NO830496L - PROCEDURE FOR DIVISION OF OIL FLAKES - Google Patents
PROCEDURE FOR DIVISION OF OIL FLAKESInfo
- Publication number
- NO830496L NO830496L NO830496A NO830496A NO830496L NO 830496 L NO830496 L NO 830496L NO 830496 A NO830496 A NO 830496A NO 830496 A NO830496 A NO 830496A NO 830496 L NO830496 L NO 830496L
- Authority
- NO
- Norway
- Prior art keywords
- oil
- accordance
- diguanidine
- acid
- carbon atoms
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 14
- 239000000463 material Substances 0.000 claims description 54
- 150000003839 salts Chemical class 0.000 claims description 29
- 235000015097 nutrients Nutrition 0.000 claims description 21
- -1 phosphorus compound Chemical class 0.000 claims description 19
- 239000013535 sea water Substances 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 244000005700 microbiome Species 0.000 claims description 13
- 239000004094 surface-active agent Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Chemical group 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 230000004060 metabolic process Effects 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 2
- 125000005843 halogen group Chemical group 0.000 claims 1
- 239000003921 oil Substances 0.000 description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 230000015556 catabolic process Effects 0.000 description 15
- 238000006731 degradation reaction Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 5
- 239000010779 crude oil Substances 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 231100000053 low toxicity Toxicity 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LFVVNPBBFUSSHL-UHFFFAOYSA-N alexidine Chemical compound CCCCC(CC)CNC(=N)NC(=N)NCCCCCCNC(=N)NC(=N)NCC(CC)CCCC LFVVNPBBFUSSHL-UHFFFAOYSA-N 0.000 description 2
- 229950010221 alexidine Drugs 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 235000013877 carbamide Nutrition 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 239000000787 lecithin Substances 0.000 description 2
- 229940067606 lecithin Drugs 0.000 description 2
- 235000010445 lecithin Nutrition 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 241001672739 Artemia salina Species 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- VWVDQDFRLHVOOB-UHFFFAOYSA-N acetic acid;dodecane-1,4-diamine Chemical compound CC(O)=O.CCCCCCCCC(N)CCCN VWVDQDFRLHVOOB-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003653 coastal water Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- GDNCXORZAMVMIW-UHFFFAOYSA-N dodecane Chemical compound [CH2]CCCCCCCCCCC GDNCXORZAMVMIW-UHFFFAOYSA-N 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- HJLHTTJLVALHOP-UHFFFAOYSA-N hexane;hydron;chloride Chemical compound Cl.CCCCCC HJLHTTJLVALHOP-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000004533 oil dispersion Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003904 phospholipids Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/32—Materials not provided for elsewhere for absorbing liquids to remove pollution, e.g. oil, gasoline, fat
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
- C02F1/682—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of chemical compounds for dispersing an oily layer on water
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
- C02F3/344—Biological treatment of water, waste water, or sewage characterised by the microorganisms used for digestion of mineral oil
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Microbiology (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Biodiversity & Conservation Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Public Health (AREA)
- Materials Engineering (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Micro-Organisms Or Cultivation Processes Thereof (AREA)
- Biological Treatment Of Waste Water (AREA)
- Fats And Perfumes (AREA)
- Removal Of Floating Material (AREA)
Description
Den foreliggende oppfinnelse vedrører en fremgangsmåteThe present invention relates to a method
til fjerning av oljeflak i sjøvann, nærmere bestemt en fremgangsmåte til forbedring av den biologiske nedbrytning av olje som forurenser sjøvann. Oppfinnelsen vedrører dessuten et dispergeringsmateriale til behandling av oljeflak. for the removal of oil flakes in seawater, more specifically a method for improving the biological breakdown of oil that pollutes seawater. The invention also relates to a dispersing material for treating oil flakes.
Forurensning av havvann med olje (råolje eller fraksjoner av råolje) på grunn av ulykker, boring til havs eller utslipp av ballastvann eller søl fra oljetankskip resulterer i dannelse av en kontinuerlig film eller et flak av olje som er tilbøyelig til å stadig spres. I åpent vann er denne oljefilm ikke ønskelig idet den utgjør en barriere for overføring av luft og lys fra atmosfæren til havvann, noe som er nødvendig for det marine liv. Contamination of seawater by oil (crude oil or fractions of crude oil) due to accidents, offshore drilling or the discharge of ballast water or spills from oil tankers results in the formation of a continuous film or fleck of oil which tends to continuously spread. In open water, this oil film is not desirable as it forms a barrier to the transfer of air and light from the atmosphere to sea water, which is necessary for marine life.
I kystfarvann skader oljefilmen skalldyrbanker og strender.In coastal waters, the oil film damages shellfish banks and beaches.
