WO1998030303A1 - Systems for ameliorating aqueous hydrocarbon spills - Google Patents

Systems for ameliorating aqueous hydrocarbon spills Download PDF

Info

Publication number
WO1998030303A1
WO1998030303A1 PCT/US1998/000385 US9800385W WO9830303A1 WO 1998030303 A1 WO1998030303 A1 WO 1998030303A1 US 9800385 W US9800385 W US 9800385W WO 9830303 A1 WO9830303 A1 WO 9830303A1
Authority
WO
WIPO (PCT)
Prior art keywords
sacks
styrene
bodies
oil
multitude
Prior art date
Application number
PCT/US1998/000385
Other languages
French (fr)
Original Assignee
Abtech Industries, Inc.
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
Application filed by Abtech Industries, Inc. filed Critical Abtech Industries, Inc.
Priority to BR9807070-3A priority Critical patent/BR9807070A/en
Priority to AT98902448T priority patent/ATE283725T1/en
Priority to EP98902448A priority patent/EP0973593B1/en
Priority to KR1019997006276A priority patent/KR100593867B1/en
Priority to JP53111398A priority patent/JP4164707B2/en
Priority to AU59110/98A priority patent/AU732308B2/en
Priority to IL13086798A priority patent/IL130867A0/en
Priority to CA002277163A priority patent/CA2277163C/en
Priority to DE69827937T priority patent/DE69827937T2/en
Publication of WO1998030303A1 publication Critical patent/WO1998030303A1/en
Priority to HK00104822A priority patent/HK1025529A1/en

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D17/00Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02Separation of non-miscible liquids
    • B01D17/0202Separation of non-miscible liquids by ab- or adsorption
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D15/00Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D17/00Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02Separation of non-miscible liquids
    • B01D17/0208Separation of non-miscible liquids by sedimentation
    • B01D17/0214Separation of non-miscible liquids by sedimentation with removal of one of the phases
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26Synthetic macromolecular compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26Synthetic macromolecular compounds
    • B01J20/261Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/68Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • C02F1/681Treatment 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/006Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to block copolymers containing at least one sequence of polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00Materials not provided for elsewhere
    • C09K3/32Materials not provided for elsewhere for absorbing liquids to remove pollution, e.g. oil, gasoline, fat
    • EFIXED CONSTRUCTIONS
    • E02HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
    • E02BHYDRAULIC ENGINEERING
    • E02B15/00Cleaning or keeping clear the surface of open water; Apparatus therefor
    • E02B15/04Devices for cleaning or keeping clear the surface of open water from oil or like floating materials by separating or removing these materials
    • E02B15/041Devices for distributing materials, e.g. absorbed or magnetic particles over a surface of open water to remove the oil, with or without means for picking up the treated oil
    • EFIXED CONSTRUCTIONS
    • E02HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
    • E02BHYDRAULIC ENGINEERING
    • E02B15/00Cleaning or keeping clear the surface of open water; Apparatus therefor
    • E02B15/04Devices for cleaning or keeping clear the surface of open water from oil or like floating materials by separating or removing these materials
    • E02B15/10Devices for removing the material from the surface
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/32Hydrocarbons, e.g. oil
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00Water conservation; Efficient water supply; Efficient water use
    • Y02A20/20Controlling water pollution; Waste water treatment
    • Y02A20/204Keeping clear the surface of open water from oil spills
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S210/00Liquid purification or separation
    • Y10S210/918Miscellaneous specific techniques
    • Y10S210/922Oil spill cleanup, e.g. bacterial
    • Y10S210/923Oil spill cleanup, e.g. bacterial using mechanical means, e.g. skimmers, pump
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S210/00Liquid purification or separation
    • Y10S210/918Miscellaneous specific techniques
    • Y10S210/922Oil spill cleanup, e.g. bacterial
    • Y10S210/924Oil spill cleanup, e.g. bacterial using physical agent, e.g. sponge, mop
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S210/00Liquid purification or separation
    • Y10S210/918Miscellaneous specific techniques
    • Y10S210/922Oil spill cleanup, e.g. bacterial
    • Y10S210/925Oil spill cleanup, e.g. bacterial using chemical agent
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S588/00Hazardous or toxic waste destruction or containment
    • Y10S588/90Apparatus
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S588/00Hazardous or toxic waste destruction or containment
    • Y10S588/901Compositions

