Related Applications

[001] This application claims convention priority to Australian provisional patent application 2020903454, filed 25 September 2020 and Australian provisional patent application 2021902642, filed 23 August 2021. The content of both AU’454 and AU’ 642 is incorporated herein by reference in its respective entirety.

Field of the Invention

[002] The present invention relates generally to a method the removal of oil or hydrocarbon pollution from water and/or soil or sand. The invention further relates to an apparatus for performing the method in situ.

Background of the Invention

[003] Any discussion of the prior art throughout the specification should in no way be considered as an admission that such prior art is widely known or forms part of common general knowledge in the field.

[004] Hydrocarbon spills or leaks represent an ever-present threat to the environment, economy, and health of our society. They may be caused, for example, by an oil tanker running aground or sinking, leaking or broken drill heads, leaking pipes or hoses or a damaged or sunk oil drilling rig or storage facility.

[005] An oil spill may spread across the surface of a body of water, contaminate miles of seashore, and destroy much aquatic life. Sizable spills may take months or even years to clean up. A spill may also impact the occupations of those that rely on the sea to provide their livelihood, such as fishermen, tourist operators and the like.

[006] Various techniques have been used to remove and protect areas of land from contamination by polluting hydrocarbons. However, if the contamination is in the form of a floating sheet of oil, the direction in which it moves is subject to changes in wind direction and marine currents which often make it difficult to determine where it will eventually come ashore.

[007] One procedure for removing hydrocarbons from a beach or soil involves the use of solvents and dispersants. This improves the surface aesthetically and mobilises the oil. Smaller oil droplets, scattered by currents, may cause less harm, and may degrade more easily. However, these chemicals may present additional contamination risks. For example, the dispersed oil droplets may infiltrate deeper water. Also, some dispersants may be toxic to marine life such as fish or corals. Also, such procedures may require the physical removal of soil or beach sand to a location remote from where the pollution has occurred so that it can be stored and then treated. Moreover, the recovery and reuse of these solvents and dispersants is typically not possible, which means they remain as pollutants themselves.

[008] Other techniques for remediating oil spills include natural dispersal (which may take months or years and is not suitable for any spills of significant scale), biological agents, filtration devices or even burning off the oil.

[009] It is an object of the present invention to overcome or ameliorate at least one of the disadvantages of the prior art, or to provide a useful alternative.

[010] There is a general need for methods for cleaning up oil spills that are applicable to a range of different types of spills, preferably methods that also enable recovery of the hydrocarbons. There is a further general need for such a method which enables the adsorbent material used in the method to be recovered and reused. This is a further need for such a method that is inexpensive and that is applicable to oil spills on land as well on water. Finally, there is a general desire that such methods are performed in situ, which of itself ameliorates some of the limitations described above.

[Oil] Unless the context clearly requires otherwise, throughout the description and the claims, the words “comprise”, “comprising”, and the like are to be construed in an inclusive sense as opposed to an exclusive or exhaustive sense; that is to say, in the sense of “including, but not limited to”.

[012] Although the invention will be described with reference to specific examples it will be appreciated by those skilled in the art that the invention may be embodied in many other forms.

Summary of the Invention

[013] According to a first aspect of the present invention there is provided a method for the in situ removal of oil or hydrocarbon from oil- or hydrocarbon-contaminated water, rock, sand or soil, comprising:

[014] (a) admixing granulate with oil- or hydrocarbon-contaminated water, rock, sand or soil, wherein the granulate comprises latex, rubber or polyolefin particles having an average diameter of approximately 0.1 mm to about 100 mm such that some or all of the oil or hydrocarbon is adsorbed onto the granulate to form a mixture comprising coated granulate; and [015] (b) separating the mixture to remove some or all of the coated granulate to yield water, rock, sand, or soil that is less contaminated with the oil or hydrocarbon

[016] wherein steps (a) and/or (b) is/are performed at the site of the contaminated water, rock, sand or soil.

[017] In some embodiments, the granulate comprises latex particles. In some embodiments, the granulate comprises rubber particles. In some embodiments, the granulate comprises polyolefin particles. In some embodiments, the particles have an average diameter from about 0.5 mm to about 100 mm. In some embodiments, the particles have an average diameter from about 0.1 mm to about 50 mm. In some embodiments, the granulate is admixed with water. In some embodiments, the admixing step occurs in an open-water environment.

