WO1993014034A1 - Composition pour retirer le petrole - Google Patents

Composition pour retirer le petrole Download PDF

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Publication number
WO1993014034A1
WO1993014034A1 PCT/GB1993/000036 GB9300036W WO9314034A1 WO 1993014034 A1 WO1993014034 A1 WO 1993014034A1 GB 9300036 W GB9300036 W GB 9300036W WO 9314034 A1 WO9314034 A1 WO 9314034A1
Authority
WO
WIPO (PCT)
Prior art keywords
oil
composition
silicon carbide
sorbant
water
Prior art date
Application number
PCT/GB1993/000036
Other languages
English (en)
Inventor
Harry James Bradbury
Original Assignee
Harry James Bradbury
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GB929200286A external-priority patent/GB9200286D0/en
Priority claimed from GB929204781A external-priority patent/GB9204781D0/en
Priority claimed from GB929204782A external-priority patent/GB9204782D0/en
Application filed by Harry James Bradbury filed Critical Harry James Bradbury
Publication of WO1993014034A1 publication Critical patent/WO1993014034A1/fr

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Classifications

    • 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
    • C02F1/681—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of solid materials for removing an oily layer on water
    • 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

Definitions

  • the present invention relates to compositions for removal of oil, especially from oil-contaminated media, for example in oil slicks.
  • Oil spills on water and land are common environmental problems. Oil spills on water are normally dealt with by some combination of mechanical action (eg. skimmers and booms) and the use of surfactants to act as dispersing agents. In some cases, other materials have been used to sorb oils at the surface of the water. For example, silica beads (sometimes impregnated with agents which cause oxidation of hydrocarbons) have been used to sorb oils into a floating structural mat.
  • composition comprising both an oil sorbant and a sealer-binder is able to remove oil from oil-contaminated media and retain the removed oil within the composition.
  • Use of the composition according to the invention permits quick and easy oil-removal and minimises potential for environmental damage resulting from the continued presence of the oil.
  • oil refers to any type of crude or refined oils which are, or are derived from, naturally occurring mineral oils or vegetable matter, or their synthetic equivalents.
  • the tem "sealer-binder” refers to a material which causes the sorbed oil to be sealed into or bound to the composition. Thus, oil sorbed by the composition of the invention is inhibited from leaching back into the surrounding medium.
  • composition as disclosed herein is non-toxic to marine or freshwater life in both its unsorbed and oil-sorbed state when judged by standard tests.
  • the composition of the invention is able to rapidly sorb oils to create a hydrocarbon-soaked mass which may be harvested at or near the surface of a water within a short period after application if such harvesting is technically achievable or desirable.
  • the reacted mass may be engineered to sink under gravity through the water, to create a non-toxic sediment at the base of the water column.
  • oil spills can be treated in a timely manner (restricting their ability to spread at or near the surface of the water column which would create thereby extensive environmental damage of surface waters, coastal environments, installations etc.) and in a manner so as to remove from the water column long- term, free oils which might otherwise escape to damage the ecosystems within or subjacent to a water mass, or the biomass which such ecosystems support.
  • composition of the present invention may be developed to include structural porosity.
  • Porosity is required for optimisation of the sorptive capacity of the product once granulated. Granulation is preferred in order to aid such sorbability, and to customise the product for ease of application, both ease of mechanical application and optimisation of surface action for such sorption.
  • Structural porosity can be created by a number of mechanisms, but is conveniently provided by oleophilic wetting of the granules during preparation and the subsequent controlled drying to create void space. Care must be taken wherever possible to preclude the induction of fracture porosity during granule manufacture, since this type of structural porosity inhibits effective sorption of oils in a manner which also allows micro-encapsulation and sealing.
  • internal porosity may be created whereby an internal void space is created by the fibrous structure of the sorbant and this may accommodate approximately 40% of the overall porosity requirements. Overall it is desirable that approximately 75% porosity be achieved within the fibrous composition if granulated, such porosity being provided in the two ways mentioned above.