En måte å håndtere disse forurensningsproblemer på er å anvende oljedispergeringsmaterialer som inneholder overflateaktive bestanddeler. Disse materialer påføres på oljeflakene ved hjelp av vanlige sprøyteanordninger. De bryter ned den kohe-sive oljefilm til små dråper og dispergerer dråpene i vannet til en dybde på flere meter under vannflaten. Filmen er således brutt, og på nytt oppnås det en luft- og lysoverføring fra atmosfæren. Dessuten unngås ødeleggelse av permanente konstruksjoner og strender langs kystene. One way to deal with these pollution problems is to use oil dispersing materials that contain surfactants. These materials are applied to the oil slicks using conventional spray devices. They break down the cohesive oil film into small droplets and disperse the droplets in the water to a depth of several meters below the water surface. The film is thus broken, and once again an air and light transmission from the atmosphere is achieved. In addition, the destruction of permanent structures and beaches along the coasts is avoided.
Oljedråpene som dispergeres under vannflaten brytes deretter ned biologisk og konsumeres av mikroorganismer som lever i sjøvann og som er aktive i oljemetabolisme. Denne biologiske nedbrytning er imidlertid en forholdsvis langsom prosess og kan følgelig ikke hindre avsetning av ikke nedbrutte oljedråper og dannelse av oljeavleiringer på sjøbunne, særlig der vannet er grunt. The oil droplets that are dispersed below the water surface are then biologically broken down and consumed by microorganisms that live in seawater and are active in oil metabolism. However, this biological degradation is a relatively slow process and consequently cannot prevent the deposition of non-degraded oil droplets and the formation of oil deposits on the seabed, particularly where the water is shallow.
En aktiv biologisk nedbrytning av oljedråper krever nærvær av en stor mengde mikroorganismer på grenseflaten mellom olje og vann. Disse organismer forekommer imidlertid i sjøvann bare i begrensete mengder. For å stimulere den biologiske nedbrytning er det av den grunn nødvendig å påskynde dannelsen av mikroorganismene. For dette er det ikke bare nødvendig med oksygen og karbon, som finnes både i vann og forurensende olje, men også nitrogen og fosfor. Vanligvis er konsentrasjonen av de to sist-nevnte stoffer meget lav i sjøvann, og således er den naturlige nedbrytning av olje en langsom prosess. An active biological breakdown of oil droplets requires the presence of a large number of microorganisms at the interface between oil and water. However, these organisms occur in seawater only in limited quantities. In order to stimulate biological degradation, it is therefore necessary to speed up the formation of the microorganisms. For this, not only is oxygen and carbon needed, which are found in both water and polluting oil, but also nitrogen and phosphorus. Generally, the concentration of the two last-mentioned substances is very low in seawater, and thus the natural breakdown of oil is a slow process.
For å øke den biologiske nedbrytningshastighet har man foreslått å tilføre sjøvannet mikrobielle næringsstoffer. Mineral-salter, f.eks. ammoniumsalter, nitrater og fosfater, er blitt anvendt. Disse salter er imidlertid altfor lettløselige i vann og har praktisk talt ingen affinitet til den forurensende olje. In order to increase the rate of biological degradation, it has been proposed to add microbial nutrients to the seawater. Mineral salts, e.g. ammonium salts, nitrates and phosphates have been used. However, these salts are too easily soluble in water and have practically no affinity for the contaminating oil.
De oppløses altfor hurtig og dispergeres i sjøvann og blir ikke holdt tilbake på olje/vanngrenseflaten hvor de behøves. They dissolve far too quickly and disperse in seawater and are not retained at the oil/water interface where they are needed.
Det er dessuten foreslått å anvende nitrogenholdige organiske næringsstoffer som er oljeløselige, f.eks. kondensasjonsprodukter av karbamid og melamin. Disse organiske forbindelser er imidlertid også løselige i vann. De dissosierer fra oljen og går tapt i den vandige fase. For å eliminere denne ulempe er det forslått å modifisere løseligheten i vann. F.eks. absor-beres kondensasjonsprodukter av karbamid og et aldehyd med mindre enn 4 karbonatomer først på en inert bærer og gjøres deretter lipofile ved belegging med en parafin- eller annen beskyttelses-kolloid. Denne behandling nødvendiggjør spesialutstyr og øker prisen på næringsstoffene. Dessuten kan dette belegg løses hurtig opp dersom den forurensende olje, f.eks. fersk råolje, inneholder aromatiske hydrokarboner. It is also proposed to use nitrogen-containing organic nutrients that are oil-soluble, e.g. condensation products of carbamide and melamine. However, these organic compounds are also soluble in water. They dissociate from the oil and are lost in the aqueous phase. To eliminate this disadvantage, it is proposed to modify the solubility in water. E.g. condensation products of carbamide and an aldehyde with less than 4 carbon atoms are first absorbed on an inert carrier and then made lipophilic by coating with a paraffin or other protective colloid. This treatment requires special equipment and increases the price of the nutrients. Moreover, this coating can dissolve quickly if the contaminating oil, e.g. fresh crude oil, contains aromatic hydrocarbons.
