11-14 | 2008-11-10 | Verbesserte detektion von markierstoffen |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP07120650 | 2007-11-14 | ||
| EP08848991A EP2209875A1 (de) | 2007-11-14 | 2008-11-10 | Verbesserte detektion von markierstoffen |
| PCT/EP2008/065187 WO2009062899A1 (de) | 2007-11-14 | 2008-11-10 | Verbesserte detektion von markierstoffen |
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| Publication Number | Publication Date |
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| EP2209875A1 true EP2209875A1 (de) | 2010-07-28 |
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| Application Number | Title | Priority Date | Filing Date |
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| EP08848991A Withdrawn EP2209875A1 (de) | 2007-11-14 | 2008-11-10 | Verbesserte detektion von markierstoffen |
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| Country | Link |
|---|---|
| EP (1) | EP2209875A1 (pt) |
| CN (1) | CN101855324A (pt) |
| BR (1) | BRPI0820313A2 (pt) |
| PE (1) | PE20091290A1 (pt) |
| RU (1) | RU2010123680A (pt) |
| WO (1) | WO2009062899A1 (pt) |
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| CN108912025A (zh) * | 2017-12-27 | 2018-11-30 | 南京晓庄学院 | 一种蒽醌衍生物 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1308547A (en) * | 1969-03-18 | 1973-02-21 | Hoechst Ag | Process for the dyeing of hydrocarbons non-polar or slightly polar organic solvents and fats |
| GB2354070A (en) * | 1999-09-07 | 2001-03-14 | Duncan William John Mccallien | Markers for identifying liquids |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4049393A (en) * | 1974-11-18 | 1977-09-20 | Morton-Norwich Products, Inc. | Colored petroleum-derived product |
| DE3700329A1 (de) * | 1987-01-08 | 1988-07-21 | Basf Ag | Verfahren zum nachweis von kennzeichnungsstoffen in dunkel gefaerbten mineraloelprodukten |
| JPH05202367A (ja) * | 1991-10-15 | 1993-08-10 | General Sekiyu Kk | 抽出による軽油の脱硫および脱硝方法 |
| US5723338A (en) * | 1994-11-04 | 1998-03-03 | Amoco Corporation | Tagging hydrocarbons for subsequent identification |
| US6320090B1 (en) * | 1999-03-10 | 2001-11-20 | Miami University | Method of removing contaminants from petroleum distillates |
| US20020036158A1 (en) * | 2000-08-08 | 2002-03-28 | Austin Douglas P. | Batch process for refining used oil |
| US6514917B1 (en) * | 2001-08-28 | 2003-02-04 | United Color Manufacturing, Inc. | Molecular tags for organic solvent systems |
| US6977177B1 (en) * | 2004-05-26 | 2005-12-20 | Rohm And Haas Company | Method for marking hydrocarbons with substituted anthraquinones |
-
2008
- 2008-11-10 BR BRPI0820313-0A patent/BRPI0820313A2/pt not_active IP Right Cessation
- 2008-11-10 CN CN200880116013A patent/CN101855324A/zh active Pending
- 2008-11-10 WO PCT/EP2008/065187 patent/WO2009062899A1/de active Application Filing
- 2008-11-10 EP EP08848991A patent/EP2209875A1/de not_active Withdrawn
- 2008-11-10 RU RU2010123680/05A patent/RU2010123680A/ru not_active Application Discontinuation
- 2008-11-14 PE PE2008001929A patent/PE20091290A1/es not_active Application Discontinuation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1308547A (en) * | 1969-03-18 | 1973-02-21 | Hoechst Ag | Process for the dyeing of hydrocarbons non-polar or slightly polar organic solvents and fats |
| GB2354070A (en) * | 1999-09-07 | 2001-03-14 | Duncan William John Mccallien | Markers for identifying liquids |
Non-Patent Citations (1)
| Title |
|---|
| See also references of WO2009062899A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| RU2010123680A (ru) | 2011-12-20 |
| PE20091290A1 (es) | 2009-09-25 |
| WO2009062899A1 (de) | 2009-05-22 |
| BRPI0820313A2 (pt) | 2015-05-26 |
| CN101855324A (zh) | 2010-10-06 |
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