  • the granules themselves may be variable in shape and size depending on the application, but should reflect wherever possible the need to optimise surface area for sorption of oil without creating a volume which might inhibit reaction time unduly by floating and soaking oils within a slick. Relatively small (preferably less than 5cm diameter granules) of quasi- spherical shape are convenient.
  • the material density of the composition can be varied by adjustment of the relative volume proportions of the components, for example sawdust and cement (optionally with the inclusion of other minor ingredients as stated below) , and the effective density of the granules can be varied by adjustment of the structural porosity.
  • adjustments can also be made to optimise the composition for marine (or other waters) conditions which are variable from place to place, and/or from time to time, in factors such as temperature and salinity, and variations in the different types of oils and their physico-chemical characteristics, such as viscosity.
  • the sorbant used in the composition must be able to rapidly and effectively remove crude or refined oils and silicon carbide (SiC) in any crystallographic form or variation is a suitable sorbant.
  • Silicon carbide is commonly used as an industrial abrasive, and is normally produced through combustion of silica (often derived from sand) with carbon in a furnace at around 2000°C.
  • silica often derived from sand
  • the structural and crystallographic state of the silicon carbide can be variable, but where possible, the chemistry should preclude possible furnace impurities such as iron oxide.
  • the tolerable mean grain size of silicon carbide used in the water pollution product varies according to the type of hydrocarbon or other oils being treated, but normally falls within the range ' 50 to 450 microns.
  • Metallurgical grade (or higher grade) silicon carbide normally processed to a mean grain diameter of less than 100 microns (but preferably less than 40 microns) has proved particularly effective in its sorbancy of crude oils of differing viscosities and chemical characteristics, as typified by crudes from the Brent field, Nigeria and the Urals.
  • this range of lithological variants (micrite, calcareous siltstone and calc-arenite) are combined into the term "micrite" for purposes of this document, a term which is used hereinafter.
  • Variation may exist in the Ca, Mg and Fe composition of carbonate minerals which constitute micrite without detriment to its effectiveness.
  • the micrite will be in fine-grained, powdered form having undergone milling by a standard rock crushing and grinding process without prior physical or chemical separation of mineralogical components save for the selection of preferred rock types.
  • milling by a standard rock crushing and grinding process without prior physical or chemical separation of mineralogical components save for the selection of preferred rock types.
  • use has been made of the micrite prepared in this manner.
  • powdered micrite created by selective drilling of hand samples of rock materials.
  • the tolerable mean grain size range for the powdered micrite varies between 10 to 100 microns grain diameter for use with 'lighter' hydrocarbon fractions, whereas grain sizes up to 400 microns may be required for 'heavier' hydrocarbon fractions (it should be noted that the term "micrite" has no geological meaning at such coarse grain sizes, and is used here for simplicity of description) .
  • the optimal grain size for micrite is dependent on the type of hydrocarbon.
  • the sorbant can constitute up to 60% of the composition but is often optimal at around 30%.
  • the sealer-binder may be, for example, mineralogical assemblages of dolomitic carbonate including Ca, Mg and Fe variants (hereinafter collectively termed "dolomite”) , and, for certain treatments, siliceous dolomite including metamorphic equivalents of greenschist and amphiboloite facies metamorphic zones, which include calc-silicate mineral assemblages.
  • dolomite dolomitic carbonate including Ca, Mg and Fe variants
  • siliceous dolomite including metamorphic equivalents of greenschist and amphiboloite facies metamorphic zones, which include calc-silicate mineral assemblages.
  • the dolomite will be in fine-grained, powdered form having undergone milling by a standard rock crushing and grinding process without prior physical or chemical separation of mineralogical components save for the selection of preferred rock types. Use has also been made of powdered dolomite created by selective drilling of hand samples of rock materials.
  • the tolerable mean grain size range for the powdered dolomite can vary from 25 to 300 microns, and is preferably in the range 150 to 250 microns for heavier fractions. Powdered dolomitic carbonate at a mean grain size normally less than 100 microns (and preferably less than 40 microns) has proved effective in acting as a sealer-binder during migration of the material product/oil-reacted mass and in its settled state as a sediment.
