NO169312B - PROCEDURE FOR AA DETERMINING THE CONTENT OF POLYCLORATED BIFENYL COMPOUNDS IN AN OIL. - Google Patents
PROCEDURE FOR AA DETERMINING THE CONTENT OF POLYCLORATED BIFENYL COMPOUNDS IN AN OIL. Download PDFInfo
- Publication number
- NO169312B NO169312B NO862756A NO862756A NO169312B NO 169312 B NO169312 B NO 169312B NO 862756 A NO862756 A NO 862756A NO 862756 A NO862756 A NO 862756A NO 169312 B NO169312 B NO 169312B
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- Prior art keywords
- oil
- pkb
- solvent
- content
- chlorine content
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 37
- 150000001875 compounds Chemical class 0.000 title claims description 18
- 239000000460 chlorine Substances 0.000 claims description 45
- 229910052801 chlorine Inorganic materials 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 35
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 33
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 28
- 239000002904 solvent Substances 0.000 claims description 27
- -1 polychlorinated biphenyl compounds Chemical class 0.000 claims description 20
- 229910052783 alkali metal Inorganic materials 0.000 claims description 19
- 150000001340 alkali metals Chemical class 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000008346 aqueous phase Substances 0.000 claims description 8
- 238000010828 elution Methods 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000003463 adsorbent Substances 0.000 claims description 6
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 4
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 3
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims 2
- 238000004587 chromatography analysis Methods 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000012071 phase Substances 0.000 claims 1
- 239000003921 oil Substances 0.000 description 85
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 10
- ORMNPSYMZOGSSV-UHFFFAOYSA-N dinitrooxymercury Chemical compound [Hg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ORMNPSYMZOGSSV-UHFFFAOYSA-N 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 238000004448 titration Methods 0.000 description 10
- 238000006298 dechlorination reaction Methods 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- ZFWAHZCOKGWUIT-UHFFFAOYSA-N 1-anilino-3-phenyliminourea Chemical compound C=1C=CC=CC=1N=NC(=O)NNC1=CC=CC=C1 ZFWAHZCOKGWUIT-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000013375 chromatographic separation Methods 0.000 description 2
- 229960004132 diethyl ether Drugs 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000000506 liquid--solid chromatography Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- YXAOOTNFFAQIPZ-UHFFFAOYSA-N 1-nitrosonaphthalen-2-ol Chemical compound C1=CC=CC2=C(N=O)C(O)=CC=C21 YXAOOTNFFAQIPZ-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 108091006149 Electron carriers Proteins 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229950011260 betanaphthol Drugs 0.000 description 1
- UDSAIICHUKSCKT-UHFFFAOYSA-N bromophenol blue Chemical compound C1=C(Br)C(O)=C(Br)C=C1C1(C=2C=C(Br)C(O)=C(Br)C=2)C2=CC=CC=C2S(=O)(=O)O1 UDSAIICHUKSCKT-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011551 heat transfer agent Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- 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
- G01N33/0004—Gaseous mixtures, e.g. polluted air
- G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
- G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
- G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
- G01N33/0047—Organic compounds
- G01N33/0049—Halogenated organic compounds
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/16—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using titration
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Pathology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Physics & Mathematics (AREA)
- Food Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Lubricants (AREA)
Description
Foreliggende oppfinnelse angår en fremgangsmåte for å bestemme innholdet av polyklorerte bifenylforbindelser i en olje. Innholdet av polyklorerte bifenylforbindelser (nedenfor forkortet til PKB eller PKB-forbindelser) i industrielle oljer bestemmes således ved titrering av kloridionene som dannes ved kjemisk destruksjon av PKB-molekyler. The present invention relates to a method for determining the content of polychlorinated biphenyl compounds in an oil. The content of polychlorinated biphenyl compounds (abbreviated below to PKB or PKB compounds) in industrial oils is thus determined by titration of the chloride ions that are formed by the chemical destruction of PKB molecules.
Det finnes 209 forskjellige PKB-forbindelser, og diverse kombinasjoner av disse PKB-forbindelser har funnet ut-strakt anvendelse i industrielle oljer for en rekke praktiske anvendelser, blant annet som dielektriske fluider for trans-formatorer, varmeoverføringsmidler, hydrauliske fluider og lignende. Tekniske PKB selges under et merke som vanligvis suppleres med et nummer (f.eks. 1254), hvor de to siste tall angir PKB-forbindelsens klorinnhold (54% i dette eksempel). I enkelte tilfeller inneholder de industrielle oljer blandinger av PKB-forbindelser. Klorinnholdet i disse blandinger er vanligvis fra 40 til 60%. There are 209 different PKB compounds, and various combinations of these PKB compounds have found extensive use in industrial oils for a number of practical applications, including as dielectric fluids for transformers, heat transfer agents, hydraulic fluids and the like. Technical PKB is sold under a brand which is usually supplemented with a number (e.g. 1254), where the last two numbers indicate the chlorine content of the PKB compound (54% in this example). In some cases, the industrial oils contain mixtures of PKB compounds. The chlorine content in these mixtures is usually from 40 to 60%.