[018] In some embodiments, the methods further comprise testing the water after the separation step. For example, the water may be tested for biochemical oxygen demand.

[019] In some embodiments, the separation step comprises the use of a sieve, a net, a conveyor, a bucket, a separation conveyor, or a combination of one or more of these devices. In some embodiments, the granulate is admixed with rock, sand, or soil.

[020] In some embodiments, the methods further comprise repeating steps (a) and/or (b) one or more times. In some embodiments, the method further comprises:

[021] removing some or all of the oil or hydrocarbon from the coated granulate using a centrifuge or a press such that granulate is recovered.

[022] In some embodiments, the press is a screw-type seed oil extraction press. In some embodiments, the methods further comprise reusing the recovered granulate in step (a).

[023] According to a second aspect of the present invention there is provided a method for the in situ removal of oil or hydrocarbon from oil- or hydrocarbon-contaminated water, rock, sand or soil, comprising:

[024] (a) admixing granulate with oil- or hydrocarbon-contaminated water, rock, sand or soil, wherein the granulate comprises latex, rubber or polyolefin particles having an average diameter of approximately 0.5 mm to about 100 mm such that some or all of the oil or hydrocarbon is adsorbed onto the granulate to form a mixture comprising coated granulate;

[025] (b) separating the mixture to remove some or all of the coated granulate to yield water, rock, sand or soil that is less contaminated with the oil or hydrocarbon;

[026] (c) transporting the coated granulate to a centrifuge or press via an agitator or an auger; and

[027] (d) removing some or all of the oil or hydrocarbon from the coated granulate using the centrifuge or the press such that granulate is recovered,

[028] wherein steps (a) and/or (b) and/or (c) and/or (d) is/are performed at the site of the contaminated water, rock, sand or soil.

[029] In an embodiment, the granulate comprises latex particles, rubber particles and/or polyolefin particles. In an embodiment, the particles have an average diameter from about 0.5 mm to about 100 mm. In an embodiment, the method further comprises the step of testing the water for biochemical oxygen demand after the separation step. In an embodiment, the method further comprises reusing at least some of the granulate recovered from step (d) in a subsequent step (a).

[030] According to a third aspect of the present invention there is provided an apparatus for the in situ removal of oil or hydrocarbon from oil- or hydrocarbon-contaminated water, rock, sand or soil, comprising:

[031] (a) means for admixing granulate with oil- or hydrocarbon-contaminated water, rock, sand or soil, wherein the granulate comprises latex, rubber or polyolefin particles having an average diameter of approximately 0.1 mm to about 100 mm such that some or all of the oil or hydrocarbon is adsorbed onto the granulate to form a mixture comprising coated granulate; and [032] (b) means for separating the mixture to remove some or all of the coated granulate to yield water, rock, sand or soil that is less contaminated with the oil or hydrocarbon,

[033] wherein steps (a) and/or (b) is/are performed at the site of the contaminated water, rock, sand or soil.

[034] In an embodiment, the granulate comprises latex particles. In an embodiment, the granulate comprises rubber particles. In an embodiment, the granulate comprises polyolefin particles.

[035] In an embodiment, the particles have an average diameter from about 0.5 mm to about 100 mm. In an embodiment, the particles have an average diameter from about 0.1 mm to about 50 mm.

[036] In an embodiment, the granulate is admixed with water. In an embodiment, the admixing step occurs in an open-water environment.

[037] In an embodiment, the apparatus further comprises means for testing the water after the separation step. In an embodiment, the water is tested for biochemical oxygen demand.

[038] In an embodiment, the separation step comprises the use of a sieve, a net, a conveyor, a bucket, a separation conveyor or a combination of one or more of these devices. In an embodiment, the granulate is admixed with rock, sand, or soil.

[039] In an embodiment, the apparatus comprises means for repeating steps (a) and/or (b) one or more times.

[040] In an embodiment, the apparatus comprises means for removing some or all of the oil or hydrocarbon from the coated granulate using a centrifuge or a press such that granulate is recovered.

[041] In an embodiment, the press is a screw-type seed oil extraction press. In an embodiment, the apparatus further comprises means for reusing the recovered granulate in step (a).