  • the proportion of dolomite within the composition is variable dependent on the type of hydrocarbon or other oil. Generally, the dolomite proportion falls within the range 5 to 35%. Where calc-silicates are included in the formulation, the dolomite proportion can fall by up to 10%.
  • sealer-binders In other formulations, as considered below, different materials act as sealer-binders, and may substitute for dolomitic carbonate. Thus, as discussed below, in some embodiments cement may function as a sealer-binder.
  • the composition may further possess the ability to sink through a liquid contaminated medium thus removing the contaminating oil from the system affected.
  • the composition should be denser than the contaminated medium.
  • the components for example the sorbant or sealer-binder materials, are naturally dense the required effect will occur automatically. This is the case for silion carbide.
  • a dense carrier material may be added to the composition to achieve the required density.
  • the composition may also comprise an agent which act as a natural surface tension reducing agent which allows limited but controlled dispersion of oils during the period of sorption thus allowing increased opportunity for composition-oil interaction.
  • a component which also acts as a sorbent or sealer-binder may also cause surface tension release in the required manner.
  • a suitable surface tension releasing agent is the feldspathic component of granitoid rocks (se ⁇ s foto) normally at a grain size less than 50 microns, which has proved effective in controlled dispersion of oil films, by progressive reduction of surface tension during break-up of the film on application.
  • granitic and granitoid rocks includes both igneous rocks such as granite and granodiorite and deformed and undeformed metamorphic mineralogical and chemical equivalents of feldspathic granites (eg. granitic gneiss, augen gneiss, blastomylonite or leucocratic migmatitic variants) .
  • feldspathic granites eg. granitic gneiss, augen gneiss, blastomylonite or leucocratic migmatitic variants
  • granitic and granitoid rocks refers to textural variants such as pegmatities, microgranites and phenocrystic granites or granitoids as well as referring to textural variants of metamorphic and/or deformed equivalents such as porphyroblastic gneisses (especially containing feldspar porphyroblasts) and augen mylonites. It has proved convenient to mill feldspathic granitoids to a mean grain size of less than 100 microns for use without separation of the feldspathic component specifically.
  • the oil is preferably micro-encapsulated within the composition either during or following sorption.
  • a combination of silicon carbide and powdered dolomitic carbonate is an example of material product able to micro-encapsulate the oil.
  • the composition is able to promote degradation of the sorbed oil over a long-term period ie. over a period of years to produce dispersable, non-toxic components to add to the natural background sediment at the base of a water column, preferably over a time-frame greater than that during which it might be anticipated that anaerobic or aerobic natural (or induced) biological activity would degrade any encapsulated residual hydrocarbons which remain from the initial reaction.
  • This can be achieved by including within the composition an energy supply or stimulus for oil-degrading micro-organisms.
  • An example would be a sucrose-fructose-glucose and/or amino acid mixture.
  • One embodiment of the invention which has proved effective is an admixture of silicon carbide and dolomitic carbonate, blended together in a volume ratio whereby silicon carbide predominates. Inclusion of powdered granitoid assemblages, or their equivalent may reduce the volume of silicon carbide to less than 50% of the product mixture.
  • the silicon carbide-dolomite +/- granitoid components are blended together after separate pre-preparation of milled grain-size fractions, or undergo coeval milling to an appropriate mean grain size after admixture. Whether or not this composition requires secondary treatment depends on the use to which the admixture is put.
  • the composition comprises sawdust derived by granulation of wood shavings to a powdered state (and preferably to a mean flake size less than 100 microns) as the sorbant.
  • the sealer-binder is conveniently provided by Portland cement or its equivalent. The ratio of sawdust to cement volume is tolerated within the range allowing sawdust to comprise up to 80% of the material volume, depending on the needs for buoyancy. Sorbability and retentivity of encapsulated oils may be enhanced by the incorporation into the composition of up to approximately 15% by material volume of silicon carbide at a mean grain size of less than 100 microns (and preferably less than 40 microns) , or an equivalent of silicon carbide as discussed earlier.
  • the sorbability of the sawdust/cement composition is satisfied (probably by capillary action and adsorption) by the combined effects associated with the presence of sawdust itself and the overall porosity created in manufacture of granules.