Det er blitt vedtatt bestemmelser for klassifisering av de industrielle oljer etter deres PKB-innhold. PKB-inneholdende oljer kan inndeles i de følgende kategorier: PKB-frie oljer: oljer som inneholder mindre enn 50 ppm PKB, Provisions have been adopted for the classification of industrial oils according to their PKB content. PKB-containing oils can be divided into the following categories: PKB-free oils: oils that contain less than 50 ppm PKB,
PKB-forurensede oljer: oljer inneholdende 50-500 ppm PKB-contaminated oils: oils containing 50-500 ppm
PKB, PKB,
PKB-oljer: oljer som inneholder mer enn 500 ppm PKB. PKB oils: oils containing more than 500 ppm PKB.
Det er kjent mange metoder for bestemmelse av PKB-innholdet i oljer, men de krever vanligvis bruk av kostbar apparatur (analyse ved hjelp av IR-spektroskopi med Fourier-transformasjon, ved hjelp av røntgenstråler, ved hjelp av gasskromatografi koblet sammen med massespektrometri, o.l.) som bare er tilgjengelig i spesialllaboratorier hvor det finnes kvalifisert personell. Andre metoder er enklere, som f.eks. metoden beskrevet i GB 2145816, men de gjør det kun mulig å bestemme hvorvidt den testede olje inneholder mindre enn 50 ppm PKB, fra 50 til 500 ppm PKB eller mer enn 500 ppm Many methods are known for determining the PKB content in oils, but they usually require the use of expensive equipment (analysis using IR spectroscopy with Fourier transformation, using X-rays, using gas chromatography coupled with mass spectrometry, etc. ) which is only available in special laboratories where there are qualified personnel. Other methods are simpler, such as the method described in GB 2145816, but they only make it possible to determine whether the tested oil contains less than 50 ppm PKB, from 50 to 500 ppm PKB or more than 500 ppm
PKB. PKB.
Det er et siktemål med den foreliggende oppfinnelse å tilveiebringe en ny, billig og hurtig metode til å bestemme PKB-innholdet i industrielle oljer. Det er videre et siktemål med oppfinnelsen å tilveiebringe en enkel metode som kan benyttes rutinemessig på arbeidsstedet for å bestemme PKB-innholdet i oljer, enten disse er forurensede oljer eller de er regenererte oljer. It is an aim of the present invention to provide a new, cheap and fast method for determining the PKB content in industrial oils. It is a further aim of the invention to provide a simple method that can be used routinely at the workplace to determine the PKB content in oils, whether these are contaminated oils or they are regenerated oils.
Med foreliggende oppfinnelse tilveiebringes det således en fremgangsmåte for å bestemme innholdet av polyklorerte bifenylforbindelser (PKB) i en olje, hvor oljen underkastes en forutgående behandling hvor inneholdte klorerte paraffiner fraskilles, før oljen bringes i kontakt med et overskudd av alkalimetall som reagerer med PKB-forbindelsene i oljen, under dannelse av alkalimetallklorid, hvorpå det uomsatte alkalimetall fjernes ved omrøring i nærvær av en sur vandig oppløs-ning som er fri for klorioner og blandingen tillates å stå, slik at det kan finne sted bunnfelling, hvoretter den vandige fase inneholdende klorionene fraskilles, og de fraskilte klorioner titreres mercurimetrisk for bestemmelse av klorinnholdet i utgangsoljen. Oppfinnelsen er kjennetegnet ved at den forutgående behandling av oljen utføres ved at oljen fortynnes med en flytende paraffinisk eller nafthenisk olje og det tilsettes en oppløsning av polycyclisk aromatisk hydrocarbon i et polart oppløsningsmiddel som er inert overfor alkalimetallene, og at oljen etter denne forutgående behandling underkastes en væske-faststoff-kromatograferingsprosess i en kolonne som inneholder et polart adsorberingsmiddel og elueres med et oppløs-ningsmiddel som er et mettet alifatisk hydrocarbon, og som eventuelt er forgrenet og inneholder 5-10 carbonatomer, at oppløsningsmidlet fjernes fra eluatet, som underkastes en oxydasjonsbehandling før klorinnholdet i det oppløsningsmid-delfrie eluat bestemmes, og at PKB-innholdet i utgangsoljen beregnes ut fra klorinnholdet i utgangsoljen og ut fra klorinnholdet i PKB-forbindeIsene inneholdt i denne olje. The present invention thus provides a method for determining the content of polychlorinated biphenyl compounds (PKB) in an oil, where the oil is subjected to a preliminary treatment where contained chlorinated paraffins are separated, before the oil is brought into contact with an excess of alkali metal which reacts with the PKB compounds in the oil, forming alkali metal chloride, after which the unreacted alkali metal is removed by stirring in the presence of an acidic aqueous solution which is free of chlorine ions and the mixture is allowed to stand, so that precipitation can take place, after which the aqueous phase containing the chlorine ions is separated , and the separated chlorine ions are titrated mercurimetrically to determine the chlorine content in the starting oil. The invention is characterized by the fact that the preliminary treatment of the oil is carried out by diluting the oil with a liquid paraffinic or naphthenic oil and adding a solution of polycyclic aromatic hydrocarbon in a polar solvent which is inert to the alkali metals, and that after this preliminary treatment the oil is subjected to a liquid-solid chromatography process in a column containing a polar adsorbent and eluted with a solvent which is a saturated aliphatic hydrocarbon, and which is optionally branched and contains 5-10 carbon atoms, that the solvent is removed from the eluate, which is subjected to an oxidation treatment before the chlorine content in the solvent-free eluate is determined, and that the PKB content in the starting oil is calculated from the chlorine content in the starting oil and from the chlorine content in the PKB compounds contained in this oil.