[042] According to a fourth aspect of the present invention there is provided an apparatus for the in situ removal of oil or hydrocarbon from oil- or hydrocarbon-contaminated water, rock, sand or soil, comprising:

[043] (a) means for admixing granulate with oil- or hydrocarbon-contaminated water, rock, sand or soil, wherein the granulate comprises latex, rubber or polyolefin particles having an average diameter of approximately 0.5 mm to about 100 mm such that some or all of the oil or hydrocarbon is adsorbed onto the granulate to form a mixture comprising coated granulate;

[044] (b) means for separating the mixture to remove some or all of the coated granulate to yield water, rock, sand or soil that is less contaminated with the oil or hydrocarbon;

[045] (c) means for transporting the coated granulate to a centrifuge or press via an agitator or an auger; and

[046] (d) means for removing some or all of the oil or hydrocarbon from the coated granulate using the centrifuge or the press such that granulate is recovered,

[047] wherein steps (a) and/or (b) and/or (c) and/or (d) is/are performed at the site of the contaminated water, rock, sand or soil.

[048] In an embodiment, the granulate comprises latex particles, rubber particles and/or polyolefin particles. In an embodiment, the particles have an average diameter from about 0.5 mm to about 100 mm.

[049] In an embodiment, the apparatus further comprises means for testing the water for biochemical oxygen demand after the separation step.

[050] In an embodiment, the apparatus further comprises means for reusing at least some of the granulate recovered from step (d) in a subsequent step (a).

[051] The apparatus of the present invention are adapted to perform the remediation method in situ due to it being operatively associated with a vessel such as a boat, which is then manoeuvred into the precise location of the oil spill (or similar) from where a scooping or pumping mechanism engages with the spill in order to facilitate on-site remediation of the spill.

Definitions

[052] The use of the word “a” or “an,” when used in conjunction with the term “comprising” in the claims and/or the specification may mean “one,” but it is also consistent with the meaning of “one or more, at least one,” and “one or more than one.”

[053] Throughout this application, the term “about” is used to indicate that a value includes the inherent variation of error for the device, the method being employed to determine the value, or the variation that exists among the study subjects.

[054] The term “adsorb” is taken to include both “adsorb” and “absorb” as well as both processes combined.

[055] The terms “comprise,” “have” and “include” are open-ended linking verbs. Any forms or tenses of one or more of these verbs, such as “comprises, comprising,” “has,” “having, includes” and “including,” are also open-ended. For example, any method that “comprises,” “has” or “includes” one or more steps is not limited to possessing only those one or more steps and also covers other unlisted steps.

[056] The term “contaminate” or contaminated” includes where one substance coats, is mixed with, or is dissolved in, in another substance. Contamination in any of these forms may be partial or complete.

[057] “Remove” or “removing” includes effecting any measurable decrease in the substance being removed.

[058] The term “effective,” as that term is used in the specification and/or claims, means adequate to accomplish a desired, expected, or intended result.

[059] The term “oil” is intended to define any nonpolar chemical substance that is a viscous liquid at ambient temperatures and is both hydrophobic and lipophilic. Oils have a high carbon and hydrogen content and are usually flammable and surface active. The general definition of oil includes classes of chemical compounds that may be otherwise unrelated in structure, properties, and uses. Oils may be animal, vegetable, or petrochemical in origin, and may be volatile or non-volatile. They are used for food, fuel, medical purposes, lubrication, and the manufacture of many types of paints, plastics, and other materials.

[060] The above definitions supersede any conflicting definition in any of the literature that is incorporated by reference herein. The fact that certain terms are defined, however, should not be considered as indicative that any term that is undefined is indefinite. Rather, all terms used are believed to describe the invention in terms such that one of ordinary skill can appreciate the scope and practise the present invention.

[061] Other objects, features and advantages of the present disclosure will become apparent from the following detailed description. It should be understood, however, that the detailed description and the specific examples, while indicating specific embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.

Brief Description of the Drawings

[062] The following drawings form part of the present specification and are included to further demonstrate certain aspects of the present disclosure. The invention may be better understood by reference to one of these drawings in combination with the detailed description of specific embodiments presented herein.

[063] FIG. 1 depicts a simplified process flow diagram of a system according to embodiments of the present invention.

[064] FIG. 2 shows a representative embodiment of the apparatus of the present invention, in this case mounted within the front deck of a boat and thereby deliverable to the site of an oil spill, from which the inventive method can be performed in situ. In this representative embodiment, the apparatus for performing the method of the invention may be operatively associated with any applicable part of the boat, in this case, the front deck.