Andre metoder er foreslått for å minske næringsstoffenes løselighet i vann, men resultatet er blitt materialer som bare flyter på vannflaten. Disse næringsstoffer letter derved ikke utviklingen av mikroorganismer i vannet under havflaten hvor oljedråpene dispergeres. Other methods have been proposed to reduce the solubility of nutrients in water, but the result has been materials that only float on the surface of the water. These nutrients thereby do not facilitate the development of micro-organisms in the water below the sea surface where the oil droplets are dispersed.
Vanskelighetene med kjente næringsstoffer er eliminertThe difficulties with known nutrients have been eliminated
ved utvikling av nye lipofile næringsstoffer for mikroorganismene i sjøvann, som er aktive ved nedbrytning av olje. Disse nye næringsstoffer gir til rimelig pris en hurtig og mer fullstendig nedbrytning av oljene biologisk. through the development of new lipophilic nutrients for the microorganisms in seawater, which are active when breaking down oil. These new nutrients provide a rapid and more complete biological breakdown of the oils at a reasonable price.
Formålet med den foreliggende oppfinnelse er å frembringe en fremgangsmåte til fjerning av oljeflak i sjøvann ved å behand le det forurensete vann med et dispergeringsmateriale og med en nitrogenholdig forbindelse som er tungtløselig og stabil i vann. The purpose of the present invention is to produce a method for removing oil flakes in seawater by treating the polluted water with a dispersing material and with a nitrogen-containing compound which is sparingly soluble and stable in water.
Et annet formål er å bedre den biologiske nedbrytningshastighet for den forurensende olje ved å behandle det forurensete vann med et dispergeringsmateriale og en nitrogenholdig forbindelse som øker utviklingen av mikroorganismer som er aktive i oljernetabolismen. Another purpose is to improve the biological degradation rate of the polluting oil by treating the polluted water with a dispersing material and a nitrogenous compound which increases the development of microorganisms active in oil metabolism.
Et ytterligere formål er å frembringe som næringsstoff for mikroorganismene en nitrogenholdig forbindelse som er løse-lig i olje og som har lav giftighet overfor fauna og flora i vannet. A further purpose is to produce as a nutrient for the microorganisms a nitrogen-containing compound which is soluble in oil and which has low toxicity towards fauna and flora in the water.
Det har ifølge oppfinnelsen vist seg at uventede resultater oppnås når det gjelder oljedispergeringseffekt og biologisk nedbrytning med mikroorganismer ved å behandle det oljeforurensete sjøvann med et dispergeringsmateriale og et nitrogenholdig næringsstoff for mikroorganismene, hvorved næringsstoffet ut-gjøres av et diguanidinsalt med den generelle formel: According to the invention, it has been shown that unexpected results are achieved in terms of oil dispersion effect and biological degradation with microorganisms by treating the oil-polluted seawater with a dispersing material and a nitrogen-containing nutrient for the microorganisms, whereby the nutrient consists of a diguanidine salt with the general formula:
hvor R er et alkylradikal med 2-12 karbonatomer og X er et halogen eller en syreanion. where R is an alkyl radical with 2-12 carbon atoms and X is a halogen or an acid anion.
Fremgangsmåten ifølge oppfinnelsen til fjerning av oljeflak i sjøvann består hovedsakelig i behandling av oljeflakene med et dispergeringsmateriale og det ovenfor angitte diguanidinsalt. The method according to the invention for removing oil flakes in seawater mainly consists of treating the oil flakes with a dispersing material and the above-mentioned diguanidine salt.
Diguanidinsaltene fremstilles på kjent måte ved å omsette et diaminsalt XH.H2N-R-NH2.HX med cyanamid H2N-C=N, hvor R og X er som angitt ovenfor. Et aminsalt eller en blanding av amin-salter kan anvendes. Molforholdet mellom diaminsaltet og cyan-amidet er minst 1:2. F.eks. fremstilles 1,6-bisguanidinheksan-hydroklorid The diguanidine salts are prepared in a known manner by reacting a diamine salt XH.H2N-R-NH2.HX with cyanamide H2N-C=N, where R and X are as stated above. An amine salt or a mixture of amine salts can be used. The molar ratio between the diamine salt and the cyanamide is at least 1:2. E.g. 1,6-bisguanidine hexane hydrochloride is prepared
av 1,6-diaminoheksan og cyanamid. Derved innføres 1 mol diamin, som er tørket på forhånd og løst i isopropylalkohol, i en kolbe som er utstyrt med rører, et termometer og et utløpsrør i forbindelse med en Dan og Stark-dekanteringsanordning med en vann-kjøler. Deretter innføres langsomt 3 mol saltsyre i kolben. of 1,6-diaminohexane and cyanamide. Thereby, 1 mole of diamine, which has been dried in advance and dissolved in isopropyl alcohol, is introduced into a flask equipped with a stirrer, a thermometer and an outlet tube in connection with a Dan and Stark decanter with a water cooler. Then slowly introduce 3 mol of hydrochloric acid into the flask.