Fremgangsmåten ifølge oppfinnelsen baserer seg på en kjemisk destruksjon av PKB-forbindelsene som inneholdes i den testede olje, idet destrueringen foretas som en dekloreringsbehandling. Denne dekloreringsbehandling må utføres fullstendig og i løpet av relativt kort tid. For dette formål har A. Oku et al. (se Chemistry and Industry, nov. 4, 1978, s. 841) beskrevet en metode for fullstendig deklorering av PKB ved hjelp av natruimnafthaien. I henhold til denne metode behand-les en oppløsning av PKB i tetrahydrofuran med natriumnaf-thalen, under nitrogenatmosfære, ved 0°C og i 10 minutter. Analyse av oppløsningen etter behandlingen har vist at den er praktisk talt fri for klor. The method according to the invention is based on a chemical destruction of the PKB compounds contained in the tested oil, the destruction being carried out as a dechlorination treatment. This dechlorination treatment must be carried out completely and within a relatively short time. For this purpose, A. Oku et al. (see Chemistry and Industry, Nov. 4, 1978, p. 841) described a method for complete dechlorination of PKB using sodium naphtha. According to this method, a solution of PKB in tetrahydrofuran is treated with sodium naphthalene, under a nitrogen atmosphere, at 0°C and for 10 minutes. Analysis of the solution after treatment has shown that it is practically free of chlorine.
I henhold til oppfinnelsen blir den testede olje inneholdene PKB fortynnet ved romtemperatur med en flytende paraffinisk eller nafthenisk olje, såsom et alkan inneholdende fra 5 til 16 carbonatomer, spesielt cyclohexan. According to the invention, the tested oil containing PKB is diluted at room temperature with a liquid paraffinic or naphthenic oil, such as an alkane containing from 5 to 16 carbon atoms, especially cyclohexane.
Til denne blanding av olje som skal testes og hydro-carbonfortynningsmiddel settes en oppløsning av polycyclisk aromatisk oppløsningsmiddel i et polart oppløsningsmiddel som ikke reagerer med alkalimetaller. Eksempler på polycycliske aromatiske hydrocarboner er nafthaien, anthracen, fenanthren og bifenyl. Det polycycliske hydrocarbon oppløses i et oppløsningsmiddel som ikke reagerer med alkalimetaller. Oppløsningsmidlet kan med fordel være en ether, såsom 2-me-thoxyether, dimethylether, diethylether, tetrahydrofuran, dioxan og lignende. To this mixture of oil to be tested and hydrocarbon diluent is added a solution of polycyclic aromatic solvent in a polar solvent which does not react with alkali metals. Examples of polycyclic aromatic hydrocarbons are naphtha, anthracene, phenanthrene and biphenyl. The polycyclic hydrocarbon is dissolved in a solvent that does not react with alkali metals. The solvent can advantageously be an ether, such as 2-methoxyether, dimethylether, diethylether, tetrahydrofuran, dioxane and the like.
Alkalimetallet settes til blandingen for å deklorere PKB-innholdet i den testede olje. For å forbedre kontakten The alkali metal is added to the mixture to dechlorinate the PKB content of the tested oil. To improve contact
og å redusere reaksjonstiden benyttes alkalimetallet fortrinnsvis i form av en dispersjon i et paraffinisk eller nafthenisk hydrocarbon som er væskeformig ved romtemperatur. Alkalimetallet kan være natrium, kalium eller lithium, idet valget av metallet avhenger av dets aktivitet og av prisen. Kalium og natrium er særlig aktive, og de vil bli benyttet i form av en dispersjon i et vannfritt paraffinisk hydrocarbon. Mengden som benyttes av alkalimetallet, vil være større enn den støkiometriske mengde som er nødvendig for å avstedkomme dekloreringen av PKB-innholdet i den testede olje. Derfor vil alkalimetallet benyttes i overskudd. Når natrium anvendes som alkalimetall, er det tilstede et overskudd av natrium i reaksjonsblandingen når sistnevnte er grafarvet. and to reduce the reaction time, the alkali metal is preferably used in the form of a dispersion in a paraffinic or naphthenic hydrocarbon which is liquid at room temperature. The alkali metal can be sodium, potassium or lithium, the choice of metal depending on its activity and price. Potassium and sodium are particularly active, and they will be used in the form of a dispersion in an anhydrous paraffinic hydrocarbon. The amount used of the alkali metal will be greater than the stoichiometric amount necessary to bring about the dechlorination of the PKB content in the tested oil. Therefore, the alkali metal will be used in excess. When sodium is used as an alkali metal, an excess of sodium is present in the reaction mixture when the latter is graphite-inherited.