[065] FIG. 3 is a top view of a representative embodiment of the present invention. In this view, the apparatus is integrally associated with a speedboat of otherwise standard configuration. In this example, the apparatus is mounted to the rear of the boat.

[066] FIG. 4 is a top view of a representative embodiment of the present invention, in extended configuration as described herein. In this preferred embodiment, the boat is a catamaran or dual-hull that, when brought into remediation proximity with an oil spill is configured to extend laterally (or “spider”) by actuating the expandable aluminium floor as shown. It will be appreciated that the spidering configuration exposes a greater surface area of the remediation apparatus (e.g., scooping means) to the spill. In this embodiment, the width of the boat expands from about 3 m when in its normal configuration to about 5 m when expanded.

[067] FIG. 5 is a side view of a preferred embodiment of the invention with the remediation apparatus mounted towards the rear of the boat. In this configuration, contaminated sea water is moved up the inclined screw conveyor, through the two-way auger and into the centrifuge where separation takes place as described. The venturi blower then serves to reintroduce the remediated sea water back into the ocean following separation, and move the waste oil to a hull cavity for storage or to a balloon bladder as described. Detailed Description of a Preferred Embodiment

[068] Disclosed herein are compositions and methods for the in situ clean-up and/or remediation of oil or hydrocarbon spills and pollution using granulate. The method is generally as depicted in FIG. 1, with the apparatus deployed substantially as shown in FIGs. 2 to 5.

[069] Referring to the preferred embodiment shown in FIG. 2, the remediation apparatus (1) is located toward the front of the boat. In alternative embodiments, the remediation apparatus can be located anywhere within the vessel.

[070] Referring now to FIG. 3, which is a top view of a boat (2) that aside from the remediation apparatus (not shown) is of largely standard configuration. The boat has standard features including anchor bed (3), anchor drop (4), toilet (5), fuel tank (6), kitchen (7), water tank (8), void (9), outboard motor/s (10), a ladder fly bridge (11), seats (12) and table (13).

[071] Referring now to FIG. 4, a top view of a boat (2), in this case a catamaran, is shown in extended or “spidered” configuration. Comparable features are numbered as per FIG. 3.

However, in addition, this embodiment comprises boom winches (14), hydraulic telescopic expander retraction means (15), an expandable/extendible aluminium floor (16) to enable “spidering” as described above, one or more venturi blower/s (17), one or more centrifuge/s (18), a two-way auger (19) and an inclined screw conveyor (20).

Referring now to FIG. 5, a side view of the embodiment shown in FIG. 4 is depicted. Comparable features are numbered as per FIG. 4. FIG. 5 shows the relationship of the boat and remediation apparatus (1) with the water line (21). In particular, the inclined screw conveyor (20) is operatively associated with the water such that contaminated water is able to be moved up the conveyor (20), through the two-way auger (19) and into the centrifuge (18) at which point the remediation step takes place as described.

[072] The most critical period following an oil spill is the first 12 hours. In the case of an offshore spill, it is necessary to arrive on site as soon as possible in order to contain the spill. Once the spill is contained, remediation can begin. The longer a spill is left uncontained, the more it will spread due to currents, wind, etc., and the longer it will take to remediate the spill. The present invention provides a ready means of addressing these concerns.

[073] Adapting the present invention for the purposes of remediating, for instance, an offshore oil spill, the present inventor has modified the inventive apparatus such that it resides in and is operable from a speed boat. The speed boat, optionally powered by two 250 horsepower outboard motors, is ideally suited to arrive quickly at the site of a spill.

[074] Upon arriving at the scene of a spill, an operator’s first duty is to assess the spill and if possible, seek to contain it. The speed boat is optionally equipped with booms that allow the spill to be contained within 360 degree circumference. Once contained, the urgency to remediate the spill is reduced. However, in situations where the spill has already dispersed beyond the radius of the booms, time is of critical importance when it comes to beginning remediation.

[075] To facilitate greater collection area coverage, the speed boat is equipped with an expandable aluminium floor. This allows the speed boat to “spider” or expand in width from about 3 m to about 5 m, as shown.

[076] A venturi blower is then associated in, under and/or on top of the spill. In combination with the natural motion of the ocean, the oil spill is agitated and turns into a mass.

