DK155041B - PROCEDURE FOR THE PREPARATION OF A MEDIUM TO PROMOTE THE BIOLOGICAL DEVELOPMENT OF CARBON HYDRODES - Google Patents
PROCEDURE FOR THE PREPARATION OF A MEDIUM TO PROMOTE THE BIOLOGICAL DEVELOPMENT OF CARBON HYDRODES Download PDFInfo
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Description
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Den foreliggende opfindelse angår en fremgangsmåde til fremstilling af et middel til fremskyndelse af den biologiske nedbrydning af carbon-hydrider, navnlig carbonhydrider i mineralolieprodukter.The present invention relates to a process for preparing an agent for accelerating the biodegradation of hydrocarbons, in particular hydrocarbons in mineral oil products.
Det er kendt, at den ved oparbejdningen af træ efter sulfitmetoden 5 opståede sulfitlud som hovedbestanddel indeholder ligni nsul fonsyre som vandopløseligt omdannelsesprodukt af lignin med SO^H-grupper.It is known that the sulphite liquor produced as the main constituent of the wood by the sulphite method 5 contains lignin sulphonic acid as a water-soluble conversion product of lignin with SO 2 H groups.
Hvad anvendeligheden af denne ligninsul fonsyre angår, findes der talrige forslag, som også i et vist omfang lader sig virkeliggøre i praksis. Man udvinder f.eks. bindemidler til briketter, klæbestoffer til 10 lim og papir, gødningsmidler ved omdannelse til humusstoffer, additiver til formstofpressemasser, emulgatorer til vejbelægningsstoffer, hjælpemidler og befugtningsmidler til tekstil forædling, brandbeskyttelsesmidler, garveekstrakter, flokkul ationsmidl er til proteinfældning og kondensationsprodukter til kautsjukindustrien. Det er endvidere kendt, at 15 1 igninsul fonsyre anvendes til geldannelse ved oxidation af chrom-(IV)-salte.Regarding the utility of this lignin sulphonic acid, there are numerous proposals that are also to some extent possible in practice. You extract, for example. briquette binders, adhesives for 10 glue and paper, fertilizers for conversion to humic substances, additives for plastics presses, emulsifiers for road coatings, auxiliaries and wetting agents for textile refinement, fire protection agents, tanning extracts, flocculants and condensation products. Furthermore, it is known that 15 l of igninsul phonic acid is used for gelation by the oxidation of chromium (IV) salts.
I calciumholdig sulfitlud med et tørstofindhold på 50 - 60% findes der endvidere sukker og carbohydrater. Ved sådanne stoffer er det kendt ved hjælp af mikroorganismer som f.eks. gærsvampe at overføre disse i 20 brugbare fedtstoffer og proteiner, ligesom det er kendt at anvende dem som ionbyttere (Rompp, Chemielexikon, afsnit Lignin; Fiedler, F. Nat.In addition, sugars and carbohydrates are found in calcium-containing sulfite liquor with a solids content of 50 - 60%. By such substances it is known by means of microorganisms such as e.g. yeast fungi to transfer these into 20 useful fats and proteins, as well as using them as ion exchangers (Rompp, Chemielexicon, section Lignin; Fiedler, F. Nat.
Diss. Univ. Greifswald 1957; Chemiker-Zeitung 1954, side 508).Diss. Univ. Greifswald 1957; Chemiker Zeitung 1954, page 508).
Det er endvidere kendt, at cerium ligesom saltene af praseodym og neodym i en koncentration af størrelsesordenen 1:10000 kan forøge gær-25 svampenes gæringskraft, ligesom koagulationen af mælk med løbe fremmes ved tilsætning af disse salte, og koagulationen af blod in vitro hæmmes eller forhindres (Hara S.: Arch. f. exper.Pathol. 100, 224; Drossbach: ZBL, Bakt. I, 21,57).Furthermore, it is known that cerium, like the salts of praseodymium and neodymium at a concentration of the order of 1: 10000, can increase the fermentation fermentation of the yeasts, as well as the coagulation of milk by running promoted by the addition of these salts and the coagulation of blood in vitro is inhibited or prevented (Hara S.: Arch. f. Exper. Pathol. 100, 224; Drossbach: ZBL, Bakt. I, 21.57).