Etter reaksjonen fjernes vann og isopropylalkohol. Xylen tilsettes deretter, og blandingen oppvarmes med tilbakekjøling for fjerning av eventuelt resterende vann. Når blandingens temperatur er sunket til 80°C tilsettes 2 mol cyanamid, og reaksjonsblandingen holdes oppvarmet på 140°C i 2 timer. Etter avkjøling filtreres reaksjonsblandingen, vaskes med alkohol, omrøres ved 60°C After the reaction, water and isopropyl alcohol are removed. The xylene is then added and the mixture heated with reflux to remove any remaining water. When the temperature of the mixture has dropped to 80°C, 2 mol of cyanamide are added, and the reaction mixture is kept heated at 140°C for 2 hours. After cooling, the reaction mixture is filtered, washed with alcohol, stirred at 60°C
i 30 minutter i nærvær av alkohol som inneholder ca. 1% aktivt kull samt filtreres gjennom et milliporefilter. Etter fjerning av resterende løsningsmiddel oppnås 1,6-bisguanidinheksan i et utbytte på 98%. for 30 minutes in the presence of alcohol containing approx. 1% activated charcoal and filtered through a millipore filter. After removal of residual solvent, 1,6-bisguanidinehexane is obtained in a yield of 98%.
Nitrogeninnholdet i diguanidinsaltene avhenger av de spesifikke R og X, men ligger normalt i intervallet 15-40%. The nitrogen content of the diguanidine salts depends on the specific R and X, but is normally in the range 15-40%.
Diguanidinsalter hvor radikalet har 12 eller flere karbonatomer kan anvendes. Imidlertid er det med hensyn til diaminets tilgjengelighet og pris mer fordelaktig å fremstille diguanidinsalter hvor radikalen R inneholder opp til 8 karbonatomer. Som en funksjon av valget av radikalene R og X kan det dessuten fremstilles diguanidinsalter som er tilstrekkelig løselige eller • som kan suspenderes i de fleste dispergeringsmaterialer til fjerning av oljeflak. Diguanidinsalter hvor radikalet R inneholder 2-6 karbonatomer har denne egenskap og kan derfor anvendes som en løsning eller suspensjon i disse dispergeringsmaterialer. Dersom diguanidinsaltet ikke er løselig eller ikke kan suspenderes i dispergeringsmaterialer, kan det enten tilsettes det forurensete vann enten etter eller før påføringen av disperge-ringsmaterialet. Diguanidine salts where the radical has 12 or more carbon atoms can be used. However, with regard to the diamine's availability and price, it is more advantageous to prepare diguanidine salts where the radical R contains up to 8 carbon atoms. As a function of the choice of the radicals R and X, diguanidine salts can also be prepared which are sufficiently soluble or • which can be suspended in most dispersing materials for the removal of oil flakes. Diguanidine salts where the radical R contains 2-6 carbon atoms have this property and can therefore be used as a solution or suspension in these dispersing materials. If the diguanidine salt is not soluble or cannot be suspended in dispersing materials, it can either be added to the contaminated water either after or before the application of the dispersing material.
I formelen ovenfor kan X være et halogen, særlig Cl, eller en syreanion, f.eks. radikalet i svovelsyre, salpetersyre, metyl-eller etylsvovelsyre, alkylbenzensulfonsyre, eddiksyre, melkesyre eller liknende. Av økonomiske årsaker kan det være fordelaktig å fremstille diguanidinsalter hvor X er Cl eller radikalet i svovelsyre, salpetersyre eller eddiksyre. Radikalet X kan også velges for fremstilling av diguanidinsalter som er løselige eller lett suspenderbare i vanlige dispergeringsmaterialer. F.eks. In the formula above, X can be a halogen, especially Cl, or an acid anion, e.g. the radical in sulfuric acid, nitric acid, methyl or ethyl sulfuric acid, alkylbenzene sulphonic acid, acetic acid, lactic acid or the like. For economic reasons, it can be advantageous to prepare diguanidine salts where X is Cl or the radical in sulfuric acid, nitric acid or acetic acid. The radical X can also be chosen for the preparation of diguanidine salts which are soluble or easily suspendable in common dispersing materials. E.g.
er diguanidinsalter hvor R er dodecylradikalet praktisk talt uløselige i de fleste dispergeringsmaterialer når X er Cl, men løselige i disse når X er melkesyreradikalet. are diguanidine salts where R is the dodecyl radical practically insoluble in most dispersing materials when X is Cl, but soluble in these when X is the lactic acid radical.