[077] In order to remediate the oil spill, the boom is retracted toward the boat, which brings the oil into association with scooping or extraction means attached to the apparatus.

Alternatively, the boat is driven to the precise location of the oil to be remediated and the oil extracted accordingly.

[078] In practice, the oil is extracted from the sea, or picked up using a sieve conveyor or any conveyor which in turn would drop the contaminated oil into a two-direction auger that will be sent to the centrifuge, where separation of oil and absorbent material occurs.

[079] Remediated oil is then pumped into either an allocated area in the hull or into an oil containment bladder which could be cast back into the water to pick up later if the spill is larger than the hull’s capacity to hold the remediated oil.

[080] The recycled absorbent material is then passed from the centrifuge to the venturi blower to be introduced back into the remaining oil spill.

[081] Once the decontamination is complete the sieve conveyor is packed into its allocated position and the expandable aluminium floor is retracted back into its original size. With the oil spill at least partially remediated, the boat is then returned to land with oil in the hull or towed in the containment bladder.

Oil spills

[082] An oil spill is the release of a liquid petroleum hydrocarbon into the environment, typically due to human activity. Often the term refers to marine oil spills, where oil is released into the ocean or coastal waters. The oil may be a variety of materials, including crude oil, refined petroleum products, such as gasoline or diesel fuel, oily refuse, or oil mixed in waste, or hydrocarbons generally. One example of a marine oil spill is that of the Exxon Valdez, in Alaska, 1989. Oil may also enter the marine environment from natural oil seeps such as Deepwater Horizon in the Gulf of Mexico, 2010. [083] The environmental effects include damage to wildlife, water purity and coastal areas. For example, oil will coat the feathers of birds, thereby reducing their insulating ability and make the birds more vulnerable to temperature fluctuations and much less buoyant in the water. Oil also impairs bird flight abilities. As they attempt to preen, birds typically ingest oil that covers their feathers, causing kidney damage, altered liver function, and digestive tract irritation. This and the limited foraging ability quickly cause dehydration and metabolic imbalances. Many birds affected by an oil spill will die unless there is human intervention.

[084] Other marine mammals are affected as well. For example, oil will coat the fur of sea otters and seals, reducing its insulation abilities and leading to body temperature fluctuations and hypothermia. Ingestion of the oil causes dehydration and impaired digestions. Beyond mammals, fish and invertebrates are also typically affected.

[085] Plant and algae species may also be affected by an oil spill. For example, because oil floats on top of water, less sunlight penetrates into the water, limiting the photosynthesis of marine plants and phytoplankton.

[086] By decreasing and disabling flora and fauna populations, part or all of a given coastal and/or marine ecosystem may be affected by an oil spill.

[087] Recovering oil depends upon many factors, including the type of oil spilled, the temperature of the water (in warmer waters, some oil may evaporate), and the types of shorelines and beaches involved.

[088] It will be appreciated that a remediation method that can be conducted in situ engenders significant advantages over an otherwise equivalent method conducted remotely, at an industrial site or in a laboratory.

Crude oil, hydrocarbons and petroleum

[089] Both crude oil and natural gas are predominantly a complex mixture of hydrocarbons of various molecular weights, and other organic compounds that are found in geologic formations beneath the Earth’s surface. Under surface pressure and temperature conditions, the lighter hydrocarbons methane, ethane, propane and butane occur as gases, while the heavier hydrocarbons from pentane upward are in the form of liquids or solids. However, in the underground oil reservoir the proportion which is gas or liquid varies depending on the subsurface conditions, and on the phase diagram of the petroleum mixture.

[090] The majority of hydrocarbons found naturally occur in crude oil, where decomposed organic matter provides an abundance of carbon and hydrogen which, when bonded, can catenate to form seemingly limitless chains. Extracted hydrocarbons in a liquid form are referred to as petroleum or mineral oil. A hydrocarbon is an organic compound consisting entirely of hydrogen and carbon. Aromatic hydrocarbons (arenes), alkanes, alkenes, cycloalkanes, and alkyne -based compounds are different types of hydrocarbons. The hydrocarbons in crude oil are mostly alkanes, cycloalkanes, and various aromatic hydrocarbons while the other organic compounds contain nitrogen, oxygen and sulphur, and trace amounts of metals such as iron, nickel, copper, and vanadium. The exact molecular composition varies widely from formation to formation.