Bestemte kolloidsystemer af salte af sjældne jordarter er som be-30 kendt desuden i stand til med virkning som sporstoffer at aktivere planters vækstudvikling, hvilket kan iagttages gennem kortere udkimningstid, tidligere kimbiadsdanelse, bedre roddannelse og tættere bestand, såvel syns- som antalsmæssigt. Ved eksperimentelle markforsøg har det kunnet påvises, at udbyttet af kulturer ved tilsætning af sådanne sporelement-35 kolloider kunne forøges med 24,6%, hvorved planterne blev mere resistente over for sygdoms- og skadedyrsangreb (H.A. Schweigart: Pflanzenernåh-rung durch Anreicherung der Saat mit Spurenelementkontaktcolloiden, Vitalstoffe, hæfte 20, 1960). I yderligere publikationer er det påvist, 2As is well known, certain colloidal systems of rare earth salts are also capable of activating plant growth development, which can be observed through shorter germination time, earlier germination, better rooting and denser stocks, both visually and numerically. Experimental field experiments have shown that the yield of crops by adding such trace element colloids could be increased by 24.6%, making the plants more resistant to disease and pest infestation (HA Schweigart: Pflanzenernåh-rung durch Anreicherung der Saat mit Trace element contact colloid, Vitalstoffe, booklet 20, 1960). In further publications it has been demonstrated, 2
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at bestemte katalasefrie bakterier, såsom Bac. Delbriiggi, kan gennemføre deres oxidative stofskifte ved hjælp af cerperoxid, altså at oxidative stofskifteprocesser under bestemte forudsætninger enten kan påvirkes af ceriumforbindelser eller bevirkes alene deraf. Herved spiller egenskab-5 erne af cerium med dets valensskiftemulighed og en spændingsforskel på 1,57 volt, redoxpotentialet, givetvis en rolle. Der henvises endvidere til, at ceriumlegeringer under udnyttelse af ceriums oxygenaffinitive egenskaber har fundet anvendelse i tændsten samt i gasgi ødestrømper (Evens; Peroc. Soc. exper. Biol.a. Med. 73, 1955, 18, 198; Dipl.-Chem.to certain catalase-free bacteria, such as Bac. Delbriiggi, can carry out their oxidative metabolism by means of cerperoxide, that is, under certain conditions, oxidative metabolic processes can either be influenced by cerium compounds or caused by them alone. Hereby, the properties of cerium with its valence change potential and a voltage difference of 1.57 volts, the redox potential, obviously play a role. It is furthermore noted that cerium alloys utilizing cerium's oxygen affinity properties have been used in flint and in gas gaseous stockings (Evens; Peroc. Soc. Exper. Biol.a. Med. 73, 1955, 18, 198; Dipl.-Chem.
10 E. Potratz, Zeitschr. fur diagnostische und therapeutische Sonder-methoden, bind IV, 1957).10 E. Potratz, Zeitschr. for diagnostic and therapeutic Sonder methods, Vol. IV, 1957).
Olieholdige affaldsprodukter, især mineralolier, der ikke længere kan anvendes, såsom spildolie eller lignende, aflejres f.eks. med henblik på kompostering i vandtæt anlagte oliegruber, hvorved komposten ng-15 en som normal biologisk nedbrydning kun forløber meget langsomt.Oil-containing waste products, especially mineral oils that can no longer be used, such as waste oil or the like, are deposited e.g. for composting in waterproofed oil pits, whereby the compost ng-15 as normal biological degradation only proceeds very slowly.
Baseret på erkendelserne med hensyn til indvirkningen på den mi krobakteriel le nedbrydning af carbonhydrider og overføringen i proteiner, og idet virkemåderne af ringe koncentrationer af salte af sjældne jordarter til forstærkning af mikroorganismers oxidative stofskifte lægges 20 til grund, er det den foreliggende opfindelses formål at tilvejebringe en fremgangsmåde til fremstilling af et middel, der kan sættes til mineralolieprodukter, som skal oplagres, og ved hjælp af hvilket den biologiske nedbrydning af disse mineralolieprodukter fremskyndes.Based on the findings regarding the effect on the microbial bacterial degradation of hydrocarbons and the transfer into proteins, and assuming the action of low concentrations of rare earth salts to enhance the oxidative metabolism of microorganisms, the object of the present invention is to provide a process for preparing an agent which can be added to mineral oil products to be stored and by which the biodegradation of these mineral oil products is accelerated.