For å lette utviklingen av mikroorganismer er diguanidinsaltene fortrinnsvis blandet med en fosforforbindelse som også funksjonerer som næringsstoff for tilførsel av fosfor. Fosfor- forbindelsen kan være et alkali- eller jordalkalimetallsalt av en fosforester av en fettalkohol, et salt eller en ester av organofosfonsyre eller et fosfatid eller liknende produkt med lav giftighet for vannets flora og fauna. Estre som er fremstilt ved nøytralisasjon av heksametylendiamintetra(metylenfosfonsyre) To facilitate the development of microorganisms, the diguanidine salts are preferably mixed with a phosphorus compound which also functions as a nutrient for supplying phosphorus. The phosphorus compound can be an alkali or alkaline earth metal salt of a phosphoric ester of a fatty alcohol, a salt or an ester of organophosphonic acid or a phosphatide or similar product with low toxicity for aquatic flora and fauna. Esters prepared by neutralization of hexamethylenediaminetetra(methylenephosphonic acid)
med formelen (H~PO,CH,J„ - N(CH_), - N(CH~PO,Hn)~med et amin,with the formula (H~PO,CH,J„ - N(CH_), - N(CH~PO,Hn)~with an amine,
Z 5 Z Z Z6ZjZ ZZ 5 Z Z Z6ZjZ Z
f.eks. monoetanolamin eller et fettamin med 12-18 karbonatomer, gir gode resultater. Fosfatider eller fosfolipider, særlig lecitin eller kefalin, funksjonerer samtidig som nitrogen- og fosfor-kilde og forsterker således diguanidinsaltenes effekt. e.g. monoethanolamine or a fatty amine with 12-18 carbon atoms gives good results. Phosphatides or phospholipids, especially lecithin or kephalin, simultaneously function as a nitrogen and phosphorus source and thus enhance the effect of the diguanidine salts.
Ifølge en foretrukket utførelse av oppfinnelsen anvendes det diguanidinsalter hvor radikalet R inneholder opp til 8 karbonatomer. De anvendes som en løsning eller suspensjon i dispergeringsmaterialer som inneholder minst én overflateaktiv forbindelse og minst ett løsningsmiddel med lav giftighet for vannets flora og fauna. According to a preferred embodiment of the invention, diguanidine salts are used where the radical R contains up to 8 carbon atoms. They are used as a solution or suspension in dispersion materials that contain at least one surface-active compound and at least one solvent with low toxicity for aquatic flora and fauna.
Som overflateaktiv forbindelse kan angis etoksylert tall-olje, mono- eller polyestre av polyoler, fortrinnsvis estre av mettede eller umettede alifatiske karboksylsyrer med 12-20 karbonatomer og av alkoholer, f.eks. sorbitol, glycerol og polyetylen-glykol. Blandinger av to eller flere av disse estre kan anvendes med valgfri tilsetning av andre overflateaktive midler, f.eks. etoksylerte fettalkoholer, alkalisalter av dialkylsulfosuccinater eller kondensasjonsprodukter av etylenoksyd eller propylenoksyd på ovennevnte estre. Ethoxylated tall oil, mono- or polyesters of polyols, preferably esters of saturated or unsaturated aliphatic carboxylic acids with 12-20 carbon atoms and of alcohols, e.g. sorbitol, glycerol and polyethylene glycol. Mixtures of two or more of these esters can be used with the optional addition of other surfactants, e.g. ethoxylated fatty alcohols, alkali salts of dialkyl sulfosuccinates or condensation products of ethylene oxide or propylene oxide on the above-mentioned esters.