Ved bruk av denne metode blir PKB-forbindelsene fullstendig deklorert reduktivt, med dannelse av alkalimetallklorid. Det polycycliske aromatiske hydrocarbon i reaksjons-mediet er elektronbæreren mellom alkalimetallet og PKB-for-bindelsen. Det reaktive kompleks (alkalimetall + polycyclisk hydrocarbon) som stabiliseres og aktiveres av det polare oppløsningsmiddel, har en betydelig reduserende evne, og dekloreringshastigheten er stor. Using this method, the PKB compounds are completely dechlorinated reductively, with the formation of alkali metal chloride. The polycyclic aromatic hydrocarbon in the reaction medium is the electron carrier between the alkali metal and the PKB compound. The reactive complex (alkali metal + polycyclic hydrocarbon) which is stabilized and activated by the polar solvent, has a significant reducing ability, and the dechlorination rate is high.
Etter dekloreringstrinnet deaktiveres det uomsatte alkalimetall ved bruk av en vandig sur oppløsning som også ekstraherer klorionene. Denne behandling utføres fortrinnsvis under omrøring. Blandingen tillates så å stå for bunnfelling når den er klar og har en orangegul farve. After the dechlorination step, the unreacted alkali metal is deactivated using an aqueous acid solution which also extracts the chlorine ions. This treatment is preferably carried out while stirring. The mixture is then allowed to settle when it is clear and has an orange-yellow colour.
Den vandige fase inneholder alkalimetallkloridet og fraskilles for titrering av klorionene ved mercurimetri. Denne vandige fase må ha en pH-verdi på fra 1 til 4. Titreringen utføres ved bruk av en oppløsning av mercurinitrat i nærvær av en farveindikator, såsom difenylcarbazon, som kan benyttes alene eller i blanding med l-nitroso-2-nafthol, og/eller bromfenol-blått. The aqueous phase contains the alkali metal chloride and is separated for titration of the chlorine ions by mercurimetry. This aqueous phase must have a pH value of from 1 to 4. The titration is carried out using a solution of mercuric nitrate in the presence of a color indicator, such as diphenylcarbazone, which can be used alone or in mixture with l-nitroso-2-naphthol, and /or bromophenol blue.
Klorinnholdet i den testede olje kan beregnes etter titreringstrinnet ved bruk av formelen I: The chlorine content in the tested oil can be calculated after the titration step using formula I:
hvor A er volumet (i milliliter) av oppløsningen av mercurinitrat som er blitt brukt, where A is the volume (in milliliters) of the mercuric nitrate solution used,
M er molariteten av denne oppløsning, og M is the molarity of this solution, and
C er vekten (i gram) av den testede olje. C is the weight (in grams) of the tested oil.
PKB-innholdet i den testede olje blir så beregnet The PKB content in the tested oil is then calculated
ut fra klorinnholdet i den testede olje ved multiplisering av klorinnholdet med 100/T, hvor T er det prosentvise klorinnhold i PKB-forbindelsen(e). based on the chlorine content of the tested oil by multiplying the chlorine content by 100/T, where T is the percentage chlorine content in the PKB compound(s).
Når den testede olje inneholder kun én teknisk PKB-for-bindelse hvis klorinnhold er kjent, f.eks. en PKB-forbin-delse inneholdende 54% klor, vil T i den ovenstående formel være 54, og fremgangsmåten ifølge oppfinnelsen gir med nøy-aktighet PKB-innholdet i den testede olje. Imidlertid kan den testede olje inneholde en blanding av PKB-forbindelser. I dette tilfelle er verdien for T vanligvis fra 40 til 60.. En valgt verdi på 50 for T benyttes ved beregningen, hvorved de oppnådde resultater blir tilfredsstillende. For å oppnå When the tested oil contains only one technical PKB compound whose chlorine content is known, e.g. a PKB compound containing 54% chlorine, T in the above formula will be 54, and the method according to the invention accurately gives the PKB content in the tested oil. However, the tested oil may contain a mixture of PKB compounds. In this case, the value for T is usually from 40 to 60. A selected value of 50 for T is used in the calculation, whereby the results obtained are satisfactory. To achieve
den størst mulige grad av sikkerhet kan T gies verdien 40, the greatest possible degree of security can be given the value 40 for T,
og det beregnede PKB-innhold i den testede olje vil da være likt med eller høyere enn det virkelige innhold. and the calculated PKB content in the tested oil will then be equal to or higher than the real content.
Det følgende eksempel illustrerer anvendelsen av fremgangsmåten ifølge oppfinnelsen. Det viser at denne enkle metode gir resultater svarende til dem som oppnåes ved en laboratorieanalyse som krever en kostbar apparatur, og som ikke lar seg anvende på feltet. The following example illustrates the use of the method according to the invention. It shows that this simple method gives results similar to those obtained by a laboratory analysis which requires expensive equipment, and which cannot be applied in the field.
Eksempel 1 Example 1
De følgende oppløsninger ble tilberedt: The following solutions were prepared:
1) katalytisk oppløsning: oppløsning (100 ml) av 5 g nafthaien 2-methyloxyethyl-ether, 2) oppløsning av mercurinitrat (titreringsreagens): oppløsning (1 liter) av mercurinitrat (0,01 mol) og salpetersyre 1) catalytic solution: solution (100 ml) of 5 g of naphtha 2-methyloxyethyl-ether, 2) solution of mercuric nitrate (titration reagent): solution (1 liter) of mercuric nitrate (0.01 mol) and nitric acid
(1 mol) i deionisert vann, (1 mol) in deionized water,
3) indikator I: oppløsning (100 ml) av 0,5 g difenylcarbazon i 95% ethanol, og 4) indikator II: oppløsning (100 ml) av 1 g l-nitroso-2-naf-thol i 95% ethanol. 3) indicator I: solution (100 ml) of 0.5 g of diphenylcarbazone in 95% ethanol, and 4) indicator II: solution (100 ml) of 1 g of 1-nitroso-2-naphthol in 95% ethanol.