Dette formål opnås ifølge opfindelsen ved en fremgangsmåde til 25 fremstilling af et middel til fremskyndelse af den biologiske nedbrydning af carbonhydrider, navnlig carbonhydrider i mineralolieprodukter, hvilken fremgangsmåde er ejendommelig ved, at calcium!igninsul fonat med et standardiseret jernindhold på 0,05 - 0,15% opløses i vand i en mængde på 50 - 150 g/1 og tilsættes en forudbestemt mængde af et salt af sjæld-30 ne jordarter, fortrinsvis cerium-(IV)-sulfat i en mængde på 30 - 50 g/1, og at denne opløsning tilsættes en forudbestemt mængde af et absorptivt virkende stof omfattende enten en blandning af 25 - 100 dele stearinsyre og 4 - 12 dele tri ethanolamin eller en 10 - 30% aluminiumsulfat-opløsning.This object is achieved according to the invention by a process for the preparation of an agent for accelerating the biodegradation of hydrocarbons, in particular hydrocarbons in mineral oil products, which is characterized in that calcium igninsulphonate having a standard iron content of 0.05-0. Dissolve 15% in water in an amount of 50 - 150 g / l and add a predetermined amount of a salt of rare earths, preferably cerium (IV) sulfate in an amount of 30 - 50 g / l, and to this solution is added a predetermined amount of an absorptive agent comprising either a mixture of 25 - 100 parts of stearic acid and 4 - 12 parts of tri-ethanolamine or a 10 - 30% aluminum sulfate solution.
35 Ifølge en foretrukket udførelsesform af opfindelsen anvendes der calcium!igninsul fonat med et standardiseret jernindhold på 0,1% i en mængde på 100 g/1, og opløsningen opvarmes til en temperatur mellem 50°C og 100T, fortrinsvis 75eC, og cerium-(IV)-sulfat tilsættes under stadig 3According to a preferred embodiment of the invention, calcium igninsulphonate having a standardized iron content of 0.1% in an amount of 100 g / l is used and the solution is heated to a temperature between 50 ° C and 100T, preferably 75 ° C. (IV) -sulfate is added while still 3
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omrøring i en mængde på 40,4 g/1. Som absorptivt stof benyttes stearinsyre og tri ethanolamin, der tilsættes i opløst form. I en alternativ udførelsesform udgøres det absorptivt virksomme stof af en 20% aluminiumsul fatopløsning, som tilsættes ved en temperatur på 25 - 45eC.stirring in an amount of 40.4 g / l. As the absorbent, stearic acid and tri ethanolamine are used which are added in dissolved form. In an alternative embodiment, the absorptively active substance is a 20% aluminum sulphate solution which is added at a temperature of 25 - 45 ° C.
5 I en anden foretrukket udførelsesform tilføres den med cerium berigede calciumligninsulfonatopløsning i en mængde på 0,5 g, 2,0 g af det absorptivt virkende stof i form af en opløsning indeholdene stearinsyre og triethanolamin i mængder på henholdsvis 50 g/1 og 8 g/1 vand, under stadig omrøring og opvarmning til 75 - 95°C, fortrinsvis 85eC.In another preferred embodiment, the cerium-enriched calcium lignin sulfonate solution is added in an amount of 0.5 g, 2.0 g of the absorbent in the form of a solution containing stearic acid and triethanolamine in amounts of 50 g / l and 8 g respectively. / 1 water, while still stirring and heating to 75 - 95 ° C, preferably 85 ° C.
10 Det har vist sig, at der som udgangsmateriale fortrinsvis kan benyttes calciumhol dige ligninsulfonater af følgende sammensætning:It has been found that, as a starting material, calcium-containing lignin sulfonates of the following composition can preferably be used:
Uopløseligt stof 0,01%Insoluble matter 0.01%
Træsukker 46,00% 15 CaO 10,00%Wood Sugar 46.00% 15 CaO 10.00%
Fe 0,10%Fe 0.10%
Na 0,10% K 0,10% 20 pH-værdi for den vandige opløsning = 4,6Na 0.10% K 0.10% 20 pH of the aqueous solution = 4.6
Det blev lagt til grund, at man ifølge oxydimetriens love kan foretage bestemmelse af jern ved hjælp af cer-(IV)-sulfat i en tiendedel normal opløsning.It was assumed that according to the laws of oxydimetry, iron can be determined by cer (IV) sulfate in a tenth of normal solution.