Definitions

  • TECHNICAL FIELD This invention is in the field of systems and methods for recovering hydrocarbons from water, including oil spills on open-water surfaces such as the ocean. BACKGROUND ART
  • oil-absorbent or oil-adsorbent such as wood chips, activated carbon, wool, cotton balls, corn husks, duck feathers, and various synthetic polymeric materials.
  • a number of polymeric materials (polypropylene, polyester, polyurethane, vinyl polymers, and others) are known to absorb or adsorb crude or refined oil. Systems for applying these materials to oil spills are less developed. Application of materials to oil have been largely limited to two types: (1) spraying particles of the oil-sorbing material on the spill, or (2) placing the material inside booms or other barriers that surround the spill.
  • Containers for oil-sorbing materials are known. These systems generally employ pillow or bale shaped containers. However, these containers have a tendency to pile up on top of each other, creating an undesirable condition in which a significant amount of the sorbent material is either below the waterline or floating above the oil, in either case out of contact with the oil. In addition, the large cross section of these types of containers tends to result in an "oil lock-out" phenomenon, in which the surface of the material becomes saturated with oil, effectively prevent- ing oil migration to the center of the material. These containers also have a propensity for folding over on themselves in heavy seas, thereby reducing the contact between oil and the sorbent material.
  • booms to surround the spill until the oil can be collected.
  • Boom systems have a number of designs, some of which employ oil sorbent materials in their construction.
  • oil-sorbent booms are not designed to sorb substantial amounts of oil, but rather are generally used to retrieve a sheen or a small oil spill or to prevent the spill from expanding or reaching a protected area such as a shoreline until it can be collected by mechanical means, typically utilizing skimmers or oil-recovery boats.
  • Containment systems employing traditional booms have numerous problems.
  • boom and skimmer systems do not work well in rough water or near obstacles.
  • Delayed response to a spill results in a number of deleterious changes.
  • a spill spreads uncontrollably and rapidly to a thin layer on water (less than 1 mm in many cases), making containment extremely difficult if not impossible.
  • the oil may wash ashore, causing severe environmental damage.
  • Lighter fractions of the oil (volatile organic compounds) are released into the atmosphere, resulting in hydrocarbon air pollution.
  • the oil will undergo aging and emulsification, which can cause the oil to sink, making cleanup even more difficult. All of these changes cause the cleanup of the spill to become much more difficult, increase the environmental impact, and raise the financial cost of the cleanup.
  • the present invention achieves the above and other objectives by use of a plurality of water- and oil-porous containers or sacks that are partially filled with a hydrophobic, compliant, oil-absorbent, copolymer material arranged in a number of bodies that (a) are generally cylindrical, (b) are porous, (c) have at least one passageway parallel to the axis of the cylinder, and (d) are dimensioned to float on water with the axis parallel to the surface of the water.
  • the material is formed with a binder in a novel extrusion process.
  • a multitude of small flakes of a rigid, inert, smooth material having a surface that is wettable with respect to hydrocarbons are embedded in the bodies.
  • Each sack is sewn in a novel way, with a perimeter stiffening ring, to retain a flat profile, and has a netting that closes to help inhibit outflow of the oil when the sack is retrieved.
  • the sacks When deployed from ship or by air onto a spill, the sacks spread into a pancake shape and the copolymer bodies form a relatively thin layer that retains the oil.
  • the inventive sacks will float indefinitely without releasing the oil or allowing it to emulsify, so the oil can remain in place until collection efforts are feasible.
  • the sacks can be burned in situ, or standard fishing boats or specialized collection boats can be used to retrieve the sacks, and the collected material can be burned to capture the energy content of the oil or processed to separate the oil from the copolymer.
  • the inventive sacks can be used in conjunction with other, known containment or retrieval equipment, such as booms or skimmers, if desired.
  • the inventive systems, devices, and methods can be used to permit (1) easy and quick deployment of containment equipment, even if a spill is in an inconvenient or distant location, (2) effective control of the spilled oil during any delays in recovery, and (3) comparatively inexpensive and easy collection of the oil during the clean-up stage.
  • the system is specifically designed for rapid deployment and efficiency in rough water.
  • FIG. 1 is an illustration showing various aspects of the inventive system in use, particularly deployment and retrieval techniques.
  • Figure 2 is a perspective view of a preferred sack used with the inventive systems and methods, depicted in a state before the sack is deployed.
  • Figure 3 is a perspective view of a preferred sack used with the inventive system, as it would appear before deployment.
  • Figure 4 is a side, cross-sectional view of the sack of Figure 2, as it would appear after deployment on open water.
  • Figure 5 is an isometric assembly diagram showing the elements of the preferred sack of Figure 2.
  • Figure 6 is a side view of an optional flange used in the preferred sack of Figure 5.
  • Figure 7 is a cross-sectional view of the perimeter of an embodiment of the preferred sack of Figure 5.
  • Figure 8 is a view of a preferred way of attaching the webbing and mesh of the preferred sack of Figure 5.
  • Figure 9 is a partially broken-away perspective view of an alternative preferred sack, modified from the version of Figure 5.
  • Figure 10 is a perspective view of a preferred form of copolymer body used in the preferred sacks of Figures 2-9.
  • Figure 11 is a detail view of a cross-section of the preferred body, such the one shown in Figure 10.
  • Figure 12 is a view of a preferred embodiment of apparatus used to collect sacks of Figures 2-9.
  • Figure 13 is a view of an alternative preferred embodiment of the collection system of Figure 12.
  • Figure 14 is a side view of a paravane assembly used with the embodiments of Figures 12 and 13.
  • Figure 15 is a view of another alternative preferred embodiment of the collection system of Figure 13.
  • Figure 16 is a view of a subsequent collection operation used in connection with the collection systems of Figures 13 or 15. Common numerals are used in the several figures to indicate similar elements.
  • the system includes the application to the oil spill of hundreds or thousands of sacks containing a quantity of appropriately formed bodies comprising copoly- mer-based materials that are known to absorb and entrap crude or refined hydrocarbon products, including crude oil of any viscosity and gasoline or other refined fuels.
  • oil refers to any hydrocarbon material.
  • Figure 1 illustrates an oil spill and certain deployment and retrieval activities in accordance with the invention, including a plurality of the inventive containers, referenced as sacks 10.
  • sacks 10 a number of different activities are shown in Figure 1, although in practice, many of those activities may take place at different times or in different locations.
  • a number of sacks 10 are shown being applied to an oil spill.
  • the containers are designed for easy application from floating platforms or ships, as shown at the left of Figure 1, or from air, as shown at the right of Figure 1.
  • Figure 1 illustrates application of sacks 10 from fishing boat 20, it is also possible to carry a quantity of sacks 10 aboard an oil tanker or other vessel (not shown) from which a spill might conceivably occur, as a precautionary measure.
  • Figure 1 also shows a number of sacks 10 being dropped from helicopter 30 on a different part of the spill.
  • the ability to deliver the sacks by air permits more rapid response to a spill, even if the spill is in a distant location or in a location that would be hazardous to approach by boat, such as in high seas, near reefs or other obstacles, in shallow water, or in the middle of a large spill.
  • open-ocean spills frequently occur in inconvenient locations or on rough seas.
  • air delivery allows application to a specific area of a large spill, which would be impossible for known sea-borne application methods.
  • One specific area usually near the center or leading edge of a spill, often contains 90% of the total oil in 10% of the geographic extent of the spill.
  • sacks 10 are easy to deploy also permits the most rapid possible form of response, namely delivery from the very tanker that has caused a spill.
  • Known spill-control systems typically require complex, specialized equipment run by well-trained crews, and cannot be readily deployed from tankers.
  • the inventive delivery system is simple enough to be deployed by tanker workers who are not skilled in handling spills, and inexpensive enough to be carried aboard tankers. It is not likely that an on-board tanker-delivery system can cure the entire 5 spill, but prompt application of a quantity of sacks 10 can assist in the initial clean-up by reducing the extent of spreading and quantity of unrecovered oil.
  • booms 70 of the sort known in the prior art, can be deployed and used with sacks 10.
  • sacks 10 can ameliorate even non-contained spills before booms 70 are deployed.
  • Figures 2 through 9 illustrate preferred embodiments of sack 10.
  • sacks 10 are suitable for compact storage. As seen in the cross-section of the preferred embodiment of Figure 3, each sack 10 is only partially filled, such that approximately 25-30% of the volume of the sack contains material 5 that can entrap oil. Each sack 10 can be folded (not shown), such as with laces or ties, into a volume much smaller than the volume occupied by the sack when it is fully inflated. Bales of up to thousands of the sacks can be created.
  • each sack 10 may measure at least several feet across and contain from a few kilograms of material that can entrap oil to many tens 0 of kilograms. Although larger sizes are also suitable, sacks 10 that measure less than a meter across have been found useful because of the ease of handling and flexibility of application. As shown in Figure 1, a large quantity of sacks 10 can be deployed on an oil spill, as densely as economically possible. However, it is preferred to allow gaps between the sacks, to avoid their coming into contact with each other, which 25 increases the chances that the oil will pass into contact with unused sorbent material. (In an alternative embodiment discussed below, where the sacks are formed into a boom, no gaps would be present, to form a continuous barrier.)
  • Figure 3 shows a cross-section of one such sack holding bodies of the oil- encapsulating copolymer.
  • sack 30 10 When deployed on open-water surface 50, however, sack 30 10 expands to a flat, pancake shape, as shown in the cross-section of Figure 4. In that shape, the interior volume of sack 10 becomes smaller than the volume of the same sack in Figure 3, so the material that can entrap oil may comprise approximately 80- 85% of the volume, in a layer that is a few inches thick. It has been found that sacks 10, when dropped onto open water 50, will quickly expand into the configuration shown in Figure 4, because of the impact of the sack and subsequent wave action. Thus, sack 10 is designed to permit the material inside to spread out across the area covered by the sack relatively uniformly. It is not necessary, therefore, to take any positive action to ensure that the copolymer extends across the maximum possible extent.
  • Sacks 10 will float on the surface of the water, and oil coming into contact with the material contained inside sacks 10 will become entrapped by those copolymers. Because the copolymer material is hydrophobic, however, it will not become water- logged. It has been found that sacks 10 containing copolymers will float on the surface of water for at least several weeks, and perhaps indefinitely, without sinking, releasing the oil, or allowing it to emulsify.
  • the copolymer material in sacks 10 can be of one color, such as white, and change color, such as to black, when oil is entrapped therein. Further details of the copolymer material are specified below.
  • An optional feature shown in Figure 2 is one or more buoyant elements 110, sewn to the material of sacks 10 at the level of the water-line. That feature assists in ensuring that sacks 10 have high visibility during prolonged periods on the spill.
  • buoyant elements 110 can assist in helping the sacks remain afloat.
  • sack 10 Another optional feature of sack 10 is a small radio transmitter 100, such as shown schematically in Figure 4, which can emit a constant signal of pre-defined characteristics. Transmitters such as those used in scientific research to tag birds or animals are of one type that may be suitable.
  • numeral 100 can comprise a patch of radar-sensitive material.
  • location device 100 can permit prompt location of sacks 10 that have floated beyond the extent of the spill or otherwise been lost. Also, in cases where sacks 10 are dropped in a remote location by air, location device 100 can provide boats approaching a spill with easy navigational guidance, allowing recovery boats to locate the spill and other boats to avoid inadvertently sailing into the midst of the spill.
  • Figure 5 shows more details of the basics of a preferred embodiment of one of the sacks 10.
  • the outer material of sack 10 is formed from two layers 200, 210 sewn together.
  • the copolymer-based material described below is placed inside sack 10 between those two layers.
  • the layers 200, 210 can be formed of polypropylene, plastic, string or cord such as used in ordinary fishing nets, nylon, or another suitable material.
  • a woven mesh formed of polypropylene was used. That material floats on water and is a strong material that is highly resistent to tearing, so if a small tear or rip opens, the material will resist its extension.
  • the sack material have enough porosity to allow passage of the spilled oil to the absorbent material contained therein. Material having gaps of three eighths of an inch has been found most suitable, particularly for use on crude oil.
  • the necessary porosity of the sacks will depend, however, on the weight of the oil being collected. For example, a tight mesh may work on diesel or gasoline spills but not on heavier crude oil. In one test, a fabric measured as having air permeability of 150 cubic feet per minute at a half inch of water was found suitable for absorbing diesel fuel but not crude oil.
  • the material of the sack must be sufficiently non-porous to contain the encapsulating copolymer matter. If the copolymer bodies specified below are used, even sack material having high porosity will be able to contain the absorbent material without leakage. Thus, larger bodies have the additional advantage of promoting the desirable goal of using high-porosity sack material, which permits better passage of oil.
  • Forming the outer material of sack 10 from two layers 200, 210 sewn together is particularly advantageous in helping sack 10 lay flat on the water, while also reducing the chance that the sack will fold over onto itself, which is undesirable because it limits the extent of sack 10.
  • the flat configuration further assists in distributing the weight of the sack across its entire lateral extent, which helps in preventing bursting from concentrations of oil-filled copolymer at any particular point.
  • the use of dual layers also promotes the wave action of the water helping to spread out the sack, as opposed to ordinary designs, in which wave action causes problems.
  • use of the inventive system permits improved collection in actual conditions encountered in real oil spills.
  • Outside of layers 200, 210 are two webs 220, 225 formed of 1.5 inch wide polyester webbing. Material with a yarn count of 1,300 per inch and a breaking point of 4,000 pounds has been found more than sufficient for the loads encountered.
  • Webs 220, 225 assist in preventing or limiting the extent of rips or tears in layers 200, 210.
  • Webbing rings 240, 250 are placed around the perimeter of sack 10 outside of webs 220, 225. Nylon webbing about 4 cm. wide with a warp yarn count of 1,680 per inch and breaking point of 6,000 pounds has been found suitable. Webbing rings
  • webbing rings 240, 250 15 webbing with a breaking point of 2,400 pounds can be used for webbing rings 240, 250.
  • webbing rings 240, 250 can be hooked to pick up sacks 10.
  • the members of web 220 are sewn so as to leave an opening for the neck of
  • flange 230 which can be made of hard plastic dip-molded material such as PVC.
  • the base of flange 230 is attached between web 220 and layer 200, such as by sewing directly through the material of the plastic.
  • Flange 230 is used as a port through which the copolymer material can be inserted into sack 10. The erect shape of the flange helps during retrieval.
  • Flange 230 has a neck 232 and a base 234, through which the sewing can be done.
  • Cap 236 mates with neck 232, either with bolts and nuts 238, as shown, or through internal screw threads, not shown, or a combination of both.
  • Eye 80 is formed, in the depicted embodiment, integrally with cap 236.
  • floats 110 Shown in Figure 2 are optional floats 110, which can also be attached near the ends of the members of webs 220, 225 of Figure 5 to add additional buoyancy.
  • Internal dividers (not shown) can optionally be used to further assist in preventing accumulation of copolymer material at certain spots. Neon colors can be used on the webbing or rings to facilitate location of sacks 10 during retrieval.
  • Webbing rings 240, 250 can also be formed of a single piece of material 245 that is folded over the edge of the perimeter of the assembly and stitched, forming a flat "U" shape in cross-section, as shown in Figure 7.
  • Double and triple stitching, or zigzag stitching, techniques are preferably used to prevent seam rupture or load failures.
  • the connector rings such as snap hooks 260 shown in Figure 7 can be added to webbing rings 240, 250 near the ends of the members of webs 220, 225 and at the perimeter of webs 220, 225, to permit attachment of multiple sacks 10 together. When so attached, sacks 10 can be used as a boom substitute.
  • ropes or cables can be added to assist in making deployment and retrieval adjustments without undue stress on the sacks 10.
  • Figure 5 shows a circular-shaped sack 10, other configurations, such as square or rectangular, are also possible. Rectangular sacks are well suited for boom usage.
  • the boom in accordance with the invention acts as a blanket, having a sizeable width to cover a large surface area.
  • the connected sacks can form a boom extending up to half a mile or so in length and holding up to 50,000 pounds of sorbent material.
  • a boom of this sort is particularly useful to deploy in contact with the leading edge of the spill.
  • double-width or wider booms can be configured easily by hooking additional rectangles together in multiple rows. Natural wave action works with such booms to prevent escape of oil, by spreading the oil across the width of the boom. By contrast, wave action hampers the effectiveness of prior art booms, including most with a "skirt" arrangement.
  • booms of this sort can be deployed near shorelines, to prevent oil from reaching land, or directly on the shoreline at water's edge, to filter oil moving on shore or as oil returns to the water.
  • the members of webs 220, 225 are attached to the woven mesh of layers 200, 210.
  • the members are preferably oriented in the same direction as the major axes of the diamond-shaped holes formed by the mesh, which is usually perpendicular to the warp of the woven material of webs 220, 225. This preferred configuration is shown in Figure 8.
  • Known containers tend to have bale-like or pillow-shaped appearances, which permit the sorbent material to form into a pile, creating the possibility of water-logged lower regions and upper regions that are out of the water. As a result, much of the sorbent material is positioned either above or below the oil slick in other known arrangements. Also, when the material becomes concentrated in a pile, the container can sink and interior parts of the material can be hidden, preventing them from encountering the oil.
  • webbing rings 240, 250 help flatten the profile of sack 10 by providing a stiff perimeter member. Also, in the circular arrangement, each segment of rings 240, 250 form a kind of an arch, creating tension that resists any tendency of webs 220, 225 to pull the perimeter radially inward.
  • the flat profile of sacks 10 therefore spreads the oil-absorbent copolymer material into an optimal position for encountering the oil; that is, in a flat layer on the surface of the water.
  • the encounter rate of the sorbent material with the oil is vastly improved with the arrangement shown, as opposed to known containers.
  • the arrangement of the sacks 10 combines with the natural buoyancy of the copolymer bodies to allow sacks 10 to remain afloat on the surface of the water for long periods of time, such as weeks or months or more. In one test, sacks remained afloat and effective for 16 weeks. Even over such extended time periods, the sacks 10 will hold the material in a flat sheet fashion, whether or not the material has sorbed oil.
  • a modified sack 10 is shown in Figure 9.
  • the Figure 9 version is particularly useful in waterway applications.
  • the overwhelming majority of aqueous spills (such as 95%) occur in waterways other than open ocean, including harbors, rivers, and lakes. Although many waterway spills are much smaller than open-sea spills, the waterway spills are very frequent and collectively environmentally significant.