De overflateaktive midler løses i minst ett løsningsmiddel med lav giftighet for vannets flora og fauna. Løsningsmidlet har dobbel funksjon: det letter håndteringen og påføringen av de overflateaktive midler, og på grunn av sin affinitet fremmer det materialets inntrengning i oljefilmen. Som løsningsmidler kan nevnes væskeformete hydrokarboner med mindre enn 5%, fortrinnsvis mindre enn 3%, aromatiske forbindelser. Væskeformete hydrokarboner med 5-2 0 karbonatomer, f.eks. parafinhydrokarboner med 6-12 karbonatomer, cykloparafinhydrokarboner, f.eks. cyklo-pentan og cykloheksan, alkylcykloparafinhydrokarboner og naften-hydrokarboner, anvendes med fordel. Alifatiske alkoholer med opp til 8 karbonatomer, f.eks. etyle-, propyl- og isopropylalko-holer, og glykolmonoetre, særlig monoalkyletre (hvor alkylradi-kalet inneholder 1-4 karbonatomer) av glykoler, såsom mono- eller dietylenglykol og mono- eller dipropylenglykol, er også egnete løsningsmidler. Det organiske løsningsmiddel kan også inneholde vann i en mengde som ikke overstiger mengden løsningsmiddel. The surfactants are dissolved in at least one solvent with low toxicity for the aquatic flora and fauna. The solvent has a dual function: it facilitates the handling and application of the surfactants, and due to its affinity it promotes the penetration of the material into the oil film. Liquid hydrocarbons with less than 5%, preferably less than 3%, aromatic compounds can be mentioned as solvents. Liquid hydrocarbons with 5-20 carbon atoms, e.g. paraffin hydrocarbons with 6-12 carbon atoms, cycloparaffin hydrocarbons, e.g. cyclopentane and cyclohexane, alkyl cycloparaffin hydrocarbons and naphthenic hydrocarbons, are used with advantage. Aliphatic alcohols with up to 8 carbon atoms, e.g. Ethyl, propyl and isopropyl alcohols, and glycol monoethers, especially monoalkylethers (where the alkyl radical contains 1-4 carbon atoms) of glycols, such as mono- or diethylene glycol and mono- or dipropylene glycol, are also suitable solvents. The organic solvent can also contain water in an amount that does not exceed the amount of solvent.
Vektforholdet overflateaktivt middel/løsningsmiddel kan variere innenfor vide grenser. Det er selvfølgelig ønskelig å anvende materialer som er så konsentrert som mulig, men mengden løsningsmiddel i materialet må være tilstrekkelig til å løse opp de overflateaktive midler og næringsstoffene samt muliggjøre påføring av materialet ved lav temperatur. Det har vist seg at materialer med mer enn ca. 85% overflateaktive midler og næringsstoffer er altfor viskøse ved lave temperaturer. Heller ikke trenger de lett inn i oljeflaket og er av den grunn mindre aktive. På den annen side har materialer med mindre enn ca. 30% overflateaktive midler og næringsstoffer en lav effekt. The surfactant/solvent weight ratio can vary within wide limits. It is of course desirable to use materials that are as concentrated as possible, but the amount of solvent in the material must be sufficient to dissolve the surface-active agents and nutrients and enable the application of the material at a low temperature. It has been shown that materials with more than approx. 85% surfactants and nutrients are far too viscous at low temperatures. They also do not easily penetrate the oil slick and are therefore less active. On the other hand, materials with less than approx. 30% surfactants and nutrients a low effect.
Mengden dialkylguanidinsalt i dispergeringsmaterialeneThe amount of dialkylguanidine salt in the dispersing materials
kan variere innenfor forholdsvis vide grenser og være så høy som 35% eller mer, regnet av materialets totalvekt. Denne mengde er avhengig av mange faktorer, f.eks. det anvendte guanidinsalt og dettes nitrogeninnhold, den eventuelle forekomst av andre næringsstoffer samt det anvendte spesifikke løsningsmiddel. Materialer med 2-20 vekt%, fortrinnsvis 5-15 vekt% dialkylguanidinsalt er meget effektive når det gjelder den biologiske nedbrytning av oljedråper som er dispergert i sjøvann. can vary within relatively wide limits and be as high as 35% or more, calculated from the total weight of the material. This amount depends on many factors, e.g. the guanidine salt used and its nitrogen content, the possible presence of other nutrients and the specific solvent used. Materials with 2-20% by weight, preferably 5-15% by weight of dialkylguanidine salt are very effective when it comes to the biological degradation of oil droplets dispersed in seawater.
Materialet ifølge den foreliggende oppfinnelsen kan også inneholde andre bestanddeler og grunnstoffer, som er nyttige for utviklingen av mikroorganismer. Materialene inneholder disse grunnstoffer i form av organiske salter, nemlig i form av magne-sium- eller kalsiumsalt av alkylbenzensulfonsyre. Mengden av disse tilsetninger overstiger generelt ikke ca. 3%, regnet av materialets totalvekt. The material according to the present invention may also contain other components and elements, which are useful for the development of microorganisms. The materials contain these elements in the form of organic salts, namely in the form of magnesium or calcium salts of alkylbenzenesulfonic acid. The amount of these additives generally does not exceed approx. 3%, calculated from the total weight of the material.
Materialene påføres på oljeflak på kjent måte. De kan anvendes etter tynning med vann. De kan sprøytes på oljeflakene fra fly eller fra båter som er utstyrt med egnete sprøyteanord-ninger. The materials are applied to oil slicks in a known manner. They can be used after thinning with water. They can be sprayed onto the oil slicks from aircraft or from boats equipped with suitable spraying devices.