3 25 Herved består relationen: 1 cm forbrugt l/10n-cer-(IV)-sulfat svarer til 5,585 mg jern. Bestemmelsen gennemføres efter tilsætning af ca. 5 cm koncentreret svovlsyre ved en forventet mængde på 0,1 til 0,2 g Fe i 100 cm af væsken, som skal testes.Hereby, the relation consists: 1 cm of consumed l / 10n-cer- (IV) -sulfate corresponds to 5.585 mg of iron. The determination is carried out after the addition of approx. 5 cm of concentrated sulfuric acid at an expected amount of 0.1 to 0.2 g Fe in 100 cm of the liquid to be tested.
Denne bestemmelsesmulighed kan udnyttes til at standardisere ind-30 holdet af jern i ligninsulfonat-udgangsmaterialet for at opnå ensartede udgangsbetingelser og endvidere til ved tilsætning af bestemte mængder af ceriumsulfatet og udregning af det aktuelle ceriumindhold at opnå det ifølge opfindelsen for virkningen optimale ceriumindhold i slutproduktet. De oxidative egenskaber af cerium og dets valensskifte lægges herved 35 til grund.This determination can be utilized to standardize the iron content of the lignin sulfonate starting material to obtain uniform starting conditions and further, by adding certain amounts of the cerium sulfate and calculating the actual cerium content of the invention for the effect of optimum cerium content in the final product. The oxidative properties of cerium and its valence change are hereby taken into account.
Under hensyntagen til de foran anførte overvejelser tager man i henhold til opfindelsen udgangspunkt i, at de anvendte mængder lignin-sulfonat under hensyntagen til et jernindhold på 0,1% med en mængde påTaking into account the foregoing considerations, the invention assumes that the amounts of lignin sulfonate used, taking into account an iron content of 0.1% with an amount of
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4 0,5 g efter forudgående cerimetri, under hensyntagen til omregningsfaktoren, indeholder 1,4 mg cerium. Denne dosering erkendtes ved den senere anvendelse af det opnåede produkt at være optimal.0.5 g after prior cerimetry, taking into account the conversion factor, contains 1.4 mg of cerium. This dosage was recognized by the subsequent use of the obtained product to be optimal.
Når det fremstillede middel ifølge en udførelsesform tilsættes en 5 absorbtivt virkende opløsning af stearinsyre og triethanolamin, fås en masse, hvormed eksempelvis gruber til spildolie kan belægges, inden spildolien tilsættes. Den fyldte grube kan også dækkes med emulsionen.When the prepared agent according to one embodiment is added to an absorbent solution of stearic acid and triethanolamine, a mass is obtained by which, for example, waste oil pits can be coated before the waste oil is added. The filled pit can also be covered with the emulsion.
Ved blanding af oliegrube-beklædningsmassen med vand i et forhold på 1 : 1 udflokkulerer fra beklædningsmassen et stof, som er olie-10 sugende, men vandafvisende. Den udflokkulerede masse sætter sig fast i randområdet, f.eks. i jordområdet, som omgiver oliegruben. Den indtrængende olie nedbrydes herved meget hurtigt biologisk, da nedbrydningen fremmes af det i den udflokkulerede masse indeholdte ceriumsalt.When mixing the oil pit coating mass with water in a ratio of 1: 1, the fabric flocculates a substance which is oil-sucking but water-repellent. The flocculated mass gets stuck in the edge area, e.g. in the soil area that surrounds the oil pit. The penetrating oil is thereby rapidly degraded biologically as the degradation is promoted by the cerium salt contained in the flocculated mass.
Olien omsættes herved til stoffer, der er værdifulde for planter. Ned-15 brydningen, f.eks. af carbonhydrider fra olie, opnås også ved oxidation.The oil is thereby converted into substances that are valuable to plants. The degradation, e.g. of hydrocarbons from oil is also obtained by oxidation.