  • FIG. 9 The configuration shown in Figure 9 is particularly useful with smaller-sized sacks, such as sacks with diameters of about two-thirds of a meter, which might have a carrying weight of about 20 kg. of oil-soaked copolymer bodies.
  • the sack of Figure 9 includes two mesh layers 200,
  • the sack of Figure 9 uses a ring 245 made of a single piece of material (as in ring 245 of Figure 7), formed from a mesh, such as a tape made of 14x12 count per inch mesh vinyl-encapsulated polyester.
  • sack 10 of Figure 9 includes ropes 222, 224 positioned across non-diametric chords. Ropes 222 cross sack 10 on top of layer 200, while ropes 224 cross sack 10 in an opposing direction below layer 210. The ends of ropes 222, 224 are attached to ring 245.
  • ring 80 and fill tube 230 have been replaced by a less expensive cloth collar 250, such as made of a 200-Denier nylon duck fabric.
  • a less expensive cloth collar 250 such as made of a 200-Denier nylon duck fabric.
  • One end of collar 250 is sewn to the top mesh layer 200, while the other end is folded over itself and sewn, forming a passageway through which a draw- string 255 passes.
  • Cloth collar 250 can also be used to replace ring 80 and fill tube 230 in the embodiment of sack 10 shown in Figures 5 and 6. If it is desired to have a pick-up ring, such as ring 80 in that embodiment, a metal ring (not shown) can be affixed to the point where the radial members of web 220 meet at the center of mesh layer 200, and cloth collar 250 can be located at any other convenient place in mesh layer 200. Alternatively, the radial members of web 220 can be attached to the sack 10 except at the very center of layer 200. The central ends of those radial members can be gathered together and attached to a metal ring, and cloth collar 250 can be affixed to the center of mesh layer 200, just below the ring.
  • COPOLYMER BODIES COPOLYMER BODIES
  • Figure 10 shows an example of a suitably formed copolymer body 300, for use inside sack 10.
  • the principal ingredient of bodies 300 is a copolymeric material that is known to sorb oil but not water.
  • the material is compliant or flexible.
  • a possible alternative to copolymers is natural or synthetic rubber, such as polyisoprene.
  • SBS styrene-butadiene-styrene
  • SIS styrene-isoprene-styrene
  • granular porous SBS with about 30% styrene has been found suitable, when sifted to retain particles in the range of sizes between 4 and 20 mesh.
  • the SBS product is manufactured without talc, contrary to the standard manufacturing process, to enhance inter-granular bonding in the formed body.
  • the binder material is a compliant or flexible, hydrophobic, olefinic polymer material in a granular form and having a melting point lower than that of the oil- absorbent copolymer.
  • Polyolefin thermoplastic elastomers such as ethylene propylene (“EP”) rubber or ethylene propylene diene monomer (“EPDM”) have been found suitable.
  • EP ethylene propylene
  • EPDM ethylene propylene diene monomer
  • An optionally third component of bodies 300 is a rigid, inert, smooth, thin flake of a material that has a surface that is wettable with respect to hydrocarbons. Any such material can be used, including mica, metal, or polymers, but polymethylpentene (“PMP") is a primary example. Alternative examples include polyethylene-terephthalate (“PET”), metallized polycarbonate, and polyvinylchloride.
  • PMP polymethylpentene
  • Alternative examples include polyethylene-terephthalate (“PET”), metallized polycarbonate, and polyvinylchloride.
  • PET polyethylene-terephthalate
  • the flakes should be relatively thin, such as less than a millimeter thick. The shapes of the flakes is not particularly important, and good results have been achieved with randomly chopped material a few millimeters across.
  • the flakes enhance the flow of oil into the center of the formed copolymer body 300, apparently by providing a channel or surface along which the oil can flow.
  • the flakes are not essential but can optionally be added.
  • 70-90% by weight of the material of bodies 300 consists of SBS and the remainder of EPDM binder.
  • the SBS and EPDM granules are mixed and formed into bodies 300 in a way that results in SBS granules in an EPDM matrix. If flakes are included, they might make up about 5% of the total weight.
  • a preferred embodiment that solves this dilemma uses a generally tube shape for bodies 300.
  • a cylinder with an outer diameter from about two to five centimeters has an hole about one to two centimeters in diameter along the longitudinal axis, resulting in a body 300 that has all of its material less than about a centimeter or two from the nearest surface.
  • the relatively large inner hole allows water and oil to pass through and between the bodies 300 easily, thereby improving the chances of oil encountering a copolymer surface. Also, removal of material from the center of body 300 reduces the amount of material in each body, without significantly reducing the quantity of oil absorbed, which further improves the quantity of oil entrapped per unit quantity of copolymer.
  • Multiple holes parallel to the cylinder's axis can be used in addition to the axial hole or instead of it.
  • three holes are arranged on radial planes separated by 120° angles, the holes being equidistant from the axis of the cylinder.
  • This arrangement permits enhanced flow-through of oil even if the oil layer does not intersect the cylinder along the axis, for example if some of the bodies 300 are partly submerged.
  • Bodies 300 should be formed with a length exceeding the outer diameter of the cylinder. This restriction is important, because it ensures that bodies 300 will float on the water with the axial hole parallel to the surface of the water, permitting better pass-through of oil.
  • sacks 10 are designed to permit bodies 300 to float in a single layer, as discussed above.
  • bodies 300 near the circumference of sack 10 tends to physically block oil from flowing to other bodies 300 closer to the center.
  • the inclusion of axial holes, and their orientation parallel to the surface of the water counteracts this tendency.
  • the preferred hole orientation permits more oil to remain inside the axial passage- way, permitting more time to complete the absorption process.
  • Bodies 300 can be supplemented with different-shaped bodies in sacks 10. Using such a mixture of bodies 300 is advantageous over the use of a uniform type of body, because regular-shaped bodies can become arranged in a more fitted-together fashion, reducing the quantity of interstitial space, which thereby lowers the encounter rate.
  • the generally cylindrical exterior 310 of bodies 300 is preferred, as it reduces the area of contact between adjacent bodies 300.
  • the pressure from many bodies 300 in sack 10 and the softness of the constituent materials tends to meld bodies 300 together, with the consequential tendency to lower the encounter rate.
  • a reduced contact area counters this undesired effect.
  • the sheets or parts can be molded in a rough-sided dimple mold.
  • bodies 300 preferably have numerous fissures 370 extending into bodies 300 from some or all exterior surfaces and passing between the grains of SBS. Again, the preferred formation process discussed below promotes this goal.
  • a sack 10 of 1.8 meters diameter can carry about 15 kg. of copolymer material, which represents nearly 400 units of the exemplary bodies 300.
  • a sack 10 of two-thirds of a meter diameter can carry about 2 kg. of copolymer material, which represents about 50 units.
  • the weight of the sacks after bodies 300 absorb oil is about an order of magnitude greater.
  • the bulk density of the resulting body is controlled, also to reduce gel blocking.
  • the SBS granules in bodies 300 are also less likely to clump to each other when soaked with oil, which also improves sorbency.
  • the SBS grain sizes identified above are selected to avoid gel blocking from either overly large chunks or agglomerated small-diameter, powdery particles.
  • bulk density greater than 0.75 g/cc tend to prevent the oil from entering the bodies, while bulk density smaller than 0.45 g/cc cause the bodies to fragment, either when dry or after absorbing oil.
  • copolymer bodies with a bulk density in the preferred range have enough inter-granular voids to permit oil to penetrate substantially throughout the thickness of bodies 300 without causing them to fall apart.
  • Bodies 300 formed in accordance with Figures 10 and 11 can alternatively be used as oil-absorbent filters, such as in a cartridge or around a pipe or shaft.
  • bodies 300 are physically held in position rather than floating, the length relative to the outer diameter is not critical and may be altered as needed. Similarly, the central hole may not be necessary.
  • a structure (not shown) is formed of a number of bodies 300 arranged side-by-side, with longitudinal axes parallel to each other. To form such a structure, multiple bodies 300 can be affixed together, or the structure can be manufactured as a unitary sheet having opposing top and bottom scalloped surfaces, with the holes located between the surfaces at the thicker regions.
  • One method of forming bodies 300 shown in Figure 10 is to use low-pressure compression molding in the presence of elevated temperature. For example, pressures about 8-20 psi and temperatures about 150-200° F. have been found suitable to manufacture a product originally consisting of SBS and EPDM granules with high absorbency and high retained coherency after absorbing oil. The heat melts the EPDM, without melting the SBS granules, to agglomerate the material into a coherent assembly without damaging the physical structure of the SBS, thereby degrading that material's absorbency.
  • a mold having a number of circular cavities can be used to form a number of bodies 300 at once.
  • Another, preferred method of forming bodies 300 applies a modified extrusion process.
  • SBS and EPDM granules are placed in the hopper of an extruder of conventional design, for example, a two-inch Bonnot lab extruder with a hot-water external barrel heater.
  • the extruder heats the granular material to a temperature not exceeding 120° F., far below normal extrusion temperatures for plastic products, and preferably not exceeding 105° F.
  • the EPDM quickly become plasticized, as a result of heat, pressure, and mechanical agitation by the screw and barrel in combination.
  • the extruder's screw mixes the plasticized EPDM and the unmelted SBS, forming a matrix of EPDM surrounding SBS granules. Because the SBS is not melted, some air bubbles remain in the mixture. The softening process occurs quite rapidly in the extruder, permitting very short dwell times (such as less than one minute), which permits rapid manufacturing.
  • the partially plasticized composite material is pressed through a circular die with a central rod or mandrel, to form the cylindrical structure with the axial hole shown in Figure 10. In one example, a four-inch long die was used.
  • the SBS granules Upon passing through the die, the SBS granules, which have been compressed somewhat by being forced through the die, reexpand, "fluffing" the extruded material while it cools and hardens. The expansion is further assisted by air remaining in the mixture. The extruded material is cut into suitable lengths to form the final bodies 300.
  • the EPDM matrix 390 When cooled and resolidified outside the extruder, the EPDM matrix 390 (see Figure 11) forms a durable but permeable structure for the SBS granules 380 and provides mechanical integrity to the resulting bodies 300.
  • bodies 300 formed in accordance with the preferred method do not break or crack absent extreme elastic deformation, despite the presence of fissures 370. Also, fragments of such bodies do not detach easily from bodies 300 in the form of flakes, crumbles, or dust, even with rough handling.
  • the fluffing effect (typically undesired in extrusion processes) is beneficial because it forms inter-granular fissures 370 in the EPDM matrix, throughout the structure.
  • the fissuring is not so great as to cause loss of structural integrity.
  • fissures are preferred to facilitate rapid passage of oil into bodies 300 and to reduce the incidence of gel blocking, permitting continued absorption.
  • any reduction in absorbency caused by the binder is more than offset by the increase rates of contact between oil and SBS caused by the fissuring and rough external texture and the reduced tendency to premature gelation.
  • SACK COLLECTION Figure 1 also shows techniques of recovering sacks 10 after the copolymer bodies have been soaked with oil. Because the sacks float and stabilize the oil in self- contained and self-sustaining sacks, special equipment is not needed to collect the oil. For example, Figure 1 shows an ordinary fishing trawler 20 using its net to scoop up quantities of oil-logged sacks 10.
  • the use of the inventive system does not preclude the utilization of more sophisticated collection boats, such as scoop boats or high-speed oil response vessels, such as known in the art.
  • more sophisticated collection boats such as scoop boats or high-speed oil response vessels, such as known in the art.
  • Figure 12 shows a collection method in which a specialized high-speed boat 400, such as a modified version of boats operated presently by Team One of Seattle, Washington, approaches the spill on a rapid-response basis.
  • Specially fitted outrigger paravanes 410 are deployed upon arrival, and sacks 10 are collected in wings 412 of paravanes 410 as boat 400 slowly advances.
  • sacks 10 are dropped onto the spill or in advance of the spill by air. Because sacks 10 retain the oil indefinitely, boat 400 can wait until the rough-water conditions dissipate to arrive on the scene and complete containment and recovery procedures, without risking dissipation of the spill by winds and seas, thus minimizing environmental damage without risk to recovery boats and crews.
  • a vacuum airstream conveyance and transfer (VACT) system can be used to collect sacks 10 using airstream induction (as opposed to pure vacuum pressure).
  • An example of such a system already on the market and known to the ordinarily skilled artisan is called the Linductor system, available from Linductor, Inc. of Seattle, Washington. This Linductor device was developed for transferring bulk solids or volumes of liquids, including removing spilled oil from the surface of water. It has been found that a VACT system that is a variant of the Linductor can be used to gather sacks 10 containing spilled oil more expediently in certain sea conditions.
  • the Linductor system as marketed and if mounted on an appropriate vessel, such as a barge is capable of picking up sacks up to three feet in diameter, but modifications can be made to allow pickup of larger sacks and conveyance on a smaller vessel.
  • Such a modified VACT system 420 is depicted in Figure 12, including receiving tank 422, widened intake pipe 424, turret assembly 426, power and induction fan unit 426, and outlet pipe 428.
  • Turret assembly 426 rotates to permit intake pipe 424 to be moved to any desired location next to the bow of boat 400. It is possible to configure a VACT system to use two intake pipes, one on either side of the bow (not shown).
  • Outlet pipe 428 is optional, because sacks 10 can be retained in receiving tank or bladder 422, or an interior connection (not shown) at the bottom of tank 422 can allow sacks 10 to drop into a hold of boat 400, or an outlet ramp (not shown) on a side of tank 422 can allow sacks 10 to exit tank 422 and accumulate in an adjacent pile. In the configuration depicted in Figure 12, however, sacks 10 are discharged through outlet pipe 428 and hurled through the air into a lightweight sled 430 towed along the side of boat 400. A powered barge can be used instead of a towed sled.
  • Figure 13 shows laborers tying retrieved sacks 10 to lines or cables 440 pulled manually off of spools 450, to form towed strings of sacks that can be collected later.
  • Those units of sacks 10 that miss intake pipe 424 are carried slowly up ramps 414 of paravanes 410 and attached manually to lines or cables 440, such as with snap hooks, after which they are slid back down to the water on a slide 415, such as made of stainless steel.
  • Figure 15 shows an alternative embodiment in which the VACT system is deleted, and manual collection and arrangement into strings is done exclusively.
  • Figure 14 shows details of a hydraulically powered paravane 410, as viewed from the far side of boat 400 in Figures 12 and 13.
  • Ramp 414 can be tilted from an initially horizontal travel position to drop scoop 416 below waterline 418. Thereaf- ter, the hydraulic system can spread wings 412 from the travel position to the 45- degree angle shown in Figures 12, 13, and 15.
  • Ramp 414 includes a powered conveyor, with a surface that can be made of a lightweight, wide mesh fabric, such as made of a Velcro material, that can grip and feed sacks 10 from scoop 416 up ramp 414.
  • paravanes 410 are depicted as being supported by boat 400, they can alternatively be mounted on one or a chain of sleds, similar to sled 430, towed along the side of or behind powered boat 400.
  • a workboat can assemble a number of strings together and attach an anchor or buoy 480 to the group of strings, preferably by attaching it to the middle of each string, forming a streamer-like arrangement 460, shown in Figure 16.
  • Anchor or buoy 480 can support a radio transmitter-like element or radar-sensitive patch 100 in Figure 4, for ease of later location, instead of that element being on each sack 10.
  • Streamers 460 can remain afloat until a collection boat or towed sled 470 attaches a line to anchor or buoy 480 and pulls the assembly aboard. Once loaded, sled 470 with its chains of sacks 10 can be towed to shore with barges.
  • DISPOSAL DISPOSAL
  • the inventive configuration of sacks 10 permits a disposal method that has been considered desirable but which is difficult if not impossible to achieve in actual practice, namely in-situ burning on the water. In-situ burning prevents the need for the boat collection techniques described above.
  • Sacks 10 either alone or in assembled chains or "streamers," can be easily ignited on the water, which creates a wicking or torch effect, thereby burning not only the sacks but also unabsorbed oil surrounding the sacks.
  • Previous attempts to burn oil spills on water have suffered from numerous difficulties, particularly the problems in ignition caused by rough water, thin oil slicks, or high emulsification.
  • Various published articles have described prior attempts at in-situ burning and the problems faced by such attempts.
  • sacks 10 are transported to dry land, they can be disposed of as waste with the oil still intact, but this is costly and environmentally not preferred. Alternatively, sacks 10 can be incinerated on land, and the energy content of the oil and copolymer can be recovered and used as power. To allow for such a disposal technique, it is preferred to use materials for the particles, for the outer material of sack 10, and for all other components of the sacks 10 that can be burned, to reduce the quantity of solid waste or air-borne pollution. The preferred materials specified in this descrip- tion are so suited. Another recycling use for oil-logged copolymers is in road building.
  • TRTM-60 Certain modifications to the TRTM-60 can allow it to work on oil-soaked copolymer bodies, at a reasonable cost: (1) because of the salt content, a higher-grade stainless steel is preferred; (2) the discharge system is changed to eliminate the magnetic separator for carbon black and steel scrap, which is produced from scrap tire but not from copolymer bodies; (3) a second, liquid seal is used at the discharge end; (4) the air condenser is replaced with a second water condenser; and (5) two screw conveyor stages are used instead of five.
  • copolymer bodies from sacks 10 are delivered to an inlet hopper of a sealed screw conveyor.
  • Commercially available as a package with the TRTM-60 is information identifying certain additives that permit better breakdown of the scrap tire, and these additives are useful with the copolymer bodies as well.
  • Two enclosed, horizontally oriented, stainless-steel screw conveyors stages powered by individual hydraulic drives and a central hydraulic pumping system, move the material including the copolymer bodies through the reactor while chemically breaking down the bodies while they are conveyed through the entire length.
  • the conveyors have top inlets and discharge chutes at each end.
  • the inlet connection to the reactor and the outlet side of the reactor are sealed, for example by liquid seals, to prevent oxygen from entering the process.
  • the reactor heats the material in a vacuum at 200-300° C.
  • Each reactor conveyor has a perforated top to vent gases produced during the process.
  • a vertical stainless steel plenum welded to each conveyor provides a means to collect these process gases.
  • the gases are "pulled" off the top of the plenum by a turbine pump.
  • the gas is then filtered to remove residue carried over from the reactor unit.
  • the gases consisting mostly of vaporized fuel oils, are then pumped through two separate condensing stages that are a water-cooled heat exchanger. Cooling is provided via an air-cooled process chiller with a circulating pumping system.
  • Non- condensable gases are collected and recycled as the fuel medium for the burners, which can be used to maintain the temperature in the reactor unit or to power an electric generator, or can be discharged to a flare and burned.
  • Oil-soaked copolymer material processed in this fashion can yield much of the output as liquid hydrocarbons. Indeed, some of the resulting liquid consists of styrene, which if separated by distillation, is five to ten times more valuable than crude oil, and can improve the recycling economics. An additional portion of the total output consists of gaseous hydrocarbons, which can be further processed to a hydrocarbon mixture that can be used as clean-burning fuel for the recycling reactor. Yet another portion, generated from the ethylene components, consists of a waxy solid residue that has commercial application as a feed stock for chemical refineries. Optimally, virtually no char will remain.