Metoden for bestemmelse av FKB-innholdet i en olje The method for determining the FKB content in an oil
er som følger: is as follows:
Ca. 10 g PKB-inneholdende olje som skal testes, inn-føres i en erlenmeyerkolbe og fortynnes med 10 ml hexan. 2 ml katalytisk oppløsning tilsettes under omrøring i løpet av ca. 30 sekunder. Det tilsettes så 0,5 g av en natrium-dispersjon. Etter omrøring i ca. 15 minutter er oppløsningen gråfarvet, dersom et overskudd av natrium er tilstede. Dersom oppløsningen ikke er farvet, tilsettes en ytterligere mengde natrium under omrøring. About. 10 g of PKB-containing oil to be tested are introduced into an Erlenmeyer flask and diluted with 10 ml of hexane. 2 ml of catalytic solution is added while stirring during approx. 30 seconds. 0.5 g of a sodium dispersion is then added. After stirring for approx. After 15 minutes, the solution is grey, if an excess of sodium is present. If the solution is not colored, a further amount of sodium is added while stirring.
Etter dekloreringsreaksjonen deaktiveres det uomsatte natrium ved tilsetning av 2 5 ml av en vandig sur oppløsning som er fri for klorioner. En egnet oppløsning inneholdende et alkalimetallsalt, såsom et alkalimetallfosfat eller -sul-fat, og en uorganisk syre, såsom salpetersyre eller fosforsyre, som er fri for klorioner og som er inert overfor den testede olje. Etter tilsetning av denne oppløsning og etter at blandingen har antatt en gulorange farve, omrøres den i ett minutt, hvoretter den tillates å stå for bunnfelling. After the dechlorination reaction, the unreacted sodium is deactivated by the addition of 25 ml of an aqueous acidic solution which is free of chlorine ions. A suitable solution containing an alkali metal salt, such as an alkali metal phosphate or sulphate, and an inorganic acid, such as nitric or phosphoric acid, which is free of chlorine ions and which is inert to the tested oil. After the addition of this solution and after the mixture has assumed a yellow-orange color, it is stirred for one minute, after which it is allowed to settle.
Den vandige fase fraskilles. Dens pH-verdi må være The aqueous phase is separated. Its pH must be
fra 1 til 4. Dersom pH-verdien er høyere enn 4, tilsettes salpetersyre eller fosforsyre. from 1 to 4. If the pH value is higher than 4, nitric acid or phosphoric acid is added.
Denne vandige fase inneholder natriumklorid som stam-mer fra dekloreringen av PKB-forbindelsen(e) med natrium. Titreringen av klorionene foretas ved bruk av oppløsningen This aqueous phase contains sodium chloride which originates from the dechlorination of the PKB compound(s) with sodium. The titration of the chlorine ions is carried out using the solution
av mercurinitrat i nærvær av 0,5 ml indikator I og 0,2 5 ml indikator II. Klorionene bindes til Hg<++->ionene under dannelse av et ikke-dissosiert HgC^-molekyl. Over ekvivalenspunktet vil eventuelle Hg<++->ioner i overskudd bli påvist ved hjelp av indikatorene, idet oppløsningens farve, som var gul, blir grålilla-purpurfarvet. of mercuric nitrate in the presence of 0.5 ml of indicator I and 0.25 ml of indicator II. The chlorine ions bind to the Hg<++-> ions, forming a non-dissociated HgC^ molecule. Above the equivalence point, any Hg<++->ions in excess will be detected with the help of the indicators, as the color of the solution, which was yellow, becomes grey-purple-purple.
Denne metode er blitt testet med flere prøver av olje inneholdende varierende mengder PKB. Klorinnholdet i det tilsatte PCB var 57,9%. Resultatene som ble oppnådd med denne metode, er oppført i den følgende tabell, hvor de er sammen-lignet med resultatene oppnådd ved røntgenstråleanalyse. This method has been tested with several samples of oil containing varying amounts of PKB. The chlorine content in the added PCB was 57.9%. The results obtained with this method are listed in the following table, where they are compared with the results obtained by X-ray analysis.
Resultatene viser at fremgangsmåten ifølge oppfinnelsen er nøyaktig og kan benyttes for bestemmelse av PKB-innholdet i industrielle oljer, uten at det er nødvendig med kostbar apparatur og skolert personell. Fremgangsmåten er mer verdi-full enn andre metoder som kun muliggjør påvisning av hvorvidt oljen inneholder PKB i menger mindre enn 50 ppm eller i menger av fra 50 til 500 ppm eller i mengder som er større enn 500 ppm, og som vil måtte forandres dersom myndighetenes regelverk skulle endres. The results show that the method according to the invention is accurate and can be used for determining the PKB content in industrial oils, without the need for expensive equipment and trained personnel. The procedure is more valuable than other methods which only enable the detection of whether the oil contains PKB in amounts less than 50 ppm or in amounts from 50 to 500 ppm or in amounts greater than 500 ppm, and which will have to be changed if the authorities' regulations had to be changed.