Det hertil nødvendige oxygen henter de ved hjælp af den omhandlede blanding stærkt formerede bakterier fra vandet, f.eks. grundvandet i jordbunden eller fra den ved olieemulsioner ved udflokkulering fra emulsionerne frigjorte vandmængde.The oxygen required for this retrieves the highly formed bacteria from the water by means of the mixture, e.g. the groundwater in the soil or from the amount of water released by the emulsions by flocculation from the emulsions.
20 Ved markforsøg kunne det påvises, at man ved anlæggelse af grubesystemer til kompostering af olieholdigt affald og samtidig underlægning med bindemateriale eller filtermateriale under anvendelse af det forannævnte stof og i forannævnte dosering kunne opnå en påviselig aerob nedbrydning med forstærket virkning af carbonhydrider ved oxidation og sam-25 tidig kunne opnå at fremme plantebevoksningen på sådanne depoter ved forbedret oxygenudnyttelse og chelatdannelse.In field experiments, it could be shown that by the construction of pit systems for composting oily waste and at the same time laying with binder or filter material using the aforementioned substance and in the aforementioned dosage, a detectable aerobic degradation with enhanced effect of hydrocarbons by oxidation and co-operation could be achieved. -25 early could promote plant growth at such depots through improved oxygen utilization and chelation.
Bevisligt bliver den biologiske nedbrydning ved hjælp af det ifølge opfindelsen udvundne materiale forstærket ved mineralolier, og oxidationshastigheden af carbonhydriderne omtrentlig fordoblet, hvorved den 30 stimulerende virkning udvirkes via ceriums redoxpotential.Evidently, the biodegradation by means of the material extracted by the invention is enhanced by mineral oils and the oxidation rate of the hydrocarbons is approximately doubled, thereby exerting the stimulating effect via the redox potential of cerium.
Et sådant forløb iagttoges over en periode af 2 år, hvorved der ved forrådne!sesprocessen iagttoges en temperatur på ca. 30°C, og ved hjælp af jordprøver måltes følgende resultater: 35 5Such a course was observed over a period of 2 years, whereby the temperature of approx. 30 ° C and by soil tests the following results were measured: 35 5
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Grubeindhold efter efter have- 2 måneder 2 år kompost 5 pH-værdi ' 5,6 4,7 5,3 jMining content after after 2 months 2 years compost 5 pH value 5.6 4.7 5.3 j
Vandindhold vægt-% 62 27 29Water content wt% 62 27 29
Por tørstoffet:Pore dry matter:
Oxidaske vægt-% 25,8 76,6 87,0 I« Askeart hovedindh. Si, Fe, Al Si, Fe, Al Si, Fe, Al bi-indh. Ba, K, Ca Ba, K, Ca Ba, K, CaOxidic weight% 25.8 76.6 87.0 I «Ash type main content. Si, Fe, Al Si, Fe, Al Si, Fe, Al bi-content. Ba, K, Ca Ba, K, Ca Ba, K, Ca
Zn, S, Pb Zn, SZn, S, Pb Zn, S
Total nitrogen vægt-% 0,25 1,26 0,46Total nitrogen weight% 0.25 1.26 0.46
Total kalium - - 0,12 0,60 0,40Total Potassium - - 0.12 0.60 0.40
Ekstraherbart organisk stof - - 50,0 2,51 0,04 15----Extractable organic matter - - 50.0 2.51 0.04 15 ----
Por det organiske stof:Pore organic matter:
Polære forbindelser g/kg 130.t0 17,2 0,26Polar compounds g / kg 130.t0 17.2 0.26
Carbonhydrider g/kg 370,0 7,9 0,14Hydrocarbons g / kg 370.0 7.9 0.14
For carbonhydriderne: 20For the hydrocarbons: 20
Begyndelseskogepunkt/ j slutkogepunkt °C 210/570 280/800 jInitial boiling point / j final boiling point ° C 210/570 280/800 j
Aromater % 14,8 48,7 jAromatics% 14.8 48.7 j
Paraffiner % 85,2 51,3 1 25Paraffins% 85.2 51.3 1 25
Udføre!seseksempler: 1. 100 g af et calciumligninsulfonat med et standardiseret jernindhold på 0,1% opløses i 1 liter vand. Til den til 75eC opvarmede opløsning 30 sættes under stadig omrøring 40,4 g cer-(IV)-sulfat. Den således vundne opløsning tjener som udgangsmateriale for de følgende eksempler.Example Examples: 1. Dissolve 100 g of a calcium lignin sulfonate with a standard iron content of 0.1% in 1 liter of water. To the solution heated to 75 ° C is added 40.4 g of cer (IV) sulfate with still stirring. The solution thus obtained serves as the starting material for the following examples.