  • a nucleation site may be provided by the presence of sawdust/cement granules rather than by the individual components or combination of components in the dispersion of grains through an oil layer.
  • a density carrier is formed by reaction between the sawdust/cement granules and the oil into which they are placed, or which interacts with such granules.
  • the granules are able to float on water in the absence of oils, then to react with oils which themselves float on water and which come into contact with the granules, and, progressively sorb oils over a period which can be adjusted to suit the needs of the environmental situation faced (but normally ranging from a few minutes to a few hours) creating a reacted product, still in granular form, the new composite density of which induces settling of the granules through the water column and the creation of sediment. Therefore, the eventual settling of the reacted oil- soaked mass is promoted by density changes which occur through reaction between the granules and oil rather than deriving initially from the primary density of one or more components of the product mix (such as silicon carbide) .
  • the sawdust/cement composition suitably coated with a hydrophobing agent may be applied either to the surface of an oil slick or as a preventitive boom at the surface of a water column which will or might become contaminated with such an oil slick within the near future (within a period normally less than one calender month) .
  • Barrier type devices which in part or in whole, use as their make-up mats or other geometries of granules essentially similar to the formulation defined here, are regarded as falling within - li ⁇ the aegis of the present invention.
  • micro-encapsulation is accommodated in the first instance chiefly by the structural porosity of the engineered granules, and. is aided by secondary actions associated with sealer-binder effects. Both during settling and sedimentation (sensu bio), cement acts as an effective sealer-binder.
  • cement has further benefits in entombing any micro- encapsulated oils within the porosity of the granules, since, in marine waters, cement reacts with water within a short period of time (a maximum of a few days) to create a protective carapace of calcium carbonate which encrusts the sedimented granules (and thereby the granular mass) and prevents escape of oil components from the internal parts of the granules.
  • a composition according to the invention designed for oil clearance from solid substrates, including the surface of land and man-made surfaces.
  • the dominant requirements are those of sorbability, micro-encapsulation, sealing-binding, and possibly promoted oil degradation.
  • reacted materials may be mechanically excavated or otherwise removed from the solid substrate and used as solid fuel in some appropriately designed combustion device, which if controlled at temperatures less than 2000°C may be designed to recover and recycle silicon carbide for reuse.
  • This feature of product recoverability and the development of soil fuel from the composition is a further feature of the invention.
  • compositions can be used for rapid immobilisation of oils spilt essentially on solid media, such as the emergency containment of oils within tankers, the oil from which might otherwise enter the environment inadvertently, or as precautionary measures which might be prudent prior to sluicing oils from the bilges of ships or in the deployment of protective barriers against oil spills or fires which could ensue.
  • the matrix After approximately 5 minutes from addition of the water pollution product, the matrix sank rapidly as it contacted the lower oil-water interface, descending in an aggregated mass in a plughole effect to the base of the container. The sedimented matrix remained aggregated and stable, with no release of oil. The water was free of residual oil components.
  • Hardwood sawdust was milled and sorted to a mean flake size of approximately 50 ⁇ m, and physically mixed with dry Portland cement in the volume proportions given. Sufficient ethanol was then applied to the admixture to allow agglomeration to take place within the wetted medium, which was then placed in an appropriate mould which allowed creation of product granules with a mean diameter of approximately 1 cm, and slowly baked for approximately one hour at a mean temperature of approximately 80°C to volatilise the ethanol and leave structural porosity.
  • the matrix After approximately 3 minutes from addition of the water pollution product, the matrix sunk rapidly as it contacted the lower oil-water interface, descending in an aggregated mass in a plughole effect to the base of the container. The sedimented matrix remained aggregated and stable, with no release of oil. The water was free of residual oil components.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Public Health (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Medicinal Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Water Supply & Treatment (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