Det kan foretaes diverse modifikasjoner av den ovenfor beskrevne utførelsesform av fremgangsmåten. Eksempelvis kan den testede olje på forhånd oppvarmes til en temperatur på ca. 200°C for å fjerne vann og oppløsningsmidler som eventuelt måtte være tilstede i oljen. Various modifications can be made to the above-described embodiment of the method. For example, the tested oil can be heated in advance to a temperature of approx. 200°C to remove water and solvents that may be present in the oil.
Videre kan det være fordelaktig å utføre en blindprøve for å regulere hvorvidt oppløsningsmidlene, syrene eller andre reagenser som benyttes ved fremgangsmåten, er frie for klor. Furthermore, it may be advantageous to carry out a blank test to regulate whether the solvents, acids or other reagents used in the method are free of chlorine.
Det har også vist seg at den testede olje kan inneholde en viss mengde reduserende stoffer som forstyrrer titreringstrinnet. I dette tilfelle kan den vandige, sure, klorione-holdige oppløsning underkastes en oxydasjonsbehandling før titreringen. Denne behandling kan utføres under anvendelse av hydrogenperoxyd. Eksempelvis kan den vandige, sure, klor-ioneholdige oppløsning oppvarmes til koketemperaturen i nærvær av en vandig oppløsning av (en 30% -oppløsning) i ca. 10 minutter. Etter avkjøling fraskilles den vandige fase ved filtrering, og filteret vaskes med vann. Det brukte vann settes til den fraskilte vandige fase. Denne blanding underkastes så titrering ved mercurimetri. It has also been shown that the tested oil may contain a certain amount of reducing substances which interfere with the titration step. In this case, the aqueous, acidic, chlorine ion-containing solution can be subjected to an oxidation treatment before the titration. This treatment can be carried out using hydrogen peroxide. For example, the aqueous, acidic, chlorine ion-containing solution can be heated to the boiling temperature in the presence of an aqueous solution of (a 30% solution) for approx. 10 minutes. After cooling, the aqueous phase is separated by filtration, and the filter is washed with water. The spent water is added to the separated aqueous phase. This mixture is then subjected to titration by mercurimetry.
Enkelte oljer kan også inneholde klorerte para- Certain oils may also contain chlorinated para-
finer som reagerer med alkalimetallet. I henhold til fremgangsmåten ifølge oppfinnelsen blir disse veneer that reacts with the alkali metal. According to the method according to the invention, these become
klorerte paraffiner fjernet selektivt fra oljen ved væske-faststoff-kromatografi. Dette separasjonstrinn går ut på chlorinated paraffins selectively removed from the oil by liquid-solid chromatography. This separation step consists of
å anvende en kolonne som inneholder et polart adsorberingsmiddel, å utføre elueringen av den for klorerte paraffiner be-fridde olje med et oppløsningsmiddel som er et mettet alifatisk hydrocarbon, eventuelt forgrenet og med 5-10 carbonatomer, å fjerne oppløsningsmidlet fra eluatet og å bestemme klorinnholdet i dette eluat. to use a column containing a polar adsorbent, to carry out the elution of the oil freed from chlorinated paraffins with a solvent which is a saturated aliphatic hydrocarbon, optionally branched and with 5-10 carbon atoms, to remove the solvent from the eluate and to determine the chlorine content in this eluate.
Den kromatografiske separasjon utføres ved anvendelse av en kolonne som inneholder et polart adsorberingsmiddel, spesielt et adsorberingsmiddel med hydroxyl-seter, såsom aluminiumoxyd eller silica. De polare stoffer i den testede olje adsorberes på kolonnen, og spesielt adsorberes de klorerte paraffiner først, i den øvre del av kolonnen. Eluering av den nu rensede olje foretaes med et oppløsningsmiddel som fortrinnsvis er et mettet alifatisk hydrocarbon, som eventuelt er forgrenet, og som inneholder fra 5 til 10 carbonatomer. Eksempler på egnede hydrocarboner er isopentan, n-hexan, n-heptan og iso-octan. Det benyttes fortrinnsvis et oppløsningsmiddel med et lavt kokepunkt, såsom hexan. The chromatographic separation is carried out using a column containing a polar adsorbent, in particular an adsorbent with hydroxyl sites, such as aluminum oxide or silica. The polar substances in the tested oil are adsorbed on the column, and in particular the chlorinated paraffins are adsorbed first, in the upper part of the column. Elution of the now purified oil is carried out with a solvent which is preferably a saturated aliphatic hydrocarbon, which is possibly branched, and which contains from 5 to 10 carbon atoms. Examples of suitable hydrocarbons are isopentane, n-hexane, n-heptane and iso-octane. A solvent with a low boiling point, such as hexane, is preferably used.
