GB2115399A - Compositions for treating oil slicks on seawater - Google Patents

Compositions for treating oil slicks on seawater Download PDF

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Publication number
GB2115399A
GB2115399A GB08304048A GB8304048A GB2115399A GB 2115399 A GB2115399 A GB 2115399A GB 08304048 A GB08304048 A GB 08304048A GB 8304048 A GB8304048 A GB 8304048A GB 2115399 A GB2115399 A GB 2115399A
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composition
salt
compositions according
oil
compositions
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GB2115399B (en
GB8304048D0 (en
Inventor
Andre Lepain
Robert Bronchart
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Labofina SA
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Labofina SA
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    • 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

Abstract

Dispersing compositions contain at least one surface-active agent, at least one solvent, and a nitrogen- containing compound which is a nutrient for the micro-organisms which are active in oil metabolism. The nitrogen- containing compound is a monoalkylguanidinium salt <IMAGE> wherein R is an aliphatic hydrocarbon radical, saturated or unsaturated, containing from 8 to 20 carbon atoms, and X is a halogen or an acid anion.

Description

SPECIFICATION Compositions and method for treating oil slicks The present invention discloses surface-active compositions for treating and dispersing oil slicks. This invention is also directed to a method for disposing of oil slicks.
Pollution of seawater by oil (crude oil or fractions of crude oil) occasioned by accidents, off-shore drilling operations, andior discharge of ballast water or spillage from oil tankers, results in the formation of a continuous film or slick of oil which tends to continuously spread. In open seas, this oily film is undesirable because it constitutes a barrier to the transfer of air and light from the atmosphere into the seawater, which are indispensable to support marine life. In coastal waters, the oily film does damage to the crustacia beds and to the beaches.
One way of dealing with such pollution problems is to use oil dispersing compositions containing surface-active compounds. These compositions are applied on the oil slicks, generally by spraying means.
They disintegrate the cohesive oily film into small droplets and disperse the droplets into the water column to a depth of several meters under the sea surface. The film is thus broken and there is again a transfer of air and light from the atmosphere. Moreover, fouling of the solid structures and beaches along the coasts is avoided.
The oil droplets which are dispersed under the sea surface are then biodegraded and consumed by micro-organisms which are living in seawater and are active in oil metabolism. This biological degradation is however a slow process and is consequently unable to prevent the settling of undegraded oil droplets and the formation of oil deposits on the floor of seas, more particularly where the water is shallow.
An active biodegradation of oil droplets needs the presence of a high amount of micro-organisms at the oil-water interface. However, these organisms are present in seawater in limited quantities. In order to stimulate the biodegradation, it is therefore necessary to speed up the proliferation of the micro-organisms.
To this end, they need not only oxygen and carbon, which are present respectively in water and in polluting oils, but also nitrogen and phosphorus. Generally, the concentration of these latter two elements is very low in seawater and consequently the natural biodegradation of oil is a very slow process.
In order to increase the biodegradation rate, it has been proposed to add microbial nutrients to seawater.
Mineral salts, such as ammonium salts, nitrates and phosphates, have been used. But these mineral salts are too water-soluble and have practically no affinity for the polluting oil. They are too quickly dissolved and dispersed into sea water and are not maintained at the oil-water interface where their presence is needed.
It has also been suggested to use nitrogen-containing organic nutrients which are oleosoluble, such as condensation products of urea or mealmine with aldehydes. However, these organic compounds are also soluble in water. They dissociate from the oil and are dissipated into the aqueous phase. In order to overcome this disadvantage, it has been proposed to modify their solubility in water. For instance, condensation products of urea and an aldehyde containing less than four carbon atoms are first absorbed on an inert carrier and are then rendered lipophilic by coating with a paraffin or other protective colloid. These treatments require special equipment and they increase the cost of nutrients. Moreover, these latter cannot be suspended in the surface-active compositions which are used for the treatment of the oil slicks.Two separate applications, one for the surface-active composition and one for the nutrients, are therefore required. Furthermore, the coating might be quickly dissolved if the polluting oil, such as a fresh crude oil, contains aromatic hydrocarbons.
Other techniques have been suggested to reduce the solubility of the nutrients in water, but the result is compositions which only float on the water surface. These nutrients will not them promote the development of micro-organisms in the water column under the sea surface where the oil droplets are dispersed.
The difficulties encountered with prior art nutrients have been overcome by the development of new lipophilic nutrients for the micro-organisms which are present in sea waters and are active in oil degradation.
These new nutrients achieve a rapid and more complete biodegradation of the oils, at low cost.
It is an object of this invention to provide liquid oil dispersing compositions containing a nutrient for micro-organisms comprising a nitrogen-containing compound which is poorly soluble in water and which is not subject to hydrolysis in water.
Afurther object of the invention is to provide oil dispersing compositions containing an oleophiiic source of nitrogen.