2. 0,5 g af den i eksempel 1 opnåede opløsning tilsættes 2,0 g af en absorptivt virkende blanding af ca. 50 g stearinsyre og 8 g triethanol- 3 amin i 1000 cm vand under stadig omrøring og opvarmning til 85eC. Det 35 således vundne produkt tjener som filtermateriale for beklædning og afdækning af ordnede depoter til grundvandssikker anbringelse af olieholdigt affald (spildolie, emulsioner).2. 0.5 g of the solution obtained in Example 1 is added 2.0 g of an absorbent mixture of approx. 50 g of stearic acid and 8 g of triethanol-3 amine in 1000 cm of water while still stirring and heating to 85 ° C. The product thus obtained serves as a filtering material for the coating and covering of arranged depots for groundwater-safe deposition of oily waste (waste oil, emulsions).
3. Den i eksempel 1 vundne opløsning tilsættes 0,5 cm af en ligeledes3. The solution obtained in Example 1 is added 0.5 cm of a likewise
Claims (4)
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DE2365170 | 1973-12-29 | ||
DE2365170A DE2365170C3 (en) | 1973-12-29 | 1973-12-29 | Manufacture of a mixture to be added to the mineral oil products to be deposited |
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DK692774A DK692774A (en) | 1975-09-08 |
DK155041B true DK155041B (en) | 1989-01-30 |
DK155041C DK155041C (en) | 1989-06-26 |
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CH (1) | CH617962A5 (en) |
DE (1) | DE2365170C3 (en) |
DK (1) | DK155041C (en) |
FI (1) | FI53588C (en) |
NO (1) | NO141443C (en) |
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SE445991B (en) | 1978-09-07 | 1986-08-04 | Poul Albert Jodehl | APPLICATION OF A LIGNIN SULPHONATE-CONTAINING PRODUCT FOR PURIFICATION OF CONTAMINATED Aqueous Media |
DE3637308C1 (en) * | 1986-11-03 | 1988-06-01 | Eberhard Potratz | Nutrient mixture for increasing the rate of biodegradation of mineral oil products and its use |
US5401718A (en) * | 1992-11-24 | 1995-03-28 | Patel; Bharat B. | Tin/cerium compounds for lignosulfonate processing |
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DK132939B (en) * | 1970-02-03 | 1976-03-01 | G H Salomone | PROCEDURE AND MEANS OF SPEEDING UP THE BIO DECOMPOSITION OF PRODUCER OIL WASTE |
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- 1974-12-20 CH CH1700574A patent/CH617962A5/en not_active IP Right Cessation
- 1974-12-23 SE SE7416261A patent/SE395471B/en not_active IP Right Cessation
- 1974-12-23 NO NO744677A patent/NO141443C/en unknown
- 1974-12-27 FI FI3763/74A patent/FI53588C/en active
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DK132939B (en) * | 1970-02-03 | 1976-03-01 | G H Salomone | PROCEDURE AND MEANS OF SPEEDING UP THE BIO DECOMPOSITION OF PRODUCER OIL WASTE |
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SE395471B (en) | 1977-08-15 |
DK692774A (en) | 1975-09-08 |
DK155041C (en) | 1989-06-26 |
NO141443C (en) | 1980-03-12 |
FI53588C (en) | 1978-06-12 |
CH617962A5 (en) | 1980-06-30 |
DE2365170B2 (en) | 1979-06-21 |
DE2365170C3 (en) | 1980-02-14 |
NO744677L (en) | 1975-07-28 |
SE7416261L (en) | 1975-07-30 |
FI53588B (en) | 1978-02-28 |
NO141443B (en) | 1979-12-03 |
DE2365170A1 (en) | 1975-07-10 |
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