Abstract

A plurality of water- and oil-porous sacks (10) are partially filled with a number of generally tubular macroscopic bodies (300) of a polymer material that entraps oil, including preferably styrene-butadiene-styrene and ethylene propylene diene monomer. The bodies (300) can be generally cylindrical with an axial hole and a length greater than the diameter, so that when afloat in water, such as in sacks (10), the axial hole parallels to the water surface. The bodies (300) are preferably formed from granular material in a novel low-temperature extrusion process that links substantially unmelted SBS granules (380) in an EPDM matrix (390). When so formed, the bodies (300) have numerous fissures (370) extending from the surfaces, yet retain structural integrity without flaking or crumbling. Novel sack structure, sack deployment, sack retrieval, and material disposition systems, including in situ burning, are also disclosed.

Description

SYSTEMS FOR AMELIORATING AQUEOUS' FTYDROCARBON SPILLS
TECHNICAL FIELD This invention is in the field of systems and methods for recovering hydrocarbons from water, including oil spills on open-water surfaces such as the ocean. BACKGROUND ART
The continuing incidence of oil spillage into both marine and inland waterways due to shipping accidents results in enormous annual costs both financially to the shipping and insurance industries and environmentally. Many spill incidents occur in bad weather or in remote locations. Current systems for ameliorating oil spills require that specialized spill-response ships containing unique heavy equipment reach the site of the spill quickly, which requires relatively calm waters. There is a limited number of units of specialized equipment, and they are not easily transported. Thus, in many cases, response to the spill is delayed for many hours or even days. The impact of a spill is greatly increased by both bad weather and delayed response. Spill damage can be mitigated if response is rapid, even in rough- water conditions.
An additional problem is the high cost of disposal of the recovered material. Current recovery systems create large quantities of waste, which must be disposed of as hazardous waste at high financial cost. This problem can be solved by employing a system that allows for recycling, reclaiming, or low cost disposal.
Known systems for the clean-up of oil spilled on water fall into two categories: (1) absorption or adsorption (sorbing) of the oil, or (2) skimming of the oil, typically in conjunction with containment.
Many materials are known to be oil-absorbent or oil-adsorbent, such as wood chips, activated carbon, wool, cotton balls, corn husks, duck feathers, and various synthetic polymeric materials. A number of polymeric materials (polypropylene, polyester, polyurethane, vinyl polymers, and others) are known to absorb or adsorb crude or refined oil. Systems for applying these materials to oil spills are less developed. Application of materials to oil have been largely limited to two types: (1) spraying particles of the oil-sorbing material on the spill, or (2) placing the material inside booms or other barriers that surround the spill.
Either method creates severe collection problems for sorbent material in particulate form, including sinking of the oil-loaded material, loss of the oil-loaded material due to dispersion by wave or wind action, and dissolution of the oil-sorbent material in the oil spill. These problems are exacerbated when the spill occurs in bad weather or near shorelines. In addition, because 90% of spilled oil is typically located in 10% of the spill area, the dissolution problem can be particularly troublesome inside barriers. Further, the application of oil-sorbing material typically employs spill boats, which rely on availability of the boat and access to the spill. Both of these can be a severe problem in remote locations or bad weather.
Containers for oil-sorbing materials are known. These systems generally employ pillow or bale shaped containers. However, these containers have a tendency to pile up on top of each other, creating an undesirable condition in which a significant amount of the sorbent material is either below the waterline or floating above the oil, in either case out of contact with the oil. In addition, the large cross section of these types of containers tends to result in an "oil lock-out" phenomenon, in which the surface of the material becomes saturated with oil, effectively prevent- ing oil migration to the center of the material. These containers also have a propensity for folding over on themselves in heavy seas, thereby reducing the contact between oil and the sorbent material.
On the other hand, oil-containment systems utilize booms to surround the spill until the oil can be collected. Boom systems have a number of designs, some of which employ oil sorbent materials in their construction. However, oil-sorbent booms are not designed to sorb substantial amounts of oil, but rather are generally used to retrieve a sheen or a small oil spill or to prevent the spill from expanding or reaching a protected area such as a shoreline until it can be collected by mechanical means, typically utilizing skimmers or oil-recovery boats. Containment systems employing traditional booms have numerous problems.
Deployment of some booms requires specialized equipment, which can be slow and difficult. If the spill is large, surrounding the spill may not be possible due to lack of sufficient boom resources. All of these problems can delay response to the spill. Therefore, boom and skimmer systems do not work well in rough water or near obstacles.
Delayed response to a spill results in a number of deleterious changes. A spill spreads uncontrollably and rapidly to a thin layer on water (less than 1 mm in many cases), making containment extremely difficult if not impossible. If close to shore, the oil may wash ashore, causing severe environmental damage. Lighter fractions of the oil (volatile organic compounds) are released into the atmosphere, resulting in hydrocarbon air pollution. The oil will undergo aging and emulsification, which can cause the oil to sink, making cleanup even more difficult. All of these changes cause the cleanup of the spill to become much more difficult, increase the environmental impact, and raise the financial cost of the cleanup.
There has been a need for some time, therefore, for an oil-recovery system that would (1) permit faster response, (2) work better in adverse conditions, such as rough water or near shorelines and obstacles, (3) prevent more of the oil from sinking, (4) contain the extent of the oil spill more quickly, (5) permit easier and more flexible deployment, (6) allow for easier collection, (7) permit economical recycling or disposal of the collected oil, and better protect the environment.
DISCLOSURE OF THE INVENTION Accordingly, it is a primary object of the present invention to achieve a more effective system for recovering oil from the surface of bodies of water, such as oceans, lakes, or rivers.
It is another object of the invention to provide methods and apparatus for applying oil-absorbent or oil-adsorbent materials to an oil spill quickly and easily, accurately, and with minimal disturbance of the environment. It is another object of the invention to provide methods and apparatus for effectively containing water-borne oil spills, even under adverse conditions or near shorelines, rocks, and reefs.
It is another object of the invention to provide methods and apparatus for ameliorating oil spills both by containment, such as within a barrier, and by entrap- ping the oil in an oil-sorbent material.
It is another object of the invention to provide a means of improving the collection of spilled oil.
It is another object of the invention to provide systems for controlling oil spills in areas of a body of water that are remote from collection vessels or in areas where shipping hazards or the oil itself prevent safe vessel operation, for later removal.
It is another object of the invention to provide collection systems that do not need to rely on the presence of specialized boats or vessels but can work with them. It is another objective of the invention to provide systems for controlling oil spills that provide for the economical recycling of the collected oil as fuel.
It is another objective of the invention to provide systems for controlling oil spills that provide for the disposal of the oil through in-situ burning of the oil. The present invention achieves the above and other objectives by use of a plurality of water- and oil-porous containers or sacks that are partially filled with a hydrophobic, compliant, oil-absorbent, copolymer material arranged in a number of bodies that (a) are generally cylindrical, (b) are porous, (c) have at least one passageway parallel to the axis of the cylinder, and (d) are dimensioned to float on water with the axis parallel to the surface of the water. The material is formed with a binder in a novel extrusion process. Optionally, a multitude of small flakes of a rigid, inert, smooth material having a surface that is wettable with respect to hydrocarbons are embedded in the bodies. Each sack is sewn in a novel way, with a perimeter stiffening ring, to retain a flat profile, and has a netting that closes to help inhibit outflow of the oil when the sack is retrieved. When deployed from ship or by air onto a spill, the sacks spread into a pancake shape and the copolymer bodies form a relatively thin layer that retains the oil. The inventive sacks will float indefinitely without releasing the oil or allowing it to emulsify, so the oil can remain in place until collection efforts are feasible. The sacks can be burned in situ, or standard fishing boats or specialized collection boats can be used to retrieve the sacks, and the collected material can be burned to capture the energy content of the oil or processed to separate the oil from the copolymer. The inventive sacks can be used in conjunction with other, known containment or retrieval equipment, such as booms or skimmers, if desired. Thus, the inventive systems, devices, and methods can be used to permit (1) easy and quick deployment of containment equipment, even if a spill is in an inconvenient or distant location, (2) effective control of the spilled oil during any delays in recovery, and (3) comparatively inexpensive and easy collection of the oil during the clean-up stage. The system is specifically designed for rapid deployment and efficiency in rough water.
Other aspects of the invention will be appreciated by those skilled in the art after a reading of the detailed disclosure of the present invention below. BRIEF DESCRIPTION OF DRAWINGS Figure 1 is an illustration showing various aspects of the inventive system in use, particularly deployment and retrieval techniques.
Figure 2 is a perspective view of a preferred sack used with the inventive systems and methods, depicted in a state before the sack is deployed.
Figure 3 is a perspective view of a preferred sack used with the inventive system, as it would appear before deployment.
Figure 4 is a side, cross-sectional view of the sack of Figure 2, as it would appear after deployment on open water. Figure 5 is an isometric assembly diagram showing the elements of the preferred sack of Figure 2.
Figure 6 is a side view of an optional flange used in the preferred sack of Figure 5.
Figure 7 is a cross-sectional view of the perimeter of an embodiment of the preferred sack of Figure 5.
Figure 8 is a view of a preferred way of attaching the webbing and mesh of the preferred sack of Figure 5.
Figure 9 is a partially broken-away perspective view of an alternative preferred sack, modified from the version of Figure 5. Figure 10 is a perspective view of a preferred form of copolymer body used in the preferred sacks of Figures 2-9.
Figure 11 is a detail view of a cross-section of the preferred body, such the one shown in Figure 10.
Figure 12 is a view of a preferred embodiment of apparatus used to collect sacks of Figures 2-9.
Figure 13 is a view of an alternative preferred embodiment of the collection system of Figure 12.
Figure 14 is a side view of a paravane assembly used with the embodiments of Figures 12 and 13. Figure 15 is a view of another alternative preferred embodiment of the collection system of Figure 13.
Figure 16 is a view of a subsequent collection operation used in connection with the collection systems of Figures 13 or 15. Common numerals are used in the several figures to indicate similar elements.
MODES FOR CARRYING OUT THE INVENTION The system includes the application to the oil spill of hundreds or thousands of sacks containing a quantity of appropriately formed bodies comprising copoly- mer-based materials that are known to absorb and entrap crude or refined hydrocarbon products, including crude oil of any viscosity and gasoline or other refined fuels. For purposes of this application, the term "oil" refers to any hydrocarbon material. SACK DEPLOYMENT
Figure 1 illustrates an oil spill and certain deployment and retrieval activities in accordance with the invention, including a plurality of the inventive containers, referenced as sacks 10. To simplify the application, a number of different activities are shown in Figure 1, although in practice, many of those activities may take place at different times or in different locations. In Figure 1, a number of sacks 10 are shown being applied to an oil spill. The containers are designed for easy application from floating platforms or ships, as shown at the left of Figure 1, or from air, as shown at the right of Figure 1. Although Figure 1 illustrates application of sacks 10 from fishing boat 20, it is also possible to carry a quantity of sacks 10 aboard an oil tanker or other vessel (not shown) from which a spill might conceivably occur, as a precautionary measure. Figure 1 also shows a number of sacks 10 being dropped from helicopter 30 on a different part of the spill. The ability to deliver the sacks by air, such as from helicopters or light planes, or in bales from larger cargo planes, permits more rapid response to a spill, even if the spill is in a distant location or in a location that would be hazardous to approach by boat, such as in high seas, near reefs or other obstacles, in shallow water, or in the middle of a large spill. After all, open-ocean spills frequently occur in inconvenient locations or on rough seas. Also, air delivery allows application to a specific area of a large spill, which would be impossible for known sea-borne application methods. One specific area, usually near the center or leading edge of a spill, often contains 90% of the total oil in 10% of the geographic extent of the spill.
The fact that sacks 10 are easy to deploy also permits the most rapid possible form of response, namely delivery from the very tanker that has caused a spill. Known spill-control systems typically require complex, specialized equipment run by well-trained crews, and cannot be readily deployed from tankers. The inventive delivery system, by contrast, is simple enough to be deployed by tanker workers who are not skilled in handling spills, and inexpensive enough to be carried aboard tankers. It is not likely that an on-board tanker-delivery system can cure the entire 5 spill, but prompt application of a quantity of sacks 10 can assist in the initial clean-up by reducing the extent of spreading and quantity of unrecovered oil.
As also shown in Figure 1, at later stages of clean-up, booms 70, of the sort known in the prior art, can be deployed and used with sacks 10. However, sacks 10 can ameliorate even non-contained spills before booms 70 are deployed. 0 SACK STRUCTURE
Figures 2 through 9 illustrate preferred embodiments of sack 10.
Before deployment, sacks 10 are suitable for compact storage. As seen in the cross-section of the preferred embodiment of Figure 3, each sack 10 is only partially filled, such that approximately 25-30% of the volume of the sack contains material 5 that can entrap oil. Each sack 10 can be folded (not shown), such as with laces or ties, into a volume much smaller than the volume occupied by the sack when it is fully inflated. Bales of up to thousands of the sacks can be created.
In a preferred embodiment, each sack 10 may measure at least several feet across and contain from a few kilograms of material that can entrap oil to many tens 0 of kilograms. Although larger sizes are also suitable, sacks 10 that measure less than a meter across have been found useful because of the ease of handling and flexibility of application. As shown in Figure 1, a large quantity of sacks 10 can be deployed on an oil spill, as densely as economically possible. However, it is preferred to allow gaps between the sacks, to avoid their coming into contact with each other, which 25 increases the chances that the oil will pass into contact with unused sorbent material. (In an alternative embodiment discussed below, where the sacks are formed into a boom, no gaps would be present, to form a continuous barrier.)
Figure 3 shows a cross-section of one such sack holding bodies of the oil- encapsulating copolymer. When deployed on open-water surface 50, however, sack 30 10 expands to a flat, pancake shape, as shown in the cross-section of Figure 4. In that shape, the interior volume of sack 10 becomes smaller than the volume of the same sack in Figure 3, so the material that can entrap oil may comprise approximately 80- 85% of the volume, in a layer that is a few inches thick. It has been found that sacks 10, when dropped onto open water 50, will quickly expand into the configuration shown in Figure 4, because of the impact of the sack and subsequent wave action. Thus, sack 10 is designed to permit the material inside to spread out across the area covered by the sack relatively uniformly. It is not necessary, therefore, to take any positive action to ensure that the copolymer extends across the maximum possible extent.
Sacks 10 will float on the surface of the water, and oil coming into contact with the material contained inside sacks 10 will become entrapped by those copolymers. Because the copolymer material is hydrophobic, however, it will not become water- logged. It has been found that sacks 10 containing copolymers will float on the surface of water for at least several weeks, and perhaps indefinitely, without sinking, releasing the oil, or allowing it to emulsify.
The copolymer material in sacks 10 can be of one color, such as white, and change color, such as to black, when oil is entrapped therein. Further details of the copolymer material are specified below.
An optional feature shown in Figure 2 is one or more buoyant elements 110, sewn to the material of sacks 10 at the level of the water-line. That feature assists in ensuring that sacks 10 have high visibility during prolonged periods on the spill.
Also if other objects, such as a heavy type of cable, is attached to the sacks 10, the buoyant elements 110 can assist in helping the sacks remain afloat.
Another optional feature of sack 10 is a small radio transmitter 100, such as shown schematically in Figure 4, which can emit a constant signal of pre-defined characteristics. Transmitters such as those used in scientific research to tag birds or animals are of one type that may be suitable. Alternatively, numeral 100 can comprise a patch of radar-sensitive material.
Such a location device 100 can permit prompt location of sacks 10 that have floated beyond the extent of the spill or otherwise been lost. Also, in cases where sacks 10 are dropped in a remote location by air, location device 100 can provide boats approaching a spill with easy navigational guidance, allowing recovery boats to locate the spill and other boats to avoid inadvertently sailing into the midst of the spill.
Figure 5 shows more details of the basics of a preferred embodiment of one of the sacks 10. The outer material of sack 10 is formed from two layers 200, 210 sewn together. The copolymer-based material described below is placed inside sack 10 between those two layers. The layers 200, 210 can be formed of polypropylene, plastic, string or cord such as used in ordinary fishing nets, nylon, or another suitable material. In one suitable embodiment, a woven mesh formed of polypropylene was used. That material floats on water and is a strong material that is highly resistent to tearing, so if a small tear or rip opens, the material will resist its extension.
It is necessary, however, that the sack material have enough porosity to allow passage of the spilled oil to the absorbent material contained therein. Material having gaps of three eighths of an inch has been found most suitable, particularly for use on crude oil.
The necessary porosity of the sacks will depend, however, on the weight of the oil being collected. For example, a tight mesh may work on diesel or gasoline spills but not on heavier crude oil. In one test, a fabric measured as having air permeability of 150 cubic feet per minute at a half inch of water was found suitable for absorbing diesel fuel but not crude oil.
The material of the sack, however, must be sufficiently non-porous to contain the encapsulating copolymer matter. If the copolymer bodies specified below are used, even sack material having high porosity will be able to contain the absorbent material without leakage. Thus, larger bodies have the additional advantage of promoting the desirable goal of using high-porosity sack material, which permits better passage of oil.
Forming the outer material of sack 10 from two layers 200, 210 sewn together is particularly advantageous in helping sack 10 lay flat on the water, while also reducing the chance that the sack will fold over onto itself, which is undesirable because it limits the extent of sack 10. The flat configuration further assists in distributing the weight of the sack across its entire lateral extent, which helps in preventing bursting from concentrations of oil-filled copolymer at any particular point. The use of dual layers also promotes the wave action of the water helping to spread out the sack, as opposed to ordinary designs, in which wave action causes problems. Thus, use of the inventive system permits improved collection in actual conditions encountered in real oil spills. Outside of layers 200, 210 are two webs 220, 225 formed of 1.5 inch wide polyester webbing. Material with a yarn count of 1,300 per inch and a breaking point of 4,000 pounds has been found more than sufficient for the loads encountered. For smaller sized sacks (three foot diameter or smaller), polypropylene webbing with a
5 breaking point of 1,200 pounds can be used. Webs 220, 225 assist in preventing or limiting the extent of rips or tears in layers 200, 210.
Webbing rings 240, 250 are placed around the perimeter of sack 10 outside of webs 220, 225. Nylon webbing about 4 cm. wide with a warp yarn count of 1,680 per inch and breaking point of 6,000 pounds has been found suitable. Webbing rings
10 240, 250 hold the elements shown in Figure 5 together while creating a stiffer edge of sack 10, which (as discussed above) helps allow sack 10 to lie flat in the water without folding over onto itself, even when dropped from the air from any original configuration. Webbing rings 240, 250 are narrow, to increase the encounter rate of the copolymer in still-water conditions. For smaller sacks, two-inch polypropylene
15 webbing with a breaking point of 2,400 pounds can be used for webbing rings 240, 250.
If desired, during recovery, webbing rings 240, 250 can be hooked to pick up sacks 10.
The members of web 220 are sewn so as to leave an opening for the neck of
20 flange 230, which can be made of hard plastic dip-molded material such as PVC. The base of flange 230 is attached between web 220 and layer 200, such as by sewing directly through the material of the plastic. Flange 230 is used as a port through which the copolymer material can be inserted into sack 10. The erect shape of the flange helps during retrieval.
25 A closer view of flange 230 is shown in Figure 6. Flange 230 has a neck 232 and a base 234, through which the sewing can be done. Cap 236 mates with neck 232, either with bolts and nuts 238, as shown, or through internal screw threads, not shown, or a combination of both. Eye 80 is formed, in the depicted embodiment, integrally with cap 236.
30 Shown in Figure 2 are optional floats 110, which can also be attached near the ends of the members of webs 220, 225 of Figure 5 to add additional buoyancy. Internal dividers (not shown) can optionally be used to further assist in preventing accumulation of copolymer material at certain spots. Neon colors can be used on the webbing or rings to facilitate location of sacks 10 during retrieval.
Webbing rings 240, 250 can also be formed of a single piece of material 245 that is folded over the edge of the perimeter of the assembly and stitched, forming a flat "U" shape in cross-section, as shown in Figure 7.
Double and triple stitching, or zigzag stitching, techniques are preferably used to prevent seam rupture or load failures. The connector rings such as snap hooks 260 shown in Figure 7 can be added to webbing rings 240, 250 near the ends of the members of webs 220, 225 and at the perimeter of webs 220, 225, to permit attachment of multiple sacks 10 together. When so attached, sacks 10 can be used as a boom substitute. To supplement the connector rings, ropes or cables can be added to assist in making deployment and retrieval adjustments without undue stress on the sacks 10. Although Figure 5 shows a circular-shaped sack 10, other configurations, such as square or rectangular, are also possible. Rectangular sacks are well suited for boom usage. When so used, the boom in accordance with the invention acts as a blanket, having a sizeable width to cover a large surface area. In this form, on the largest spills, the connected sacks can form a boom extending up to half a mile or so in length and holding up to 50,000 pounds of sorbent material. A boom of this sort is particularly useful to deploy in contact with the leading edge of the spill. In addition, double-width or wider booms can be configured easily by hooking additional rectangles together in multiple rows. Natural wave action works with such booms to prevent escape of oil, by spreading the oil across the width of the boom. By contrast, wave action hampers the effectiveness of prior art booms, including most with a "skirt" arrangement.
Also, booms of this sort can be deployed near shorelines, to prevent oil from reaching land, or directly on the shoreline at water's edge, to filter oil moving on shore or as oil returns to the water. In a preferred embodiment, the members of webs 220, 225 are attached to the woven mesh of layers 200, 210. Specifically, the members are preferably oriented in the same direction as the major axes of the diamond-shaped holes formed by the mesh, which is usually perpendicular to the warp of the woven material of webs 220, 225. This preferred configuration is shown in Figure 8. When sack 10 is picked up during retrieval with eye 80, the weight of the oil-filled bodies opposing the tension on the webbing members causes mesh 200, 210 to close in between those members, as shown in the lower half of Figure 8. This facilitates the removal of sacks 10 contain- ing the oil-logged copolymer-based material while also capturing excess oil not entrapped in the copolymer, or fragmented copolymer bodies, that are inside sack 10 at the time of retrieval.
The unique construction of the sort shown in the example of Figures 5-8 allows sacks 10 to expand on the surface of the water such that the formed copoly- mer bodies spread into a thin layer, creating a pancake shape and giving the sacks 10 minimal cross-sectional height on the spill, such as three inches. The arrangement limits the tendency of a sack 10 to fold onto itself, which can reduce the effectiveness of the system. It also causes the copolymer bodies to disburse uniformly throughout the entire width of the sack 10, as the sewn layers of the sack prevent the sorbent material from forming into a pile, also improving effectiveness. Known containers tend to have bale-like or pillow-shaped appearances, which permit the sorbent material to form into a pile, creating the possibility of water-logged lower regions and upper regions that are out of the water. As a result, much of the sorbent material is positioned either above or below the oil slick in other known arrangements. Also, when the material becomes concentrated in a pile, the container can sink and interior parts of the material can be hidden, preventing them from encountering the oil.