It is also an object of this invention to provide oil dispersing compositions containing a nutrient and which exhibit a low toxicity towards aquatic flora and fauna.
Another object of the invention is to provide liquid oil dispersing compostions wherein the nitrogencontaining nutrient is easily dispersed.
It has now been found that compositions for treating oil slicks exhibit unexpected advantageous characteristics in terms of oil-dispersing efficiency and biodegradation by micro-organisms when a monoalkyl-guanidinium salt having the general formula
(wherein R is an aliphatic hydrocarbon radical, saturated or not, containing from about 8 to about 20 carbon atoms and X is a halogen or acid anion), is added to a dispersing mixture contaning at least one surface-active agent and at least one solvent.
A composition according to the present invention for dispersing oil slicks into oil droplets and for promoting their biodegradation by micro-organisms comprises at least one surface-active agent which disintegrates the oil slick into oil droplets, at least one solvent and, as a source of oleophilic, nitrogen-containing nutrient, a mono-alkylguanidinium salt as hereinabove defined.
In accordance with another object of this invention, there is provided a method for dispersing oil slicks and for promoting their biodegradation by micro-organisms, comprising the step of applying a surface-active composition of the above-described type to the surface of the oil slick.
The compositions of the present invention comprise at least a surface-active agent, acting as dispersing agent, a mono-alkylguanidinium salt acting as nutrient, and at least one solvent, these compositions being liquid and easily sprayed by usual means.
According to one of their characteristics, these compositions contain, as an olephilic source of nitrogen for micro-organisms, a mono-alkylguanidium salt having the general formula
wherein R is an aliphatic hydrocarbon radical, saturated, unsaturated, or partially saturated), containing from about 8 to about 20 carbon atoms, and X is a halogen or acid anion.
The moalkylguanidinium salts are easily prepared by a known method which consists in reacting cyanamid (H2N-CrN) with a salt of primary amine (R-NH2.HX, wherein R and X are as above mentioned).
Mixtures of amine salts may also be used. After purification, the resultant products are monoalkylguanidium salts having a nitrogen content which depends on the specific R and X, but which is generally at about 6.5 to about 25%.
The radicals R and X are selected in order to obtain monoalkylguanidinium salts which are poorly soluble in water, are lipophilic, are soluble or at least easily dispersed into the solvents contained in the compositions used for treating oil slicks, and are stable towards these solvents and water. For these reasons, monoalkylguanidium salts wherein the radical R contains from about 8 to about 20, and more particularly between about 12 and 18 carbon atoms, are preferably used. On the other hand, X is generally a halogen, particularly Cl, or an acid anion, such as CHUBS04, C2H5SO4, NO3, HSO4, CH3-C #~ or R1 -C5H4SO3, wherein R1 is H or an alkyl radical having between 1 and about 12 carbon atoms.For economic reasons, monoalkylguanidium salts wherein X is Cl, HSO4 or NO3, are preferable.
In order to promote the development of micro-organisms at the oil-water interface, the monoalkylguanidinium salts, acting as source of nitrogen, are advantageously employed in admixture with a phosphorous compound, acting also as a nutrient to supply phosphorous. The phosphorous compound may be an alkaline or alkaline-earth salt of phosphoric ester of fatty alcohol, a salt or an ester of organophosphonic acid, or a phosphatide or similar product having a low toxicity towards aquatic flora and fauna. Esters obtained by neutralization of hexamethylene diamine tetra (methylene phosphonic acid) having the formula (H2PO3CH2)2-H(CH2)6-N(CH2PO3H2)2), with an amine, such as monoethanolamine or a fatty amine containing from 12 to 18 carbon atoms, give good results.Phosphatides or phospholipids, more particularly lecithin or kephaline, act at the same time as a source of nitrogen and phosphorous, and thus they reinforce the action of the monoalkylguanidinium salts.
The compositions of the present invention comprise at least one surface-active agent having a low toxicity towards aquanticflaura and fauna. Preferable surface-active agents include ethoxylated tall oil, mono- and polyesters of polyhydroxylic alcohols, and more particularly, the esters of saturated or unsaturated aliphatic carboxylic acids containing from 12 to 20 carbon atoms, and of alcohols, such as sorbitane, glycerol and polyethyleneglycol. Mixtures of two or more of these esters may be used, with the optional additon of other surface-active agents, such as ethoxylated fatty alcohols, alkaline salts of dialkyl sulphosuccinates or condensation products of ethylene oxide and/or propylene oxide on the above-mentioned esters.
The liquid compositions of the invention are prepared by dissolving the active components into a solvent or a mixture of solvents having a low toxicity towards aquatic flora and fauna. Preferable solvents include the liquid hydrocarbons containing less than about 5 %, and preferably less than 3% of aromatic compounds, and more particularly liquid hydrocarbons containing from 5 to 20 carbon atoms, such as paraffinic hydrocarbons containing from 6 to 12 carbon atoms, cycloparaffinic hydrocarbons such as cyclopentane and cyclohexane, alkylcycloparaffinic hydrocarbons and napthenic hydrocarbons.Aliphatic alcohols containing up to 8 carbon atoms, such as ethyl-, propyl- and isopropyl alcohols, and glycol monoethers, more particularly monoalkylethers (where the alkyl radical contains from 1 to 4 carbon atoms) of glycols such as mono-or di-ethyleneglycol and mono- or di-propyleneglycol, are also suitable solvents. The organic solvent may also contain water in an amount which does not exceed the amount of organic solvent and which is generally between about 10 and 50%, based on the weight of the organic solvent.