Eksempel 1Example 1
Følgende dispergeringsmateriale ble fremstilt:The following dispersion material was prepared:
Dette materialets giftighet ble bestemt ved at arten Arte-mia salina ble utsatt for økende doser av materialet for bestem-melse av den maksimale mengde materiale som etter 24 timer etter-lot 50% av den testede art i live (test CL 50-24 timer). Det viste seg at giftigheten var 3500 ppm. The toxicity of this material was determined by exposing the species Artemia salina to increasing doses of the material to determine the maximum amount of material which after 24 hours left 50% of the tested species alive (test CL 50-24 hours ). It turned out that the toxicity was 3500 ppm.
Den biologiske nedbrytningseffekt ble bestemt på følgende måte: 200 ppm av det testede materiale ble tilsatt usterilisert sjøvann (700 ml) som inneholdt 5000 ppm råolje. Dette ble hensatt for inkubasjon i 41 dager ved 25°C og blanding ved hjelp av luftbobling. Resterende olje ble deretter ekstrahert. Det viste seg at den biologiske nedbrytningseffekt med ovennevnte materiale var 1,8 ganger større enn med et tilsvarende materiale som ikke inneholdt næringsstoffer, og 1,4 ganger større enn et tilsvarende materiale som inneholdt ammoniumnitrat istedenfor guanidinbutan-hydroklorid. The biological degradation effect was determined as follows: 200 ppm of the tested material was added to unsterilized seawater (700 ml) containing 5000 ppm crude oil. This was reserved for incubation for 41 days at 25°C and mixing by air bubbling. Residual oil was then extracted. It turned out that the biological degradation effect with the above-mentioned material was 1.8 times greater than with a corresponding material that did not contain nutrients, and 1.4 times greater than a corresponding material that contained ammonium nitrate instead of guanidine butane hydrochloride.
Eksempel 2Example 2
Et materiale som i eksempel 1 ble fremstilt med bisguanidin-etanhydroklorid som diguanidinsalt. A material which in example 1 was prepared with bisguanidine-ethane hydrochloride as diguanidine salt.
Dette materialets egenskaper når det gjelder giftighetThe properties of this material in terms of toxicity
og biologisk nedbrytningseffekt var de samme som for materialet i eksempel 1. and biodegradation effect were the same as for the material in example 1.
Eksempel 3Example 3
Det ble fremstilt følgende dispergeringsmateriale: The following dispersion material was produced:
Med dette materiale var den biologiske nedbrytningseffekt 1,8 ganger større enn for et liknende, næringsstoffritt materiale. With this material, the biological degradation effect was 1.8 times greater than for a similar, nutrient-free material.
Eksempel 4Example 4
Det ble fremstilt et materiale som i eksempel 3 med bis-guanidinheksanlaktat som nitrogenholdig næringsstoff. A material was produced as in example 3 with bis-guanidine hexane lactate as nitrogenous nutrient.
Den biologiske nedbrytningseffekt var 1,6 ganger større enn for det næringsstoffrie materiale. The biological degradation effect was 1.6 times greater than for the nutrient-free material.
Eksempel 5Example 5
Bisguanidindodekanacetat ble fremstilt av 1,4-diaminodode-kanacetat og cyanamid. 50 ppm av en blanding av 65% av dette bisguanidinsalt og 35% lecitin ble tilsatt til usterilisert sjøvann (700 ml) som inneholdt råolje. 150 ppm av et kommersielt dispergeringsmateriale ble deretter tilsatt. Blandingen ble holdt på 25°C i 41 dager under omrøring ved hjelp av luftbobling. Restolje ble ekstrahert med metylenklorid. Bisguanidine indodecane acetate was prepared from 1,4-diaminododecane acetate and cyanamide. 50 ppm of a mixture of 65% of this bisguanidine salt and 35% lecithin was added to unsterilized seawater (700 ml) containing crude oil. 150 ppm of a commercial dispersant was then added. The mixture was kept at 25°C for 41 days under agitation by air bubbling. Residual oil was extracted with methylene chloride.
Den biologiske nedbrytningseffekt var 1,7 ganger større enn for et næringsstoffritt dispergeringsmateriale. The biological degradation effect was 1.7 times greater than for a nutrient-free dispersing material.