Sammenligningsforsøk har vist at denne metode er særlig selektiv og at de klorerte paraffiner som er tilstede i den testede olje, fjernes fullstendig. Disse tester er blitt utført ved bruk av tre oppløsninger: Comparison tests have shown that this method is particularly selective and that the chlorinated paraffins present in the tested oil are completely removed. These tests have been carried out using three solutions:
- oppløsning I: olje + 5 vekt% klorerte paraffiner, - solution I: oil + 5% by weight chlorinated paraffins,
- oppløsning II: olje + 5 vekt% PKB, og - solution II: oil + 5 wt% PKB, and
- oppløsning III: olje + 5 vekt% klorerte paraffiner og 5% PKB. En kolonne inneholdende silica ble benyttet for kromatografisk separasjon av hver oppløsning. De følgende oppløsningsmidler ble benyttet, det ene etter det andre: hexan, toluen, diklor-methan, diethylether, aceton og methanol. Røntgenanalyse viste at det første eluat (eluat med hexan) inneholdt: - solution III: oil + 5% by weight chlorinated paraffins and 5% PKB. A column containing silica was used for chromatographic separation of each solution. The following solvents were used, one after the other: hexane, toluene, dichloromethane, diethyl ether, acetone and methanol. X-ray analysis showed that the first eluate (eluate with hexane) contained:
- med oppløsning I: kun olje, - with solution I: only oil,
- med oppløsning II: olje og PKB, - with solution II: oil and PKB,
- med oppløsning III: olje og PKB. - with solution III: oil and PKB.
Det følgende eluat (eluat med toluen) inneholdt de klorerte paraffiner med oppløsninger I og III. De øvrige eluater (eluater med de øvrige oppløsningsmidler) var frie for klorerte paraffiner og PKB. The following eluate (eluate with toluene) contained the chlorinated paraffins with solutions I and III. The other eluates (eluates with the other solvents) were free of chlorinated paraffins and PKB.
Behandlingen av en industriell olje i henhold til denne utførelsesform resulterer i fjerning av klorerte paraffiner og dannelse av et eluat inneholdende olje, PKB og opp-løsningsmiddel. Oppløsningsmidlet blir så avdampet. Klorinnholdet i den gjenvundne olje inneholdende PKB bestemmes som ovenfor beskrevet. The treatment of an industrial oil according to this embodiment results in the removal of chlorinated paraffins and the formation of an eluate containing oil, PKB and solvent. The solvent is then evaporated. The chlorine content in the recovered oil containing PKB is determined as described above.
Klorinnholdet i utgangsoljen eksklusive PKB beregnes ved bruk av formel II The chlorine content in the starting oil excluding PKB is calculated using formula II
hvor er klorinnholdet i utgangsoljen eksklusive PKB, where is the chlorine content in the starting oil excluding PKB,
er klorinnholdet i oljen etter eluering og avdamping is the chlorine content in the oil after elution and evaporation
av oppløsningsmidlet, of the solvent,
W2 er vekten av oljen etter eluering og avdamping av W2 is the weight of the oil after elution and evaporation
oppløsningsmidlet, og the solvent, and
er vekten av utgangsoljen. is the weight of the starting oil.
Denne utførelsesform kan utføres ved at man blander en gitt mengde W., av utgangsoljen (vanligvis fra 5 til 10 g) med den samme mengde hexan eller annet lignende oppløs-ningsmiddel. Blandingen innføres i den øvre del av en kromatografisk kolonne (høyde 40 cm, diameter 1 cm) inneholdende aluminiumoxyd eller, fortrinnsvis, silica. Elueringen foretaes med hexan eller annet lignende oppløsningsmiddel. Eluatet, som inneholder olje, PKB og oppløsningsmiddel, men som er fritt for klorerte paraffiner, oppsamles. Dette eluat oppvarmes for å avdampe oppløsningsmidlet, og den gjenvundne olje veies (V^ ) . Denne oljes klorinnhold 0.^ bestemmes under anvendelse av den ovenfor beskrevne metode. This embodiment can be carried out by mixing a given amount of W., of the starting oil (usually from 5 to 10 g) with the same amount of hexane or other similar solvent. The mixture is introduced into the upper part of a chromatographic column (height 40 cm, diameter 1 cm) containing aluminum oxide or, preferably, silica. The elution is carried out with hexane or another similar solvent. The eluate, which contains oil, PKB and solvent, but is free of chlorinated paraffins, is collected. This eluate is heated to evaporate the solvent, and the recovered oil is weighed (V^ ). This oil's chlorine content 0.^ is determined using the method described above.
Denne utførelsesform ble testet, slik det fremgår This embodiment was tested, as it appears
av de følgende eksempler. of the following examples.
Eksempel 2 Example 2
PKB og klorerte paraffiner ble satt til en basismi-neralolje. Klorinnholdet i den resulterende olje eller den testede olje var 451 ppm, nemlig henholdsvis 151 ppm eksklusive klorerte paraffiner og 300 ppm eksklusive PKB. Fjeirnin-gen av de klorerte paraffiner ble foretatt under anvendelse av en kromatografisk kolonne inneholdende silica og n-hexan som elueringsmiddel. PKB and chlorinated paraffins were added to a base mineral oil. The chlorine content of the resulting oil or the tested oil was 451 ppm, namely 151 ppm excluding chlorinated paraffins and 300 ppm excluding PKB respectively. The removal of the chlorinated paraffins was carried out using a chromatographic column containing silica and n-hexane as eluent.
Mengden W, av testet olje var 5 g, og mengden W., av gjenvunnet olje etter eluering og avdamping av oppløsnings-midlet var 4,75 g. The amount W, of tested oil was 5 g, and the amount W, of recovered oil after elution and evaporation of the solvent was 4.75 g.