The construction produces the flat profile in part for the following reasons: Webbing rings 240, 250 help flatten the profile of sack 10 by providing a stiff perimeter member. Also, in the circular arrangement, each segment of rings 240, 250 form a kind of an arch, creating tension that resists any tendency of webs 220, 225 to pull the perimeter radially inward.
The flat profile of sacks 10 therefore spreads the oil-absorbent copolymer material into an optimal position for encountering the oil; that is, in a flat layer on the surface of the water. The encounter rate of the sorbent material with the oil is vastly improved with the arrangement shown, as opposed to known containers.
The arrangement of the sacks 10 combines with the natural buoyancy of the copolymer bodies to allow sacks 10 to remain afloat on the surface of the water for long periods of time, such as weeks or months or more. In one test, sacks remained afloat and effective for 16 weeks. Even over such extended time periods, the sacks 10 will hold the material in a flat sheet fashion, whether or not the material has sorbed oil.
A modified sack 10 is shown in Figure 9. The Figure 9 version is particularly useful in waterway applications. The overwhelming majority of aqueous spills (such as 95%) occur in waterways other than open ocean, including harbors, rivers, and lakes. Although many waterway spills are much smaller than open-sea spills, the waterway spills are very frequent and collectively environmentally significant.
The configuration shown in Figure 9 is particularly useful with smaller-sized sacks, such as sacks with diameters of about two-thirds of a meter, which might have a carrying weight of about 20 kg. of oil-soaked copolymer bodies.
Like the sack of Figure 5, the sack of Figure 9 includes two mesh layers 200,
210 (only 200 is clearly shown in Figure 9) and a stiffening ring 245. Instead of heavy nylon rings 240, 250 (see Figure 5), the sack of Figure 9 uses a ring 245 made of a single piece of material (as in ring 245 of Figure 7), formed from a mesh, such as a tape made of 14x12 count per inch mesh vinyl-encapsulated polyester.
In place of webs 220, 225 consisting of diametric straps (see Figure 5), sack 10 of Figure 9 includes ropes 222, 224 positioned across non-diametric chords. Ropes 222 cross sack 10 on top of layer 200, while ropes 224 cross sack 10 in an opposing direction below layer 210. The ends of ropes 222, 224 are attached to ring 245.
In sack 10 of Figure 9, ring 80 and fill tube 230 (see Figure 6) have been replaced by a less expensive cloth collar 250, such as made of a 200-Denier nylon duck fabric. One end of collar 250 is sewn to the top mesh layer 200, while the other end is folded over itself and sewn, forming a passageway through which a draw- string 255 passes.
Cloth collar 250 can also be used to replace ring 80 and fill tube 230 in the embodiment of sack 10 shown in Figures 5 and 6. If it is desired to have a pick-up ring, such as ring 80 in that embodiment, a metal ring (not shown) can be affixed to the point where the radial members of web 220 meet at the center of mesh layer 200, and cloth collar 250 can be located at any other convenient place in mesh layer 200. Alternatively, the radial members of web 220 can be attached to the sack 10 except at the very center of layer 200. The central ends of those radial members can be gathered together and attached to a metal ring, and cloth collar 250 can be affixed to the center of mesh layer 200, just below the ring. COPOLYMER BODIES
Figure 10 shows an example of a suitably formed copolymer body 300, for use inside sack 10.
The principal ingredient of bodies 300 is a copolymeric material that is known to sorb oil but not water. Preferably, the material is compliant or flexible. A possible alternative to copolymers is natural or synthetic rubber, such as polyisoprene.
Particularly suitable types of copolymers fall within the class of thermoplastic elastomers, such as styrene-butadiene-styrene ("SBS"), which is a styrenic block copolymer. Styrenic block copolymers were developed for applications that require impact resistance, and this is still their primary use. SBS is highly sorbent, non-toxic, and remains coherent after it is oil saturated. An alternative styrenic block copolymer is styrene-isoprene-styrene ("SIS"). In a preferred embodiment formed in accordance with the preferred process described below, SBS material formed into granules is mixed with granulated binder material. In that embodiment, granular porous SBS with about 30% styrene has been found suitable, when sifted to retain particles in the range of sizes between 4 and 20 mesh. Preferably, the SBS product is manufactured without talc, contrary to the standard manufacturing process, to enhance inter-granular bonding in the formed body.
The binder material is a compliant or flexible, hydrophobic, olefinic polymer material in a granular form and having a melting point lower than that of the oil- absorbent copolymer. Polyolefin thermoplastic elastomers, such as ethylene propylene ("EP") rubber or ethylene propylene diene monomer ("EPDM") have been found suitable. The binder prevents formed bodies 300 from crumbling while being handled in dry form, yet also absorbs a certain quantity of oil, although perhaps not as fast as SBS.
An optionally third component of bodies 300 is a rigid, inert, smooth, thin flake of a material that has a surface that is wettable with respect to hydrocarbons. Any such material can be used, including mica, metal, or polymers, but polymethylpentene ("PMP") is a primary example. Alternative examples include polyethylene-terephthalate ("PET"), metallized polycarbonate, and polyvinylchloride. The flakes should be relatively thin, such as less than a millimeter thick. The shapes of the flakes is not particularly important, and good results have been achieved with randomly chopped material a few millimeters across. In some embodiments, the flakes enhance the flow of oil into the center of the formed copolymer body 300, apparently by providing a channel or surface along which the oil can flow. In other embodiments, including those formed in accordance with the preferred process described below, the flakes are not essential but can optionally be added.
In the preferred embodiment, 70-90% by weight of the material of bodies 300 consists of SBS and the remainder of EPDM binder. As explained below, the SBS and EPDM granules are mixed and formed into bodies 300 in a way that results in SBS granules in an EPDM matrix. If flakes are included, they might make up about 5% of the total weight.
Because of the desire, as noted above, to allow the copolymer material to remain in a flat layer, it is desirable to create a relatively large body 300, so that the material does not pile on top of itself. However, large bodies result in a greater distance between outer surface 310 and center surface 320, which is disadvantageous because oil would require a much longer time of exposure to soak into the center. Because in real oil spills, a particular quantity of oil may encounter body 300 only sporadically, in a large body, the center material largely remains unused.
A preferred embodiment that solves this dilemma uses a generally tube shape for bodies 300. For example, a cylinder with an outer diameter from about two to five centimeters has an hole about one to two centimeters in diameter along the longitudinal axis, resulting in a body 300 that has all of its material less than about a centimeter or two from the nearest surface.
The relatively large inner hole allows water and oil to pass through and between the bodies 300 easily, thereby improving the chances of oil encountering a copolymer surface. Also, removal of material from the center of body 300 reduces the amount of material in each body, without significantly reducing the quantity of oil absorbed, which further improves the quantity of oil entrapped per unit quantity of copolymer.
Multiple holes parallel to the cylinder's axis can be used in addition to the axial hole or instead of it. For example, in one arrangement (not shown) three holes are arranged on radial planes separated by 120° angles, the holes being equidistant from the axis of the cylinder. This arrangement permits enhanced flow-through of oil even if the oil layer does not intersect the cylinder along the axis, for example if some of the bodies 300 are partly submerged. Bodies 300 should be formed with a length exceeding the outer diameter of the cylinder. This restriction is important, because it ensures that bodies 300 will float on the water with the axial hole parallel to the surface of the water, permitting better pass-through of oil. This is particularly important for bodies 300 used with the inventive sacks 10, because sacks 10 are designed to permit bodies 300 to float in a single layer, as discussed above. When afloat amidst oil, bodies 300 near the circumference of sack 10 tends to physically block oil from flowing to other bodies 300 closer to the center. The inclusion of axial holes, and their orientation parallel to the surface of the water, counteracts this tendency. In addition, in some circumstances, the preferred hole orientation permits more oil to remain inside the axial passage- way, permitting more time to complete the absorption process.
Bodies 300 can be supplemented with different-shaped bodies in sacks 10. Using such a mixture of bodies 300 is advantageous over the use of a uniform type of body, because regular-shaped bodies can become arranged in a more fitted-together fashion, reducing the quantity of interstitial space, which thereby lowers the encounter rate.
The generally cylindrical exterior 310 of bodies 300 is preferred, as it reduces the area of contact between adjacent bodies 300. The pressure from many bodies 300 in sack 10 and the softness of the constituent materials tends to meld bodies 300 together, with the consequential tendency to lower the encounter rate. A reduced contact area counters this undesired effect.
Another undesired effect is called "matting" or "gel blocking," in which the first quantity of absorbed oil combines with an outer layer of grains in body 300 to form a barrier, preventing unabsorbed oil from continuing into the part to reach inner layers of grains and be absorbed thereby. To increase the surface area of the bodies 300, consequently permitting faster oil absorption and less gel blocking, without increasing the distance from surface to center, it is desirable to have inner and outer surfaces 310 and 320 roughened somewhat. The same is true of end surfaces 350 and 360. The preferred process of formation discussed below promotes this goal. Alternatively, cutting or stamping bodies 300 from sheets of molded material has been found to roughen surfaces 310, 320, while first cutting the sheets from blocks roughens surfaces 350, 360. Also, the sheets or parts can be molded in a rough-sided dimple mold. Also to reduce gel blocking, bodies 300 preferably have numerous fissures 370 extending into bodies 300 from some or all exterior surfaces and passing between the grains of SBS. Again, the preferred formation process discussed below promotes this goal.
In one example, a body 300 measuring about 3.5 cm. across and about 7.5 cm. long, with a 1 cm. diameter axial hole, was found suitable. That body 300 has a bulk density of about 0.62 g/cc and weighed, therefore, just over 40 grams. A sack 10 of 1.8 meters diameter can carry about 15 kg. of copolymer material, which represents nearly 400 units of the exemplary bodies 300. A sack 10 of two-thirds of a meter diameter can carry about 2 kg. of copolymer material, which represents about 50 units. The weight of the sacks after bodies 300 absorb oil is about an order of magnitude greater.
The bulk density of the resulting body is controlled, also to reduce gel blocking. With the preferred bulk density, the SBS granules in bodies 300 are also less likely to clump to each other when soaked with oil, which also improves sorbency. Similarly, the SBS grain sizes identified above are selected to avoid gel blocking from either overly large chunks or agglomerated small-diameter, powdery particles.
With the preferred materials discussed above, bulk density greater than 0.75 g/cc tend to prevent the oil from entering the bodies, while bulk density smaller than 0.45 g/cc cause the bodies to fragment, either when dry or after absorbing oil. For example, copolymer bodies with a bulk density in the preferred range have enough inter-granular voids to permit oil to penetrate substantially throughout the thickness of bodies 300 without causing them to fall apart.
Bodies 300 formed in accordance with Figures 10 and 11 can alternatively be used as oil-absorbent filters, such as in a cartridge or around a pipe or shaft. In this usage, because bodies 300 are physically held in position rather than floating, the length relative to the outer diameter is not critical and may be altered as needed. Similarly, the central hole may not be necessary. In another extension of the inventive form, a structure (not shown) is formed of a number of bodies 300 arranged side-by-side, with longitudinal axes parallel to each other. To form such a structure, multiple bodies 300 can be affixed together, or the structure can be manufactured as a unitary sheet having opposing top and bottom scalloped surfaces, with the holes located between the surfaces at the thicker regions. FORMING THE COPOLYMER BODIES
One method of forming bodies 300 shown in Figure 10 is to use low-pressure compression molding in the presence of elevated temperature. For example, pressures about 8-20 psi and temperatures about 150-200° F. have been found suitable to manufacture a product originally consisting of SBS and EPDM granules with high absorbency and high retained coherency after absorbing oil. The heat melts the EPDM, without melting the SBS granules, to agglomerate the material into a coherent assembly without damaging the physical structure of the SBS, thereby degrading that material's absorbency. A mold having a number of circular cavities can be used to form a number of bodies 300 at once.
Another, preferred method of forming bodies 300 applies a modified extrusion process. SBS and EPDM granules are placed in the hopper of an extruder of conventional design, for example, a two-inch Bonnot lab extruder with a hot-water external barrel heater. The extruder heats the granular material to a temperature not exceeding 120° F., far below normal extrusion temperatures for plastic products, and preferably not exceeding 105° F.
In the barrel of the extruder, the EPDM quickly become plasticized, as a result of heat, pressure, and mechanical agitation by the screw and barrel in combination. The extruder's screw mixes the plasticized EPDM and the unmelted SBS, forming a matrix of EPDM surrounding SBS granules. Because the SBS is not melted, some air bubbles remain in the mixture. The softening process occurs quite rapidly in the extruder, permitting very short dwell times (such as less than one minute), which permits rapid manufacturing. The partially plasticized composite material is pressed through a circular die with a central rod or mandrel, to form the cylindrical structure with the axial hole shown in Figure 10. In one example, a four-inch long die was used. Upon passing through the die, the SBS granules, which have been compressed somewhat by being forced through the die, reexpand, "fluffing" the extruded material while it cools and hardens. The expansion is further assisted by air remaining in the mixture. The extruded material is cut into suitable lengths to form the final bodies 300.
When cooled and resolidified outside the extruder, the EPDM matrix 390 (see Figure 11) forms a durable but permeable structure for the SBS granules 380 and provides mechanical integrity to the resulting bodies 300. Thus, bodies 300 formed in accordance with the preferred method do not break or crack absent extreme elastic deformation, despite the presence of fissures 370. Also, fragments of such bodies do not detach easily from bodies 300 in the form of flakes, crumbles, or dust, even with rough handling.
The fluffing effect (typically undesired in extrusion processes) is beneficial because it forms inter-granular fissures 370 in the EPDM matrix, throughout the structure. However, the fissuring is not so great as to cause loss of structural integrity. As noted above, fissures are preferred to facilitate rapid passage of oil into bodies 300 and to reduce the incidence of gel blocking, permitting continued absorption.
In bodies 300 formed according to the preferred method, any reduction in absorbency caused by the binder (compared to a body composed exclusively of higher-absorbent material, such as SBS) is more than offset by the increase rates of contact between oil and SBS caused by the fissuring and rough external texture and the reduced tendency to premature gelation. SACK COLLECTION Figure 1 also shows techniques of recovering sacks 10 after the copolymer bodies have been soaked with oil. Because the sacks float and stabilize the oil in self- contained and self-sustaining sacks, special equipment is not needed to collect the oil. For example, Figure 1 shows an ordinary fishing trawler 20 using its net to scoop up quantities of oil-logged sacks 10. Although it is not required, the use of the inventive system does not preclude the utilization of more sophisticated collection boats, such as scoop boats or high-speed oil response vessels, such as known in the art. For example, if a large spill is contained in the vicinity of a base for such equipment, it may be advantageous to use such boats to collect sacks 10 at the same time as floating oil not yet held by sacks 10 is skimmed from the surface. It is also possible to fish sacks 10 out of the water using a hook.
Figure 12 shows a collection method in which a specialized high-speed boat 400, such as a modified version of boats operated presently by Team One of Seattle, Washington, approaches the spill on a rapid-response basis. Specially fitted outrigger paravanes 410 are deployed upon arrival, and sacks 10 are collected in wings 412 of paravanes 410 as boat 400 slowly advances. In rough-water conditions, sacks 10 are dropped onto the spill or in advance of the spill by air. Because sacks 10 retain the oil indefinitely, boat 400 can wait until the rough-water conditions dissipate to arrive on the scene and complete containment and recovery procedures, without risking dissipation of the spill by winds and seas, thus minimizing environmental damage without risk to recovery boats and crews.
A vacuum airstream conveyance and transfer (VACT) system can be used to collect sacks 10 using airstream induction (as opposed to pure vacuum pressure). An example of such a system already on the market and known to the ordinarily skilled artisan is called the Linductor system, available from Linductor, Inc. of Seattle, Washington. This Linductor device was developed for transferring bulk solids or volumes of liquids, including removing spilled oil from the surface of water. It has been found that a VACT system that is a variant of the Linductor can be used to gather sacks 10 containing spilled oil more expediently in certain sea conditions. The Linductor system as marketed and if mounted on an appropriate vessel, such as a barge, is capable of picking up sacks up to three feet in diameter, but modifications can be made to allow pickup of larger sacks and conveyance on a smaller vessel.
Such a modified VACT system 420 is depicted in Figure 12, including receiving tank 422, widened intake pipe 424, turret assembly 426, power and induction fan unit 426, and outlet pipe 428. Turret assembly 426 rotates to permit intake pipe 424 to be moved to any desired location next to the bow of boat 400. It is possible to configure a VACT system to use two intake pipes, one on either side of the bow (not shown). Outlet pipe 428 is optional, because sacks 10 can be retained in receiving tank or bladder 422, or an interior connection (not shown) at the bottom of tank 422 can allow sacks 10 to drop into a hold of boat 400, or an outlet ramp (not shown) on a side of tank 422 can allow sacks 10 to exit tank 422 and accumulate in an adjacent pile. In the configuration depicted in Figure 12, however, sacks 10 are discharged through outlet pipe 428 and hurled through the air into a lightweight sled 430 towed along the side of boat 400. A powered barge can be used instead of a towed sled.
Figure 13 shows laborers tying retrieved sacks 10 to lines or cables 440 pulled manually off of spools 450, to form towed strings of sacks that can be collected later. Those units of sacks 10 that miss intake pipe 424 are carried slowly up ramps 414 of paravanes 410 and attached manually to lines or cables 440, such as with snap hooks, after which they are slid back down to the water on a slide 415, such as made of stainless steel. Figure 15 shows an alternative embodiment in which the VACT system is deleted, and manual collection and arrangement into strings is done exclusively.
Figure 14 shows details of a hydraulically powered paravane 410, as viewed from the far side of boat 400 in Figures 12 and 13. Ramp 414 can be tilted from an initially horizontal travel position to drop scoop 416 below waterline 418. Thereaf- ter, the hydraulic system can spread wings 412 from the travel position to the 45- degree angle shown in Figures 12, 13, and 15. Ramp 414 includes a powered conveyor, with a surface that can be made of a lightweight, wide mesh fabric, such as made of a Velcro material, that can grip and feed sacks 10 from scoop 416 up ramp 414. Although paravanes 410 are depicted as being supported by boat 400, they can alternatively be mounted on one or a chain of sleds, similar to sled 430, towed along the side of or behind powered boat 400.
In the collection methods depicted in Figures 13 and 15, after a quantity of sacks 10 are tied into a string, the line 440 can be cut and the chain of sacks released to allow it to float in the water. Then, a workboat can assemble a number of strings together and attach an anchor or buoy 480 to the group of strings, preferably by attaching it to the middle of each string, forming a streamer-like arrangement 460, shown in Figure 16. Anchor or buoy 480 can support a radio transmitter-like element or radar-sensitive patch 100 in Figure 4, for ease of later location, instead of that element being on each sack 10. Streamers 460 can remain afloat until a collection boat or towed sled 470 attaches a line to anchor or buoy 480 and pulls the assembly aboard. Once loaded, sled 470 with its chains of sacks 10 can be towed to shore with barges. DISPOSAL
The inventive configuration of sacks 10 permits a disposal method that has been considered desirable but which is difficult if not impossible to achieve in actual practice, namely in-situ burning on the water. In-situ burning prevents the need for the boat collection techniques described above.
Sacks 10, either alone or in assembled chains or "streamers," can be easily ignited on the water, which creates a wicking or torch effect, thereby burning not only the sacks but also unabsorbed oil surrounding the sacks. Previous attempts to burn oil spills on water have suffered from numerous difficulties, particularly the problems in ignition caused by rough water, thin oil slicks, or high emulsification. Various published articles have described prior attempts at in-situ burning and the problems faced by such attempts.
If sacks 10 are transported to dry land, they can be disposed of as waste with the oil still intact, but this is costly and environmentally not preferred. Alternatively, sacks 10 can be incinerated on land, and the energy content of the oil and copolymer can be recovered and used as power. To allow for such a disposal technique, it is preferred to use materials for the particles, for the outer material of sack 10, and for all other components of the sacks 10 that can be burned, to reduce the quantity of solid waste or air-borne pollution. The preferred materials specified in this descrip- tion are so suited. Another recycling use for oil-logged copolymers is in road building.
Also, it is possible to remove the oil from the copolymer using various processes, to allow recycling of the oil with no remaining hazardous material (or possibly reuse of the copolymer product in sacks 10). For example, a fully automated process for extraction of refined oil from the copolymer bodies has been developed within a reactor unit originally formed to break down scrap tire chips into the resalable commodities of scrap steel, carbon black, and refined oil. The reactor heats the oil-soaked copolymer bodies in a sealed environment to break down the molecular structure of the copolymers. Such a reactor is a modification of a scrap-tire reactor commercially available from Tire Recycling Technologies Corporation of Albuquerque, New Mexico, called the TRTM-60 tire decomposition machine.
Certain modifications to the TRTM-60 can allow it to work on oil-soaked copolymer bodies, at a reasonable cost: (1) because of the salt content, a higher-grade stainless steel is preferred; (2) the discharge system is changed to eliminate the magnetic separator for carbon black and steel scrap, which is produced from scrap tire but not from copolymer bodies; (3) a second, liquid seal is used at the discharge end; (4) the air condenser is replaced with a second water condenser; and (5) two screw conveyor stages are used instead of five.
As thus modified, the reactor works as follows:
The copolymer bodies from sacks 10 are delivered to an inlet hopper of a sealed screw conveyor. Commercially available as a package with the TRTM-60 is information identifying certain additives that permit better breakdown of the scrap tire, and these additives are useful with the copolymer bodies as well.
Two enclosed, horizontally oriented, stainless-steel screw conveyors stages, powered by individual hydraulic drives and a central hydraulic pumping system, move the material including the copolymer bodies through the reactor while chemically breaking down the bodies while they are conveyed through the entire length. The conveyors have top inlets and discharge chutes at each end. The inlet connection to the reactor and the outlet side of the reactor are sealed, for example by liquid seals, to prevent oxygen from entering the process.
The reactor heats the material in a vacuum at 200-300° C. Each reactor conveyor has a perforated top to vent gases produced during the process. A vertical stainless steel plenum welded to each conveyor provides a means to collect these process gases. The gases are "pulled" off the top of the plenum by a turbine pump. The gas is then filtered to remove residue carried over from the reactor unit. The gases, consisting mostly of vaporized fuel oils, are then pumped through two separate condensing stages that are a water-cooled heat exchanger. Cooling is provided via an air-cooled process chiller with a circulating pumping system. Non- condensable gases are collected and recycled as the fuel medium for the burners, which can be used to maintain the temperature in the reactor unit or to power an electric generator, or can be discharged to a flare and burned.
Oil-soaked copolymer material processed in this fashion can yield much of the output as liquid hydrocarbons. Indeed, some of the resulting liquid consists of styrene, which if separated by distillation, is five to ten times more valuable than crude oil, and can improve the recycling economics. An additional portion of the total output consists of gaseous hydrocarbons, which can be further processed to a hydrocarbon mixture that can be used as clean-burning fuel for the recycling reactor. Yet another portion, generated from the ethylene components, consists of a waxy solid residue that has commercial application as a feed stock for chemical refineries. Optimally, virtually no char will remain. Although the invention has been described with reference to specific embodi¬ ments, many modifications and variations of such embodiments can be made without departing from the innovative concepts disclosed. Thus, it is understood by those skilled in the art that alternative forms and embodiments of the invention can be devised without departing from its spirit and scope.