The solvent has a double action : it facilitates the handling and the application of the surface-active agents, and moreover, due to its affinity, it promotes the penetration of the compostion into the oil film. It is therefore advantageous to use compostions wherein the amount of wter (if present) does not exceed about 25% of the total amount of organic solvent and water.
The weight ratio of surface-active agents to solvent may vary between wide limits. It is of course desirable to employ compositions which are as concentrated as possible, but the amount of solvent in composition must be sufficient to dissolve the surface-active agents and nutrients and also allow the application of the composition at low temperatures. It has been found that compositions containing more than about 85 % of surface-active agents and nutrients are too viscous at low temperatures. Moreover, they do not easily penetrate into the oil slick and are therefore less active. On the other hand, compositions containing less than about 30 % of surface-active gents and nutrients have a low effectiveness.
The amount of monoalkylguanidinium salt in the compositions of this invention may vary between relatively wide limits and may be as high as 35% or even more, based on the total weight of composition.
This amount depends upon many factors, including the specific quanidinium salt used and its nitrogen content, the optional presence of other nutrients, and the specific solvent used. Compositions containing from about 2 to 20wt%, and more particularly from about 5 to about 15 wt %, of monoalkyl-guanidinium salt are very effective with respect to the biodegradation of oil droplets dispersed in seawater.
The compositions of the present invention may also contain other components and elements such as magnesium and calcium which are useful for the development of micro-organisms. The compositions contain these elements in the form of organic salts, namely in the form of a magnesium or calcium salt of alkylbenzenesulphonic acid. The amount of these additives does not generally exceed about 3 %, based on the total weight of the composition.
The compositions are applied to the oil slicks by using any known method. They may be used without water or after dilution by water. They may be sprayed on the oil slicks from aircraft or from boats which are provided with suitable spraying means.
The present compositions meet current specification relating to dispersants for treating oil spills, including the tests for toxicity, dispersing effectiveness, and bio-degradation.
The toxicity test consists in subjecting a particular live species, such as Artemia Salina, to increasing doses of the composition to determine the maximum amount of composition which, after 24 hours, will still leave 50% of the tested species alive (test CL 50-24 hours).
Dispersing effectiveness is determined by the MIL method, which consists in pouring 100 cc of crude oil into a vessel containing 133 litres of water, adding thereafter, 100 cc of a 10% aqueous solution of the composition. This is allowed to set for 90 seconds. The mixture is then stirred for 10 minutes to disperse the oil. Samples of the dispersion are withdrawn and the oil contained in these samples is extracted. The dispersing effectiveness is given by the percentage of extracted oil vs the total amount of oil.
Biodegradation effectiveness is determined by the following method 200 ppm of the tested composition are added to unsterilized sea water (700 ml) containing topped crude oil (500 ppm). This is left to incubate for 41 days at 250C, while being stirred by air bubling. The residual is then extracted.
Results of these tests are given in the following examples.
Example 1.
Monododecylguanidinium chloride was prepared by a known process from dodecylamine hydrochloride and cyanamid.
A dispersing composition was then prepared containing (parts by weight): 13 parts sorbitol monolaurate 47 parts polyethyleneglycol monooleate (molecular weight of the glycol: 400), 15 parts monobutylether, 5 parts water 15 parts monododecylguanidinium chloride, 5 parts hexamethylenediaminotetra (methylene-phosphonic acid) dodecylamine ester.
This composition had the following characteristics: - toxicity (ppm) zdaphnia magna 850 ppm artemia salina 1000 ppm - dispersing effectiveness (%) 72 - biodegradation: 2.4 times higher than a similar composition containing no guanidinium salt and no phosphorous compound.
Example 2: A composition was prepared as in Example 1, but by using a guanidinium salt prepared from a mixture of primary C12-18 amine hydrochlorides.
The characteristics of this composition, with respect to toxicity, dispersing effectiveness and biodegradation, were the same as the characteristics of the composition of Example 1.
Example 3: Monodecylguanidinium nitrate was prepared by a conventional process from decylamine nitrate and cyannamid.
A dispersing composition was then prepared containing (parts by weight): 16.75 parts sorbitol monooleate; 13.50 parts ethoxylated sorbitol monooleate (about 20 moles of ethylene oxide) 24 parts sodium salt of di-(-ethylhexyl) sulfosuccinate (a 75 % aqueous solution), 11.25 parts water 12 parts ethyleneglycol monobutyl ether, 2.5 parts diethyleneglycol, 15 parts monodecylguanidinium nitrate, 5 parts hexamethylenediaminotetra (methylenephosphonic acid) ethanolamine ester The biodegradation rate with this composition was 1.8 times higher than with a similar, but nutrient-free composition.
Example 4: A dispersing composition was prepared as described in Example 1, but by using monododecylguanidinium acetate, prepared from dodecylamine acetate and cyanamid, as guanidinium salt.
The biodegradation rate with this composition was 2 times higher than with a similar, but nutrient-free composition.
Example 5: For this example, 8-octodecenylguanidinium chloride having the formula:
was prepared from 9-octadecenylamine hydrochloride and cyanimid.
A dispersing composition was then prepared containing (parts by weight): 6.2 parts sorbitan monolaurate, 21 parts polyethyleneglycol monooleate (mixture of glycols having molecular weights of 200 and 400), 45.5 parts diethyleneglycol monobutylether, 8.3 parts water, 12 parts of the above guanidinium salt, 7 parts lecithin Said compostion was 1.8 times more active, with respect to the biodegradation process, than a similar composition that was nutrient-free.