[091] Hydrocarbons are one of the Earth’s most important energy resources. The predominant use of hydrocarbons is as a combustible fuel source. In their solid form, hydrocarbons take the form of asphalt. The Ce through Cio alkanes, alkenes and isomeric cycloalkanes are the top components of gasoline, naphtha, jet fuel and specialised industrial solvent mixtures. With the progressive addition of carbon units, the simple non-ring structured hydrocarbons have higher viscosities, lubricating indices, boiling points, solidification temperatures, and deeper colour.

[092] The proportion of light hydrocarbons in the petroleum mixture is typically highly variable between different oil fields and ranges from as much as 97 % by weight in the lighter oils to as little as 50% in the heavier oils and bitumen.

[093] As defined above, the term “oil” used herein encompasses crude oil, petroleum as well as refined or fractionated petroleum products and organic materials, including, fats, vegetable oils, fish oils and animal oils.

Hydrocarbon adsorption compositions

[094] In some aspects of the present disclosure, there are provided compositions for the adsorption or absorption of petroleum, oil or hydrocarbons. The compositions comprise adsorbents, which comprise granular material. In some embodiments the granular material comprises granulates of latex, polyolefins, rubber or mixtures thereof. In certain embodiments, the granular material used herein may be recycled waste latex, polyolefins, rubber or mixtures thereof.

[095] Granulates may be made or obtained from a variety of sources. For example, latex granulates may be derived from latex foam mattresses or pads, polyolefin granulates may be derived from polyolefin pads or mats, and rubber granulates may be derived from rubber foam pads or mats. These materials are readily available worldwide and utilised in different areas such as in bed mattresses, outdoor mats, pillows, and flooring.

[096] In some embodiments, granulates are obtained by cutting mattresses, mats, pads, or pillows into strips. In some of these embodiments, the strips are sized to accommodate the requirements of shredder. The strips may then be shredded into granules using a shredder or other cutting or grinding machinery.

[097] In some embodiments, the granulates have an average size from about 0.01 mm to about 100 mm, from about 0.02 mm to about 25 mm, or from about 0.05 to about 10 mm.

[098] In some embodiments, the granulates have a size diameter within any of the following ranges: 0.5 mm to 100 mm, 0.1 mm to 50 mm, 0.2 mm to 40 mm, 0.3 mm to 30 mm, 0.5 mm to 20 mm, 0.7 mm to 10 mm, 0.8 mm to 5 mm, or 1 mm to 2 mm. In some embodiments, the granulates have an average size of 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1 mm, 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, 10 mm, 20 mm, 30 mm, 40 mm, 50 mm, 60 mm, 70 mm, 80 mm, 90 mm, or 100 mm.

[099] In some embodiments, the some or all of the granulate may be open or closed cell foam material. In some embodiments, the granulate has a density lower than water. In some embodiments, some, or all of the granulate has edges.

[0100] In some embodiments, the granulate is stored vacuum bags. In some embodiments, it may be transported by road, rail, air, and sea.

In situ clean-up methods using granulate and reuse of granulate material

[0101] In some aspects of the present disclosure, there are provided methods for the adsorption or absorption of oil or hydrocarbons using granular material disclosed herein. The invention may be used to remove oil from contaminated sand, soil or other solids, or from contaminated water, for examples lakes, rivers, bays inlets, seas or oceans, or it may be used to remove oil from a stream of gas, example by passing the gas through the particulate foam of the invention [0102] The amount of granulate may be varied depending on the size of the oil or hydrocarbon spill. In some embodiments, the weight ratio of granulate to oil/hydrocarbon to be applied will be approximately 1:3, 1:4, 1:5, 1:7, 1:10 or 1:15. In some embodiments the granulate will be applied loosely, in other embodiments, a more densely packed granulate may be more suitable. [0103] In a water environment, the granulate may be applied, for example, using air, air pumps or venturi pumps. As shown in the example below, 100 grams of latex foam granulate material (mixture of 0.5 mm and 4 mm average diameter) will adsorb 400 grams of fuel oil. An additional test on an actual oil spill showed that 100 grams of granulate material (mixture of 0.5 mm and 3 mm average diameter) adsorbed 1 kg of fuel oil.

[0104] In a site comprising a mixture of sand or soil and optionally water, removal of oil or hydrocarbon may be accomplished in situ using the method of Example 2, below. This method may be further modified and optimised using the principles and techniques of environmental engineering. For example, the contaminated sand or soil and optionally water may be placed in a mixer. In the mixer, the contaminated sand or soil may be further mixed with diesel in order to liquefy any especially viscous hydrocarbon or oil.