Claims

CLAIMS We claim:
I. A composition of matter comprising styrene-butadiene-styrene and ethylene propylene diene monomer.
2. The composition of claim 1 substantially consisting of styrene-butadien e-styrene and ethylene propylene diene monomer.
3. The composition of claim 2 consisting of styrene-butadiene-styrene and ethylene propylene diene monomer.
4. The composition of claim 3 wherein the ethylene propylene diene monomer is in the range of about 10-30% by weight.
5. The composition of claim 1 wherein the styrene-butadiene-styrene is about 30% styrene.
6. A device for absorbing oil comprising a solid, compliant body comprised of styrene-butadiene-styrene and ethylene propylene diene monomer.
7. The device of claim 6 wherein the body substantially consisting of styrene-butadiene-styrene and ethylene propylene diene monomer.
8. The device of claim 7 wherein the body consists of styrene-butadiene- styrene and ethylene propylene diene monomer.
9. The device of claim 8 wherein the ethylene propylene diene monomer is in the range of about 10-30% by weight.
10. The device of claim 6 wherein the styrene-butadiene-styrene is about 30% styrene.
II. The device of claim 6 further comprising a multitude of inert flakes wettable with respect to oil.
12. The device of claim 6 wherein the device is between about two and about five centimeters across.
13. The device of claim 6 wherein the body is formed generally cylindrical-
14. The device of claim 13 wherein the length along the major axis exceeds the diameter.
15. The device of claim 14 wherein the outer diameter is between about two and about five centimeters.
16. The device of claim 14 wherein the body is formed around a hole along the major axis of the cylinder.
17. The device of claim 16 wherein the diameter of the hole and the diameter of the cylinder differ by less than two centimeters.
18. The device of claim 16 wherein the outer diameter is between about two and about five centimeters and the diameter of the hole is between about one and two centimeters.
19. The device of claim 14 wherein the body is formed around a plurality of holes parallel to the major axis of the cylinder.
20. The device of claim 16 wherein the external surfaces of the body contain a multitude of fissures.
21. The device of claim 20 consisting of styrene-butadiene-styrene having about 30% styrene content and ethylene propylene diene monomer in the range of about 10-30% by weight.
22. The device of claim 6 wherein the body is formed from a multitude of granules of styrene-butadiene-styrene and a multitude of granules of ethylene propylene diene monomer bound together.
23. The device of claim 22 wherein the body consists of styrene-butadiene- styrene and ethylene propylene diene monomer.
24. The device of claim 23 wherein the granules of ethylene propylene diene monomer are in the range of about 10-30% by weight and the granules of styrene-butadiene-styrene are in the range of about 4-20 mesh and lack talc.
25. A process of forming a solid, compliant body for absorbing oil comprising: (a) mixing styrene-butadiene-styrene and ethylene propylene diene monomer;
(b) heating the mixture to a temperature below the melting point of the styrene-butadiene-styrene material, wherein the ethylene propylene diene monomer material of the mixture becomes plasticized; (c) extruding the resulting mixture through a die; and
(d) allowing the extruded mixture to cool and expand.
26. The process of claim 25 wherein part (a) comprises mixing only styrene-butadiene-styrene and ethylene propylene diene monomer.
27. The process of claim 26 wherein part (a) comprises mixing granules of styrene-butadiene-styrene and granules of ethylene propylene diene monomer.
28. The process of claim 25 wherein part (a) comprises mixing granules of styrene-butadiene-styrene with a styrene content of about 30% and without talc.
29. The process of claim 25 wherein part (a) comprises mixing granules of styrene-butadiene-styrene that are sifted to retain particles in the range of about 4-20 mesh with granules of ethylene propylene diene monomer.
30. The process of claim 25 wherein part (a) comprises mechanically agitating the materials in the barrel of an extruder.
31. The process of claim 25 wherein part (b) comprises heating the mixture to a temperature between about 105┬░ F. and 120┬░ F.
32. The process of claim 25 wherein part (c) comprises using a circular die and a central mandrel to form the extruded material into a tubular shape.
33. The process of claim 32 further comprising cutting the extruded mixture into lengths that are longer than the diameter of the circular die.
34. The process of claim 25 wherein air is allowed to remain in the extruded mixture and whereby the expansion of part (d) causes fissures to form in the surfaces of the resulting body.
35. A device for ameliorating oil spills comprising: (a) a sack comprised of two sheets of a mesh material that is porous to both water and oil, which sheets are affixed together and stiffened around their perimeter;
(b) wherein each sack forms a compartment containing a multitude of tubular bodies comprised of an oil-entrapping polymer; (c) wherein each of the multitude of polymer bodies is formed to surround an axial hole of the polymer body; and
(d) wherein each of the multitude of polymer bodies has its longest dimension parallel to the axial hole.
36. The device of claim 35 further comprising an eye and a port coupled to the sack.
37. The device of claim 35 further comprising a plurality of ropes coupled to the sack, each positioned across non-diametric chords of the sheets.
38. The device of claim 35 further comprising a flexible ring affixed around the perimeter of the sheets.
39. The device of claim 38 wherein the ring is folded over and affixed to the outside of both sheets, thereby forming the ring into a double layer.
40. The device of claim 39 wherein the sheets are round and further comprising a pair of ropes on both sides of the sack, each rope being coupled to the ring at each end and positioned across non-diametric chords of the adjacent sheet, wherein the pair of ropes on one side of the sack is not parallel to the pair of ropes on the other side of the sack.
41. The device of claim 35 further comprising a multitude of additional bodies, not tubular, that are also comprised of an oil-entrapping polymer and also contained within the sack.
42. The device of claim 35 wherein the two sheets are rectangular, and further comprising attachment devices on each edge at the perimeter of the sack.
43. The device of claim 35 wherein each of the multitude of polymer bodies consist of styrene-butadiene-styrene and ethylene propylene diene monomer.
44. The device of claim 43 wherein the ethylene propylene diene monomer is in the range of about 10-30% by weight and wherein the styrene-butadiene-styrene is about 30% styrene.
45. The device of claim 35 wherein each of the multitude of polymer bodies is between about two and about five centimeters across.
46. The device of claim 35 wherein each of the multitude of polymer bodies is formed generally cylindrically with a length along the major axis that exceeds the diameter.
47. The device of claim 46 wherein, for each of the multitude of polymer bodies, the diameter of the hole and the diameter of the cylinder differ by less than a centimeter.
48. The device of claim 47 wherein the external surfaces of each of the multitude of polymer bodies contain a multitude of fissures.
49. The device of claim 35 wherein each of the multitude of polymer bodies is formed from a multitude of granules of styrene-butadiene-styrene and a multitude of granules of ethylene propylene diene monomer bound together.
50. The device of claim 49 wherein each of the multitude of polymer bodies is formed from a multitude of granules of styrene-butadiene-styrene in the range of about 4-20 mesh lacking talc.
51. The device of claim 49 wherein each of the multitude of polymer bodies (a) consist of granules of styrene-butadiene-styrene and granules of ethylene propylene diene monomer, (b) are formed generally cylindrically with a length along the major axis that exceeds the diameter and a diameter between two and five centimeters, (c) surround an axial hole that has a width no more than two centimeters less than the diameter, and (d) having external surfaces that contain a multitude of fissures.
52. A process for recovering oil floating on water comprising:
(a) deploying onto oily water a plurality of sacks, each comprised of two sheets of a mesh material that is porous to both water and oil, which sheets are affixed together and stiffened around their perimeter; (b) wherein each sack forms a compartment containing a multitude of tubular bodies comprised of an oil-entrapping polymer; and
(c) maintaining the sacks afloat amidst the oil for a time sufficient to allow the bodies in the sacks to entrap a quantity of the oil;
(d) wherein each of the multitude of polymer bodies is formed to surround an axial hole of the polymer body; and
(e) wherein each of the multitude of polymer bodies has its longest dimension parallel to the axial hole.
53. The process of claim 52 wherein the act of deploying the sacks comprises dropping at least some of the plurality of sacks onto the oily water by air.
54. The process of claim 52 further comprising deploying the sacks inside a barrier enclosing an oil spill.
55. The process of claim 52 wherein the act of deploying the sacks comprises dropping at least some of the plurality of sacks onto the oily water from a vessel that is spilling oil onto the water.
56. The process of claim 52 further comprising retrieving the sacks from the surface of the water at least a day after the act of deploying the sacks.
57. The process of claim 52 further comprising retrieving the sacks from the surface of the water by netting the sacks with a net coupled to a boat.
58. The process of claim 52 further comprising retrieving the sacks from the surface of the water using an airstream induction system supported by a boat.
59. The process of claim 58 wherein using an airstream induction system includes hurling the sacks into a floating vessel towed by the boat.
60. The process of claim 52 further comprising retrieving the sacks from the surface of the water by moving through the water a boat that supports a pair of wings positioned at a forward angle from the sides of the boat, thereby funnelling the sacks next to the sides of the boat.
61. The process of claim 60 wherein the act of retrieving the sacks further comprises power-conveying the sacks, after they are funnelled next to the sides of the boat, up a ramp.
62. The process of claim 61 further comprising connecting a quantity of the sacks together with a line and returning the resulting string of sacks to the surface of the water.
63. The process of claim 62 further comprising attaching together a buoy and the string of sacks.
64. The process of claim 62 further comprising forming a plurality of strings of sacks and attaching together the strings and a buoy, and further comprising later collecting the plurality of strings of sacks as a unit.
65. The process of claim 52 further comprising connecting a quantity of the sacks together and burning the connected sacks, together with the oil entrapped by the polymer of the bodies, while the connected sacks remain afloat amidst the water.
66. The process of claim 52 further comprising burning the sacks together with the oil entrapped by the polymer of the bodies while the sacks remain afloat amidst the oily water.
67. The process of claim 52 further comprising retrieving the sacks from the surface of the water and later incinerating the sacks together with the oil entrapped by the polymer of the bodies and the bodies themselves.
68. The process of claim 52 further comprising retrieving the sacks from the surface of the water, and later heating the polymer bodies in a reactor to recover hydrocarbons.
69. The process of claim 52 wherein the act of deploying the sacks comprises using sacks having an eye coupled thereto, and further comprising retrieving the sacks by hooking the eye.
70. The process of claim 62 wherein the act of deploying the sacks compris- es using sacks having an eye coupled thereto, and wherein the act of connecting the sacks together with a line comprises connecting the line to the eye of the sack.
71. The process of claim 52 wherein the act of deploying the sacks comprises using sacks having a port coupled thereto.
72. The process of claim 52 wherein the act of deploying the sacks compris- es using sacks having a plurality of ropes coupled to the sack, each positioned across non-diametric chords of the sheets.
73. The process of claim 72 wherein the act of deploying the sacks comprises using sacks having a collar and a pick-up ring.
74. The process of claim 52 wherein the act of deploying the sacks compris- es using sacks having a flexible ring affixed around the perimeter of the sheets of the sacks.
75. The process of claim 74 wherein the act of deploying the sacks comprises using sacks having the ring folded over and affixed to the outside of both sheets, thereby forming the ring into a double layer.
76. The process of claim 52 wherein the act of deploying the sacks comprises using sacks having two round sheets.
77. The process of claim 52 wherein the act of deploying the sacks comprises using sacks having two rectangular sheets, and further including attachment devices on each edge at the perimeter of the sack.
78. The process of claim 52 wherein the act of deploying the sacks comprises using sacks formed of sheets of a woven polypropylene mesh.
79. The process of claim 52 wherein the act of deploying the sacks comprises using sacks having a plurality of buoyant elements coupled thereto.
80. The process of claim 52 wherein the act of deploying the sacks compris- es using sacks containing polymer bodies having a multitude of plastic fragments scattered throughout.
81. The process of claim 80 wherein the act of deploying the sacks comprises using sacks containing polymer bodies, wherein the multitude of plastic fragments are inert flakes wettable with respect to hydrocarbons.
82. The process of claim 80 wherein the act of deploying the sacks compris- es using sacks containing polymer bodies comprising SBS and the plastic fragments.
83. The process of claim 52 wherein the act of deploying the sacks comprises using sacks containing polymer bodies comprised of EPDM and SBS.
84. The process of claim 52 wherein the act of deploying the sacks comprises using sacks containing polymer bodies consisting of EPDM and SBS.
85. The process of claim 84 wherein the act of deploying the sacks comprises using sacks containing polymer bodies having formed from a multitude of granules of styrene-butadiene-styrene and a multitude of granules of ethylene propylene diene monomer bound together.
86. The process of claim 84 wherein the act of deploying the sacks compris- es using sacks containing polymer bodies having a diameter between two and five centimeters, an axial hole that has a width no more than two centimeters less than the diameter.
87. The process of claim 52 wherein the act of deploying the sacks comprises using sacks containing polymer bodies having external surfaces that contain a multitude of fissures.
88. The process of claim 87 wherein the act of deploying the sacks comprises using sacks containing polymer bodies substantially consisting of SBS and EPDM.
89. The process of claim 52 wherein the act of deploying the sacks comprises using sacks containing polymer bodies formed of a multitude of granules between 4 and 40 mesh of SBS agglomerated together.
90. The process of claim 52 wherein the act of deploying the sacks comprises using sacks containing polymer bodies having a density between 0.45 and 0.75 g/cc.
91. The process of claim 52 wherein the act of deploying the sacks compris- es using sacks further containing a multitude of additional bodies not having axial holes, which are also comprised of an oil-entrapping polymer.
92. The process of claim 91 wherein the multitude of polymer bodies nad the multitude of additional bodies both have surfaces containing a multitude of fissures.
93. A process for recovering oil floating on water comprising: (a) forming a plurality of sacks of two sheets of a mesh material that is porous to both water and oil, which sheets are affixed together and stiffened around their perimeter to form a single compartment;
(b) partially filling each of the sacks with a multitude of tubular bodies comprised of an oil-entrapping polymer, each of which bodies surrounds an axial hole of the polymer body and has its longest dimension parallel to the axial hole;
(c) deploying the sacks onto oily water;
(d) maintaining the sacks afloat amidst the oil for a time sufficient to allow the bodies in the sacks to entrap a quantity of the oil; and (e) retrieving the sacks from the surface of the water at least a day later.
94. The process of claim 93 further comprising moving a boat through the water, which boat supports a pair of wings positioned at a forward angle from sides of the boat, thereby funnelling the sacks next to the sides of the boat.
95. The process of claim 94 further comprising using an airstream induction system supported by the boat to retrieve at least some of the sacks next to at least one side of the boat.
96. The process of claim 95 further comprising retrieving others of the sacks next to at least one side of the boat manually.
97. The process of claim 96 wherein the act of manual retrieval comprises:
(a) conveying the sacks not retrieved by the airstream induction system, after they are funnelled next to the sides of the boat, up a ramp;
(b) connecting a quantity of the sacks together with a line; and
(c) returning the resulting string of sacks to the surface of the water.
98. The process of claim 93 wherein retrieving the sacks comprises conveying sacks up a ramp next to a side of the boat.
99. The process of claim 98 further comprising thereafter connecting a quantity of the sacks together and returning the resulting string of sacks to the surface of the water.
100. The process of claim 99 further comprising burning the strings of sacks on the surface of the water.
101. The process of claim 99 further comprising later retrieving the strings of sacks from the surface of the water.
102. The process of claim 101 further comprising later incinerating the sacks together with the oil entrapped by the polymer of the bodies and the bodies them- selves.
103. The process of claim 101 further comprising later heating the polymer bodies in a reactor to recover hydrocarbons.
104. The process of claim 93 further comprising later incinerating the retrieved sacks together with the oil entrapped by the polymer of the bodies and the bodies themselves.
105. The process of claim 93 further comprising later heating the polymer bodies in a reactor to recover hydrocarbons.
106. The process of claim 93 wherein the act of forming a plurality of sacks comprises folding over both sheets a flexible ring extending around the perimeter of the sheets and affixing the ring to the outside of the sheets, thereby forming the ring into a double layer.
107. The process of claim 106 wherein the act of forming a plurality of sacks comprises forming each sack of two round sheets comprised of a woven polypropylene mesh.
108. The process of claim 93 wherein the act of partially filling each of the sacks comprises placing in each of the sacks a multitude of polymer bodies, each body comprised of SBS and a multitude of inert plastic flakes scattered throughout the body that are wettable with respect to hydrocarbons.
109. The process of claim 93 wherein the act of forming a plurality of sacks further comprises attaching a port to each of the sacks, and wherein partially filling each of the sacks comprises placing the multitude of polymer bodies in the sacks through the ports.
110. The process of claim 93 wherein the act of partially filling each of the sacks comprises placing in each of the sacks a multitude of polymer bodies comprised of EPDM and SBS.
111. The process of claim 110 wherein the act of partially filling each of the sacks comprises placing in each of the sacks a multitude of polymer bodies substantially consisting of SBS and EPDM.
112. The process of claim 111 wherein the act of partially filling each of the sacks comprises placing in each of the sacks a multitude of polymer bodies having external surfaces that contain a multitude of fissures.
113. The process of claim 112 further comprising first forming polymer bodies by low-temperature extrusion, and wherein the act of partially filling the sacks comprises placing a multitude of the resulting, extruded polymer bodies in each of the sacks.
114. A process for recovering oil floating on water comprising: (a) forming a plurality of sacks of two sheets of a mesh material that is porous to both water and oil, which sheets are affixed together and stiffened around their perimeter;
(b) placing in each of the sacks a multitude of tubular bodies comprised of an oil-entrapping polymer, each of which bodies surrounds an axial hole of the polymer body and has its longest dimension parallel to the axial hole;
(c) deploying the sacks onto oily water;
(d) maintaining the sacks afloat amidst the oil for a time sufficient to allow the bodies in the sacks to entrap a quantity of the oil; and (e) later burning the floating sacks.
115. The process of claim 114 further comprising, before the act in part (e), securing together a plurality of the sacks.
116. The process of claim 115 wherein the sacks are secured together after entrapping a quantity of oil.
117. The process of claim 116 wherein the sacks are secured together by:
(a) conveying the sacks up a ramp;
(b) connecting a quantity of the sacks together with a line; and
(c) returning the resulting string of sacks to the surface of the water.
118. The process of claim 117 further comprising, before the conveying act, moving through the water a boat that supports a pair of wings positioned at a forward angle from the sides of the boat, thereby funnelling the sacks next to the sides of the boat.
119. The process of claim 117 further comprising forming a plurality of strings of sacks, and further comprising later connecting the plurality of strings of sacks together.
120. The process of claim 115 wherein the sacks are secured together before entrapping a quantity of oil.
121. The process of claim 114 wherein the act of forming a plurality of sacks comprises folding over both sheets a flexible ring extending around the perimeter of the sheets and affixing the ring to the outside of the sheets, thereby forming the ring into a double layer.
122. The process of claim 121 wherein the act of forming a plurality of sacks comprises forming each sack of two round sheets comprised of a woven polypropylene mesh.
123. The process of claim 114 wherein the act of placing in each of the sacks a multitude of bodies comprises using polymer bodies comprising SBS and a multitude of substantially flat inert plastic flakes wettable with respect to hydrocar- bons.
124. The process of claim 114 further comprising maintaining the sacks afloat admidst the oily water within a surrounding boom.
PCT/US1998/000385 1997-01-10 1998-01-09 Systems for ameliorating aqueous hydrocarbon spills WO1998030303A1 (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
BR9807070-3A BR9807070A (en) 1997-01-10 1998-01-09 Systems for improving hydrocarbon spills in water.
AT98902448T ATE283725T1 (en) 1997-01-10 1998-01-09 SYSTEMS FOR IMPROVED TREATMENT OF HYDROCARBON CONTAMINANTS IN AQUEOUS ENVIRONMENTS
EP98902448A EP0973593B1 (en) 1997-01-10 1998-01-09 Systems for ameliorating aqueous hydrocarbon spills
KR1019997006276A KR100593867B1 (en) 1997-01-10 1998-01-09 Systems for ameliorating aqueous hydrocarbon spills
JP53111398A JP4164707B2 (en) 1997-01-10 1998-01-09 Method for improving leakage of hydrocarbons containing water
AU59110/98A AU732308B2 (en) 1997-01-10 1998-01-09 Systems for ameliorating aqueous hydrocarbon spills
IL13086798A IL130867A0 (en) 1997-01-10 1998-01-09 System for ameliorating aqueous hydrocarbon
CA002277163A CA2277163C (en) 1997-01-10 1998-01-09 Systems for ameliorating aqueous hydrocarbon spills
DE69827937T DE69827937T2 (en) 1997-01-10 1998-01-09 SYSTEMS FOR IMPROVED TREATMENT OF HYDROCARBONS IN AQUEOUS MILIEU
HK00104822A HK1025529A1 (en) 1997-01-10 2000-08-02 Systems for ameliorating aqueous hydrocarbon spills