Claims (12)

1. Dispersing compositions for treating oil slicks on seawater, characterized in comprising at least one surface-active agent, at least one solvent, and a monoalkylguanidinium salt having the general formula:
wheren R is an aliphatic hydrocarbon radial containing from about 8 to about 20 carbon atoms, and X is a halogen or an acid anion.
2. Compositions according to claim 1, characterized in that R is an aliphatic hydrocarbon radical containing from about 12 to about 18 carbon atoms.
3. Compositions according to claim 1, characterized in that X is an acid anion selected from the group comprising -Cl, -CH3SO4, -C2H5SO4, -NO3, -HSO4, CH3-C Oo#, and R1# C6H4SO3; and wherein R1 is H or an alkyl radical containing from 1 to 12 carbon atoms.
4. Compositions according to claim 1 characterized in that X is Cl, -NO3 or -HSO4.
5. Compositions according to claim 1, characterized in containing up to 35% of monoalkylguanidinium salt, based on the total weight of composition.
6. Compositions according to claim 5, characterized in containing from about 2 to about 20% of monoalkylaguanidinium salt, based on the total weight of composition.
7. Compositions according to claim 6, characterized in containing from about 5 to about 15% of monoalkylguanidinium salt, based on the total weight of composition.
8. Compositions according to claim 5, characterized in further comprising a phosphorus compound acting as a nutrient for micro-organisms.
9. Compositions according to claim 8, characterized in that the total weight of surface-active agent, monoalkyl-guanidinium salt, and phosphorous compound is between about 30 and about 85 percent, based on the total weight of the composition.
10. Compositions according to claim 9, characterized in further comprising an alkylbenzenesulfonic acid magnesium salt or calcium salt in an amount not higher than about 3%, based on the total weight of composition.
11. A method for reducing an oil slick on sea water, characterized in comprising applying to the oil slick a dispersing composition comprising a surface-active agent, a solvent, and a moalkylguanidium salt having the general formula:
wherein R is an aliphatic hydrocarbon radical containing from about 8 to about 20 carbon atoms, and X is a halogen or an acid anion.
12. The method according to claim 11 characterized in that said composition solvent comprises a liquid hydrocarbon containing less than 5 percent aromatic compounds, plus less than 50 percent water.
GB08304048A 1982-02-19 1983-02-14 Compositions for treating oil slicks on seawater Expired GB2115399B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
LU83961A LU83961A1 (en) 1982-02-19 1982-02-19 COMPOSITIONS AND METHOD FOR REMOVAL OF OIL PATCHES FROM THE SURFACE OF WATERS