Klorinnholdet i den gjenvundne olje ble bestemt under anvendelse av den ovenfor beskrevne metode (titrering ved mercurimetri) og ble funnet å være 310 ppm. The chlorine content of the recovered oil was determined using the method described above (titration by mercurimetry) and was found to be 310 ppm.
Ved bruk av formel II ble det utregnet at den testede oljes klorinnhold eksklusive PKB var 295 ppm. Deretter ble de klorerte paraffiner fjernet fullstendig. Using formula II, it was calculated that the tested oil's chlorine content excluding PKB was 295 ppm. The chlorinated paraffins were then completely removed.
Eksempel 3 Example 3
Metoden beskrevet i eksempel 2 ble gjentatt, idet The method described in example 2 was repeated, whereby
det imidlertid ble benyttet isopentan istedenfor n-hexan. however, isopentane was used instead of n-hexane.
Det viste seg at den testede oljes klorinnhold eksklusive PKB var 291 ppm. It turned out that the tested oil's chlorine content excluding PKB was 291 ppm.
Eksempel 4 Example 4
Metoden beskrevet i eksempel 2 ble gjentatt, idet The method described in example 2 was repeated, whereby
det imidlertid ble benyttet iso-octan eller 2,2,4-trimethyl-pentah istedenfor n-hexan. however, iso-octane or 2,2,4-trimethyl-pentah was used instead of n-hexane.
Det ble funnet at den testede oljes klorinnhold eksklusive PKB var 2 96 ppm. It was found that the tested oil's chlorine content excluding PKB was 2 96 ppm.
Claims (6)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| LU85992A LU85992A1 (en) | 1985-07-09 | 1985-07-09 | METHOD OF TREATING OILS CONTAINING CHLORINATED BIPHENYLS |
| LU86253A LU86253A1 (en) | 1986-01-16 | 1986-01-16 | Determn. of polychlorinated bi:phenol(s) in oils - by decomposition and determn. of chloride by mercurimetry |
| LU86285A LU86285A1 (en) | 1986-01-31 | 1986-01-31 | Determn. of polychlorinated bi:phenol(s) in oils - by decomposition and determn. of chloride by mercurimetry |
Publications (4)
| Publication Number | Publication Date |
|---|---|
| NO862756D0 NO862756D0 (en) | 1986-07-08 |
| NO862756L NO862756L (en) | 1987-01-12 |
| NO169312B true NO169312B (en) | 1992-02-24 |
| NO169312C NO169312C (en) | 1992-06-03 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO862756A NO169312C (en) | 1985-07-09 | 1986-07-08 | PROCEDURE FOR AA DETERMINING THE CONTENT OF POLYCLORATED BIFENYL COMPOUNDS IN AN OIL. |
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| Country | Link |
|---|---|
| BE (1) | BE905031A (en) |
| DE (1) | DE3622928A1 (en) |
| ES (1) | ES2000484A6 (en) |
| FR (1) | FR2584821B3 (en) |
| GB (1) | GB2177794B (en) |
| IT (1) | IT1190345B (en) |
| NO (1) | NO169312C (en) |
| TN (1) | TNSN86104A1 (en) |
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|---|---|---|---|---|
| CN106645443A (en) * | 2016-09-23 | 2017-05-10 | 深圳天祥质量技术服务有限公司 | Method for detecting short-chain chlorinated paraffin (SCCP) and medium-chain chlorinated paraffin (MCCP) in consumer goods |
| RU2721559C1 (en) * | 2020-02-04 | 2020-05-20 | федеральное государственное автономное образовательное учреждение высшего образования «Национальный исследовательский Томский политехнический университет» | Method of determining organochlorine compounds in oil |
-
1986
- 1986-06-13 IT IT20787/86A patent/IT1190345B/en active
- 1986-06-27 FR FR8609327A patent/FR2584821B3/en not_active Expired
- 1986-07-01 GB GB8616003A patent/GB2177794B/en not_active Expired
- 1986-07-02 BE BE1/011514A patent/BE905031A/en not_active IP Right Cessation
- 1986-07-08 NO NO862756A patent/NO169312C/en unknown
- 1986-07-08 DE DE19863622928 patent/DE3622928A1/en not_active Withdrawn
- 1986-07-09 ES ES8600215A patent/ES2000484A6/en not_active Expired
- 1986-07-09 TN TNTNSN86104A patent/TNSN86104A1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| FR2584821B3 (en) | 1987-10-09 |
| FR2584821A1 (en) | 1987-01-16 |
| GB8616003D0 (en) | 1986-08-06 |
| NO862756D0 (en) | 1986-07-08 |
| BE905031A (en) | 1986-11-03 |
| IT8620787A1 (en) | 1987-12-13 |
| IT1190345B (en) | 1988-02-16 |
| IT8620787A0 (en) | 1986-06-13 |
| TNSN86104A1 (en) | 1990-01-01 |
| NO862756L (en) | 1987-01-12 |
| GB2177794B (en) | 1989-04-26 |
| ES2000484A6 (en) | 1988-03-01 |
| GB2177794A (en) | 1987-01-28 |
| NO169312C (en) | 1992-06-03 |
| DE3622928A1 (en) | 1987-01-15 |
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