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US3467797P 1997-01-10 1997-01-10
US60/034,677 1997-01-10

Publications (1)

Publication Number Publication Date
WO1998030303A1 true WO1998030303A1 (en) 1998-07-16

Family

ID=21877913

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1998/000385 WO1998030303A1 (en) 1997-01-10 1998-01-09 Systems for ameliorating aqueous hydrocarbon spills

Country Status (13)

Country Link
US (4) US6344519B1 (en)
EP (1) EP0973593B1 (en)
JP (1) JP4164707B2 (en)
KR (1) KR100593867B1 (en)
CN (1) CN1251782C (en)
AT (1) ATE283725T1 (en)
AU (1) AU732308B2 (en)
BR (1) BR9807070A (en)
CA (1) CA2277163C (en)
DE (1) DE69827937T2 (en)
HK (1) HK1025529A1 (en)
IL (1) IL130867A0 (en)
WO (1) WO1998030303A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003023156A1 (en) 2001-09-13 2003-03-20 Abtech Industries, Inc. Dual-action decontamination system
WO2020227636A1 (en) * 2019-05-09 2020-11-12 Abtech Industries, Inc. Compositions, articles, and methods for abatement of hydrocarbon, metals, and organic pollutants

Families Citing this family (46)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2277163C (en) * 1997-01-10 2005-05-10 Abtech Industries, Inc. Systems for ameliorating aqueous hydrocarbon spills
US7297267B2 (en) * 2003-03-11 2007-11-20 Parker-Hannifin Corporation Oil-sorbing filter element
EP1582576A1 (en) * 2004-04-02 2005-10-05 KRATON Polymers Research B.V. Process for the prevention or restriction of oil spiLls
US20080017561A1 (en) * 2006-07-18 2008-01-24 Shaw Mark D Combined filtration and anti-microbial treatment trench filter device for storm water pipes and drainage trenches
US7771633B2 (en) * 2006-08-18 2010-08-10 Rta Systems, Inc. Method of manufacture of three-dimensional objects for absorption of hydrocarbons and low-polarity chemicals
US7329355B1 (en) 2006-08-18 2008-02-12 Rta Systems, Inc. Method for absorption of hydrocarbons and low-polarity chemicals
NL1033808C1 (en) * 2007-05-04 2008-11-06 Holland Novochem B V Absorbents based on natural oils and derivatives.
AR061179A1 (en) * 2007-06-04 2008-08-06 Ciancaglini Y Asoc S A R A HYDROCARBON SEQUESTRATIVE PRODUCT, METHOD FOR OBTAINING THE PRODUCT, METHOD FOR THE HYDROCARBON SEQUESTRATION AND PROVISION FOR THE HYDROCARBON SEQUESTRATION.
US7988870B2 (en) * 2007-06-13 2011-08-02 David Belasco Watershed runoff treatment device & method
US20090057217A1 (en) * 2007-09-05 2009-03-05 Seawax International, Inc. Apparatus for contaminant recovery
EA020950B1 (en) * 2007-09-17 2015-03-31 Баррик Гольд Корпорейшн Method to improve recovery of gold from double refractory gold ores
US8262770B2 (en) 2007-09-18 2012-09-11 Barrick Gold Corporation Process for controlling acid in sulfide pressure oxidation processes
WO2009037594A2 (en) * 2007-09-18 2009-03-26 Barrick Gold Corporation Process for recovering gold and silver from refractory ores
US20100193418A1 (en) * 2009-01-29 2010-08-05 David Belasco Storm water treatment system, modular drain vault, tube cleaning tool and methods
US20100197183A1 (en) * 2009-01-30 2010-08-05 Drapela David C Industrial absorbent from cotton regin
US8758629B2 (en) 2010-03-03 2014-06-24 Soane Energy, Llc Treatment of oil-contaminated solids
US20110284450A1 (en) * 2010-05-20 2011-11-24 Chadwick Daniel O'blair Reusable Pads For Removing Liquid Contaminants
US8785347B2 (en) * 2010-06-11 2014-07-22 William Redvers Belisle Gulf oil spill underwater oleophilic hydrophobic oil-capturing water permeable drag-net
US8628669B2 (en) 2010-06-18 2014-01-14 Global Green Products, Llc Methods to recover and reclaim hydrocarbons or hydrophobic substances in an aqueous environment
US20120009017A1 (en) * 2010-07-07 2012-01-12 Advanced Innovative Marketing, Inc. Oil spill reclamation system
US20120061326A1 (en) * 2010-09-14 2012-03-15 Christopher Cox Method for the Environmental Remediation of Oil Spills and Other Chemical Contaminants
US8894866B1 (en) 2010-10-18 2014-11-25 Stormwater Filters Corp. Storm water treatment system and method
US20120176859A1 (en) * 2011-01-11 2012-07-12 Schlumberger Technology Corporation Marine seismic streamers
US20120228234A1 (en) * 2011-03-08 2012-09-13 Christopher Price Filter Adapted for use in a Road Gully or Water Course
WO2012136225A1 (en) * 2011-04-06 2012-10-11 Yacht Sales V/Villy Lauring Method for oil spill collection on water
US20120305490A1 (en) * 2011-06-03 2012-12-06 General Atomics Oil absorbant polyolefin foam
WO2013140420A2 (en) 2012-03-19 2013-09-26 Council Of Scientific & Industrial Research Hydrocarbon absorbing materials and a process for the preparation thereof
WO2013159182A1 (en) * 2012-04-23 2013-10-31 Nicole Gastle Methods for oil spill remediation
US9045875B2 (en) 2013-02-06 2015-06-02 Inkastrans (Canada) Ltd. Device for oil spill cleanup
US9708196B2 (en) 2013-02-22 2017-07-18 Anschutz Exploration Corporation Method and system for removing hydrogen sulfide from sour oil and sour water
US11440815B2 (en) 2013-02-22 2022-09-13 Anschutz Exploration Corporation Method and system for removing hydrogen sulfide from sour oil and sour water
WO2014144798A1 (en) * 2013-03-15 2014-09-18 Massachusetts Institute Of Technology Polymer particles and methods of using these for oil recovery
US8927456B2 (en) 2013-06-11 2015-01-06 Inkastrans (Canada) Ltd. Absorbent fibrous granules
US10456771B2 (en) 2013-09-17 2019-10-29 Darryl Bossaer Oil absorbent pad
JP6222845B2 (en) * 2013-10-22 2017-11-01 住友ゴム工業株式会社 Paper feed roller
US8889011B1 (en) * 2014-04-08 2014-11-18 Roger Lee Corn Method of oil-spill removal
US10081923B2 (en) * 2014-05-02 2018-09-25 Opflex Technologies, Llc Spill removal method and system
US8968480B1 (en) 2014-08-26 2015-03-03 Oil Spill Solutions, LLC Method of sequestering hydrocarbons or vegetable derived oil contaminants from a surface
US9909069B2 (en) * 2014-11-13 2018-03-06 Abtech Industries, Inc. Process for recycling oil-sorbing polymeric media
WO2016183125A1 (en) * 2015-05-11 2016-11-17 Anschutz Exploration Corporation Hydrogen sulfide removal system
RU2638855C1 (en) * 2017-03-13 2017-12-18 Михаил Николаевич Уразаев Method of producing sorbent for water surface purifying from oil and oil products
US11396456B1 (en) * 2018-03-02 2022-07-26 Renel A. Anderson Devices, systems, and methods for removing contaminants from water
WO2020180698A1 (en) 2019-03-01 2020-09-10 New Pig Corporation Oil-absorbent skimmers
CN109930571A (en) * 2019-04-08 2019-06-25 武汉理工大学 A kind of novel spilled oil on water surface collection oil fence based on principle of negative pressure
USD954898S1 (en) 2020-02-28 2022-06-14 New Pig Corporation Oil absorbent skimmer
CN113060779B (en) * 2020-12-18 2022-12-23 广州市悦瑞环境工程有限公司 Suspended solid adsorption ball plate in molting type sewage

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3567660A (en) * 1970-02-02 1971-03-02 Joseph Winkler Method of conversion of oil-spills into improved,rubberized carbon-black and fiber fortified asphaltic materials
US4248758A (en) * 1978-05-10 1981-02-03 Phillips Petroleum Company Crosslinked EPDM/thermoplastic elastomer blend