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GB8304048D0 GB8304048D0 (en) 1983-03-16
GB2115399A true GB2115399A (en) 1983-09-07
GB2115399B GB2115399B (en) 1985-02-27

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JP (1) JPS58153530A (en)
AU (1) AU1053483A (en)
BE (1) BE895840A (en)
CA (1) CA1205720A (en)
DE (1) DE3305655A1 (en)
DK (1) DK68483A (en)
ES (1) ES519806A0 (en)
FI (1) FI830469L (en)
FR (1) FR2522008B1 (en)
GB (1) GB2115399B (en)
GR (1) GR71921B (en)
IT (1) IT1163114B (en)
LU (1) LU83961A1 (en)
NL (1) NL8300399A (en)
NO (1) NO830495L (en)
PT (1) PT76251A (en)
SE (1) SE8300733L (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993024612A1 (en) * 1992-06-03 1993-12-09 Cognis Gesellschaft Für Bio- Und Umwelttechnologie Mbh Improved mixture of nutrients for the bioremediation of polluted soils and waters
WO1994024057A1 (en) * 1993-04-22 1994-10-27 Bionutratech, Inc. Method and composition for enhanced bioremediation of petroleum

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2573770A1 (en) * 1984-11-26 1986-05-30 Labofina Sa Nutrients for mineral oil-biodegrading microorganisms

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2122705A6 (en) * 1971-01-20 1972-09-01 Salomone Georges Petroleum emulsifying compositions - optionally in powder form containing extra nitrogen sources as substrate
FR2324354A1 (en) * 1974-07-25 1977-04-15 Equip Automobile Ste Fse COMPOSITION FOR THE BIODEGRADABLE AQUEOUS EMULSION OF HYDROCARBONS AND FATS AND ITS PREPARATION PROCESS
FR2394602A1 (en) * 1977-03-25 1979-01-12 Ugine Kuhlmann Biodegradable cleaning compsn. for hydrocarbon spillages - contg. mixt. of specified mono and di-phosphoric acid ester(s)
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

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993024612A1 (en) * 1992-06-03 1993-12-09 Cognis Gesellschaft Für Bio- Und Umwelttechnologie Mbh Improved mixture of nutrients for the bioremediation of polluted soils and waters
US5635392A (en) * 1992-06-03 1997-06-03 Henkel Kommanditgesdellschaft Auf Aktien Nutrient mixtures for the bioremediation of polluted soils and waters
WO1994024057A1 (en) * 1993-04-22 1994-10-27 Bionutratech, Inc. Method and composition for enhanced bioremediation of petroleum
US5725885A (en) * 1993-04-22 1998-03-10 Bionutratech Composition for enhanced bioremediation of oil

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DK68483D0 (en) 1983-02-17
GB2115399B (en) 1985-02-27
PT76251A (en) 1983-03-01
CA1205720A (en) 1986-06-10
FI830469L (en) 1983-08-20
GR71921B (en) 1983-08-18
FR2522008A1 (en) 1983-08-26
IT8319643A0 (en) 1983-02-18
NL8300399A (en) 1983-09-16
IT1163114B (en) 1987-04-08
BE895840A (en) 1983-05-30
DK68483A (en) 1983-08-20
ES8601289A1 (en) 1985-11-01
AU1053483A (en) 1983-08-25
LU83961A1 (en) 1983-09-02
FR2522008B1 (en) 1985-09-06
JPS58153530A (en) 1983-09-12
GB8304048D0 (en) 1983-03-16
FI830469A0 (en) 1983-02-11
DE3305655A1 (en) 1983-09-08
SE8300733L (en) 1983-08-20
NO830495L (en) 1983-08-22
SE8300733D0 (en) 1983-02-11
ES519806A0 (en) 1985-11-01

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