[0105] An auger or an agitator may be used to transport the mixture to a centrifuge. The centrifuge may be used to separate the liquid hydrocarbons for the solid materials. Once separated, the liquid hydrocarbons are then typically pumped into a storage unit or tank. The remaining solids may be further treated in a separator comprising a sieve unit. There is the sand and/or soil particles may be rinsed and/or agitated with water to release the remainder of the hydrocarbon or oil. Once separated the lighter oil or hydrocarbon will float up, while the said or soil particles will typically settle to the bottom. The process may be repeated until the sand or soil is sufficiently clean to be reintroduced to the environment. The granulate material disclosed herein may be used before, during or after any of these steps.

[0106] In one aspect, the invention provides an adsorbent capable of reducing hydrocarbon pollution to an acceptable level. In some embodiments, the method removes greater than 90%, 95% or 98% of the hydrocarbon from the contaminated site, for example, from water or shoreline.

[0107] In some embodiments, admixing the adsorbent with oil or hydrocarbon polluted water will cause the oil to adsorb or absorb onto some or all of the granulate. Such oil/hydrocarbon adsorbed granulate may become a gelatinous mass that floats at the surface of the water, thereby simplifying recovery and removal of the oil/hydrocarbon from the water.

[0108] In accordance with the present invention there are provided methods of reusing granulate by removing any adsorbed or adsorbed hydrocarbons from the granulate. In some embodiments the oil or hydrocarbon is removed from the adsorbent using a centrifuge or a press. In some embodiments such a removal may occur in a series of stages. In some embodiments, this will cause most of or all of the oil or hydrocarbon to be separated from the adsorbent.

[0109] FIG. 1 depicts a simplified process flow diagram illustrating general, exemplary embodiments of the apparatuses and method of the present disclosure. This diagram is offered for illustrative purposes only, and thus it merely depicts specific embodiments of the present invention and is not intended to limit the scope of the claims in any way.

[0110] In the embodiment shown in FIG. 1, granulate 1 is be admixed with oil and/or hydrocarbon contaminated water in open water environment.

[0111] Aspects of the present invention include a method and apparatus for performing the process flow diagram as shown in FIG. 1. The apparatus in operatively mounted on a floating vessel such as a boat, where it can be readily delivered to the site of a spill, thereby enabling the in situ performance of the inventive method.

[0112] In some embodiments, the granulates will be transported to the oil or hydrocarbon spill site using bags. In some embodiments, the granulate may be dispersed using a blower or venturi. Dispersed granulates may be agitated together with the contaminated water mechanically, for example using agitator.

[0113] In some embodiments, the agitator is mechanical. In other embodiments, agitation is accomplished manually or naturally, for example, through currents or wave action. During the mixing and or agitation process the granulate will become coated with oil and/or hydrocarbons. The coated granulate may be reclaimed using, for example, sieves, nets, conveyors, or buckets, such as crane buckets. Further separation of the coated granulate from the water may achieved using separation conveyor.

[0114] The oil and/or hydrocarbons are then removed from the coated granulate using separator attached to a tank, optionally configured with an overflow protector. In some embodiments, the separator is a centrifuge, either continuous or discontinuous. In other embodiments, the separator is a press, either continuous or discontinuous. The cleaned water is transported into storage tank.

[0115] In some embodiments, the water is tested, for example, for biochemical oxygen demand. If the water is sufficiently clean, it may be reintroduced into the environment. In some embodiments, it may be necessary to further clean the water through additional granulate cleaning cycles or using other purification techniques before it can be reintroduced into the environment. Decorated granulate may transferred for reuse using a variety of devices, including blower conveyors, augers or venturi pumps.

[0116] In some embodiments, the granulate may be reused 30 times. In some embodiments, the granulate may be reused 50 times. Subsequently, any used or unused granulate by be recycled back into manufacturing, for example as primary filler or converted in booms and pillows.

Combination with other clean-up and recovery methods

[0117] The methods and compositions provided herein may be combined with other clean-up methods, including bioremediation, use of accelerators, controlled burning, use of dispersants or detergents, skimming, use of booms, use of vacuums.

[0118] Bioremediation involves the use of microorganisms or biological agents to break down or remove oil.