Family Cites Families (186)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US248559A (en) 1881-10-18 jackson
US1471819A (en) 1923-10-23 Catch basin
US425641A (en) 1890-04-15 Sink-trap
US543740A (en) 1895-07-30 George franklin kuiins
US530816A (en) 1894-05-11 1894-12-11 George wright
US1032700A (en) 1912-02-09 1912-07-16 Ira N Pickett Rain-water filter.
US1164527A (en) 1915-06-04 1915-12-14 Kelly Separator Company Grease-trap.
US1274227A (en) 1916-04-06 1918-07-30 John M Woodson Liquid-filter.
US1363792A (en) 1919-11-26 1920-12-28 Thomas J Claffey Drainage-trap
US1935642A (en) 1929-06-06 1933-11-21 Filtration Equipment Corp Clarifier
US1972513A (en) 1933-05-23 1934-09-04 Christian E Drehmann Drain inlet
US2102310A (en) 1934-04-04 1937-12-14 George F Egan Construction of sewers and sewer basins and receptacles for use in sewer basins
US2182795A (en) 1937-08-07 1939-12-12 Louis J Day Surface drain
US2467021A (en) 1944-11-22 1949-04-12 Dorr Co Inc Sewage screening apparatus
US2557079A (en) 1945-08-06 1951-06-19 Rocco J Cutri Rescuing device
US2615526A (en) 1950-12-21 1952-10-28 Lane Frank Sewer catch basin unit
US2889928A (en) 1954-07-30 1959-06-09 Lulu E Sisk Finish rims for surface drains
US2813745A (en) 1955-01-04 1957-11-19 Frieder Cargo sling
FR1296708A (en) 1961-05-12 1962-06-22 Method and devices for unclogging filters placed in fluid circuits operating under pressure or under vacuum
US3147216A (en) 1961-09-28 1964-09-01 Du Pont Separation of hydrocarbon/water mixtures
US3246582A (en) 1962-09-11 1966-04-19 Wade Inc Adjustable square drain
US3324630A (en) 1965-06-07 1967-06-13 Aaron J Teller Crossflow scrubbing process
US3538020A (en) 1966-09-23 1970-11-03 Kata Mfg & Filtering Co The Fluid purification device containing a cartridge of polymer entrapped aggregate particles
US3415745A (en) 1966-11-07 1968-12-10 Sinclair Research Inc Method of flocculating a water-borne oil slick
SE322735B (en) 1967-05-26 1970-04-13 H Fahlvik
US3536616A (en) 1967-06-24 1970-10-27 Agency Ind Science Techn Method for removal of oils floating on surface of water
US3617566A (en) 1967-11-06 1971-11-02 Aiko Nagao Method and material for separating oil from oil-containing water
US3607793A (en) 1968-02-23 1971-09-21 Hercules Inc Process for forming porous structures
US3929631A (en) 1968-04-30 1975-12-30 Aniela Winkler Compositions and systems to recover oils from aqueous and solid surfaces
US3539013A (en) 1968-06-24 1970-11-10 Millard F Smith Oil collection boom
US3494862A (en) 1969-01-21 1970-02-10 Polymer Research Corp Of Ameri Recovery of hydrocarbon liquids
US3537587A (en) 1969-06-05 1970-11-03 Calvin L Kain Flexible filtration boom
US3518183A (en) 1969-06-09 1970-06-30 Shell Oil Co Process for separation of oil films from water
US3594335A (en) 1969-06-12 1971-07-20 Nat Gypsum Co Shaped bodies of bonded rigid polyurethane foam particles
US3565257A (en) 1969-12-05 1971-02-23 Cesare Cavalieri Floating barrier for water pollutants
US3679058A (en) 1970-01-27 1972-07-25 Millard F Smith Oil collection boom
US3607741A (en) * 1970-02-19 1971-09-21 Alfred Sohnius Oil slick removal system
US3667608A (en) 1970-04-24 1972-06-06 Hercules Inc Apparatus for removing oil spills from the surface of a body of water
US3739913A (en) * 1970-07-16 1973-06-19 Johns Manville Device for fencing and absorbing contaminating oil spills on water
US3800950A (en) 1971-01-08 1974-04-02 H Hess Apparatus for removing oil from water
US3702657A (en) 1971-02-11 1972-11-14 Exxon Production Research Co Pollution containment barrier
US3681237A (en) 1971-03-26 1972-08-01 Membrionics Corp Oil spillage control process
US3783621A (en) 1971-04-27 1974-01-08 J Gallagher Convertible barrier for substances floating on water
US3667235A (en) 1971-04-27 1972-06-06 Paul Preus Convertible barrier for substances floating on water
US3713539A (en) 1971-05-26 1973-01-30 C Thompson Strainer device for use in drainage receptacles
US3756948A (en) 1971-07-15 1973-09-04 Grantley Co Ion and recovery method and means for absorbing crude oil and the like for transportat
US4039489A (en) 1972-02-22 1977-08-02 Nasa Oil and fat absorbing polymers
US3831760A (en) 1972-06-28 1974-08-27 Carborundum Co Activated carbon chemical adsorption assembly
GB1433873A (en) 1972-07-21 1976-04-28 Lucas Industries Ltd Coanda-type filter apparatus
US3837494A (en) 1972-08-16 1974-09-24 B Stevenson Sewage treatment apparatus
US4002177A (en) 1972-08-21 1977-01-11 Philip Morris Incorporated Microporous styrene polymers and method of making same
US3888766A (en) 1973-03-09 1975-06-10 Uniroyal Inc Oil sorption material
US4207378A (en) 1973-03-16 1980-06-10 Max Klein Expanded styrene-polymers and polyolefin micro-bits and their preparation
US3923472A (en) 1973-10-05 1975-12-02 Du Pont Fuel made from thermoplastic fibers and oil
US3916969A (en) 1973-10-26 1975-11-04 Goodyear Tire & Rubber Method of building a radial tire
US4060487A (en) 1973-12-17 1977-11-29 Samsel Frank J Apparatus for cleaning oil spills
USRE29996E (en) 1974-03-11 1979-05-15 Jet Aeration Company Upflow filter
US3915859A (en) 1974-04-11 1975-10-28 Conwed Corp Apparatus for removing oil from water
US4332854A (en) 1975-05-22 1982-06-01 Parker James H Polypropylene oil removal structure
US4102783A (en) 1975-12-08 1978-07-25 Daicel Ltd. Adsorbent process for oily materials
US4061807A (en) 1976-02-09 1977-12-06 Shaler Amos J Adsorbent body and method for making same
US3998060A (en) 1976-04-14 1976-12-21 Paul Preus Barrier for water carried pollutants
CH613245A5 (en) 1976-05-07 1979-09-14 Raymond Vuffray Settling tank for sewage
US4031839A (en) 1976-05-19 1977-06-28 Pedone Vito S Reusable oil absorbent bilge and fuel tank opening pads
US4084380A (en) 1976-06-03 1978-04-18 Ab Sjuntorp Oil fence
US4070287A (en) 1976-09-14 1978-01-24 Conweb Corporation Polymeric and cellulosic fiber material for removing oil from water
CA1048799A (en) 1976-10-05 1979-02-20 Paul Preus Barrier construction for water carried pollutants
US4052306A (en) 1976-10-12 1977-10-04 Minnesota Mining And Manufacturing Company Oil sweep
US4099619A (en) 1976-12-01 1978-07-11 Conwed Corporation Sorbent boom with flotation and apparatus and method for stuffing same
JPS603116B2 (en) * 1977-02-17 1985-01-25 三菱レイヨン株式会社 Method for producing oil-containing wastewater treatment agent
US4427157A (en) 1977-09-15 1984-01-24 Max Klein Preparation of styrene-polymer and polyolefin micro-bits
FR2430350B1 (en) 1978-07-04 1981-10-23 Ouest Ets Generaux Meca
DE2904428A1 (en) 1979-02-06 1980-08-14 Philipp Dipl Ing Schreck Transverse sloping bridge roadway drainage - involves outside screen and gutter with outflow ducts carried to supports
EP0023084B1 (en) 1979-06-26 1985-08-07 The British Petroleum Company p.l.c. Cross-linked polymer compositions and production thereof
US4261823A (en) 1979-07-26 1981-04-14 Summit Engineering Corporation Storm drain catch basin
CA1163570A (en) 1979-10-10 1984-03-13 Alfred F. Crotti Removal of oil from water
JPS572383A (en) 1980-06-05 1982-01-07 Asahi Chem Ind Co Ltd Oil-absorbing material composed of synthetic resin
US4420400A (en) 1980-06-05 1983-12-13 General Technology Applications, Inc. Hydrocarbon products damage control systems
SE431617B (en) 1980-08-05 1984-02-20 Eriksson Hans WAY TO REMOVE LIQUID
US4366067A (en) 1980-10-20 1982-12-28 Golding Gordon R Method and apparatus for removal and recovery of oil
US4801386A (en) 1981-06-19 1989-01-31 Mitsubishi Rayon Co., Ltd. Process of using a porous water-treating material
US4519918A (en) 1981-07-27 1985-05-28 Papyrus Kopparfors Ab Process for the absorption of organic liquids by use of a hydrophobic fibrous material
US4429065A (en) 1981-08-10 1984-01-31 Gancy Alan B Controlled density hydraulic fluids
SE427680B (en) 1981-10-01 1983-04-25 Oscar Sven Arntyr DEPARTMENT FOR SEPARATION AND COLLECTION OF POLLUTANTS AT DAYWATER TOWNS
JPS5893709A (en) 1981-11-30 1983-06-03 Japan Synthetic Rubber Co Ltd High-styrene content styrene/butadiene copolymer
US4454039A (en) 1982-07-19 1984-06-12 Mccoy Archibald H R Frame and cover members for constructing apertures in road surfaces
US4592690A (en) 1982-10-08 1986-06-03 Bonded Products, Inc. Hot melt gasketing compositions and processes for applying them
GB2144140B (en) * 1983-07-26 1987-07-22 Cummins Engine Co Inc High swell gasket material
US4497712A (en) 1983-10-14 1985-02-05 Geotech Development Corporation Absorbent pillow
ES295930Y (en) 1984-07-04 1988-05-16 Societe Anonyme Dite L'equipement Routier. PERFECTED CORNICE FOR ARTWORKS.
US4594157A (en) 1984-12-31 1986-06-10 Mcgowan Bernard J Inlet clamp and screen
US4640730A (en) 1985-03-22 1987-02-03 Ashland Oil, Inc. Method of adhering roofing materials
US4740435A (en) 1985-11-15 1988-04-26 Duracell Inc. Cell sealant
US4776722A (en) 1986-04-01 1988-10-11 Gaudin Carl J Self sealing sewer cover assembly
DE3634289A1 (en) 1986-10-08 1988-04-21 Gottfried Biener Kerbstone
US4965129A (en) 1987-02-09 1990-10-23 E. I. Du Pont De Nemours And Company Article for absorbing liquids
US4980229A (en) 1987-03-03 1990-12-25 Raychem Corporation Article surface coated with curable particulate or filamentary material
US4737394A (en) 1987-06-17 1988-04-12 E. I. Du Pont De Nemours And Company Article for absorbing oils
KR970008597B1 (en) 1987-12-28 1997-05-27 닛뽄 세키유가가쿠 가부시키가이샤 Process for preparing thermoplastic resin composition
US5248729A (en) 1987-12-28 1993-09-28 Nippon Petrochemicals Company Limited Process for preparing thermoplastic resin composition
US5032640A (en) 1988-06-29 1991-07-16 Marco Fachini Composition for giving bituminous conglomerates high mechanical characteristics and resistance to high and low temperatures, also by using sludge obtaining from the treatment of waste lubricating oil
FR2635332B1 (en) 1988-06-30 1994-05-20 Norsolor ARTICLE AND METHOD FOR ABSORBING POLLUTANTS
US4929349A (en) 1988-08-24 1990-05-29 Beckman William J Bio-filtration apparatus and method for wastewater treatment
NO165968C (en) 1988-10-27 1991-05-15 Norva Invest As OIL COLLECTING.
US5360548A (en) 1989-02-14 1994-11-01 Elf Atochem, S.A. Process for absorbing organic polluting products
US5432000A (en) 1989-03-20 1995-07-11 Weyerhaeuser Company Binder coated discontinuous fibers with adhered particulate materials
US4919820A (en) 1989-04-17 1990-04-24 Lafay William T Oil absorption method
US4941978A (en) 1989-08-07 1990-07-17 Albert Gabrick Controlling and recovering oil spills from the environment
US5104548A (en) 1989-08-07 1992-04-14 Albert Gabrick Controlling and recovering oil spills from the environment
EP0485524B1 (en) 1989-09-01 1994-03-09 Wool Research Organisation Of New Zealand Inc. Absorbent materials and use thereof
US5374600A (en) 1990-01-29 1994-12-20 Nippon Shokubai Kagaku Kogyo Co., Ltd. Oil-absorbent polymer and use therefor
IT1238006B (en) 1990-02-06 1993-06-21 Himont Inc PROCEDURE FOR REPAIRING PLASTIC COATINGS OF METAL TUBES
US5075014A (en) 1990-05-04 1991-12-24 Imc-International Marketing Of Canada Corp. Oil recovery system and apparatus
US5135578A (en) 1990-05-12 1992-08-04 Billings Lanny D Method of cleaning oil slicks and chemical spills
US5037541A (en) 1990-05-30 1991-08-06 Ruey Jang Shiau Sanitary device for sewerage channel
US5179611A (en) 1990-07-17 1993-01-12 Tokai Rubber Industries, Ltd. Optical fiber cable having a water absorptive member
US5009790A (en) 1990-08-20 1991-04-23 Damcosur S.A. De C.V. Method for absorbing liquids using dealginate kelp
US5427679A (en) 1990-10-23 1995-06-27 Daniels; Byron C. Septic system filter assembly, filter arrangement
GB9023801D0 (en) 1990-11-01 1990-12-12 Bp Chem Int Ltd Cleaning compositions
US5468539A (en) * 1990-12-21 1995-11-21 Crivelli; Henry Precast surface paving overlay comprising rubber crumbs and clay particles
US5135660A (en) 1991-01-07 1992-08-04 Dow Corning Corporation Method of recovering oil from the surface of water
IT1247231B (en) 1991-01-22 1994-12-12 O C S Officine Costruzioni Spe BUCKET STRUCTURE FOR AQUATIC VEHICLES FOR THE COLLECTION OF FLOATING MATERIALS.
CA2035753C (en) 1991-02-06 2001-01-30 John Van Egmond Storm water infiltration
US5133619A (en) 1991-03-18 1992-07-28 Murfae George W Storm water filtration system for use with conventional storm water collection sewers
US5180704A (en) * 1991-04-19 1993-01-19 Regents Of The University Of Minnesota Oil sorption with surface-modified rubber
US5211858A (en) 1991-05-07 1993-05-18 Union Oil Company Of California Lanthanide-crosslinked polymers for subterranean fluid containment
GB9110201D0 (en) 1991-05-10 1991-07-03 Robertson William Treatment of agricultural nitrate pollution
US5227072A (en) 1991-05-15 1993-07-13 Brinkley Herman E Method of recovering oil-based fluid
CA2070854A1 (en) 1991-06-14 1992-12-15 Calvin D. Blystra Recovery of organic liquid spills
IT1250639B (en) 1991-07-04 1995-04-21 Enichem Elastomers METHOD FOR THE REMOVAL OF HYDROCARBON PRODUCTS FROM THE SURFACE OF A WATER MEDIUM
US5407600A (en) * 1991-07-23 1995-04-18 Nissan Chemical Industries, Ltd. Stable aqueous alumina sol and method for preparing the same
US5165821A (en) 1991-08-21 1992-11-24 Minnesota Mining And Manufacturing Co. Oil-sorbing boom
US5223154A (en) 1991-11-01 1993-06-29 Emcon Northwest, Inc. System for filtering liquids in a catch basin using filters in series and overflow channels
US5297367A (en) 1992-01-17 1994-03-29 Sainz Jorge R Removable storm drainage cartridge
US5186831A (en) 1992-01-21 1993-02-16 Leucadia, Inc. Oil sorbent products and method of making same
US5407575A (en) 1992-01-24 1995-04-18 Vinsonhaler; Charles W. Oil spill cleanup and recovery system
US5173182A (en) 1992-02-12 1992-12-22 Debellian Gabriel J Multi-purpose environmental work vessel
US5232587A (en) 1992-03-02 1993-08-03 Tom Hegemier Stormwater inlet filter
US5364535A (en) 1992-03-09 1994-11-15 Buckalew Charles O Method for separating oily pollutants from water runoff
US5788849A (en) 1992-06-01 1998-08-04 Hutter, Jr.; James E. Filter system
IT1255419B (en) 1992-07-09 1995-10-31 Sviluppo Settori Impiego Srl MODULAR ELEMENT FOR THE ABSORPTION OF OIL SUBSTANCES FROM WATER BODY SURFACES AND POLLUTION SYSTEM USING SUCH ELEMENTS.
US5281463A (en) 1992-07-28 1994-01-25 Kimberly-Clark Corporation Structure for selectively absorbing oily contaminants and process
US5284580A (en) 1992-08-04 1994-02-08 Shyh Shyh Yuan Refuse collecting frame for sewer
FR2699187B1 (en) 1992-12-14 1995-02-17 Total Raffinage Distribution Bitumen-polymer aqueous emulsions, their preparation process and their applications.
FR2699186B1 (en) 1992-12-14 1995-03-10 Total Raffinage Distribution Bitumen-polymer compositions, their preparation process and their applications.
US5405539A (en) 1993-03-04 1995-04-11 Schneider; Thomas W. Storm drain filter system
US5324429A (en) 1993-04-19 1994-06-28 Holland Herbert W Bilge oil absorber and solidifier
US5439590A (en) 1993-05-25 1995-08-08 Envirogen, Inc. Methods for treating toxic material
DE4326326A1 (en) * 1993-08-05 1995-02-09 Happich Gmbh Gebr Plastic molding and method of manufacturing the same
US5391295A (en) 1993-09-27 1995-02-21 Wilcox; Jack M. Spill containment system
US5679246A (en) 1993-09-27 1997-10-21 Wilcox; Jack M. Spill containment system
US5372714A (en) 1993-10-21 1994-12-13 Logue, Jr.; George E. Storm sewer catch basin and filter
CH685877A5 (en) 1993-11-03 1995-10-31 Brugg Ag Kabelwerke A process for the production of moldings from cross-linked polymers
US5480254A (en) 1993-11-19 1996-01-02 Autry; James L. Storm drain box filter and method of use
CH685878A5 (en) 1993-12-08 1995-10-31 Brugg Ag Kabelwerke Process for the preparation of an additive-loaded porous Traegermaterials
US5403474A (en) 1994-02-24 1995-04-04 Emery; Grant R. Curb inlet gravel sediment filter
US5573349A (en) 1994-10-20 1996-11-12 Paoluccio; John A. Sediment dike with absorber apparatus
US5830967A (en) 1994-10-24 1998-11-03 Amcol International Corporation Process for producing an oil and water adsorbent polymer capable of entrapping solid particles and liquids and the product thereof
US5632888A (en) 1995-05-11 1997-05-27 Dandy Enterprises Limited Environmental filter
US5624576A (en) 1995-05-30 1997-04-29 Csf Treatment Systems, Inc. Pelletized composition for treatment of storm water runoff
US5712358A (en) 1995-06-07 1998-01-27 Amcol International Corporation Process for producing an oil sorbent copolymer and the product thereof
US5632889A (en) 1995-06-09 1997-05-27 Tharp; Gary D. Filter cartridge for separating liquid hydrocarbons from water
US5820762A (en) 1995-06-20 1998-10-13 Bamer; Jonathan Michael Filter insert for a storm drain
WO1997016609A1 (en) 1995-10-30 1997-05-09 Rsf Patent Pty. Ltd. Storm water filter arrangement
US5720574A (en) 1995-11-02 1998-02-24 Kristar Enterprises, Inc. Contaminant absorbing drainage trough apparatus
US5869555A (en) 1995-11-16 1999-02-09 H. B. Fuller Licensing & Financing Inc. Polymeric composition in pellet form
US5744048A (en) 1996-03-01 1998-04-28 Storm Water Systems, Inc. Clog resistant storm drain filter
US5707527A (en) 1996-04-30 1998-01-13 Stormwater Treatment Llc Apparatus and method for treating storm water runoff
US5863440A (en) 1996-05-24 1999-01-26 Abtech Industries, Inc. Methods for ameliorating oil spills in marine and inland waters
US5733445A (en) 1996-07-25 1998-03-31 Fanelli; Anthony T. Storm sewer catch basin filter
NZ299114A (en) 1996-08-01 1998-01-26 Enviropod Nz Ltd Filter for removing solids from stormwater drain
US5925241A (en) 1996-10-25 1999-07-20 Calgon Carbon Corporation Floor drain odor control device
US5767060A (en) * 1996-10-30 1998-06-16 Advanced Water Systems Bonded polymer filter medium and its use
CA2277163C (en) * 1997-01-10 2005-05-10 Abtech Industries, Inc. Systems for ameliorating aqueous hydrocarbon spills
US6541569B1 (en) * 1997-01-10 2003-04-01 Abtech Industries, Inc. Polymer alloys, morphology and materials for environmental remediation
US5762790A (en) 1997-06-02 1998-06-09 Zoeller Co. Septic tank filtering system
US6099723A (en) 1997-06-06 2000-08-08 Abtech Industries, Inc. Catchbasin systems for filtering hydrocarbon spills
US5849198A (en) 1997-08-09 1998-12-15 Sharpless; Robert Grate suspended storm drain filter with oil absorbing media
US5958226A (en) 1997-12-29 1999-09-28 Fleischmann; Charles R. Storm drain filter with removable debris tray
EP1073610B1 (en) 1998-02-18 2009-04-01 Abtech Industries, Inc. Curb-inlet storm drain systems for filtering trash and hydrocarbons
US6261444B1 (en) 1998-06-18 2001-07-17 J. Mark Forse Storm sewer filtering apparatus
US6080307A (en) 1998-09-29 2000-06-27 Abtech Industries, Inc. Storm drain systems for filtering trash and hydrocarbons
US6086758A (en) 1998-11-13 2000-07-11 Pactec, Inc. Storm drain liner
US6214216B1 (en) 1999-10-04 2001-04-10 Ronald Isaacson Drain filter support
US6531059B1 (en) * 2000-10-05 2003-03-11 Abtech Industries, Inc. Suspended runoff water filter
US6712976B2 (en) * 2001-09-13 2004-03-30 Abtech Industries, Inc. Dual-action decontamination system

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3567660A (en) * 1970-02-02 1971-03-02 Joseph Winkler Method of conversion of oil-spills into improved,rubberized carbon-black and fiber fortified asphaltic materials
US4248758A (en) * 1978-05-10 1981-02-03 Phillips Petroleum Company Crosslinked EPDM/thermoplastic elastomer blend

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003023156A1 (en) 2001-09-13 2003-03-20 Abtech Industries, Inc. Dual-action decontamination system
EP1436470A1 (en) * 2001-09-13 2004-07-14 Abtech Industries, Inc. Dual-action decontamination system
EP1436470A4 (en) * 2001-09-13 2006-03-08 Abtech Industries Inc Dual-action decontamination system
WO2020227636A1 (en) * 2019-05-09 2020-11-12 Abtech Industries, Inc. Compositions, articles, and methods for abatement of hydrocarbon, metals, and organic pollutants
KR20210154268A (en) * 2019-05-09 2021-12-20 어비텍 인더스트리스, 인코포레이티드 Compositions, articles and methods for the abatement of hydrocarbon, metal and organic pollutants
AU2020270136B2 (en) * 2019-05-09 2022-03-03 Abtech Industries, Inc. Compositions, articles, and methods for abatement of hydrocarbon, metals, and organic pollutants
KR102464555B1 (en) 2019-05-09 2022-11-07 어비텍 인더스트리스, 인코포레이티드 Compositions, articles and methods for the reduction of hydrocarbon, metal and organic pollutants

Also Published As

Publication number Publication date
CN1251782C (en) 2006-04-19
DE69827937D1 (en) 2005-01-05
DE69827937T2 (en) 2005-12-22
US6344519B1 (en) 2002-02-05
US20020165318A1 (en) 2002-11-07
US7229560B2 (en) 2007-06-12
KR100593867B1 (en) 2006-07-03
CA2277163A1 (en) 1998-07-16
CN1243450A (en) 2000-02-02
ATE283725T1 (en) 2004-12-15
EP0973593B1 (en) 2004-12-01
BR9807070A (en) 2000-05-02
EP0973593A1 (en) 2000-01-26
JP4164707B2 (en) 2008-10-15
AU732308B2 (en) 2001-04-12
KR20000070056A (en) 2000-11-25
JP2002515087A (en) 2002-05-21
IL130867A0 (en) 2001-01-28
US7048878B2 (en) 2006-05-23
CA2277163C (en) 2005-05-10
US6723791B2 (en) 2004-04-20
US20030225211A1 (en) 2003-12-04
AU5911098A (en) 1998-08-03
US20050151289A1 (en) 2005-07-14
HK1025529A1 (en) 2000-11-17
EP0973593A4 (en) 2002-08-21

Similar Documents

Publication Publication Date Title
US7229560B2 (en) Sack-based processes for recovering oil floating on water
US5863440A (en) Methods for ameliorating oil spills in marine and inland waters
US5688075A (en) Boom system
US6099723A (en) Catchbasin systems for filtering hydrocarbon spills
US5102261A (en) Floating containment boom
US4139470A (en) System for separating, removing and recovering contaminant materials from a body of water
US5779392A (en) Systems for containing and collecting oil spills
AU621157B2 (en) Oil collector
US20110306491A1 (en) Gulf oil spill underwater oleophilic hydrophobic oil-capturing water permeable drag-net
WO1999019570A1 (en) Method and apparatus for controlling suspended particulates or marine life
Fingas Physical spill countermeasures
US3579994A (en) Barrier for control of substances in bodies of water
KR200374610Y1 (en) Net for oill-spill clean up on the sea
US3844941A (en) Use of sulfur for combatting oil spills
US20120111798A1 (en) Process and Means for Treatment of an Oil Spill
US6444611B1 (en) Sorbent composition and apparatus for removing oil or oily substances from water, and process of manufacturing said composition
US4226711A (en) Oil spill recovery method and apparatus
MXPA99006469A (en) Systems for ameliorating aqueous hydrocarbon spills
JP3006134U (en) Oil spill absorber
WO2022061408A1 (en) An in situ decontamination method and apparatus
Harper Oil soaked straw harvesting techniques
Henager et al. Concept Evaluation: Recovery of Floating Oil Using Polyurethane Foam Sorbent
Wisaksono Oil pollution abatement

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 130867

Country of ref document: IL

Ref document number: 98801774.1

Country of ref document: CN

AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GE GH GM GW HU ID IL IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US UZ VN YU ZW AM AZ BY KG KZ MD RU TJ TM

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SZ UG ZW AT BE CH DE DK ES FI FR GB GR IE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
ENP Entry into the national phase

Ref document number: 2277163

Country of ref document: CA

Ref document number: 2277163

Country of ref document: CA

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: PA/a/1999/006469

Country of ref document: MX

WWE Wipo information: entry into national phase

Ref document number: 1019997006276

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 1998902448

Country of ref document: EP

Ref document number: 59110/98

Country of ref document: AU

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWP Wipo information: published in national office

Ref document number: 1998902448

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1019997006276

Country of ref document: KR

WWG Wipo information: grant in national office

Ref document number: 59110/98

Country of ref document: AU

WWG Wipo information: grant in national office

Ref document number: 1998902448

Country of ref document: EP

WWG Wipo information: grant in national office

Ref document number: 1019997006276

Country of ref document: KR