Claims (11)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| LU84445A LU84445A1 (en) | 1982-10-28 | 1982-10-28 | PROCESS FOR THE TREATMENT OF POLLUTED SEAWATER WITH MINERAL OILS |
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| Publication Number | Publication Date |
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| NO830496L true NO830496L (en) | 1984-04-30 |
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ID=19729973
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO830496A NO830496L (en) | 1982-10-28 | 1983-02-15 | PROCEDURE FOR DIVISION OF OIL FLAKES |
Country Status (17)
| Country | Link |
|---|---|
| JP (1) | JPS5982995A (en) |
| AU (1) | AU1070483A (en) |
| BE (1) | BE895841A (en) |
| CA (1) | CA1188241A (en) |
| DE (1) | DE3305686A1 (en) |
| DK (1) | DK68583A (en) |
| ES (1) | ES8403090A1 (en) |
| FI (1) | FI830470L (en) |
| FR (1) | FR2535338B1 (en) |
| GB (1) | GB2128979B (en) |
| GR (1) | GR71922B (en) |
| IT (1) | IT1163113B (en) |
| LU (1) | LU84445A1 (en) |
| NL (1) | NL8300400A (en) |
| NO (1) | NO830496L (en) |
| PT (1) | PT76252A (en) |
| SE (1) | SE8300732L (en) |
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|---|---|---|---|---|
| FR2573770A1 (en) * | 1984-11-26 | 1986-05-30 | Labofina Sa | Nutrients for mineral oil-biodegrading microorganisms |
| US5342525A (en) * | 1991-10-28 | 1994-08-30 | Rowsell Farrell D | Method for aiding microbial degradation of spilled oil |
| GB2277889A (en) * | 1993-05-11 | 1994-11-16 | Astrid Ericksson | Cleaning process |
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| US2906595A (en) * | 1957-04-29 | 1959-09-29 | American Cyanamid Co | Process water treatment |
| US3769164A (en) * | 1970-06-03 | 1973-10-30 | Bioteknika International | Microbial degradation of petroleum |
| US3856667A (en) * | 1970-06-03 | 1974-12-24 | Bioteknika Int Inc | Microbial degradation of petroleum |
| ZA773557B (en) * | 1977-06-14 | 1979-01-31 | Inter Ocean Investments Ltd | Water treatment |
| FR2479251A1 (en) * | 1980-03-28 | 1981-10-02 | Labofina Sa | Compsn. for dispersing oil spills on the surface of water - contg. polyethylene glycol or sorbitan ester(s) of fatty acids, glycol ether solvent and calcium or magnesium sulphonate |
-
1982
- 1982-10-28 LU LU84445A patent/LU84445A1/en unknown
-
1983
- 1983-01-24 AU AU10704/83A patent/AU1070483A/en not_active Abandoned
- 1983-02-03 NL NL8300400A patent/NL8300400A/en not_active Application Discontinuation
- 1983-02-08 BE BE1/10719A patent/BE895841A/en not_active IP Right Cessation
- 1983-02-11 FI FI830470A patent/FI830470L/en not_active Application Discontinuation
- 1983-02-11 SE SE8300732A patent/SE8300732L/en not_active Application Discontinuation
- 1983-02-14 FR FR8302305A patent/FR2535338B1/en not_active Expired
- 1983-02-14 GB GB08304049A patent/GB2128979B/en not_active Expired
- 1983-02-15 NO NO830496A patent/NO830496L/en unknown
- 1983-02-15 ES ES519805A patent/ES8403090A1/en not_active Expired
- 1983-02-15 GR GR70503A patent/GR71922B/el unknown
- 1983-02-17 PT PT76252A patent/PT76252A/en unknown
- 1983-02-17 DK DK68583A patent/DK68583A/en not_active Application Discontinuation
- 1983-02-18 DE DE19833305686 patent/DE3305686A1/en not_active Withdrawn
- 1983-02-18 IT IT19642/83A patent/IT1163113B/en active
- 1983-02-22 CA CA000422112A patent/CA1188241A/en not_active Expired
- 1983-03-14 JP JP58040857A patent/JPS5982995A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| BE895841A (en) | 1983-05-30 |
| GB2128979B (en) | 1986-04-03 |
| ES519805A0 (en) | 1984-03-16 |
| DK68583D0 (en) | 1983-02-17 |
| FI830470A0 (en) | 1983-02-11 |
| SE8300732D0 (en) | 1983-02-11 |
| IT1163113B (en) | 1987-04-08 |
| IT8319642A0 (en) | 1983-02-18 |
| SE8300732L (en) | 1984-04-29 |
| GR71922B (en) | 1983-08-18 |
| CA1188241A (en) | 1985-06-04 |
| JPS5982995A (en) | 1984-05-14 |
| AU1070483A (en) | 1984-05-03 |
| DK68583A (en) | 1984-04-29 |
| ES8403090A1 (en) | 1984-03-16 |
| PT76252A (en) | 1983-03-01 |
| GB8304049D0 (en) | 1983-03-16 |
| LU84445A1 (en) | 1984-05-10 |
| GB2128979A (en) | 1984-05-10 |
| NL8300400A (en) | 1984-05-16 |
| FI830470L (en) | 1984-04-29 |
| FR2535338A1 (en) | 1984-05-04 |
| DE3305686A1 (en) | 1984-05-03 |
| FR2535338B1 (en) | 1985-06-28 |
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