On décrit une composition destinée à retirer le pétrole de milieux contaminés par celui-ci, par exemple la mer. La composition comprend un agent de sorption de pétrole et un agent de scellement-fixation qui retiennent le pétrole dans la composition. La composition peut éventuellement comporter un constituant dense de façon à ce que la composition de pétrole sorbé puisse s'enfoncer dans un milieu liquide, devenant un sédiment et éliminant ainsi le pétrole polluant.
PCT/GB1993/000036 1992-01-08 1993-01-08 Composition pour retirer le petrole WO1993014034A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
GB929200286A GB9200286D0 (en) 1992-01-08 1992-01-08 Silicate-carbonate materials
GB9200286.4 1992-01-08
GB9204781.0 1992-03-05
GB929204781A GB9204781D0 (en) 1992-03-05 1992-03-05 Materials for environmental cleanup and remediation
GB9204782.8 1992-03-05
GB929204782A GB9204782D0 (en) 1992-03-05 1992-03-05 Control of algal blooms and nutrients

Publications (1)

Publication Number Publication Date
WO1993014034A1 true WO1993014034A1 (fr) 1993-07-22

Family

ID=27265993

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1993/000036 WO1993014034A1 (fr) 1992-01-08 1993-01-08 Composition pour retirer le petrole

Country Status (2)

Country Link
AU (1) AU3263293A (fr)
WO (1) WO1993014034A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001043893A2 (fr) * 1999-12-14 2001-06-21 Spanovic Milli Traitement et elimination des fonds de cale
WO2007051338A1 (fr) * 2005-11-07 2007-05-10 Swisstech Holding Ag Composition et procede de biorestauration d'eaux polluees par des hydrocarbures
WO2007053961A1 (fr) * 2005-11-08 2007-05-18 Swisstech Holding Ag Composition et procede de biorestauration d’eau polluee par des hydrocarbures

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1719459A1 (de) * 1968-02-01 1971-08-12 Omya Sa Verfahren zum Bekaempfen der OElpest auf dem Wasser
CA1107267A (fr) * 1978-04-18 1981-08-18 Douglas S. Alexander Compose absorbeur d'huile et de liquides analogues
EP0149396A2 (fr) * 1983-12-27 1985-07-24 Lafarge Coppee Matériau solide à propriétés oléophiles et hydrofuges et son utilisation pour l'absorption d'hydrocarbures
EP0353605A1 (fr) * 1988-07-31 1990-02-07 Günther Dr. Marx Emploi d'une substance minérale pour l'absorption de liquides, émulsions et suspensions toxiques
EP0368138A1 (fr) * 1988-11-05 1990-05-16 MERCK PATENT GmbH Adsorbant pour chromatographie
US5030591A (en) * 1989-09-15 1991-07-09 Cole James A Hydrocarbon absorbing compositions

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1719459A1 (de) * 1968-02-01 1971-08-12 Omya Sa Verfahren zum Bekaempfen der OElpest auf dem Wasser
CA1107267A (fr) * 1978-04-18 1981-08-18 Douglas S. Alexander Compose absorbeur d'huile et de liquides analogues
EP0149396A2 (fr) * 1983-12-27 1985-07-24 Lafarge Coppee Matériau solide à propriétés oléophiles et hydrofuges et son utilisation pour l'absorption d'hydrocarbures
EP0353605A1 (fr) * 1988-07-31 1990-02-07 Günther Dr. Marx Emploi d'une substance minérale pour l'absorption de liquides, émulsions et suspensions toxiques
EP0368138A1 (fr) * 1988-11-05 1990-05-16 MERCK PATENT GmbH Adsorbant pour chromatographie
US5030591A (en) * 1989-09-15 1991-07-09 Cole James A Hydrocarbon absorbing compositions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 7646, Derwent Publications Ltd., London, GB; AN 76-85917X *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001043893A2 (fr) * 1999-12-14 2001-06-21 Spanovic Milli Traitement et elimination des fonds de cale
WO2001043893A3 (fr) * 1999-12-14 2002-01-31 Milli Spanovic Traitement et elimination des fonds de cale
WO2007051338A1 (fr) * 2005-11-07 2007-05-10 Swisstech Holding Ag Composition et procede de biorestauration d'eaux polluees par des hydrocarbures
EA016981B1 (ru) * 2005-11-07 2012-08-30 Свистек Холдинг Аг Композиция и способ биоремедиации воды, загрязненной углеводородами
WO2007053961A1 (fr) * 2005-11-08 2007-05-18 Swisstech Holding Ag Composition et procede de biorestauration d’eau polluee par des hydrocarbures

Also Published As

Publication number Publication date
AU3263293A (en) 1993-08-03

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