[0119] Accelerators are hydrophobic chemicals, containing no bacteria, which chemically and physically bond to both soluble and insoluble hydrocarbons. The accelerator acts as a herding agent in water and on the surface, floating molecules to the surface of the water to form gel-like agglomerates.

[0120] Controlled burning can effectively reduce the amount of oil in water. Dispersants and detergents will typically cluster around oil globules, allowing them to be carried away in the water.

[0121] Dredging may be used for oils dispersed with detergents and other oils denser than water.

[0122] Skimming may be used in combination the methods and compositions disclosed herein. Typically, this requires relatively calm waters.

[0123] The present methods and compositions may be combined with booms, which are large floating barriers that round up oil and may lift the oil off the water.

[0124] Vacuums may be used to remove oil from beaches and water surface. Similarly, shovels and other road equipment’s may be used to clean up oil on beaches

Examples

[0125] The following examples are included to demonstrate preferred embodiments of the invention. It should be appreciated by those of skill in the art that the techniques disclosed in the examples which follow represent techniques discovered by the inventor to function well in the practise of the invention, and thus can be considered to constitute preferred modes for its practise. However, those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed and still obtain a like or similar result without departing from the spirit and scope of the invention.

Example 1 — In situ remediation of contaminated sea water

[0126] Experimental design: 400 grams of fuel oil were mixed with 1.5 L of sea water. 100 grams of latex foam granulate material (mixture of 0.5 mm and 4 mm average diameter) material was added and mixed for 15 minutes. The latex foam granulate was made using plastic shredder. Floating material was skimmed with sieve (485 grams on air dried basis) from the water. The recovered materials were tested for oil and grease. Water was also tested for biochemical oxygen demand (BOD5).

[0127] The weight of the fuel oil after extraction from the water and subsequent air drying was 376 g/kg. After treatment, the BOD5 value was 19.5 mg/L. The granulate absorbed < 0.1% of water. [0128] Results:

[0129] This test shows that 100 grams of granulate adsorbs 400 grams of fuel oil. The data ably demonstrate the efficacy of the claimed method.

Example 2 — Contaminated sand test

[0130] Experimental design: Sand mixture containing 200 g/kg with fuel oil was obtained. 400 g sample of “clean” sand containing 200 g fuel oil were mixed with 20 g of granulate (mixture of 0.5 mm and 6 mm average diameter). Water at 35 °C (200 mL) were added and mixed for another 15 minutes. Floating material was skimmed with a sieve (weighed 155 g on air dried basis). Samples were tested and result and results are shown below.

[0131] This test showed that 20 grams of granulate adsorbed 135 grams of fuel oil, which represents a ratio of 1:7. The data further demonstrate the efficacy of the claimed method.

Example 3 — In situ gulf oil and water test

[0132] Materials:

[0133] Pillow stuffed with shredded latex particles from 1 mm to 10 mm in size.

[0134] A five-gallon bucket.

[0135] Crude oil from the Gulf of Mexico.

[0136] Hand strainer with 1 mm holes (normally for kitchen use).

[0137] Wash cloth.

[0138] Water, 4 gallons.

[0139] Process and results: In a simulated open water environment, conduced from the platform of a boat upon which the inventive apparatus was operatively mounted, the five-gallon bucket was filled with four gallons of water. A crude oil sample was taken from the container and placed it in a washcloth. The crude oil sample was squeezed into the washcloth to strain the crude oil into the bucket of water while keeping the sand in the washcloth.

[0140] At this point, the crude oil in the bucket of water was observed to float on or near the surface. One cup of shredded latex foam was spread across the surface of the oil/water. The mixture was agitated gently for 5 seconds. At this point the oil/latex foam granulate was observed to congeal, with the oil adhering to the latex foam.

[0141] The handheld strainer was used to scoop up the latex foam particles with the crude oil adhered to them. The water drains through the strainer back into the bucket leaving only the latex form with crude oil attached remaining in the strainer.

[0142] All of the methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. While the methods of this invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations may be applied to the methods and in the steps or in the sequence of steps of the method described herein without departing from the concept, spirit and scope of the invention.

[0143] More specifically, it will be apparent that certain agents which are both chemically and physiologically related may be substituted for the agents described herein while the same or similar results would be achieved.

[0144] All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the invention as defined by the appended claims.